JPH0723439B2 - Heat-resistant resin composition with good weather resistance - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition containing a copolymer having an aromatic vinyl monomer residue and an unsaturated dicarboxylic acid imide derivative residue. Molded articles obtained from the resin composition of the present invention include automotive panel parts such as instrument panels and meter hoods, surface panel materials, rail vehicle or ship application parts such as coating materials, solar water heater constituent parts, and weather resistance in addition to heat resistance. It can be preferably used in the field where the property is required.

(Prior Art) A so-called imidized copolymer (USP 3642949) containing an aromatic vinyl monomer and an unsaturated dicarboxylic acid imide has extremely high heat resistance, but is half-brittle and can be put to practical use by itself. Limited range of use. Therefore, many attempts have been made to effectively utilize this imidized copolymer, and in JP-A-60-23438, a monomer mixture containing an aromatic vinyl monomer in the copolymer and a rubber-like polymer are disclosed. By blending a rubber-reinforced resin graft product composed of a coalescence, a composition having sufficient heat resistance and significantly improved impact resistance is disclosed. However, in this disclosed example, since polybutadiene is used as the rubber component of the rubber-reinforced resin graft product, the weather resistance of the finally obtained composition is poor, and the heat resistance and resistance that can be applied to various automobile parts and the like are low. Despite its impact resistance, it has the drawback of being limited in long-term outdoor use. 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. In addition, the rigidity and heat resistance of the composition containing the resin graft product as a constituent component are reduced. Therefore, even if a rubber-reinforced resin graft product having an acrylic rubber as a constituent component is blended with the imide copolymer, the weather resistance is improved as compared with the case where a polybutadiene-containing rubber-reinforced resin graft product is blended. In order to obtain impact resistance equivalent to that, it is necessary to increase the rubber content and 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. Copolymer obtained by graft-polymerizing a monomer mixture containing an aromatic vinyl monomer into a linear polymer using a polyfunctional radical initiator (high molecular weight of resin component) (that is, acrylic rubber reinforced) By blending (resin graft)) with the imide copolymer, it has sufficient impact resistance even if it does not contain a large amount of acrylic rubber-like polymer, and has a high level of heat resistance and weather resistance. It was found that a heat resistant resin composition was obtained, and the present invention was completed.

(Structure of the Invention) That is, the present invention is as follows: Component A: aromatic vinyl monomer residue 35 to 80% by weight, unsaturated dicarboxylic acid imide derivative residue 20 to 65% by weight, other vinyl monomer residue 0 ~ 30% by weight and rubber-like polymer 0
10 to 90% by weight of a copolymer containing 30 to 30% by weight, and B component: 60 to 99.99% by weight of an alkyl acrylate having an alkyl group having 1 to 13 carbon atoms, and a vinyl monomer copolymerizable therewith 0 Aromatic vinyl monomer based on 5 to 80 parts by weight of an acrylic rubber-like polymer composed of 0.01 to 20% by weight of a crosslinkable compound having 40 to 40% by weight and two or more carbon-carbon unsaturated bonds in one molecule. Monomer mixture for graft polymerization comprising 40 to 90% by weight of a vinyl cyanide monomer, 0 to 40% by weight of a vinyl cyanide monomer and 0 to 40% by weight of a vinyl monomer copolymerizable therewith.
20 to 95 parts by weight of 0.02 per 100 parts by weight of the monomer mixture.
~ 10 parts by weight of a graft copolymer obtained by graft copolymerization using 1 part by weight of a polyfunctional radical initiator, C component: 40 to 90% by weight of an aromatic vinyl monomer, vinyl cyanide A heat-resistant resin composition having good weather resistance, comprising 0 to 40% by weight of a monomer and 0 to 80% by weight of 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. 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 ° C to 350 ° C, preferably 100 to 300 ° C. When the temperature is lower than 80 ° C, the reaction rate is slow and the reaction takes a long time, which is not practical. On the other hand, 350 ° C
If it exceeds the range, 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.

