KR100358230B1 - Manufacturing method of weather resistant resin excellent in heat resistance - Google Patents

Abstract

The present invention relates to a method for producing a thermoplastic resin, and more particularly, to a weatherproof resin manufacturing method excellent in heat resistance, thermal stability and impact resistance.

The present invention relates to a method of kneading with ASA resin after preparing a copolymer having a heat deformation temperature of 105 ° C. or higher through a coagulation and drying step after synthesizing a copolymer having excellent heat resistance by emulsion polymerization to improve heat resistance of the weather resistant resin.

Description

Manufacturing method of weather resistant resin excellent in heat resistance

The present invention relates to a method for producing a thermoplastic resin, and more particularly, to a weatherproof resin manufacturing method excellent in heat resistance, thermal stability and impact resistance.

Ternary copolymer consisting of ASA (Acrylate-Styrene-Acrlonitrile); ASA resins are excellent in weatherability, chemical resistance, and thermal stability, and are widely used in outdoor electrical and electronic parts and building materials, sporting goods, etc., but they lack heat resistance and are applied to parts of electrical and electronic products, automotive interior materials and parts. This has been extremely limited. Recently, in order to meet such demands, research on manufacturing a weather resistant resin containing a heat resistant copolymer which can be used at high temperature without heat deformation and has excellent impact resistance and thermal stability is required.

Literature related to the prior art for producing weatherable ASA resins is U.S. Patent No. 3426l01, Japanese Patent Application Laid-Open No. 4-l80949, 5-202264, 7-316243, and West German Patent No. 1260l35. The production method for improving the impact resistance, colorability and the like has been proposed, but no method for improving the heat resistance has been proposed.

The present invention relates to a method of kneading with ASA resin after preparing a copolymer having a heat deformation temperature of 105 ° C. or higher through a coagulation and drying step after synthesizing a copolymer having excellent heat resistance by emulsion polymerization to improve heat resistance of the weather resistant resin.

The present invention is described in detail as follows.

1) Weathering ASA Resin Manufacturing Method

As for the method of manufacturing a weather resistant ASA resin, the three-step emulsion polymerization method is preferable. In the first stage polymerization, a crosslinked large-diameter acrylate rubber is first made by using an acrylate monomer and a crosslinking agent or a grafting agent without using an emulsifier; In the two-stage polymerization, the rubber made in the one-stage polymerization is used as a seed, and the alkyl acrylate, the crosslinking agent, and the grafting agent are added thereto to make the acrylate rubber particles larger, thereby preparing a large diameter acrylate rubber; In the three-step polymerization, weather-resistant ASA resin is prepared by grafting aromatic vinyl compound and vinyl cyanide monomer to the large-diameter acrylate rubber prepared in step 2.

This will be described in more detail as follows.

In preparing the cross-linked acrylate rubber in the first stage polymerization, the main monomer is butyl acrylate, and its amount is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the total composition, and examples of the crosslinking agent include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol methacrylate, neopentyl glycol dimethacrylate, trimethylol propane trimethacrylate, trimethylol methane triacrylate And the amount thereof is preferably in the range of 0.05 to 0.3 parts by weight based on 100 parts by weight of the total composition. The crosslinking agent and optionally a grafting agent may be used. As the grafting agent, aryl methacrylate (AMA), triaryl isocyanurate (TAIC), triarylamine (TAA), diarylamine (DAA), or the like may be used. It is possible.

As the electrolyte, NaHCO ₃ , Na ₂ S ₂ O ₇ , K ₂ CO _3, and the like may be used, and the amount of use thereof is preferably 0.05 to 0.4 parts by weight based on 100 parts by weight of the total composition. As an initiator, an inorganic or organic peroxide compound is used, and both a water-soluble initiator and an oil-soluble initiator can be used. Specific examples thereof include water-soluble initiators such as potassium persulfate, sodium persulfate and ammonium persulfate, and oil-soluble initiators such as cumene hydroperoxide and benzoyl peroxide. The amount of the polymerization initiator to be used is preferably 0.05 to 0.2 parts by weight based on 100 parts by weight of the monomer.

