TWI481655B - Rubber modified methacrylate-based resin composition - Google Patents

Description

Rubber modified methacrylate resin composition

The present invention relates to a rubber modified methacrylate resin composition, in particular to a rubber modified methacrylic acid comprising a methacrylate polymer and a styrene-unsaturated dicarboxylic anhydride copolymer. An ester resin composition.

Most of the components contained in plastic molded articles for electrical equipment, household goods, and the like are rubber-modified styrene resins, polycarbonate resins, rubber-modified methacrylate resins, and the like. Wherein, the rubber modified methacrylate resin is a ternary graft copolymer comprising acrylonitrile, styrene and acrylate rubber, and has a lower double bond content than a rubber modified styrene resin. The acrylate rubber replaces the butadiene rubber, so the weather resistance is improved substantially. It is about 10 times higher than the rubber modified styrene resin. It can be directly used outdoors, and is typically used in automotive fields such as exterior mirrors. Outdoor components such as radiator grille, tail baffle, lampshade, etc.; or used in electrical and electronic fields, such as sewing machines, telephones, kitchen equipment, satellite antennas, etc.; or in the construction field. However, the impact strength of the rubber-modified methacrylate resin is inferior to that of the rubber-modified styrene resin, and the resin properties of the rubber-modified methacrylate resin, for example, impact strength and heat resistance. The physical properties still cannot meet the requirements of the industry; therefore, the physical properties of the rubber modified methacrylate resin need to be improved to enhance its application value.

In view of the above, there is still a need to develop a table with better impact strength, A rubber modified methacrylate resin composition with surface gloss and heat resistance to meet the needs of the industry.

Accordingly, a first object of the present invention is to provide a rubber-modified methacrylate resin composition having a good physical property balance such as high impact strength, surface gloss and heat resistance.

Thus, the rubber modified methacrylate resin composition of the present invention comprises: 60% by weight to 85% by weight of the continuous phase formed by the copolymer (A), and 15% by weight to 40% by weight of the acrylate rubber The dispersed phase of the rubber particles of the graft copolymer (B) is 100% by weight based on the total amount of the copolymer (A), and the copolymer (A) comprises: 2% by weight to 27% by weight of styrene - Acrylonitrile-based copolymer (A ₁ ), 42% by weight to 80% by weight of methacrylate polymer (A ₂ ), and 8% by weight to 32% by weight of styrene-unsaturated dicarboxylic anhydride copolymerization (A ₃ ).

Preferably, the styrene-acrylonitrile-based copolymer (A ₁ ), 45% by weight to 78% by weight, based on 100% by weight of the total copolymer (A), comprises 5% by weight to 25% by weight of the styrene-acrylonitrile-based copolymer (A ₁ ) The acrylate-based polymer (A ₂ ), and 10% by weight to 30% by weight of the styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ).

More preferably, the total amount of the copolymer (A) is 100% by weight, including 10% by weight to 22% by weight of the styrene-acrylonitrile-based copolymer (A ₁ ), and 50% by weight to 75% by weight of the nail The acrylate-based polymer (A ₂ ), and 12% by weight to 30% by weight of the styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ).

Preferably, the styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ) has a weight average molecular weight of 60,000 to 180,000.

More preferably, the styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ) has a weight average molecular weight of from 80,000 to 140,000.

Preferably, the styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ) comprises 70% by weight to 83% by weight of styrene monomer units and 17% by weight to 30% by weight of unsaturated dicarboxylic anhydride. Body unit.

Preferably, the styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ) comprises from 72% by weight to 80% by weight of styrene monomer units and from 20% by weight to 28% by weight of unsaturated dicarboxylic anhydride series Body unit.

Preferably, the styrene-acrylonitrile-based copolymer (A ₁ ) comprises 68% by weight to 73% by weight of a styrene monomer unit and 27% by weight to 32% by weight of an acrylic monomer unit.

Preferably, the copolymer (A) is contained in an amount ranging from 65% by weight to 77% by weight based on 100% by weight of the total of the rubber modified methacrylate resin composition, and the acrylate rubber is grafted. The content of the copolymer (B) ranges from 23% by weight to 35% by weight.