The vinyl monomer copolymerizable with the aromatic vinyl monomer and the unsaturated dicarboxylic acid anhydride and / or the unsaturated dicarboxylic acid imide is a vinyl cyanide monomer such as acrylonitrile, methacrylonitrile or α-chloroacrylonitrile. Body, alkyl acrylate monomer having an alkyl group having 1 to 13 carbon atoms, methacrylic acid alkyl ester monomer having an alkyl group having 1 to 4 carbon atoms, acrylic acid,
There are vinylcarboxylic acid monomers such as methacrylic acid, acrylic acid amides, methacrylic acid amides and the like, and of these, monomers such as acronitrile, methacrylic acid alkyl ester, acrylic acid and methacrylic acid are preferable.

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 aggregate, and a copolymer of an acrylic acid alkyl ester and a vinyl monomer copolymerizable therewith are used. Considering the weather resistance of the finally obtained composition, ethylene-
A propylene copolymer and an alkyl acrylate copolymer are particularly preferable. 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 80% 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 0.01
If it is less than wt%, 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 or chlorostyrene. And styrene and α-methylstyrene are particularly preferable among them. 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 monomers for graft polymerization, 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.

The most distinctive feature of the present invention is that a polyfunctional radical initiator is used in the graft polymerization of the component B to the rubber, and the graft resin has a high molecular weight.

As the polyfunctional radical initiator, one having a decomposition temperature of about 70 to 100 ° C for obtaining a half-life of 10 hours exhibits the greatest effect of increasing the molecular weight. Preferred polyfunctional radical initiators are 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, di-t-butylperoxyhexahydroterephthalate, 4- (t-butylperoxy). Carbonyl) -3-hexyl-6- (7- (t-butylperoxycarbonyl) heptyl) cyclohexene, di-t-butylperoxyazelate, 2,5-dimethyl-2,5-di (benzoylperoxy) Hexane, 1,1
-Di-t-butylperoxycyclohexane, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-di- (t-butylperoxy) butane and the like. These may be used alone or in combination of two or more.

When a polymerization initiator having a high decomposition temperature is used, formaldehyde sulfoxylate, L-ascorbic acid,
It is preferable to carry out so-called redox polymerization using a reducing agent such as glucose, a metal salt such as ferrous sulfate and cobalt chloride, a pyrophosphoric acid, or a chelating agent such as disodium ethylenediaminetetraacetate.

In the graft polymerization, the amount of the polyfunctional radical initiator used is 0.0 with respect to 100 polymerization parts of the monomer mixture for graft polymerization.
It is 2 to 1 part by weight, preferably 0.05 to 0.8 part by weight. 0.02
If it is less than 1 part by weight, the polymerization rate is remarkably slow, and if it exceeds 1 part by weight, the amount of oligomer produced increases, so that the molecular weight does not increase and sufficient impact strength cannot be obtained.

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.

Further, in carrying out the graft polymerization to rubber in the present invention, sulfur compounds such as normal decyl mercaptan, t-dodecyl mercaptan, nonyl mercaptan, xanthogen disulfide, carbonization such as terpene, tetrahydronaphthalene and 9,10-dihydroanthracene. A chain transfer agent such as a hydrogen compound may be used.

The resin composition of the present invention exhibits sufficient impact resistance although it contains a rubber-reinforced resin graft product (that is, component B) containing an acrylic rubber having relatively weak rubber elasticity as a component. It is considered that this is because the graft resin in the component B has a high molecular weight, so that the rigidity is increased, and the compatibility with the component A, which itself has extremely rigid properties, 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. Examples of the means include a Banbury mixer, a Henschel mixer, a tumbler mixer, a mixing roll, a single shaft or two.
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 proportions of blending each of the components A, B and C are 10 to 90% by weight for the A component, 10 to 90% by weight for the B component, and 0 to 80% by weight for the C component. The reason for limiting the ratio is to keep various properties such as weather resistance, heat resistance, impact resistance and moldability in a balanced manner in the finally obtained composition.