In the two-stage polymerization, a step for large-diameter curing is performed using the polymerized rubber latex used in the first step as a seed. The monomer used here is butyl acrylate, and its amount is preferably 29 to 49 parts by weight in 100 parts by weight of the total composition. As the pH of the aqueous solution, derivatives of carboxylic acid metal salts such as fatty acid metal salts or rosin acid metal salts having a carbon number of C ₁₂ to C ₂₀ or so may be used. For example, dioctylsulfosuccinate, sodium lauryl sulfate or potassium rosinate is not preferred. As the grafting agent, aryl methacrylate (AMA), triaryl isocyanurate (TAIC), triarylamine (TAA), diarylamine (DAA), and the like can be used, and the amount thereof is preferably 0.01 to 0.07 parts by weight. The pH of the crosslinked large diameter acrylate rubber polymer latex after polymerization is in the range of 5-9. In addition, the particle size of the large-diameter rubber polymer is preferably in the range of 2500 to 5000 mm 3.

Three-step polymerization is a step of grafting the large diameter acrylate rubber polymerized in step 2 by using an aromatic vinyl compound and a vinyl cyanide compound, and 30 to 60 parts by weight of an aromatic vinyl compound and 10 to 20 parts by weight of vinyl in 100 parts by weight of the total composition. It is good to use a cyanide compound, and if necessary, it is also possible to graft copolymerize a (meth) acrylic acid ester compound and a functional monomer. In step 3, the same emulsifier as step 2 is used, for example dioctylsulfosuccinate, but sodium lauryl sulfate is not preferred. As the molecular weight modifier, tertiary dodecyl mercaptan may be used. After the completion of the polymerization, the polymerization conversion was 95% or more, and a thermal stabilizer was added to the latex to coagulate with an aqueous calcium chloride solution at a temperature of 90 ° C or higher, followed by dehydration and drying to obtain a powder.

The latex stability of the weathering ASA polymer prepared above is determined by measuring the solidified solid content (%) as follows. The graft rate and the latex particle size are measured by the following formula and method.

1) Solid Coagulation (%) = Weight of Formed Coagulant in Reactor (g) / Weight of Total Monomers Administered * 100

2) Graft Rate (%) = Grafted Monomer Weight / Gum Weight * 100

3) Particle diameter: Measured using Nicomp (model name: 370 HPL) by the dynamic laser light skating method.

2) Heat resistant copolymer resin manufacturing method

The synthesis of the heat-resistant copolymer was performed by 120 to 180 parts by weight of ion-exchanged water, 65 to 80 parts by weight of α-methylstyrene and 5 to 20% by weight of styrene, and α, β-unsaturated carboxyl, based on the weight of α-methylstyrene. The polymerization is carried out using 5 parts by weight or less of acid, 25 parts by weight or less of vinyl cyan compound, 10 parts by weight or less of acryl-based monomer, and 10 parts by weight or less of methacrylamide or acrylamide. Examples of the emulsifier include rosin acids such as potassium rosin and sodium rosin, fatty acid salts such as potassium oleate, sodium oleate and sodium stearate, and alkylaryl sulfonates. Polymerization initiators include peroxides such as cumene hydroperoxide (CHP), diisopropylbenzene hydroperoxide (DIPHP), persulfate, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose Oxidation-reduction catalysts made of a mixture with a reducing agent such as sodium pyrrolate, sodium sulfite, and the like may be used. More preferably, a mixture of diisopropylbenzene hydroperoxide and persulfate is appropriate. The amount of oxidant in the use of the redox catalyst is 0.2 to 0.4 parts by weight based on 100 parts by weight of the total composition, and the method of administration takes the form of a divided dosage form and a continuous dosage form. The molecular weight modifier is used in an amount of 0.5 parts by weight or less per 100 parts by weight of the total composition. After the completion of the polymerization, the polymerization conversion was 95% or more, and the obtained latex was solidified at 110 ° C. and dried to obtain a solid powder. The intrinsic viscosity of the copolymer measured at 30 DEG C in methyl ethyl ketone was 0.35 to 0.6 dl / g, and the heat deformation temperature was 105 DEG C or higher. The ^l3 C-NMR using tetramethylsilane was measured and 147.5. It was confirmed that the weight% of the monomer chain having a structure of-{α-methylstyrene (MS) -α-methylstyrene-α-methylstyrene}-appearing in the range of ˜150 ppm was 13% or less. When there are many monomer chains composed of α-methylstyrene (MS), the glass transition temperature appears high, but pyrolysis occurs during processing, and thus the effect of thermal stability intended in the present invention cannot be achieved. In order to appropriately control such monomer chains, the weight ratio of the remaining monomers to α-MS, the administration method, and the polymerization temperature control affect them.