Preferably, the copolymer (A) is contained in an amount ranging from 66% by weight to 75% by weight based on 100% by weight of the total of the rubber modified methacrylate resin composition, and the acrylate rubber is grafted. The content of the copolymer (B) ranges from 25% by weight to 34% by weight.

Preferably, the rubber particles have a weight average particle diameter of from 0.05 μm to 1 μm. More preferably, the rubber particles have a weight average particle diameter of 0.05 μm to 0.22 μm or a weight average particle diameter of 0.26 μm to 0.55 μm, or a mixture thereof Different particle sizes.

The effect of the present invention is that the rubber modified methacrylate resin composition of the present invention is permeable to the methacrylate polymer (A ₂ ) and the specific weight average molecular weight of the styrene-unsaturated dicarboxylic anhydride system. The copolymer (A ₃ ), and the content of the components A ₁ , A ₂ and A ₃ , can make the rubber modified methacrylate resin composition have better physical properties such as impact strength, surface gloss and heat resistance. To achieve a good physical balance of the resin composition.

A rubber modified methacrylate resin composition of the present invention comprising: 60% by weight to 85% by weight of a continuous phase formed by the copolymer (A), and 15% by weight to 40% by weight of an acrylate rubber The dispersed phase of the rubber particles of the graft copolymer (B) is 100% by weight based on the total amount of the copolymer (A), and the copolymer (A) comprises: 2% by weight to 27% by weight of styrene - Acrylonitrile-based copolymer (A ₁ ), 42% by weight to 80% by weight of methacrylate polymer (A ₂ ), and 8% by weight to 32% by weight of styrene-unsaturated dicarboxylic anhydride copolymerization (A ₃ ).

The styrene-acrylonitrile copolymer (A ₁ ) and the acrylate rubber graft copolymer (B) form a graft copolymer mixture, which is described in detail as follows: the above graft copolymer mixture includes an acrylate system 100 parts by weight (dry weight) of the rubber emulsion and 20 parts by weight to 120% by weight of the monomer mixture containing 60% by weight to 74% by weight of the styrene-based monomer, and 26% by weight to 40% by weight of the acrylonitrile-based monomer. Graft polymerization obtained.

The above acrylate rubber emulsion is preferably produced by an emulsion polymerization method. on The acrylate-based rubber emulsion is obtained by polymerizing an acrylate-based monomer as a main component, and specific examples of the acrylate-based monomer are, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, and acrylic acid-2- Ethylhexyl ester, dodecyl acrylate, etc., of which n-butyl acrylate is preferred. The above acrylate rubber emulsion can be prepared by adding a graft bridging agent for polymerization. Specific examples of the graft bridging agent are dibutyl acrylate, divinyl benzene, butylene glycol dimethacrylate, and Methacrylate, trimethylolpropane tris(meth)acrylate, allyl methacrylate, diallyl methacrylate, diallyl maleate, diallyl fumarate, hydrazine Diallyl acrylate, triallyl methacrylate, triallyl cyanurate, triallyl isocyanurate, acrylate of tricyclodecenol, diacrylic acid of polyalkylene glycol The ester grafting agent may be used singly or in combination of two or more kinds thereof, and the graft grafting agent is preferably used in an amount of 0.1 to 10% by weight based on 100% by weight of the total of the acrylate monomer and the graft bridging agent. .

The above acrylate rubber emulsion may have a weight average particle diameter of 0.05 μm to 1 μm, preferably an acrylate rubber emulsion having a weight average particle diameter of 0.05 μm to 0.2 μm or an acrylate having a weight average particle diameter of 0.26 μm to 0.5 μm. A rubber emulsion, or a mixture of the two.

The graft polymerization of the above graft copolymer mixture comprises graft polymerization of a monomer mixture comprising a styrene monomer and an acrylonitrile monomer in the presence of the above acrylate rubber emulsion, and the obtained graft copolymerization The weight average particle diameter of the rubber particles of the mixture may be a unimodal distribution type or a bimodal distribution type, and the rubber particles have a weight average particle diameter of 0.05 μm to 1 μm, preferably a weight average particle diameter of 0.05 μm to 0.22. Mm or weight average The particle size is from 0.26 μm to 0.55 μm, or a mixture of the two.

