JPH0725965B2 - Weather resistant heat resistant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a copolymer composition having an aromatic vinyl monomer residue and an unsaturated dicarboxylic acid imide derivative residue. Molded articles obtained from the composition are parts for automobiles such as instrument panels and meter hoods,
Parts for railway vehicles or ships such as surface panel materials and coating materials,
It can be preferably used in a field requiring weather resistance in addition to heat resistance, such as a solar water heater component.

(Prior Art) A rubber-reinforced resin graft product comprising a monomer mixture containing an aromatic vinyl monomer in a so-called imidized copolymer containing an aromatic vinyl monomer and an unsaturated dicarboxylic acid imide, and a rubber-like polymer. A composition containing (JP-A-60-23438)
Since it gives a molded product having an excellent heat resistance-impact resistance balance, it is expected to be applied to applications such as automobile parts. However, the conventional compositions including this disclosed example have a difficulty in weather resistance of the finally obtained composition because polybutadiene is used as a rubber component in the rubber-reinforced resin graft product, and thus various automotive parts. However, it has a drawback that it has a limit in outdoor use for a long period of time, although it has heat resistance and impact resistance enough to be used for such purposes. In order to obtain a rubber-reinforced resin graft product having excellent weather resistance, a method is generally known in which the rubber component is replaced with a rubber having good weather resistance, for example, an acrylic rubber mainly containing alkyl acrylate.

(Problems to be solved by the invention) However, acrylic rubber is generally slightly inferior in rubber elasticity to polybutadiene rubber, and in order to obtain impact resistance equivalent to that of polybutadiene, the rubber content in the resin graft product must be increased. However, the rigidity and heat resistance of the composition comprising the resin graft product as a constituent component are deteriorated. Therefore, even if a rubber-reinforced resin graft product having an acrylic rubber as a constituent is blended with the imidized copolymer, the weather resistance is improved as compared with the case where a polybutadiene-containing rubber-reinforced resin graft product is blended, while polybutadiene is used. In order to obtain the same impact resistance as in the above case, the result is that the rubber content must be increased to lower the heat resistance level.

(Means for Solving the Problems) Then, the inventors of the present invention have diligently studied to obtain a resin composition having such weather resistance and sufficient heat resistance and impact resistance. Polymerization of a monomer mixture containing an aromatic vinyl monomer into a linear polymer in the absence of a chain transfer agent (as is added in ordinary graft polymerization for the purpose of improving resin moldability). By blending the resulting graft copolymer (having a high molecular weight of the resin component) (that is, an acrylic rubber-reinforced resin graft product) with the imidized copolymer, a large amount of an acrylic rubber-like polymer is not included. It was found that a weather-resistant heat-resistant resin composition having sufficient impact resistance and a high level of heat resistance was obtained, and the present invention was completed.

That is, the present invention comprises the following component A of 10 to 90% by weight and component B of 10 to
A heat-resistant resin composition having excellent weather resistance consisting of 90% by weight and 0 to 80% by weight of C component. A component: 35 to 80% by weight of aromatic vinyl monomer residue, unsaturated dicarboxylic acid imide derivative. Residue 20-65% by weight, vinyl monomer residue 0-30% by weight other than these, and rubber-like polymer 0
Copolymer containing about 30 to 30% by weight, component B: 60 to 99.99% by weight of an alkyl acrylate having an alkyl group having 1 to 13 carbon atoms, 0 to 40% by weight of a vinyl monomer copolymerizable therewith, and one Aromatic vinyl monomer 40 to 90% by weight based on 5 to 80 parts by weight of an acrylic rubber-like polymer consisting of 0.01 to 20% by weight of a crosslinkable compound having two or more carbon-carbon unsaturated bonds in the molecule. A monomer mixture for graft polymerization, comprising 0 to 40% by weight of a vinyl cyanide monomer and 0 to 40% by weight of a vinyl monomer copolymerizable therewith
Graft copolymer obtained by polymerizing 20 to 95 parts by weight in the absence of a chain transfer agent, C component: aromatic vinyl monomer 40 to 90% by weight, vinyl cyanide monomer 0 to 40% by weight And a copolymer comprising 0 to 40% by weight of a vinyl monomer copolymerizable therewith.

