JPS61233040A - Heat-resistant and impact-resistant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a composition containing a diene-acrylic copolymer, methyl methacrylate and N-arylmaleimide and having high fluidity and balanced and excellent heat-resistance and impact-resistance. CONSTITUTION:The objective composition containing 1-50wt% fattened rubbery copolymer is obtained by compounding (A) a diene-acrylate graft copolymer produced by (1) mixing (i) 100pts.(wt.) (in terms of polymer) of a rubber copolymer latex obtained by the emulsion polymerization of a 2-8C alkyl acrylate and 1,3-butadiene with (ii) 0.1-5pts. of polymer latex of an acid group-containing copolymer obtained by the emulsion polymerization of an unsaturated acid unit and a 1-12C alkyl acrylate and/or an alkali metal or alkaline earth metal salt of an oxyacid of an element of the 2nd or 3rd period of the group IIIA-VIA, and (2) polymerizing 10-1,000pts. of methyl methacrylate or styrene in the presence of 100pts. of the above latex fattened to an average particle diameter of 0.12-0.4mum and (B) a thermoplastic resin produced by polymerizing methyl methacrylate and N-arylmaleimide.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a thermoplastic resin with excellent heat resistance and impact resistance. The present invention relates to a thermoplastic resin composition comprising a thermoplastic resin comprising maleimide and optionally an aromatic vinyl compound, and gold.

[Prior art]

Until now, as a method to obtain thermoplastic resins with excellent heat resistance and impact resistance, graft copolymers, which are made by graft copolymerizing styrene or acrylonitrile to diene rubber, have been used.
A method of mixing a terpolymer consisting of α-methylstyrene, methyl methacrylate, and acrylonitrile (Japanese Unexamined Patent Publication No. 70143/1982) or a method of mixing a polycarbonate resin and a diene rubber (JP-A-57-70143). 1
No. 5225) and the like have been proposed. However, with these methods, it is difficult to obtain a thermoplastic resin with a good balance of heat resistance and impact resistance, and in the case of a mixture of /IJ car & nate and diene rubber, the flow processability is significantly reduced. The reality is that a material that has both heat resistance and impact resistance has not yet been developed.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a thermoplastic resin composition that has good flow processability and has an excellent balance of heat resistance and impact resistance.

[Means for solving problems]

The above objects of the present invention are H) 51 to 99% by weight of acrylic acid alkyl ester units having a full group having 2 to 8 carbon atoms, 49 to 1% by weight of 193-butadiene units, and other units copolymerizable with these; Rubbery copolymer [I] obtained by emulsion polymerization of a monomer mixture consisting of 10 to 0% by weight of functional or polyfunctional vinyl monomer units, based on 100 parts by weight of the polymer content of latex , (b) acrylic acid, methacrylic acid, itaconic acid,
3 to 40% by weight of at least one unsaturated acid unit selected from the group consisting of crotonic acid, maleic acid, hexamaric acid, cinnamic acid, sorbic acid and p-styrenesulfonic acid;
97 to 35% by weight of at least one acrylic acid alkyl ester unit whose alkyl group has 1 to 12 carbon atoms and 0 to 40% by weight of other copolymerizable monomer units or in different composition ratios. An acid group-containing copolymer (A) in a polymer latex state obtained by emulsion polymerization in stages or in multiple stages and/or a copolymer containing acid groups in the periodic table of elements At least one kind of oxyacid salt (B) selected from alkali metal salts or alkaline earth metal salts of oxyacids, zinc, nickel, and aluminum salts, mainly containing elements selected from the element group to which they belong (B) t - Adding 0.1 to 5 parts by weight to form a comb-like copolymer CI)
The latex is enlarged and the average particle size is adjusted to O, XZ ~ 0.
4 μm range, and further this enlarged rubbery copolymer [
I]' In the presence of 100 parts by weight of latex, (c) 50 to 100% by weight of at least one monomer unit selected from methyl methacrylate and styrene, and other monofunctional units copolymerizable therewith. The number of polyfunctional monomer units is 50
A monomer mixture consisting of ~0% by weight (010-1,000
Diene-acrylic graft copolymer C11 obtained by polymerizing in one step or more in two or more steps, with the same composition and proportions differing in parts by weight, and methyl methacrylate 99-
Thermoplastic resin (II)', which is a polymer of 35% by weight, 1 to 35% by weight of N-arylmaleimide, and 0 to 30% by weight of an aromatic vinyl compound and 10 to 98% by weight in the composition. 1 to 50% by weight of enlarged rubbery copolymer [:
This can be achieved by using a thermoplastic resin composition characterized by containing -I].