The graft polymerization reaction of the above graft copolymer mixture comprises graft-polymerizing the monomer mixture onto the acrylate-based rubber; the acrylate rubber can be simultaneously obtained according to the ratio of the monomer addition and the polymerization conditions. a monomer unit copolymer and a monomer unit copolymer not grafted onto the acrylate rubber. The styrene-acrylonitrile-based copolymer (A ₁ ) of the present invention is a styrene-acrylonitrile monomer unit copolymer which is not grafted onto the acrylate rubber; the acrylate rubber graft copolymer (B) The acrylate rubber and the styrene-acrylonitrile monomer unit grafted on the acrylate rubber are formed.

The styrene-acrylonitrile-based copolymer (A ₁ ) includes 65% by weight to 74% by weight of a styrene monomer unit and 26% by weight to 35% by weight of an acrylic monomer unit. Preferably, the styrene-acrylonitrile-based copolymer (A ₁ ) comprises 68% by weight to 73% by weight of a styrene monomer unit and 27% by weight to 32% by weight of an acrylic monomer unit. More preferably, the styrene-acrylonitrile-based copolymer (A ₁ ) comprises 68% by weight to 70% by weight of a styrene monomer unit and 30% by weight to 32% by weight of an acrylic monomer unit.

The graft ratio of the above acrylate rubber graft copolymer (B) can be controlled by polymerization conditions, for example, polymerization temperature, initiator, emulsifier, activator, chain transfer agent amount and type, single The amount of the body and the method of addition are controlled. The above chain transfer agent is specifically, for example, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, Trit-dodecyl mercaptan. The above emulsifier is not particularly limited, in order to In the emulsion polymerization, the stability of the emulsion is excellent, and the polymerization rate is improved, and various carboxylates, alkyl sulfates, and alkyl groups selected from sodium succinate, potassium fatty acid, sodium fatty acid, dipotassium alkenyl succinate, and rose acid soap are selected. An anionic emulsifier such as various sulfonate salts such as sodium benzenesulfonate or sodium phthalate sulfonate is preferred. The above activator is specifically, for example, ferrous sulfate, sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate, tetrasodium pyrophosphate or the like.

The molecular weight of the above graft copolymer mixture can also be adjusted by the polymerization temperature, the kind and amount of the initiator, the addition method of the monomer, etc., and the reaction temperature of the graft polymerization is below 90 ° C, especially in It is preferably between 25 ° C and 40 ° C. The grafting monomer may be added at once, or may be added in portions, or may be continuously added or graft-polymerized into various monomers. The above-mentioned initiator may use various conventional radical polymerization initiators, which may be added in a single addition or continuously or incrementally, etc.; specific examples of the above initiators: bis-tert-butyl peroxide Benzoyl peroxide, layroyl peroxide, oleyl peroxide, toluyl peroxide, cumene peroxide Dicumyl peroxide, tert-butyl-peroxide, di-tert-butyl-diperphthalate, tert-butyl peracetate (tert- Butyl-peracetate), tert-butyl-perbenzoate, isoperopyl peroxy dicarbonate, 2,5-dimethyl-2,5-di 3,5-dimethyl-2,5-di(tert-butyl peroxy)hexane, 2,5-dimethyl-2,5-di(third butyl peroxide) -hexyl-3-tert-butyl hydroperoxide [2,5-dimethyl-2,5-di(tert-butylperoxy)hexane- 3-tert-butyl hydroperoxide], cumene hydroperoxide, p-methane hydroperoxide, cyclopentane hydroperoxide, diisophoric Diisopropylbenzene hydroperoxide, p-tert-butylcumene hydroperoxide, pinane hydroperoxide, 2,5- a mixture of dimethyl-hexyl-2,5-dihydroperoxide, or the like, or a mixture thereof. The above initiator can be used in an amount of from 0.01% by weight to 5% by weight.

Specific examples of the styrene monomer used in the graft polymerization of the aforementioned graft copolymer mixture: styrene, α-methylstyrene, p-t-butylstyrene, p-methylstyrene, ortho -methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, α-methyl-p-methylstyrene, and bromostyrene, among which styrene Or α-methylstyrene is preferred. Specific examples of the above-mentioned acrylonitrile-based monomer include acrylonitrile and α-methacrylonitrile, and among them, acrylonitrile is preferred.