In the present invention, 80 to 90% by weight of the total monomers after the start of the reaction in a batch and the temperature is raised to 65 ℃ over about 1 hour 30 minutes and then 80% by weight of the remaining monomers for 5 hours after continuous administration 72 The reaction was terminated after the temperature was raised to ˜75 ° C., the remaining monomers and the persulfate were administered, and aged for about 1 hour. Initially, α-MS is administered in batches, 5-20% by weight of styrene and acrylonitrile in the α-MS content is accelerated to accelerate the reaction rate, and 5 parts by weight of metalacrylamide or acrylamide is added to add latex stability. It is administered below.

3) kneading process

After the antioxidant and the light stabilizer were added to the weathering ASA resin prepared by the method 1) and the heat-resistant copolymer resin prepared by the method 2), pellets were prepared using an extruder kneader at 200 ° C. to 250 ° C. Injection was carried out again to measure physical properties. Physical properties were measured by the ASTM method.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited by Examples.

<Example 1>

A) Weathering ASA Resin Manufacturing Process

(1 step polymerization reaction)

70 parts by weight of ion-exchanged water

Butyl acrylate (BA) 2 parts by weight

0.07 part by weight of ethylene glycol dimethacrylate (EDMA)

0.1 parts by weight of sodium bicarbonate

0.05 parts by weight of potassium persulfate (KPS)

The composition was placed in a nitrogen-substituted polymerization reactor and heated to 70 ° C. and reacted for 1 hour.

(2-step polymerization reaction)

45 parts by weight of ion-exchanged water

0.5 parts by weight of dioctylsulfosuccinate

Butyl acrylate (BA) 38 parts by weight

0.12 parts by weight of ethylene glycol dimethacrylate (EDMA)

Aryl methacrylate (AMA) 0.04 parts by weight

0.1 parts by weight of sodium bicarbonate

0.06 parts by weight of potassium persulfate

Acrylonitrile (AN) 3 parts by weight

Methyl methacrylate (MMA) 2 parts by weight

All the compositions except the potassium persulfate catalyst in the composition was made into a mixture, and then the mixture and the catalyst prepared in the first-stage polymerization reactant were continuously introduced at 70 ° C. for 4 hours, respectively.

The particle size of the latex obtained at this time was 4000 Pa, pH was 8, and the polymerization conversion rate was 98%.

(3-step polymerization reaction)

63 parts by weight of ion-exchanged water

0.5 parts by weight of dioctylsulfosuccinate

Styrene (SM) 40 parts by weight

15 parts by weight of acrylonitrile (AN)

0.05 parts by weight of tertiary dodecyl mercaptan (TDDM)

0.1 part by weight of potassium persulfate

In the composition, all the compositions except for the potassium persulfate catalyst were made into a mixture, and then the catalyst and the mixture were continuously added to the two-stage polymerization reaction at 70 ° C. for 3 hours, followed by polymerization to increase the polymerization conversion at 80 ° C. After further reacting for 1 hour at, it was cooled to 60 ° C.

At this time, the particle size of the polymerized latex was 4800 mm 3, the polymerization conversion rate was 99%, the pH was 9.5, the graft rate was 45%.

The latex obtained was aggregated at 90 ° C. with an aqueous calcium chloride solution, dehydrated and dried to obtain weatherable ASA powder particles.

B) Heat Resistant Copolymer Resin Manufacturing Method

(1 step polymerization)

100 parts by weight of ion-exchanged water

72 parts by weight of α-methylstyrene

Styrene 5 parts by weight

8.2 parts by weight of acrylonitrile

2 parts by weight of sodium dodecylbenzenesulfonate

0.3 parts by weight of tertiary dodecyl mercaptan (TDDM)

2 parts by weight of methacrylamide

0.3 part by weight of diisopropylbenzenehydroperoxide

Sodium Ethylenediaminetetraacetate0.1 parts by weight

0.005 parts by weight of ferrous sulfate

Formaldehyde sodium sulfoxylate 0.2 parts by weight

0.5 parts by weight of potassium rosin

The composition was administered in a batch to a nitrogen-substituted polymerization reactor to raise the reaction temperature continuously to 65 ° C. for 1 hour and 30 minutes for 1 hour. Initially, α-MS is dosed in batches and 5-20% by weight of styrene and acrylonitrile in the α-MS content is added to accelerate the reaction rate, and 5 parts by weight of metal acrylate or acrylamide is added to add latex stability. It is administered below.