The resin composition of the present invention may be composed of only the component A and the component B, but the aromatic vinyl copolymer of the component C may be mixed therein in an amount of 80% by weight or less. Since the excellent properties of the thermoplastic resin are not deteriorated, it has an advantage that a large amount of inexpensive aromatic vinyl copolymer can be blended.

First, the component A will be described.

The aromatic vinyl monomer residue constituting the copolymer is a styrene monomer such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, or a substitution product thereof. Is particularly preferable. The unsaturated dicarboxylic acid imide derivative residue contained in the copolymer is an imide derivative obtained by copolymerizing an unsaturated dicarboxylic acid anhydride and then reacting it with ammonia and / or a primary amine. Good
Alternatively, it may be obtained by directly copolymerizing an imide monomer such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, or N-naphthylmaleimide.

However, as a method for producing a copolymer, the former method, that is, a method in which an unsaturated dicarboxylic acid anhydride is copolymerized with an aromatic vinyl monomer and then imidized is more preferable in terms of copolymerizability and physical properties of the copolymer. preferable.

Examples of unsaturated dicarboxylic acid anhydrides include anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid.
Of these, maleic anhydride is particularly preferred.

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

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 may be used. 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 80-350 ° C, preferably 1
It is from 00 to 300 ° C. If the temperature is below 80 ° C, the reaction rate will be slow,
The reaction takes a long time and 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 to be reacted is preferably 0.8 molar equivalent or more with respect to the unsaturated dicarboxylic acid anhydride group. When it is less than 0.8 molar equivalent, the acid anhydride group becomes large in the imidized polymer, and the thermal stability and hot water resistance deteriorate, which is not preferable.

A vinyl monomer residue other than the aromatic vinyl monomer residue and the unsaturated dicarboxylic acid imide derivative residue is the same as the aromatic vinyl monomer and the unsaturated dicarboxylic acid anhydride and / or the unsaturated dicarboxylic acid imide. It is a monomer residue based on a polymerized vinyl monomer.

Vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc., as vinyl monomers copolymerizable with aromatic vinyl monomers and unsaturated dicarboxylic acid anhydrides and / or unsaturated dicarboxylic acid imides , Acrylic acid alkyl ester monomers having an alkyl group having 1 to 13 carbon atoms, methacrylic acid alkyl ester monomers having an alkyl group having 1 to 4 carbon atoms, vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid , Acrylic acid amide, methacrylic acid amide and the like, and of these, acrylonitrile, methacrylic acid alkyl ester, acrylic acid and methacrylic acid are preferred. Incidentally, when the aromatic vinyl monomer and the imide monomer are directly copolymerized, unsaturated dicarboxylic acid anhydrides are also included. Further, when the aromatic vinyl monomer and the unsaturated dicarboxylic acid anhydride are copolymerized and then imidized, the unsaturated dicarboxylic acid anhydride residue remaining without being imidized is also a monomer based on the vinyl monomer. As a body residue.

As the rubber-like polymer, a butadiene polymer, a copolymer of a vinyl monomer copolymerizable with butadiene, ethylene-
A propylene copolymer, a block copolymer of butadiene and aromatic vinyl, an acrylic acid alkyl ester polymer, and a copolymer of an acrylic acid alkyl ester and a vinyl monomer copolymerizable therewith are used. Among these, ethylene-propylene copolymer and alkyl acrylate copolymer are particularly preferable in consideration of the weather resistance of the finally obtained composition. However, when considering the final balance of physical properties (weather resistance and impact resistance), a butadiene copolymer can be sufficiently used.

The aromatic vinyl monomer residue contained in the component A is 35 to 85% by weight, and if it is less than 35% by weight, the moldability and dimensional stability characteristic of the aromatic vinyl compound are impaired. Also,
Unsaturated dicarboxylic acid imide derivative residue is 20-
If it is contained in an amount of 65% by weight and less than 20% by weight, the heat resistance of the finally obtained composition will be insufficient, and if it exceeds 65% by weight, the copolymer will be brittle and the moldability will be markedly deteriorated.

A vinyl monomer residue and a rubber-like polymer other than the aromatic vinyl monomer residue and the unsaturated dicarboxylic acid imide derivative residue,
Each of them can be used in a range not exceeding 30% by weight in the component A, but if it exceeds 30% by weight, it is not preferable in terms of heat resistance and molding processability.

Next, the B component will be described.