The methacrylate polymer (A ₂ ) of the present invention is selected from a methacrylate homopolymer, a methacrylate-acrylate copolymer, or a combination thereof.

Preferably, the methacrylate-acrylate copolymer comprises 80% by weight to 99.8% by weight of the methacrylate monomer unit and 0.2% by weight to 20% by weight of the acrylate monomer unit; more preferably The methacrylate polymer (A ₂ ) comprises 85% by weight to 98% by weight of the methacrylate monomer unit and 2% by weight to 15% by weight of the acrylate monomer unit: the weight average thereof The molecular weight is from 50,000 to 450,000, preferably from 70,000 to 200,000, most preferably from 70,000 to 150,000.

The above methacrylate-acrylate copolymer includes a monomethacrylate monomer and an acrylate monomer obtained by polymerization. The polymerization can be carried out by bulk, solution, suspension or emulsion polymerization. Preferably, the polymerization is carried out at a temperature ranging from 50 ° C to 160 ° C.

The above methacrylate monomers may be used singly or in combination, and the methacrylate monomers are, for example but not limited to, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate. , benzyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, methacrylic acid Methylaminoethyl ester, ethylene dimethacrylate, or neopentyl dimethacrylate. Preferably, the methacrylate monomer is selected from methyl methacrylate, butyl methacrylate, or a combination thereof.

The acrylate monomer may be used singly or in combination, and the acrylate monomer is, for example but not limited to, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, or polyethylene glycol diacrylate. Preferably, the acrylate monomer is butyl acrylate.

Preferably, the styrene-unsaturated dicarboxylic anhydride copolymer (A ₃ ) comprises 70% by weight to 83% by weight of styrene monomer units and 17% by weight to 30% by weight of unsaturated dicarboxylic anhydride. Body unit. More preferably, the styrene-unsaturated dicarboxylic anhydride copolymer (A ₃ ) comprises from 72% by weight to 80% by weight of styrene monomer units and from 20% by weight to 28% by weight of unsaturated dicarboxylic anhydride series Body unit.

The styrene-unsaturated dicarboxylic anhydride-based copolymer is obtained by a polymerization reaction of a reaction component comprising a styrene monomer and an unsaturated dicarboxylic anhydride monomer. Further, a solvent and/or a functional reagent may be added to the polymerization reaction. The functional reagents are as described above and will not be described again.

The styrene-based monomer of the styrene-unsaturated dicarboxylic anhydride-based copolymer may be used singly or in combination, and the styrene-based monomer is, for example but not limited to, styrene, α -methylstyrene, and p-third. Butylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, α -methyl-p-methyl Styrene, or brominated styrene. Preferably, the styrenic monomer is selected from the group consisting of styrene, alpha -methylstyrene, or a combination thereof. Preferably, the styrene monomer is used in an amount ranging from 50% by weight to 90% by weight based on 100% by weight of the total of the reaction components.

The unsaturated dicarboxylic anhydride-based monomer of the styrene-unsaturated dicarboxylic anhydride-based copolymer may be used singly or in combination, and the unsaturated dicarboxylic anhydride-based monomer is, for example but not limited to, maleic anhydride or methyl group. Maleic anhydride, itaconic anhydride, or aconite anhydride, and the like. Preferably, the unsaturated dicarboxylic anhydride-based monomer is maleic anhydride. Preferably, the unsaturated dicarboxylic anhydride-based monomer is used in an amount ranging from 10% by weight to 50% by weight based on 100% by weight of the total of the reaction components.

The polymerization reaction for preparing the styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ) is, for example but not limited to, a solution polymerization reaction, a bulk polymerization reaction, a suspension polymerization reaction, or an emulsion polymerization reaction, etc., and the polymerization reaction may be Batch or continuous polymerization.