The composition of the present invention is characterized by the diene-acrylic copolymer (I) component and a thermoplastic resin (II[) made of methyl methacrylate, N-arylmaleimide, and optionally an aromatic vinyl compound. Through the synergistic effect with the other components, it is possible to exhibit excellent, well-balanced properties in heat resistance, impact resistance, and flow processability.

The diene-acrylic graft copolymer [■] has the effect of imparting impact resistance to the target resin composition,
A suitable amount is 2 to 90% by weight of the total resin composition, more preferably 5 to 50% by weight.

If the amount is less than 1 part by weight, the impact resistance will be poor, and if it exceeds 90% by weight, the heat resistance will be poor, both of which are not preferred.

Regarding the enlarged ratio comb-like copolymer [I]', it is appropriate to contain it in an amount of 1 to 50% by weight in the entire resin composition.

As mentioned above, the most important feature of the present invention is that the rubber-like copolymer CD is made of acrylic acid alkyl ester and 1,3-butanoene, which have a relatively low glass transition point (Tg), as the main copolymer components. and in their composition ratio, a predominant amount of alkyl 9acrylate unit, which has excellent weather resistance, is used, and a subordinate amount of 1,3-butadiene, which has excellent rubber properties, is used within a range that does not affect weather resistance; Next, the rubber-like copolymer is completely enlarged with a substance having a special structure as shown in (A) and (B) above to achieve a specific particle size range, and then hard resin is used to improve impact resistance. Graft copolymer obtained by graft polymerization of components (1
13 is used. Further, this graft copolymer can also be used by blending and dispersing it in other hard thermoplastic resins.

The rubbery copolymer [I] contains 51 to 99% by weight of an acrylic acid alkyl ester having 2 to 8 carbon atoms and 1,
It is obtained by total emulsion polymerization of a monomer mixture consisting of 49 to 1% by weight of 3-putazoene and 0 to 10% by weight of other copolymerizable monomers.

The acrylic acid alkyl ester used here is preferably butyl acrylate or 2-ethylhexyl acrylate. Other copolymerizable monomers include acrylonitrile, methacrylic acid alkyl esters such as methyl methacrylate, divinylbenzene, ethylene glycol dimethacrylate, butylene glycol diacrylate, and triaryl. These are polyfunctional monomers such as lucyanurate, triallylisocyanurate, trimethylolpropane triacrylate, and tantaerythritol tetraacrylate.

Emulsion polymerization itself can be carried out according to known methods.

Incidentally, when obtaining the rubbery copolymer, it is also possible to add a chain transfer agent such as mercaptan.

The particle size of the rubbery copolymer CI) obtained by emulsion polymerization is preferably in the range of 0.03 to 0.20 μm, and is preferably in the range of 0.03 to 0.20 μm.
The range of 0.05 to 0.15 μm is more preferable. Outside this range, it will be difficult to control the polymerization rate and polymerization temperature, the desired particle size will not be achieved during enlargement in the post-process, and the first polymerization system will become unstable, and the impact resistance of the final composition will deteriorate. Problems such as deterioration of appearance may occur.

Next, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and cinnamic acid.

A copolymer matrix containing at least one unsaturated acid monomer selected from sorbic acid and p-styrene sulfonic acid is used to thicken the rubbery copolymer latex.

It is essential that the copolymer contains the above-mentioned unsaturated acid monomer and acrylate, and at least one alkyl acrylate whose alkyl group has 1 to 12 carbon atoms is selected as the acrylate. It will be done.

However, in addition to acrylates, from 0 to 40 wt.
It is possible to use other copolymerizable monomers in combination. 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 amount of the unsaturated acid monomer used is 3 to 40% by weight. 3
If it is less than 40% ffi, the enlarging ability is small, and if it exceeds 40% ffi, the enlarging ability is too strong, which is not preferable, as it produces particles that are larger than 1 μm.