The rubber component in the component B is an alkyl acrylate ester having an alkyl group having 1 to 13 carbon atoms, preferably methyl acrylate, ethyl acrylate, butyl acrylate,
2-ethyl-hexyl acrylate is a main component, but vinyl or vinylidene monomers copolymerizable with them, for example, styrene-based monomers such as styrene, α-methylstyrene and vinyltoluene, acrylonitrile,
Vinyl cyanide monomer such as α-chloroacrylonitrile, methacrylic acid alkyl ester monomer having an alkyl group having 1 to 4 carbon atoms, vinylcarboxylic acid monomer such as acrylic acid and methacrylic acid, acrylic acid amide, methacrylic acid It is also possible to copolymerize acid amide, N, N'-dimethylacrylamide, vinyl norbornene and the like within a range not exceeding 40% by weight. If it exceeds 40% by weight, rubber elasticity, etc.
The characteristics of the rubber may be impaired, which is not preferable. Acrylic rubber is susceptible to deformation during molding and processing in the uncrosslinked state, which may result in deterioration of physical properties. Therefore, when polymerizing rubber, two or more C = C in one molecule
A crosslinking compound having an unsaturated bond is added, and crosslinking is carried out simultaneously with the polymerization. Examples of the crosslinkable compound include divinylbenzene, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, and other diacrylate compounds, trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylolmethane triacrylate, and other triacrylate compounds. Acrylate compounds, dimethacrylate compounds such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate and triethylene glycol dimethacrylate, diaryl compounds such as diaryl phthalate and diaryl maleate, unsaturated carboxylic acid aryls such as aryl acrylate and aryl methacrylate, Dicyclopentadiene, ethylidene norbornene, vinyl norbornene, norbo Najien, triallyl cyanurate, triallyl isocyanurate and the like. The amount of these crosslinkable compounds used should be in the range of not more than 20% by weight, preferably 10% by weight, in the rubber.
If the amount exceeds 50% by weight, the rubber elasticity is significantly reduced. Also, 0.
If it is less than 01% by weight, a sufficient crosslinking effect cannot be obtained. The method for polymerizing rubber is not particularly limited, but emulsion polymerization is preferably performed. In this case, it is convenient that the emulsion graft polymerization of the resin component can be performed subsequent to the polymerization of the rubber.

As an emulsifier that can be used in the emulsion polymerization method, sodium stearate, fatty acid soap such as potassium oleate, disproportionated potassium rosinate, potassium lauryl sulfate,
Examples include organic sulfonates such as sodium dioctyl sulfosuccinate and sodium dodecylbenzene sulfonate, but since fatty acid soap or disproportionated rosin acid soap may cause hydrolysis of alkyl acrylate, PH in the vicinity, preferably pH 4 to
Organic sulfonates that can be polymerized with 8 are preferred.

Polymerization initiators that can be used in the emulsion polymerization method include benzoyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, hydrogen peroxide, sodium peroxide, ammonium persulfate, and potassium persulfate. Catalysts, azo catalysts such as azobisisobutyronitrile and reducing agents such as formaldehyde sulfoxylate, L-ascorbic acid, glucose, ferrous sulfate, metal salts such as cobalt chloride, pyrophosphoric acid or ethylenediamine 4 The redox catalyst etc. which use a chelating agent like disodium acetate together are mentioned.

Among these, potassium persulfate and the like may cause the pH in the polymerization system to be remarkably lowered due to decomposition, and sodium acetate, sodium carbonate, and weak acid such as sodium hydrogen carbonate as a buffer may be used for the purpose of avoiding corrosion of the polymerization apparatus. It is preferable to add a small amount of salt. Polymerization temperature is 30-100 ℃, especially 40
About 80 ° C is preferable.

When emulsion polymerization is carried out, it is possible to obtain a desired rubber particle size by a known seed polymerization method, which is appropriately controlled depending on a monomer addition method, a rate, an emulsifier addition amount and the like. A preferred rubber particle size is a weight average particle size of 0.05.
˜5 μ, and more preferably 0.1 to 2 μ. If less than 0.05μ, the impact resistance of the obtained resin composition is insufficient,
If it exceeds 5 μ, the surface gloss of the molded product decreases.