Preferably, the styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ) is prepared by continuous solution polymerization. The styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ) has a weight average molecular weight of 60,000 to 180,000, preferably 80,000 to 140,000; more preferably 80,000 to 120,000. When the weight average molecular weight of the styrene-based unsaturated dicarboxylic anhydride-based copolymer (A ₃ ) is within the above range, the impact strength and softening point temperature of the composition are preferable.

The rubber particles of the present invention have a weight average particle diameter of 0.05 μm to 1 μm, preferably a weight average particle diameter of 0.05 μm to 0.22 μm or a weight average particle diameter of 0.26 μm to 0.55 μm, or a mixed particle diameter thereof.

The preparation method of the rubber-modified methacrylate resin composition of the present invention is not particularly limited, and a general mixing method such as a styrene-acrylonitrile-based copolymer (A ₁ ) and the acrylate may be employed. The graft copolymer mixture formed by the rubber graft copolymer (B) is uniformly mixed with the methacrylate polymer (A ₂ ) and the styrene-unsaturated dicarboxylic anhydride copolymer (A ₃ ) mixture. Further, optionally, an additive may be separately added to the mixture; in order to obtain the rubber modified methacrylate resin composition of the present invention, the mixing method is representative: Han Hugh in general use The mixer is dry blended and then melt mixed by a mixer such as an extruder, a kneader or a Banbury mixer.

The rubber modified methacrylate resin composition of the present invention further contains an additive selected from the group consisting of an antioxidant, a plasticizer, a processing aid, an ultraviolet stabilizer, a UV absorber, a filler, a reinforcing agent, and a coloring agent. Agent, slip agent, antistatic agent, flame retardant, flame retardant, thermal stabilizer, coupling agent, or a combination thereof. The additive may be respectively polymerized in the polymerization reaction of the above graft copolymer mixture with the methacrylate polymer (A ₂ ) or the styrene-unsaturated dicarboxylic anhydride copolymer (A ₃ ), after the polymerization reaction, and coagulated. It is added before or during the preparation of the rubber-modified methacrylate resin composition. The content of the additive is 100 parts by weight based on the total amount of the graft copolymer mixture and the methacrylate polymer (A ₂ ) and the styrene-unsaturated dicarboxylic anhydride copolymer (A ₃ ). The range is from 0.01 part by weight to 20 parts by weight.

The antioxidant may be used singly or in combination, and the antioxidant is, for example but not limited to, a phenol-based antioxidant, a thioether-based antioxidant, or a phosphorus-based antioxidant.

The content of each component of the rubber modified methacrylate resin composition of the present invention, particularly the methacrylate polymer (A ₂ ) and the styrene-unsaturated dicarboxylic anhydride copolymer (A ₃ ) The content is in the above range, and has physical properties such as better impact strength, surface gloss and heat resistance, and achieves a good physical property balance of the resin composition.

The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.

【Test items】 1. Melting coefficient (indicating liquidity, melt index, referred to as MI) measurement:

The rubber-modified methacrylate resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were specified in accordance with D-1238 at 220 ° C × 10 kg. Test, unit: g/10min.

2. Softening point temperature (Vicat softening temp.) measurement: (heat resistance)

The rubber modified methacrylate resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were measured for softening point temperature in accordance with ASTM D-1525, and the unit was °C.

3. Impact resistance (Izod) measurement:

The rubber-modified methacrylate-based resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were injection molded into a 1/8-inch thick test piece with a notch, and were subjected to a standard method according to ASTM D-256 (23 ° C). Standard test pieces were prepared for testing with a gap of 1/8 inch thick, and the unit was Kg-cm/cm.

4. Surface gloss (Gloss) measurement:

The rubber-modified methacrylate-based resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were injection-molded test pieces (diameters of 5.5 cm in diameter) and specified in accordance with ASTM D-523 test method, unit: %.

5. Determination of the weight average particle diameter of the rubber particles of the rubber modified methacrylate resin composition:

The rubber-modified methacrylate resin composition is photographed by an ultra-thin sectioning method of an electron microscope and is calculated by the following formula, and the photograph contains at least 300 particles or more:

Wherein ni represents the particle diameter of the rubber particles; Di represents the number of rubber particles.