The optimum content of primary and unsaturated acid monomers varies depending on the degree of hydrophilicity of the acrylate used, and when the acrylate is highly hydrophilic, the amount of unsaturated acid monomers is small in the region where enlargement is prevented. Although this is effective, an increase in the amount of the unsaturated acid monomer is undesirable because the latex will be destroyed. Conversely, when the hydrophilicity of acrylate is low, the enlargement effect is small in the region where the amount of unsaturated acid monomer is low, and the effect is not seen until the amount of unsaturated acid monomer increases beyond a certain level. Not coming. For example, in the case of methyl acrylate and ethyl acrylate, which are highly hydrophilic acrylates, it is optimal when the amount of unsaturated acid monomer is 5 to 10.
In the case of butyl acrylate and 2-ethylhexyl acrylate, which are hydrophobic alkyl acrylates in which the alkyl group has 4 or more carbon atoms, the optimum amount is 13 to 20 units of unsaturated acid monomer. In addition, when a highly hydrophilic acrylate is used, the system tends to become unstable even when the amount of unsaturated acid monomer is 5 to 10%, and therefore cullets (coarse particles) are likely to occur. On the other hand, if a hydrophobic acrylate like the one described above is used, the system will not become unstable and uniform enlarged particles can often be obtained.

The acid group-containing copolymer (A) latex used in the present invention contains 3 to 40% by weight of at least one unsaturated acid selected from the above-mentioned unsaturated acids, and an alkyl group having 1 to 12 carbon atoms. At least one alkyl acrylate 97
~35% by weight and other copolymerizable monomers 0-4
Although it is possible to polymerize a monomer mixture consisting of 0% by weight at once, it is possible to polymerize a portion of the monomer mixture that is 5 to 90% by weight and does not contain the above-mentioned unsaturated acid. After that, the remainder of the monomer containing the unsaturated acid is
It is also possible to obtain a latex having a multilayer structure of two or more layers by successively polymerizing 10% by weight without forming new particles, that is, by polymerizing in two or more stages.

Alkali metal salts of oxyacids mainly consisting of elements selected from the group of elements belonging to the second and third periods of Groups 111A to VIA in the periodic table of the elements, and alkaline earth metal salts;
At least one oxyacid salt (B) selected from zinc, nickel and aluminum salts is also used as a thickening agent for the rubbery copolymer CD latex described above. Specific examples of such oxyacid salts include salts of sulfuric acid, nitric acid, phosphoric acid, etc., and potassium, sodium, magnesium, calcium, zinc, nickel, aluminum, etc. Preferred examples include potassium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, sodium phosphate, and magnesium phosphate.

As stated above, the acid group-containing copolymer (A) and the oxygen acid salt (B) may be used alone or in combination.

The acid group-containing copolymer latex and the oxyacid salt (B) are added to the rubbery copolymer [I]. When each of these is used alone, the amount of the acid group-containing copolymer (A) latex to be added is from 0 to 5 parts by weight, based on the base rubber [11,100 parts by weight, as the solid content of the polymer], preferably 0. .5 to 3 parts by weight. Further, the amount of the oxyacid salt (B) added is 100 parts by weight of the base rubber (:I)! D is 0.1 to 5 parts by weight, preferably 0.1 to 4 parts by weight. By adding an appropriate amount, the base rubber can be enlarged more efficiently.
The stability of the obtained large particle diameter rubber latex is also greatly improved.

When carrying out the enlargement treatment of the present invention using the acid group-containing copolymer (A), - of the base rubber (1) latex is preferably 7 or more. If the value is on the acidic side, even if the acid group-containing copolymer (A) latex is added, the enlargement efficiency will be low, and the composition targeted by the present invention may not be advantageously produced. be.

When the pH of the base rubber [I] latex is adjusted to 17 or higher, the tone adjustment may be performed during the production of the base rubber [I] or separately before the enlargement treatment.

Rubber-like copolymer subjected to enlargement treatment in this way [■
]' By polymerizing 10 to 1,000 parts by weight of monomer (C) r containing 50% by weight or more of styrene and/or methyl methacrylate in the presence of 100 parts by weight of latex, the desired impact-resistant resin can be obtained. is obtained. As monomers to be grafted to rubber latex, styrene alone,
In addition to methyl methacrylate alone, there are also styrene-acrylonitrile monomer mixtures, styrene-acrylic ester monomer mixtures, methyl methacrylate-acrylonitrile monomer mixtures, methyl methacrylate-acrylic ester monomer mixtures, etc. A monomer mixture of three or more of these monomers can also be used.