Among the monomer mixture for graft polymerization in which the rubber is graft-polymerized in the component B, the aromatic vinyl monomer is a styrene-based monomer such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene and the like. It is a substituted monomer, and among these, styrene and α-methylstyrene are particularly preferable. The vinyl cyanide monomer includes acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc., and acrylonitrile is particularly preferable. As the vinyl monomer copolymerizable with these, alkyl acrylate having an alkyl group having 1 to 13 carbon atoms, methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, acrylic acid, methacrylic acid, etc. Vinyl carboxylic acid monomers, acrylic acid amides, methacrylic acid amides, N-alkyl-substituted maleimides, N-aromatic-substituted maleimides and the like. The amount of the monomer mixture for graft polymerization used is 20 to 95 relative to 5 to 80 parts by weight of rubber.
If the amount is less than 20 parts by weight, the moldability and surface appearance of the obtained molded product are poor and the rigidity is low. If it exceeds 95 parts by weight, the impact resistance becomes insufficient. Aromatic vinyl monomers account for 40-90% by weight of the monomer mixture
However, if it is less than 40 parts by weight, the moldability and dimensional stability of the obtained molded product will be impaired. Further, the proportion of the vinyl cyanide monomer in the monomer mixture is 0 to 40% by weight, but if it exceeds 40% by weight, the moldability is deteriorated, which is not preferable.

In the graft polymerization of the monomer mixture for graft polymerization onto the rubber, the polymerization method is not particularly limited, but the rubber obtained by emulsion polymerization may be subjected to graft polymerization by emulsion polymerization or suspension polymerization from the viewpoint of operability. It is preferable to carry out.

Examples of suspension stabilizers that can be used in the suspension polymerization method include polyvinyl alcohol, methyl cellulose, carboxyethyl cellulose, gelatin, calcium phosphate, magnesium carbonate, bentonite, and talc.

As an emulsifier that can be used in the emulsion polymerization method, sodium stearate, fatty acid soap such as potassium oleate, disproportionated potassium rosinate, potassium lauryl sulfate,
Examples thereof include organic sulfonates such as sodium dioctyl sulfosuccinate and sodium dodecylbenzene sulfonate.

The addition method of the monomer mixture for graft polymerization is batch addition,
There are methods such as partial partial addition and continuous partial addition of all graft polymerization monomers, but continuous partial addition is most preferable because graft copolymerization to the rubbery polymer is effectively performed. The polymerization temperature is preferably 30 to 80 ° C, especially about 50 to 75 ° C.

Examples of usable initiators include benzoyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butylperoxyacetate, hydrogen peroxide, sodium peroxide, ammonium persulfate and potassium persulfate. Peroxide catalysts, azo catalysts such as azobisisobutyronitrile and reducing agents such as formaldehyde sulfoxylate, L-ascorbic acid, glucose, ferrous sulfate, metal salts such as cobalt chloride, pyrophosphoric acid or A redox catalyst that uses a chelating agent such as ethylenediaminetetraacetic acid disodium salt may be used.

The method of adding the polymerization initiator is batch addition, partial addition in portions,
There is also a method of continuously dividing and adding the whole amount, but continuous dividing and addition are most preferable from the viewpoints of easy control of the polymerization rate and grafting efficiency to rubber.

The most distinctive feature of the present invention is that the graft polymerization on the rubber in the component B is carried out in the absence of a chain transfer agent so that the graft resin component has a high molecular weight. The chain transfer agent here is usually added in order to control the molecular weight of the resin component to a certain low level in the emulsion graft polymerization of the resin monomer onto rubber, and normal decyl mercaptan, t-dodecyl mercaptan, nonyl mercaptan, There are sulfur compounds such as xanthogen disulfide, hydrocarbon compounds such as terpenes, tetrahydronaphthalene, and 9,10-dihydroanthracene.

Generally, emulsion polymerization yields a resin having an extremely high molecular weight, which has a high melt viscosity, which results in poor fluidity and makes molding extremely difficult. Therefore, it is indispensable to add a chain transfer agent during the graft polymerization to lower the molecular weight of the resin.

However, when the copolymer having an unsaturated dicarboxylic acid imide derivative residue (that is, the component A) is used as one component like the composition of the present invention, the molding process is performed at a temperature much higher than that of a usual styrene resin. Therefore, even if the molecular weight of the graft resin in the component B is high, there was no problem in the beginning concerning the moldability.