[Preparation Example 1] Graft Copolymer Mixture

The styrene-acrylonitrile-based copolymer (A ₁ ) and the rubbery acrylate graft copolymer (B) form a graft copolymer mixture, and the graft copolymer mixture is produced as follows:

(1) First, an acrylate-based rubber emulsion having a weight average particle diameter of 0.1 μm is obtained by polymerizing 99.0% of n-butyl acrylate and 1.0% of allyl methacrylate, and has a solid content of about 38% and a weight average particle diameter. It is 0.1 μm.

(2) Secondly, an acrylate rubber emulsion having a weight average particle diameter of 0.4 μm is obtained by polymerizing 99.0% of n-butyl acrylate and 1.0% of allyl methacrylate, and has a solid content of about 38% and a weight average particle diameter of 0.4 μm.

(3) Finally, 70% by weight of the acrylate rubber emulsion having a weight average particle diameter of 0.1 μm and 30% by weight of the acrylate rubber emulsion having a weight average particle diameter of 0.4 μm were graft-polymerized according to the following formulation. .

After polymerization for 5 hours, the calcium chloride (CaCl ₂ ) is coagulated, dehydrated, and then dried to a moisture content of 2% or less to obtain a graft copolymer mixture having a weight average particle diameter of 0.12 μm. , 0.45 μm bimodal distribution pattern. The acrylonitrile monomer unit content of the styrene-acrylonitrile-based copolymer (A ₁ ) in the above graft copolymer mixture was 28% by weight.

[Preparation Example 2] methacrylate copolymer (A ₂ )

It is manufactured by Chi Mei Co., Ltd., and its model number is Acryrex CM-211.

[Preparation Example 3] Styrene-unsaturated dicarboxylic anhydride copolymer (A ₃ -1)

SZ-26080 manufactured by Polyscope Co., Ltd. had a maleic anhydride monomer unit content of 26% by weight, a styrene monomer unit content of 74% by weight, and a weight average molecular weight of 80,000.

[Preparation Example 4] Styrene-unsaturated dicarboxylic anhydride copolymer (A ₃ -2)

SZ-23110 manufactured by Polyscope Co., Ltd. had a maleic anhydride monomer unit content of 23% by weight, a styrene monomer unit content of 77% by weight, and a weight average molecular weight of 110,000.

[Example 1]

In a dry state, by a 38.5 wt% [Example 1] Preparation of the obtained graft copolymer prepared mixture (B + A _1), 51.5 wt% of [2] Preparation of methacrylate was obtained - acrylate The copolymer (A ₂ ) and 10% by weight of the styrene-unsaturated dicarboxylic anhydride copolymer (A ₃ ) obtained in [Preparation Example 3] were kneaded at a kneading temperature of 230 ° C by a biaxial extruder. The rubber modified methacrylate resin composition of the present invention was obtained by mixing with an extruder, and the physical properties thereof are shown in Table 2.

[Examples 2 to 7 and Comparative Examples 1 to 3]

Examples 2 to 7 and Comparative Examples 1 to 3 are the same as in Embodiment 1. The rubber modified methacrylate resin composition was prepared by a kneading extrusion method, and the difference was that the types and usage amounts of the respective raw materials were changed, as shown in Table 1, and the analysis and physical property evaluation results are shown in Table 2.

As is clear from the experimental results in Table 2, it is understood from the experimental results in Table 2 that the rubber-modified acrylate-based resin composition of Comparative Example 1 does not use a styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ). When the amount of the methacrylate polymer (A ₂ ) is too large, the composition has a softening point temperature difference, poor heat resistance, and a slightly low gloss, and a composition having a good physical balance cannot be obtained.

In the rubber-modified acrylate-based resin composition of Comparative Example 2, the styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ) was not used, and the MS-NB (styrene-Malaysia) manufactured by electrochemistry was used instead. Amine copolymer), the composition has poor impact strength and cannot obtain a composition with good physical balance.

In the rubber-modified acrylate-based resin composition of Comparative Example 3, the amount of the styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ) was too large, so that the impact resistance of the composition was poor, and a composition having a good physical balance could not be obtained. Things.