Alternatively, a known polyfunctional monomer (divinylbenzene, 1.4-'j'' tandiol diacrylate, etc.) may be added to the monomer or mixture thereof that is primarily composed of methyl methacrylate and/or styrene gold. It is also possible to carry out polymerization in two or more steps, such as a method in which a monomer or a mixture thereof is graft-polymerized without adding a polyfunctional monomer after graft polymerization by adding a polyfunctional monomer.

In this emulsion graft polymerization, commonly known emulsifiers and catalysts are used, and there are no particular restrictions on the type and amount added.

The thermoplastic resin [■] in the present invention contains 99 to 35% by weight of methyl methacrylate and 1 to 35% by weight of N-arylmaleimide.
It is a polymer containing 0 to 30% by weight of an aromatic vinyl compound and has the basic FC function of imparting heat resistance and flow processability to the final resin composition. Thermoplastic resin C
The composition ratio of the constituent units of methyl methacrylate, N-arylmaleimide, and aromatic vinyl compound in I [I] is determined from the balance of heat resistance, weather resistance, polymerization rate, flow processability, etc. of the thermoplastic resin [■]. If any of the monomer components is outside the above range, problems such as poor heat resistance and weather resistance, extremely low productivity, etc. will occur.

N-arylmaleimide used in the present invention N
- Phenylmaleimide and its substituted derivatives, from the viewpoint of industrial production, are particularly suitable for the following formula (1) (wherein R1, R2 and R3 are each hydrogen, carbon number 1 -
An arsenic compound represented by an alkyl group or a halogen of 4 is preferred. The above halogen substituted products are preferably chlorine and bromine substituted products.

To give a specific example, N-(2-chlorophenyl)ma1
/'fmi)', N-(2-bromphenyl)maleimide, N-(A-chlorophenyl)maleimide, N-(2
,4,6-)lychlorphenyl)maleimide, N-(2
-1tylphenyl)maleimide, N-(A-methylphenyl)maleimide, N-(2-tbutylphenyl)maleimide, N-(A-tbutylphenyl)maleimide)',
N-(2,6-dimethylphenyl)maleimide, and N
-(2-ethylphenyl)maleimide and the like.

Furthermore, in order to improve the physical properties of the thermoplastic resin composition of the present invention (for example, to reduce water absorption), or to improve the productivity of the thermoplastic resin CI[], the thermoplastic resin (I[[] In the production of , aromatic vinyl compounds can be used as necessary.

The amount used is 0 to 30% by weight based on the total amount of the monomer mixture.
, preferably in the range of #ii to 30% by weight.

The role of aromatic vinyl compounds in improving the productivity of thermoplastic resin [■] will be explained as follows.

The copolymerizability of methyl methacrylate and N-arylmaleimide is relatively low for N-arylmaleimide;
- When producing thermoplastic resin (:II[)' from a monomer mixture containing a large amount of arylmaleimide, a large amount of unreacted N-arylmaleimide remains.

A large amount of residual monomer causes deterioration of the moldability and heat resistance of the target thermoplastic resin composition. It is preferable to use the obtained polymer beads after washing them with a solvent that does not dissolve the polymer beads (for example, methanol solution).

In this case, the amount of remaining monomer should be 2 or less.

,! =<KN-arylmaleimide is desirably reduced to 1% or less. On the other hand, by substituting a part of methyl methacrylate with an aromatic vinyl compound, the copolymerizability of N-arylmaleimide is improved and the amount of residual monomer is reduced to the desired value. The thermoplastic resin [■] obtained even in a polymerization system with a relatively high proportion of .

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

Typical examples of aromatic vinyl compounds used in the present invention include styrene, aralkylstyrene, etc.
- and p-methylstyrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, alethylstyrene,
p-tertiary butylstyrene, etc., α-methylstyrene, α
-ethylstyrene, α-methyl-p-methylstyrene,
Examples include monovinylidene aromatic hydrocarbons such as vinylnaphthalene, alhalomonovinylidene aromatic hydrocarbons such as 0-lm- and p-chlorostyrene, 2,4-dipromostyrene, and 2-methyl-4-chlorostyrene. .