As will be described later, the resin composition of the present invention exhibits sufficient impact resistance even though it contains a rubber-reinforced resin graft product (that is, component B) containing an acrylic rubber having relatively weak rubber elasticity as a constituent element. However, it is considered that this is because the graft resin in the B component has a high molecular weight, so that the rigidity is increased and the compatibility with the A component, which originally has a very rigid property, is improved.

Next, the C component will be described. The aromatic vinyl monomer used as the C component is a styrene-based monomer such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, or a substitution product thereof. Among these, styrene and α-Methylstyrene is particularly preferred.

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

Vinyl monomers copolymerizable with these have 1 to 1 carbon atoms.
Acrylic acid ester monomer having 13 alkyl groups, methacrylic acid ester monomer having alkyl group having 1 to 4 carbon atoms, vinylcarboxylic acid monomer such as acrylic acid and methacrylic acid, acrylic acid amide, methacrylic acid Examples thereof include amide, acenaphthylene, N-vinylcarbazole, N-alkyl-substituted maleimide, and N-aromatic-substituted maleimide.

In the C component, the proportion of the aromatic vinyl monomer is 40 to 90% by weight, and that of the vinyl cyanide monomer is 0 to 40% by weight. And B
This is because the compatibility with the components was taken into consideration.

For the polymerization, any known polymerization method can be adopted, and examples thereof include suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization and precipitation polymerization of the produced polymer in a non-solvent.

The composition of the present invention is a mixture of the above-mentioned component A and component B, if necessary, with component C, but the mixing method is not particularly limited, and known means can be used. As the means, for example, Banbury mixer, Hensiel mixer, tampler mixer, mixing roll, single shaft or 2
A shaft extruder or the like can be used. Examples of the mixing form include ordinary melt mixing, melt kneading at each stage using master pellets, and a method of obtaining a composition by blending in a solution.

The ratio of blending each of the components A, B, and C is 10 to 90% by weight for the A component, 10 to 90% by weight for the B component, and C.
Although the components are 0 to 80% by weight, the reason for limiting the blending ratio in this way is that the composition finally obtained has weather resistance,
This is to keep various physical properties such as heat resistance, impact resistance, and moldability in a well-balanced manner.

Further, if necessary, the composition of the present invention further includes a stabilizer, a flame retardant, a plasticizer, a lubricant, an ultraviolet absorber, a colorant and talc,
Fillers such as silica, clay and calcium carbonate may be added.

(Examples) Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist. All parts and% in the examples are expressed on a weight basis.

Experimental Example 1 (Synthesis of component A without using rubbery polymer) 58 parts of styrene and 90 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, the system was replaced with nitrogen gas, and then the temperature was raised to 85 ° C. Then, 42 parts of maleic anhydride and 0.15 part of benzoyl peroxide are added to 180 parts of methyl ethyl ketone.
The solution dissolved in 1 part was continuously added in 6 hours. The temperature was kept at 85 ° C. for a further 5 hours after the addition. As a result of sampling a part of the viscous reaction liquid and quantifying the unreacted monomer by gas chromatography, the polymerization rate was 97.7.
% And maleic anhydride 99.5%. The copolymer solution obtained here was mixed with an equivalent amount of aniline to maleic anhydride.
40 parts and triethylamine 0.3 part were added, and the mixture was reacted at 150 ° C. for 5 hours. 300 parts of methyl ethyl ketone was added to the reaction solution, cooled to room temperature, poured into 3000 parts of vigorously stirred methanol, precipitated, filtered and dried to obtain an imidized copolymer. From C-13 NMR analysis, the conversion rate of acid anhydride groups to imide groups was 99.3%. This imidized copolymer was a copolymer containing 56.2% of N-phenylmaleimide units as an unsaturated dicarboxylic acid imide derivative, and was used as a polymer.