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) 60 parts of styrene and 75 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. to give maleic anhydride 40 Parts and benzoyl peroxide 0.15 parts methyl ethyl ketone 200
The solution dissolved in 1 part was continuously added in 6.5 hours. The temperature was maintained at 85 ° C for an additional 4 hours after the addition. As a result of sampling a part of the viscous reaction liquid and quantifying the unreacted monomer by gas chromatography, the polymerization rate was 9%.
It was 6.0% and 99.0% of maleic anhydride. To the copolymer solution obtained here, 38 parts of aniline and 0.3 parts of triethylamine, which are equivalent to maleic anhydride, were added and reacted at 150 ° C. for 5 hours. Methyl ethyl ketone (200 parts) was added to the reaction solution, cooled to room temperature, and stirred vigorously in methanol 3000.
The mixture was poured into a portion, precipitated, filtered, and dried to obtain an imidized copolymer. According to C-13 NMR analysis, the conversion rate of acid anhydride groups to imide groups was 98.8%. This imidized polymer was a copolymer containing 54.3% of N-phenylmaleimide units as an unsaturated dicarboxylic acid imide derivative, and was used as a polymer.

Experimental Example 2 (Synthesis of Component A) 60 parts of styrene, 90 parts of methyl ethyl ketone, and 12 parts of acrylic rubber AR-101 made by JSR cut into small pieces were charged in the same autoclave as in Experimental Example 1, and the mixture was stirred overnight at room temperature and then acrylic. After the rubber AR-101 was dissolved, 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, 0.08 part of benzoyl peroxide and 0.08 part of azobisisobutyronitrile in 220 parts of methyl ethyl ketone was continuously added over 7 hours. After this, Experimental Example 1
Exactly the same operation was performed. The polymerization rate is 97.8% styrene,
It was 99.2% maleic anhydride. The conversion rate of acid anhydride groups to imide groups was 97.8%. This imidized polymer was a copolymer containing 49.0% of N-phenylmaleimide units as an unsaturated dicarboxylic acid imide derivative, and was used as a polymer.

Experimental Example 3 (Synthesis of Component A) 52 parts of styrene and 8 parts of acrylonitrile were charged in the same autoclave as in Experimental Example 1, and 0.15 parts of benzoyl peroxide of Experimental Example 1 was added to 0.15 of azobisisobutyronitrile.
The procedure was exactly the same as in Experimental Example 1 except that 38 parts of aniline was replaced with 32 parts of aniline and 2 parts of methylamine. Polymerization rate is styrene 96.7%, acronitrile 95.1%,
It was 99.6% maleic anhydride. The conversion rate of acid anhydride groups to imide groups was 99.9%. This imidized polymer was a copolymer containing 53.4% of N-phenylmaleimide as an unsaturated dicarboxylic acid imide derivative and N-methylmaleimide unit, and this was used as a polymer.

Experimental Example 4 (Synthesis of Component B) (1) Polymerization of Rubber 35 parts of ion-exchanged pure water in an autoclave equipped with a stirrer,
Charge 0.15 part of sodium acetate and 0.06 part of sodium dodecylbenzene sulfonate, raise the temperature to 70 ° C with stirring, add 0.03 part of potassium persulfate, and add 20 parts of butyl acrylate.
Parts and 0.6 parts of divinylbenzene are added continuously over 3 hours. After the addition, stirring is continued at 70 ° C. for another 2 hours. Next, 350 parts of ion-exchanged pure water, 1.5 parts of sodium acetate, sodium dodecylbenzene sulfonate were added to this reaction system.
0.2 part is charged, the temperature is again raised to 70 ° C. with stirring, 0.35 part of potassium persulfate is added, and then a mixture of 230 parts of butyl acrylate and 6.6 parts of divinylbenzene is continuously added in 3 hours. After the addition, the mixture was further stirred at 70 ° C for 2 hours, and then 3800 parts of ion-exchanged pure water, 15 parts of sodium acetate and sodium dodecylbenzenesulfonate were newly added to the reaction system.
2.0 parts were charged, the temperature was raised to 70 ° C. again with stirring, and 3 parts of potassium persulfate was added. After that, a mixture of 2500 parts of butyl acrylate and 60 parts of triallyl isocyanurate was continuously added over 3 hours, and then the mixture was further stirred at 70 ° C for 2 hours, further heated at 80 ° C and stirred for 2 hours to obtain a latex of acrylic rubber. To get The final polymerization rate of butyl acrylate was 99.7%. 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 0.39μ. The gel content in rubber was 90.5%.