In long-term production using alhalomonovinylidene aromatic hydrocarbons, it is necessary to take measures against corrosion of the equipment. From the viewpoint of productivity and balance in physical properties, it is particularly desirable to use at least one selected from the group consisting of styrene, vinyltoluene and α-methylstyrene.

If necessary, up to 10% of other copolymerizable monomers can be used as the fourth component within a range that does not impede the spirit of the present invention. Acrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms or 2 to 1 carbon atoms
Preferred examples include methacrylic acid alkyl esters having an alkyl group of 0. One or more types of these may be used.

In addition, thermoplastic resin [1[1]' is mixed with diene-acrylic copolymer [1[] and other resins (IVI) to develop good compatibility and give a desirable flow to the final resin composition. Resin [111) 2 to impart properties
Intrinsic viscosity in chloroform at 5°C is 0.3 to 0.8 dl
It is preferably in the range of li.

The blending ratio of the thermoplastic resin CII [) is 10 to 98% by weight, preferably 20 to 90% by weight, in the final resin composition.
If it is less than 0% by weight, heat resistance and flow processability tend to be poor, and if it exceeds 98% by weight, impact resistance tends to be poor.

The resin [■] can be produced by a commonly used polymerization method such as suspension polymerization, bulk polymerization, or solution polymerization of the above monomer mixture using a radical polymerization initiator.

The enlarged rubbery copolymer [I]'t-
Although it can be contained in an amount of 1 to 50% by weight, it is particularly preferably contained in an amount of 5 to 40% by weight.

Outside this range, disadvantages such as poor impact resistance and low heat deformation temperature occur, which is undesirable.

In the series of emulsion polymerizations up to the production of the graft copolymer [■], commonly known emulsifiers and catalysts are used, and their types and amounts are not particularly limited. The diene-acrylic graft copolymer (11) latex obtained by the emulsion polymerization method is coagulated and dried by a known method.

In the present invention, diene-acrylic graft copolymer [■]
and thermoplastic resin [■]. Depending on the purpose of use, other methacrylic resins, polycarbonate,
AS resin, methyl methacrylate-styrene copolymer, ?
At least one resin selected from listyrene, polyester (polyethylene terephthalate, polybutylene terephthalate), and polyamide may be added to the IVI composition in an amount of 89% by weight or less, preferably 70% by weight or less. For example, when extremely good weather resistance is required, methacrylic resins and polyethylene terephthalate resins are suitable; when a high degree of flow processability is required, polystyrene, AS resins and methyl methacrylate-styrene resins are suitable. Copolymers are used.

Furthermore, in the composition of the present invention, stabilizers, lubricants, plasticizers, dyes and pigments, fillers, etc. are added as appropriate, and mixed in a V-type blender, Henschel mixer, etc., and then mixed. Melt mixing is performed at 150 to 300°C using a roll or screw extruder.

The present invention will be explained in more detail based on the following examples.

In the examples, "part" means part by weight, and "chi" means % by weight.

Manufacture Nibutyl Acrylate 6
Yu1,3-butadiene
4kg diisopropylbenzene hydroperoxide 2
0. 9 Beef tallow fatty acid potassium 100 1N
- Sodium lauroyl dercosinate 50 〃Sodium birophosphate 50 “
Ferrous sulfate 0.5N Dextrose 30 Deionized water 20 kg Among the substances with the above composition ratios, for substances other than 1,3-butadiene, the oxygen contained therein is replaced with nitrogen to substantially polymerize. The reaction was not inhibited. After that, the material was placed in a T-401 autoclave and polymerized at 50℃. Polymerization was almost completed in 9 hours, and a rubber latex with a conversion rate of 97% and a particle size of 0.07 μm was obtained.

Formation: A mixture of the above composition was placed in a 51 glass round bottom flask and polymerized at 70°C for 1.5 hours, followed by dropwise addition of the mixture t-1 at 70°C over a period of 1 hour, followed by 1 hour. Stirring was continued to obtain a copolymer latex with a conversion rate of 98%.