Experimental Example 2 (Synthesis of Component A Using a Rubbery Polymer) 55 parts of styrene, 5 parts of acrylonitrile, 100 parts of methyl ethyl ketone and 100 parts of methyl ethyl ketone were cut into small pieces in an autoclave similar to that of Experimental Example 1, and made by Japan Synthetic Rubber Co., Ltd. Rubber "AR
10 parts of "-101" was charged, and the acrylic rubber "AR-101" was dissolved by stirring at room temperature for a whole day and night, then the system was replaced with nitrogen gas, and the temperature was raised to 85 ° C. A solution prepared by dissolving 40 parts of maleic anhydride, 0.075 part of benzoyl peroxide and 0.075 part of azobisisobutyronitrile in 250 parts of methyl ethyl ketone was continuously added over 8 hours. 5 hours after addition
It was kept at 85 ° C. A part of the viscous reaction solution was sampled and the amount of unreacted monomer was quantified by gas chromatography. As a result, the polymerization rate was 96.4% for styrene and 9
It was 8.9% and acrylonitrile 93.3%. In the copolymer solution having a rubbery polymer obtained here, 38 parts of aniline equivalent to maleic anhydride, triethylamine.
3 parts was added and reacted at 150 ° C. for 5 hours. 300 parts of methyl ethyl ketone was added to the reaction solution, cooled to room temperature, poured into 3000 parts of vigorously stirred methanol, precipitated, filtered and dried to obtain an imidized copolymer. From C-13 NMR analysis, the conversion rate of acid anhydride groups to imide groups was 98.1%. The imidized copolymer having this rubbery polymer has N-phenylmaleimide units as an unsaturated dicarboxylic acid imide derivative.
It was a copolymer containing 50.0%, and was used as a polymer.

Experimental Example 3 (Synthesis of component B) (1) Polymerization of rubber In an autoclave equipped with a stirrer, 40 parts of ion-exchanged pure water,
Charge 0.1 part of sodium acetate and 0.06 part of sodium dodecylbenzenesulfonate, raise the temperature to 70 ° C with stirring and add 0.04 part of potassium persulfate, and then add butyl acrylate 22
Parts and 0.8 parts of divinylbenzene are added continuously over 3 hours. After the addition, the stirring is continued at 70 ° C. for another 2 hours. Next, 400 parts of ion-exchanged pure water, 1.2 parts of sodium acetate, and sodium dodecylbenzenesulfonate were added to this reaction system.
0.2 part was charged, the temperature was again raised to 70 ° C. with stirring, 0.35 part of potassium persulfate was added, and then a mixture of 250 parts of butyl acrylate and 8.5 parts of divinylbenzene was continuously added in 3 hours. After the addition, the mixture was further stirred at 70 ° C for 2 hours, and then 4000 parts of ion exchange pure water, 15 parts of sodium acetate and sodium dodecylbenzenesulfonate were newly added to the reaction system.
0.5 part was charged, the temperature was raised again to 70 ° C. with stirring, and 4 parts of potassium persulfate was added. After that, a mixture of 3000 parts of butyl acrylate and 70 parts of triallyl isocyanurate was continuously added in 3 hours, and then the mixture was further stirred at 70 ° C. for 2 hours, further heated to 80 ° C. and stirred for 2 hours. Get the latex. The final polymerization rate of butyl acrylate was 99.0%. Further, polystyrene latex having a known weight average particle diameter was used. The weight average particle diameter of the rubber latex synthesized here was determined by a calibration curve showing the relationship between the absorbance and the weight average particle diameter, and was 0.42μ. The gel content in rubber was 92%.

(2) Graft polymerization to rubber 100 parts of the rubber latex obtained in (1) in terms of solid content, 400 parts of ion-exchanged pure water, and 0.5 parts of sodium dodecylbenzenesulfonate were charged into an autoclave equipped with a stirrer, and 50
After the temperature is raised to 0 ° C, 0.35 part of sodium formaldehyde sulfoxylate, 0.02 part of sodium ethylenediamine tetraacetate and 0.01 part of ferrous sulfate are added. After this styrene 75
Parts, 25 parts of acrylonitrile and 0.15 parts of t-butyl peroxyacetate are added continuously over a period of 3 hours. After addition, t-butyl peroxyacetate 0.
After 1 part was added and the temperature was raised to 70 ° C., stirring was continued for 3 hours. The polymerization rates of styrene and acrylonitrile were determined by gas chromatography, and the values were 98.7% and 96.3%, respectively. The latex obtained was coagulated with calcium chloride, washed with water and dried to obtain a graft copolymer as a white powder. This is a polymer.

The weight average molecular weight (Mw) of the THF-soluble component (that is, graft resin) of the polymer was 138,000 as determined by GPC measurement.