(2 stage polymerization)

40 parts by weight of ion-exchanged water

5 parts by weight of acrylonitrile

2 parts by weight of methacrylamide

2 parts by weight of methacrylic acid

0.5 parts by weight of potassium rosin

When the temperature reaches 65 ° C., 80% by weight of the monomers are continuously administered over 5 hours in a two-step polymerization reaction. Then, the polymerization temperature is raised to 72 to 75 ° C. and the remaining three stages of polymerization are performed. After the monomer and persulfate have already been administered, it is aged for about 1 hour and then the reaction is terminated.

(3-step polymerization)

15 parts by weight of ion-exchanged water

3.5 parts by weight of acrylonitrile

Persulfate 0.15 parts by weight

0.3 part by weight of methacrylic acid

0.05 parts by weight of potassium rosin

Grade 3 dodecyl mercaptan (TDDM) 0.04 part by weight

Physical property measurement results are shown in Table 1.

<Example 2>

In Example 1 A) was carried out in the same manner as in Example 1 except that the composition of the two-stage polymerization and three-stage integration was added continuously for 4 hours. Physical property measurement results are shown in Table 1.

<Example 3>

In Example 1 A), the same procedure as in Example 1 was conducted except that TAIC was used instead of EDMA. Physical property measurement results are shown in Table 1.

Comparative Example 1

In Example 1 A), the polymerization was carried out in the same manner as in Example 1 except that sodium lauryl sulfate was used instead of dioctylsulfosuccinate. Physical property measurement results are shown in Table 2.

Comparative Example 2

The polymerization was carried out in the same manner as in Example 1, except that potassium rosin was used instead of dioctylsulfosuccinate in the two-stage synthesis in Example 1). Physical property measurement results are shown in Table 2.

Comparative Example 3

In Example A), the polymerization was carried out in the same manner as in Example 1 except that acrylonitrile was added to the three-step polymerization in the two-step polymerization, and methyl methacrylate of the two-step polymerization was replaced with styrene. Was carried out. Physical property measurement results are shown in Table 2.

<Example 4>

20 parts by weight of the heat resistant copolymer prepared in Example 1) and 20 parts by weight of the graft copolymer prepared in Example 1) of A) had a weight average molecular weight of 100,000 and an acrylonitrile content of 30% by weight. Styrene-acrylonitrile copolymer (SAN 1) 60 parts by weight and the lubricant and heat stabilizer commonly used for ABS extrusion are administered and extruded to make pellets and injected to measure the physical properties of the specimen. In addition, a sheet for thermal deformation temperature test is prepared by sheet extrusion. Properties and heat deflection temperatures are shown in Table 3.

Example 5

30 parts by weight of the heat resistant polymer prepared in B) of Example 1 and 10 parts by weight of the graft copolymer prepared in A) of Example 1 were styrene-acryl with a weight average molecular weight of 100,000 and an acrylonitrile content of 30% by weight. Nitrile copolymer (SAN 1) 60 parts by weight, a lubricant and a heat stabilizer commonly used for ABS extrusion are administered and extruded to make pellets and injected to measure the physical properties of the specimen. In addition, the sheet is extruded to prepare a test specimen for thermal deformation. Properties and heat deflection temperatures are shown in Table 3.

<Example 6>

10 parts by weight of the heat-resistant polymer prepared in Example B) and 30 parts by weight of the graft copolymer prepared in Example A) are styrene-acrylonitrile having a weight average molecular weight of 100,000 and an acrylonitrile content of 30% by weight. 60 parts by weight of the copolymer (SAN 1) and the lubricant and heat stabilizer used in general ABS extrusion are administered and extruded to make pellets and injected to measure the physical properties of the specimen. In addition, the sheet is extruded to prepare a specimen for heat deflection temperature. Physical properties are shown in Table 3.

<Comparative Example 4>

20 parts by weight of the weather resistant copolymer prepared in Comparative Example 1 and 20 parts by weight of the heat resistant polymer prepared in Example B) have a styrene-acrylonitrile copolymer having a weight average molecular weight of 100,000 and an acrylonitrile content of 30% by weight ( SAN l) 60 parts by weight, lubricant and heat stabilizer used in general ABS extrusion are administered and extruded to make pellets and injected to measure the physical properties of the specimen. In addition, a sheet for thermal deformation temperature test is manufactured by sheet extrusion. Physical properties are shown in Table 3.