Preparation of enlarged rubbery polymer [I]′: Rubbery copolymer CI containing polymer solids content 10kf9)
While stirring the *60J autoclave containing latex, add 10% sodium sulfate aqueous solution i, s kg'6
, after adding at an internal temperature of 50°C and holding for 15 minutes, (A-1)
152 g of latex was added and held for 30 minutes. The average particle diameter of the obtained mucilaginous polymer [■]' with a sub-thickening ratio of 0.14
Production of 〇kusu with a diameter of 8 μm Polymer solid content of enlarged rubbery copolymer [I]′ 10 k
Contains enlarged latex containing g. Into the enlarged reaction vessel, 9 g of deionized water, 20 g of sodium formaldehyde sulfoxylate (so, pt) of sodium N-lauroyl dercosinate were added, and the internal temperature was raised to 75°C, and the following material t-90 was added. Polymerization was carried out by continuous addition at a rate of 9 minutes.

Methyl methacrylate 4320
11 Ethyl acrylate 18
0 11 normal octyl mercaptan
6.75 #cumene hydroperoxide
After the addition of 16 g was completed, polymerization was continued for an additional 60 minutes, and the conversion rate of methyl submethacrylate was approximately 100%.

Styrenated phenol 5 was added to the resulting specific polymer latex.
8 g, dilauryl thiopropionate 44.9, triphenyl phosphite 581, diluted with 0.25% sulfuric acid water at 50°C, latex/water = 1/
2 and then kept at 85° C. for 5 minutes.

The resulting slurry polymer was washed, dehydrated, and dried at 65°C for 36 hours to obtain a white powder. This powdered resin [I
[-D.

Rubber-like copolymer [13k] Powder resin [1l-2E ~ [Toro]
I got it.

In addition, the composition and ratio of the monomer mixture components constituting the acid group-containing copolymer (llA), the amount of the acid group-containing copolymer (A) latex added to the rubber latex [■], and the type of oxyacid salt. and the amount as shown in Table 2, and except for the following, [1
1-13 in exactly the same way as manufacturing […-7] ~
Cl-133 was produced.

Furthermore, except for changing the composition ratio and the amount of the monomer mixture (C) when carrying out graft polymerization as shown in Table 3 [1-1
[1l-14) ~ Cl0
I remember -183.

In addition, in [1l-18), the graft polymerization was performed at the t-2 stage. First, monomer mixture (C-1) was continuously added for 30 minutes to polymerize, and after the addition was completed, polymerization was continued for another 60 minutes. Next, 7 tons of monomer mixture (C-2) was continuously added for 90 minutes to polymerize, and after the addition was completed, polymerization was continued for another 60 minutes. (C-1).

The same amount of cumene hydroxyperoxide as CI[-D was added to (C-2).

(2) Production of thermoplastic resin CII[): CI[[-
13 Using a pressure-resistant polymerization kettle with an internal volume of 507 cm, 27 parts, 9 parts deionized water, 1 part copolymer 3I consisting of methyl methacrylate and 2-sulfoethyl methacrylate as a dispersant, and sodium sulfate 90Ii? Charge, 80 parts of methyl methacrylate, N-
18 kg of a monomer solution consisting of 20 parts of phenylmaleimide, 0.26 parts of n-octyl mercaptan, 0.1 part of azobisisobutyronitrile, and 0.1 part of stearic acid monoglyceride was charged and heated with nitrogen at 101/min while stirring at 200 rpm. Bubble the mixture for 20 minutes at the same rate to remove oxygen from the system, and heat it to 80°C for 2 hours to carry out suspension polymerization.
The temperature was further raised to 105°C and held for 15 minutes for post-treatment, followed by cooling, washing with water, and drying to obtain bead-shaped polymers with an average particle size of 0.3 ◎ (III-23 and (II-33 monomer solution) Except for the following convention (:lll-1
) to obtain bead-like polymers with an average particle size of 0.3 .mu.m.

Monomer solution composition In both CI[[-1] and CII[-21], N-arylmaleimide in the bead-like polymer is 1%.
Therefore, 300 parts by weight of methanol was added to 100 parts by weight of bead-like I reamer, washed at 40° C. for 1 hour, and dried. The residual monomer in the beads after treatment was 0.3% or less in all cases.

[''111-43 The procedure was the same as CI [-1] except that the monomer solution was used as shown below and the polymerization time was 3 hours to obtain a bead-shaped polymer with an average particle size of 0.3.