Experimental Example 4 (Synthesis of component B) (1) Polymerization of rubber In an autoclave equipped with a stirrer, 40 parts of ion-exchanged pure water,
Charge 0.1 part of sodium acetate and 0.06 part of sodium dodecylbenzenesulfonate, raise the temperature to 70 ° C with stirring and add 0.04 part of potassium persulfate, and then add 15 parts of butyl acrylate.
Parts and ethyl acrylate 5 parts and divinylbenzene 0.
6 parts of the mixture are added continuously in 3 hours. 70 ℃ after addition
Continue stirring for 2 hours. Next, 350 parts of ion-exchanged pure water, 1.2 parts of sodium acetate and 0.2 part of sodium dodecylbenzenesulfonate were charged to this reaction system, the temperature was raised again to 70 ° C. with stirring and 0.35 part of potassium persulfate was added,
A mixture of 150 parts of butyl acrylate, 50 parts of ethyl acrylate and 7 parts of divinylbenzene is added continuously over 3 hours. After the addition, the mixture was further stirred at 70 ° C for 2 hours, and then 4000 parts of ion-exchanged pure water, 15 parts of sodium acetate and sodium dodecylbenzenesulfonate were newly added to the reaction system.
Charge 2.5 parts, raise the temperature to 70 ° C. again with stirring, and add 4 parts of potassium persulfate. After this, a mixture of 2000 parts of butyl acrylate, 670 parts of ethyl acrylate, and 55 parts of triallyl isocyanurate was continuously added over 3 hours, and the temperature was raised to 70 ° C for 2 hours and then to 80 ° C for 2 hours.
Continue stirring for a time to obtain a latex of acrylic rubber.
The final polymerization rates of butyl acrylate and ethyl acrylate were 98.9% and 97.2%, respectively. Further, the weight average particle diameter of the rubber latex synthesized here was determined by a calibration curve showing the relationship between the absorbance and the weight average particle diameter using polystyrene latex having a known weight average particle diameter, and it was 0.40 μm. The gel content in rubber was 89%.

(2) Graft polymerization to rubber 100 parts of the rubber latex obtained in (1) in terms of solid content, 400 parts of ion-exchanged pure water, and 0.5 parts of sodium dodecylbenzenesulfonate were charged into an autoclave equipped with a stirrer, and 50
After heating to ℃ 0.35 parts sodium formaldehyde sulfoxylate, ethylenediaminetetraacetic acid-2-sodium 0.
Add 02 parts and 0.01 parts ferrous sulfate. After this, a mixture of 67.5 parts of styrene, 22.5 parts of acrylonitrile, 10 parts of methyl methacrylate and 0.15 parts of t-butylperoxyacetate is continuously added over 3 hours. After the addition, add 0.1 part of t-butyl peroxyacetate and add
After the temperature was raised to 0 ° C., stirring was continued for 3 hours. Styrene, the polymerization rate of acrylonitrile and methyl methacrylate was determined by gas chromatography, each 96.7%,
The values of 97.0% and 99.0% were obtained. The latex obtained was coagulated with calcium chloride, washed with water and dried to obtain a graft copolymer as a white powder. This is a polymer.

The THF-soluble matter Mw of the polymer was 133,000.

Experimental Example 5 (Synthesis of Comparative B Component) Except for adding 0.3 part of t-dodecyl mercaptan in Experimental Example 3 (2) during polymerization, the same operation as in Experimental Example 3 (2) was performed to obtain a graft copolymer. . This is a polymer. The THF-soluble matter Mw of the polymer was 89,000.

Experimental Example 6 (Synthesis of Comparative B Component) Except for adding 0.3 part of t-dodecyl mercaptan in Experimental Example 4 (2) during polymerization, the same operation as in Experimental Example 4 (2) was performed to obtain a graft copolymer. . This is a polymer. The THF-soluble matter Mw of the polymer was 87,000.

Experimental Example 7 (Synthesis of Comparative B Component) Polybutadiene latex 100 parts (solid content conversion, weight average particle diameter 0.36μ, gel content 90%), potassium stearate 1 part, sodium aldehyde sulfoxylate 0.1 part,
Ethylenediaminetetraacetic acid disodium 0.04 parts, sulfuric acid No. 1
0.01 parts of iron and 380 parts of water are heated to 50 ° C., 75 parts of styrene, 25 parts of acrylonitrile, 0.3 part of t-dodecyl mercaptan and 0.18 part of diisopropylbenzene hydroperoxide are added thereto over 5 hours, and 75 ° C. after the addition. Up to
The stirring was continued for 3 hours to complete the polymerization. Polymerization rate is styrene
It was 97.0% and acrylonitrile 98.1%. Experimental example 4
The white powdery graft copolymer was recovered in the same manner as in (2). This is a polymer.