(2) Graft polymerization of 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 55
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, 75 parts of styrene, 25 parts of acrylonitrile, 0.2 parts of t-dodecyl mercaptan and 0.2 parts of di-t-butyl peroxyazelate.
The mixture of parts is added continuously over 3 hours. After the addition, 0.1 part of di-t-butylperoxyazelate was added, the temperature was raised to 75 ° C., and stirring was continued for 3 hours. The polymerization rates of styrene and acrylonitrile were determined by gas chromatography, and the values were 98.5% and 97.6%, 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 146,000 as determined by GPC measurement.

Experimental Example 5 (Synthesis of Comparative B Component) The same operation as in Experimental Example 4 (2) was performed except that diisopropylbenzene hydroperoxide was used instead of di-t-butylperoxyazelate in Experimental Example 4 (2). A graft copolymer was obtained. This is a polymer. The THF-soluble matter Mw of the polymer was 97,000. (GP
C) Experimental Example 6 (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 sterene, 25 parts of acrylonitrile, 0.2 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 98.3% and acrylonitrile 95.5%. 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) 70 parts of styrene, 30 parts of acrylonitrile, 2.5 parts of potassium stearate, 0.4 parts 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 98.2%. 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 Henschel 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: Izod at 83 ° C (no rainfall) with a carbon arc sunshine weather meter (WE-SUN-DC type)
It was examined by irradiating one piece with light 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-D 1525 4) GPC: Showa Denko GPC column Shodex KF-80M was used with THF as an eluent at a flow rate of 1 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.

(Effects of the invention) From Table 1, the composition of the present invention was obtained by graft polymerization using a polyfunctional radical initiator, and was prepared from an acrylic rubber reinforced resin graft product (that is, B component) having an increased molecular weight of the resin component. It is clear that the inclusion of such a heat-resistant molded product has excellent impact resistance and good weather resistance.

Claims (1)

[Claims] 1. Component A: aromatic vinyl monomer residue 35 to 80% by weight, unsaturated dicarboxylic acid imide derivative residue 20 to 65% by weight, other vinyl monomer residue 0 to 30% by weight And 10 to 90% by weight of a copolymer containing 0 to 30% by weight of a rubber-like polymer
And B component: 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 2 or more carbons in one molecule. 40% to 90% by weight of an aromatic vinyl monomer and 0% to a vinyl cyanide monomer based on 5 to 80 parts by weight of an acrylic rubber polymer composed of 0.01 to 20% by weight of a crosslinkable compound having a carbon unsaturated bond. -40% by weight and 0-40% by weight of a vinyl monomer copolymerizable therewith, a monomer mixture for graft polymerization
20 to 95 parts by weight of 0.02 per 100 parts by weight of the monomer mixture.
~ 10 parts by weight of a graft copolymer obtained by graft copolymerization using 1 part by weight of a polyfunctional radical initiator, C component: 40 to 90% by weight of an aromatic vinyl monomer, vinyl cyanide A heat-resistant resin composition having good weather resistance, comprising 0 to 40% by weight of a monomer and 0 to 80% by weight of a copolymer comprising 0 to 40% by weight of a vinyl monomer copolymerizable therewith.