Methyl methacrylate 70 parts N
-7 Enylmaleimide 15 parts Styrene z 5 parts α Methyl styrene 7.5 parts n-
Octyl mercaptan 0.15 parts Azobisisobutyronitrile 0.3 parts Stearic acid monoglyceride 0.1 part CII[-51 Except for using the monomer solution as follows [:II[-4
In the same manner as in 3, bead-shaped polymers with an average particle size of 0.3 gourd were obtained.

Methyl methacrylate 84 parts N
-(2-methylphenyl)maleimide 9 parts α-methylstyrene 6 parts Methyl acrylate 1 part n-octyl mercaptan 0.18 parts Azobisisobutyronitrile 0.3 parts Stearin ζ monoglyceride 0.1 part Cm-6] d[:II[-] except that the monomer solution is as follows:
The procedure was carried out in exactly the same manner as in No. 43 to obtain bead-shaped polymers with an average particle size of 0.3 m.

Monomer solution composition Methyl methacrylate 75 parts N-(2-chlorophenyl)maleimide 15 parts α
-Methylstyrene 6p-methylstyrene 4n-octylmercaptan 0.14 Azobisisobutyronitrile 0.35 Stearic acid monoglyceride 0.1C1[1-4]~
In Clll-61, the residual monomer in the beads was 2% or less, and the N-arylmaleimide content was 0.2% or less, so it was used as is without any post-treatment.

Example 1 Powder resin Cl-1) 2.9 kg and thermoplastic resin CI
[-3]7.1 kg, stearic acid monoglyceride IOF, ultraviolet absorber (Tinupin-P/Sanol LS7
70: Ciba Geigy/Sankyo ■Ura product) 20Ii/30,
9) Mix in a 201 capacity Henschel mixer;
Next, a 30 mφ twin-screw extruder (PCM manufactured by Ikegai Iron Works)
-30) at a temperature of 230 to 250°C and a rotational speed of 25 Orpm. This pellet-shaped resin was molded into a 110xl 10x2 screw injection molding machine (manufactured by Nippon Koshiko Co., Ltd.: Ankerperk V-17-65 type) at a cylinder temperature of 250°C and an injection pressure (Guno pressure) of 50 kg/cm2. (Thickness) Proverbs and 70X12.5
A WO test piece of X6.2 (thickness) was prepared and the results shown in Table 4 were obtained.

Example 2 Example 1 except that [lll-5) is used as the thermoplastic resin
The results in Table 4 were obtained in exactly the same manner as above. In Examples 1 and 2, the amount of enlarged rubbery copolymer [I]' in all the resins was 20.

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

The heat resistance was measured in exactly the same manner as in Example 1 except that a methacrylic resin (Acrypella VH) was used instead of the thermoplastic resin CI[].The results were 94℃ and Izod impact strength (2
3℃) is 94kgc! n/- type Examples 1 and 2 have excellent properties.

Examples 3 to 7: Comparative Examples 1 to 5 Diene-acrylic copolymer (Il) and thermoplastic resin [
A resin composition was obtained in exactly the same manner as in Example 1, except that the type and blending ratio of 1[1] were as shown in Table 5. The results are summarized in Table 5.

The proportions of the enlarged rubbery copolymer in all the resins in Examples 3 to 7 were 15.5%, 15.5%, and 15.5%, respectively.
, 10.3%, and 24.1%.

The results in Table 5 show that compared to the compositions according to the present invention (Examples 3 to 5), rubbers with more butadiene units have inferior heat stability and weather resistance (Comparative Examples). 1).

Rubber containing a large amount of styrene units has poor impact resistance (Comparative Example-2).

Rubber containing no butadiene units has poor low-temperature impact resistance (Comparative Example-3).

If the blending ratio is outside the range of the present invention, fluidity may be poor or
Impact resistance is poor (Comparative Examples 4 and 5).

Examples-8 to 11. Comparative Examples 6 to 8 Composition and ratio of monomer mixture components forming 1 m of acid group-containing copolymer (A), amount of acid group-containing copolymer (A) latex added to rubber latex [■], oxygen acid Changed the type and amount of salt [Door] ~ [l-13] Except for being all around,
An impact-resistant thermoplastic resin composition was obtained in exactly the same manner as in Example-1. The evaluation results are shown in Table-6.

From this result, it can be seen that the products produced by methods other than the present invention do not have enlarged combs and have inferior physical properties.

The proportion of the enlarged rubbery copolymer [I]' in the total resin is 15.5%.