Experimental Example 7 (Synthesis of Component C) 75 parts of styrene, 25 parts of acrylonitrile, 2.0 parts of potassium stearate, 0.4 part of t-dodecyl mercaptan, and 230 parts of ion-exchanged pure water were heated to 70 ° C., and potassium persulfate was added thereto. Polymerization was initiated by adding 0.05 parts. Six hours after the initiation of the polymerization, 0.03 part of potassium persulfate was further added, and the temperature was raised to 80 ° C. and maintained for 3 hours to complete the polymerization. The polymerization rate was 98.8%. The latex obtained is coagulated with calcium chloride, washed with water and dried to obtain a white powder copolymer,
This was used as a polymer.

Examples 1 to 6 Component A, component B and component C were mixed in the proportions shown in Table 1, to which 1.2 parts of 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, octadecyl-3 were added.
-(3,5-di-t-butyl-4-hydroxyphenyl)
After adding 0.8 parts of propionate, it was mixed with a Hensiel mixer. This mixture was extruded into pellets with a screw extruder equipped with a 30 mmφ devolatilizer. After molding the pellets by an injection molding machine, physical properties were measured, and the results are shown in Table 1.

Comparative Examples 1 to 6 A component, comparative B component and C component were blended in the ratios shown in Table 1, and after adding the same stabilizer as in Example, pelletization,
After molding and measuring the physical properties, the results are shown in Table 1.

The physical properties were measured by the following methods.

1) Weather resistance: It was examined by irradiating the Izod piece with light at 83 ° C. (without rainfall) using a carbon arc sunshine weather meter (WE-SUN-DC type) and measuring the Izod intensity after 1000 hours.

2) Izod strength: Measured according to ASTM-D256.

3) Vicat softening point: load 5 kg, measured according to ASTM-D1525 4) GPC: Showa Denko KPC GPC column Shodex KF-80M was used with THF as an eluent at a flow rate / ml / min. (Detection was carried out by UV (240 nm).) The calibration curve was prepared by standard polystyrene.

5) Gel content: The gel content of rubber was determined as follows. That is, calcium chloride was added to rubber latex, coagulated, washed with water, dried, dissolved in methyl ethyl ketone, and the proportion of the insoluble matter was determined in% by weight, which was defined as the gel content.

(Effect of the invention) From Table 1, the composition of the present invention is obtained by carrying out graft polymerization in the absence of a chain transfer agent, the acrylic resin reinforced resin graft product (that is, the B component) having a high molecular weight of the resin component It is clear that the inclusion of) gives a weather-resistant and heat-resistant molded article having good impact resistance.

Claims (1)

[Claims] 1. A heat-resistant resin composition comprising 10 to 90% by weight of the following component A, 10 to 90% by weight of component B, and 0 to 80% by weight of component C and having excellent weather resistance. Component A: 35-80% by weight of aromatic vinyl monomer residue, 20-65% by weight of unsaturated dicarboxylic acid imide derivative residue, 0-30% by weight of vinyl monomer residue other than these, and rubber-like polymer 0
Component B: 60 to 99.99% by weight of alkyl acrylate having alkyl group having 1 to 13 carbon atoms, 0 to 40% by weight of vinyl monomer copolymerizable therewith, and one molecule 40 to 90% by weight of an aromatic vinyl monomer, based on 5 to 80 parts by weight of an acrylic rubber-like polymer consisting of 0.01 to 20% by weight of a crosslinkable compound having two or more carbon-carbon unsaturated bonds. Monomer mixture for graft polymerization comprising 0 to 40% by weight of vinyl cyanide monomer and 0 to 40% by weight of vinyl monomer copolymerizable therewith
Graft copolymer obtained by polymerizing 20 to 95 parts by weight in the absence of a chain transfer agent C component: 40 to 90% by weight of aromatic vinyl monomer, 0 to 40% by weight of vinyl cyanide monomer, and Copolymer consisting of 0 to 40% by weight of a vinyl monomer copolymerizable with these