Comparative Example 5

10 parts by weight of the graft copolymer prepared in Comparative Example 1 and 30 parts by weight of the heat resistant polymer prepared in B) of Example 1 were styrene-acrylonitrile copolymers having a weight average molecular weight of 100,000 and an acrylonitrile content of 30% by weight. (SAN 1) 60 parts by weight of a lubricant and a heat stabilizer used in general extrusion ABS is administered, extruded to make a pellet and injected to measure the physical properties of the specimen. In addition, a sheet for thermal deformation temperature test is prepared by sheet extrusion. Physical properties are shown in Table 3.

Comparative Example 6

30 parts by weight of the graft copolymer prepared in Comparative Example 1 and 10 parts by weight of the heat resistant copolymer prepared in B) of Example 1 were styrene-acrylonitrile aerials having a weight average molecular weight of 100,000 and an acrylonitrile content of 30% by weight. Coalescing (SAN 1) 60 parts by weight of a lubricant and a thermal stabilizer commonly used for ABS extrusion are administered and extruded to make pellets which are then injected to measure the physical properties of the specimen. In addition, the sheet is extruded to produce a thermal deformation temperature specimen. Physical properties are shown in Table 3.

Comparative Example 7

20 parts by weight of the graft copolymer prepared in Comparative Example 3 20 parts by weight of the graft copolymer B prepared in Example 1 is a styrene-acrylonitrile copolymer having a weight average molecular weight of 100,000 and an acrylonitrile content of 30% by weight ( SAN 1) Apply 60 parts by weight of lubricant and heat stabilizer, which is used for general ABS extrusion, and extrude to make pellet. In addition, a sheet for thermal deformation temperature test is manufactured by sheet extrusion. Physical properties are shown in Table 3.

According to the results of the Examples and Comparative Examples of Table 3, the heat distortion temperature by the ASTM D648 measuring method is compared with the average weather resistance resin of 85 ℃, it is found that the heat resistance is improved by kneading with the heat resistant copolymer Can be. In addition, dioctylsulfosuccinate should be used as an emulsifier in the preparation of weatherable ASA resins in order to prevent mechanical properties such as impact resistance of weatherable ASA resins having improved heat resistance as shown in Comparative Examples of Tables 1, 2 and 3. do.

Example 1 Example 2 Example 3 Particle diameter of rubber latex 4500 Å 4600 Å 4600 Å Drop size of final latex 5300 yen 5510 yen 4800 yen Wet Powder Moisture Content (%) 0.43 0.45 0.42 Atmospheric Condensation Good Good Good Impact strength 32 27 25 liquidity 13 10 12 Final judgment ◎ ◎ ◎

Comparative Example 1 Comparative Example 2 Comparative Example 3 Particle diameter of rubber latex 2950 yen 3260 yen 3580 yen Drop size of final latex 3760 yen 4800 yen 3770 yen Wet Powder Moisture Content (%) 0.65 0.35 0.50 Atmospheric Condensation Bad Good usually Impact strength 11 3.5 12 liquidity 9 32 11 Final judgment × × ×

◎: Large improvement effect

○: some improvement effect

×: does not meet the purpose

Example Comparative Example 4 5 6 4 5 6 7 Izod notched impact strength, 20 ℃ ASTM D256 (kg cm / cm) 12 8 15 6 4 8 8 Liquidity Index (MI) 7 9 5 7 9 4 4 Heat Deflection Temperature ASTM D648 94 96 91 91 93 88 92 Weather resistance Good Good Good Good Good Good Good

In the present invention, a heat-resistant copolymer having excellent heat resistance is synthesized by emulsion polymerization, and a copolymer having a heat deformation temperature of 105 ° C. or higher through a solidification and drying step is kneaded with an ASA resin to improve the heat resistance of the weather resistant resin. At the same time, it overcomes the deterioration in impact resistance that may occur by kneading with the heat resistant copolymer.