Examples-12 to 16 Composition ratio and amount of monomer mixture (C) when performing graft polymerization, and thermoplastic resin (II
An impact-resistant thermoplastic resin composition was obtained in exactly the same manner as in Example 1, except that the type and amount of I) and the cylinder temperature during injection molding were changed as shown in Table 7. The evaluation results are shown in Table-7. The proportion of the enlarged plumy copolymer [■]' in all the resins of Examples 12 to 16 was 15.
5.15.5°15.0, 15.5, 15.5%.

Examples 17 to 22; Comparative Examples 9 and 10 The types and blending amounts of resin powder [■], thermoplastic resin (III), and other resins (IV) were changed to those shown in Table 8, and the injection molding temperatures were The results shown in Table 8 were obtained by carrying out the same procedure as in Example 1, except that Step 8 was used.

In addition, the proportion of the enlarged mucous copolymer [1]' in all the resins of Examples 17 to 22 was approximately 10°24.1, respectively.
0, 7, 14, 10chi.

Methacrylic resin (manufactured by Mitsubishi Rayon ■, Acrivet (trademark) VH); MS resin (methyl methacrylate-styrene copolymer) (
Clear rack (trademark) M-10 manufactured by Mitsubishi Rayon (I)
0): Polycarbonate resin (manufactured by Mitsubishi Chemical Industries, Ltd., Tubarex (trademark) 7022A): Polyethylene terephthalate resin (manufactured by Mitsubishi Rayon, Ltd., Diamond (trademark) M-500); Polybutylene terephthalate resin (Mitsubishi Rayon (manufactured by (E), Toughpet (trademark) NIloo): Polystyrene resin (made by Mitsubishi Monsanto Kasei@), Dialex (trademark) HH1
02): [Effects of the Invention] As detailed above, by molding the thermoplastic resin composition of the present invention using an extrusion molding machine, an injection molding machine, etc., heat resistance and impact resistance can be improved. Since excellent molded products can be obtained, it is useful for applications such as vehicle exterior parts, solar system equipment parts, and electrical equipment parts.

Claims (2)

[Claims] (1) (i) 51 to 99% by weight of acrylic acid alkyl ester units whose alkyl group has 2 to 8 carbon atoms, 49 to 1% by weight of 1,3-butadiene units, and other monofunctional units copolymerizable with these or polyfunctional vinyl monomer unit 10-0
Rubber-like copolymer [I] latex obtained by emulsion polymerization of a monomer mixture consisting of 100% by weight
(b) at least one unsaturated member selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid, sorbic acid, and p-styrenesulfonic acid, based on the weight part; 3-4 acid units
0% by weight, 97% to 35% by weight of at least one acrylic acid alkyl ester unit whose alkyl group has 1 to 12 carbon atoms, and 0% to 40% by weight of other copolymerizable monomer units, in the same or different compositions. Acid group-containing copolymer (A) in a polymer latex state obtained by emulsion polymerization in one step or in multiple steps and/or the second and third period of Groups IIIA to IVA of the periodic table of elements. At least one oxyacid salt (B) selected from alkali metal salts or alkaline earth metal salts of oxyacids, salts of zinc, nickel, and aluminum, mainly containing elements selected from the element group belonging to The rubbery copolymer [I] latex is enlarged by adding 0.1 to 5 parts by weight of
μm range, and furthermore, this enlarged rubbery copolymer [
I]' In the presence of 100 parts by weight of latex, (c) 50 to 100% by weight of at least one monomer unit selected from methyl methacrylate and styrene, and other monofunctional units copolymerizable with this; 50 or more functional or polyfunctional monomer units
Monomer mixture (C) consisting of 0% by weight 10-1,000
Diene-acrylic graft copolymer [II] obtained by polymerizing parts by weight in one step or two or more steps with the same or different compositions and proportions, and methyl methacrylate 99-3
5% by weight, 1 to 35% by weight of N-arylmaleimide, and 0 to 30% by weight of an aromatic vinyl compound. % of a thickened rubbery copolymer [I]'. (2) At least one resin selected from methacrylic resin, polycarbonate, AS resin, methyl methacrylate-styrene copolymer, polystyrene, polyester, and polyamide [IV] 89% by weight or less is added in Claim 1 2.Resin composition.