Claims (18)

In preparing weather resistant ASA (Acrylate-Styrene-Acrylonitrile) resin, a) iii) preparing an acrylate rubber using an alkyl acrylate monomer and a crosslinking or grafting agent; Ii) adding a emulsifier, a grafting agent and a crosslinking agent to the acrylate rubber to produce a large diameter acrylate rubber polymer having a particle diameter of 2500 to 5000 mm 3; And Iii) grafting the aromatic compound and the vinyl cyanide compound on the large-diameter rubber polymer Weathering ASA resin manufacturing step comprising a; b) iii) reacting after the batch administration of α-methyl styrene, 5-20 wt% of styrene of α-methyl styrene, 5-20 wt% of vinyl cyanide compound of α-methyl styrene and methacrylamide or acrylamide ; Ii) reacting while continuously administering 80% by weight of the remaining styrene, vinylcyanide compound and acrylic monomer after step iii); And Iii) administering the remaining styrene, vinylcyanide compound, acrylic monomer and persulfate after step ii) Step of producing a heat-resistant copolymer resin comprising a; And c) kneading the weatherable ASA resin and the heat resistant resin Weather resistant ASA resin manufacturing method excellent heat resistance comprising a. The method of claim 1, A method for producing a weather resistant ASA resin having excellent heat resistance, wherein the emulsifier of step a) ii) is dioctylsulfosuccinate. The method of claim 1, A method of producing a weather resistant ASA resin having excellent heat resistance in which dioctylsulfosuccinate is added as an emulsifier in step a) iii). The method of claim 1, 12.5 to 87.5% by weight of the weatherable ASA resin and 12.5 to 87.5% by weight of the heat-resistant copolymer comprising the step of kneading excellent weather resistance ASA resin manufacturing method. The method of claim 1, A method for producing a weather resistant ASA resin having excellent heat resistance integrating ii) and iii) of step a). The method of claim 1, A method for producing a weather resistant ASA resin having excellent heat resistance, wherein the alkyl acrylate is butyl acrylate. The method of claim 1, A method for producing a weather resistant ASA resin having excellent heat resistance, wherein the aromatic vinyl compound is styrene. The method of claim 1, The vinyl cyanide compound is acrylonitrile excellent weather resistance ASA resin production method. The method of claim 1, The heat-resistant copolymer is a weatherproof ASA resin manufacturing method excellent in heat resistance, the chain content of-{α-methylstyrene-α-methylstyrene-α-methylstyrene}-is less than 13%. The method of claim 1, A method of producing a weather resistant ASA resin having excellent heat resistance by reacting the step b) in an elevated temperature at 65 ° C .; The method of claim 1, A method for producing a weather resistant ASA resin having excellent heat resistance which is reacted while heating at 72 to 75 ° C. in step b) ii). a) 29.5 to 54 parts by weight of alkyl acrylate, 30 to 60 parts by weight of aromatic vinyl compound, 10 to 20 parts by weight of vinyl cyanide compound, 0.17 to 0.42 parts by weight of crosslinking agent, 0.01 to 0.07 parts by weight of grafting agent and emulsifier for polymerization and grafting. 12.5 to 87.5 weight percent of weathered ASA resin; And b) 65 to 80 parts by weight of α-methyl styrene, 3.25 to 16 parts by weight of styrene, 16 parts by weight or less of vinyl cyanide compounds, 10 parts by weight or less of acrylic monomers, 10 parts by weight or less of methacrylamide or acrylamide, and α, β 12.5 to 87.5 weight% of heat-resistant copolymer resin polymerized below 5 parts by weight of unsaturated carboxylic acid Excellent weather resistance ASA resin composition comprising a. The method of claim 12, The weatherable ASA resin composition excellent in heat resistance whose emulsifier of said weatherable ASA resin is dioctylsulfosuccinate. The method of claim 12, The weather-resistant ASA resin composition excellent in the heat resistance which the 12.5-87.5 weight% of said weather-resistant ASA resin and 12.5-87.5 weight% of said heat resistant copolymers knead | mixed. The method of claim 12, A weather resistant ASA resin composition having excellent heat resistance wherein the alkyl acrylate is butyl acrylate. The method of claim 12, A weather resistant ASA resin composition having excellent heat resistance wherein the aromatic vinyl compound is styrene. The method of claim 12, The weather-resistant ASA resin composition excellent in heat resistance whose said vinyl cyanide compound is acrylonitrile. The method of claim 12, A weather resistant ASA resin composition having excellent heat resistance, wherein the heat resistant copolymer has a chain content of-{α-methylstyrene-α-methylstyrene-α-methylstyrene}-less than 13%.