As described above, the rubber modified acrylate resin composition of the present invention is permeable to the methacrylate polymer (A ₂ ) and the styrene-unsaturated dicarboxylic anhydride copolymer (A ₃ ), and the The content of the components can be such that the rubber-modified acrylate-based resin composition has better physical properties such as impact strength and heat resistance, and the resin composition has a good physical property balance, so that the object of the present invention can be achieved.

The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.

Claims (13)

A rubber modified methacrylate resin composition comprising: 60% by weight to 85% by weight of a continuous phase formed by the copolymer (A), and 15% by weight to 40% by weight of an acrylate-based rubber graft copolymerization The dispersed phase of the rubber particles of the material (B) is 100% by weight based on the total amount of the copolymer (A), and the copolymer (A) comprises: 2% by weight to 27% by weight of the styrene-acrylonitrile system Copolymer (A ₁ ), 42% by weight to 80% by weight of methacrylate polymer (A ₂ ), and 8% by weight to 32% by weight of styrene-unsaturated dicarboxylic anhydride copolymer (A) ₃ ). The rubber-modified methacrylate-based resin composition according to claim 1, wherein the total amount of the copolymer (A) is 100% by weight, and the styrene-acrylonitrile is included in an amount of 5% by weight to 25% by weight. Copolymer (A ₁ ), 45% by weight to 78% by weight of methacrylate polymer (A ₂ ), and 10% by weight to 30% by weight of styrene-unsaturated dicarboxylic anhydride copolymerization (A ₃ ). The rubber-modified methacrylate-based resin composition according to claim 2, wherein the total amount of the copolymer (A) is 100% by weight, and the styrene-acrylonitrile is included in an amount of 10% by weight to 22% by weight. Copolymer (A ₁ ), 50% by weight to 75% by weight of methacrylate polymer (A ₂ ), and 12% by weight to 30% by weight of styrene-unsaturated dicarboxylic anhydride copolymerization (A ₃ ). The rubber-modified methacrylate-based resin composition according to claim 3, wherein the styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ) has a weight average molecular weight of 60,000 to 180,000. The rubber-modified methacrylate-based resin composition according to claim 4, wherein the styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ) has a weight average molecular weight of 80,000 to 140,000. The rubber-modified methacrylate-based resin composition according to claim 1, wherein the styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ) comprises 70% by weight to 83% by weight of a styrene-based single a bulk unit, and 17% by weight to 30% by weight of an unsaturated dicarboxylic anhydride monomer unit. The rubber-modified methacrylate-based resin composition according to claim 6, wherein the styrene-unsaturated dicarboxylic anhydride-based copolymer (A ₃ ) comprises 72% by weight to 80% by weight of a styrene-based single a bulk unit, and 20% to 28% by weight of an unsaturated dicarboxylic anhydride monomer unit. The rubber-modified methacrylate-based resin composition according to claim 1, wherein the styrene-acrylonitrile-based copolymer (A ₁ ) comprises 65% by weight to 74% by weight of a styrene-based monomer unit, and 26% by weight to 35% by weight of the acrylic monomer unit. The rubber-modified methacrylate-based resin composition according to claim 8, wherein the styrene-acrylonitrile-based copolymer (A ₁ ) comprises 68% by weight to 73% by weight of a styrene-based monomer unit, and 27% by weight to 32% by weight of the acrylic monomer unit. The rubber-modified methacrylate-based resin composition according to claim 1, wherein the copolymer (A) is 100% by weight based on the total amount of the rubber-modified methacrylate resin composition. The content ranges from 65% by weight to 77% by weight, and the content of the acrylate-based rubber graft copolymer (B) ranges from 23% by weight to 35% by weight. The rubber-modified methacrylate-based resin composition according to claim 10, wherein the total amount of the rubber-modified methacrylate-based resin composition is 100% by weight, based on the copolymer (A) The content ranges from 66% by weight to 75% by weight, and the content of the acrylate-based rubber graft copolymer (B) ranges from 25% by weight to 34% by weight. The rubber-modified methacrylate-based resin composition according to claim 1, wherein the rubber particles have a weight average particle diameter of from 0.05 μm to 1 μm. The rubber-modified methacrylate-based resin composition according to claim 12, wherein the rubber particles have a weight average particle diameter of from 0.05 μm to 0.22 μm or a weight average particle diameter of from 0.26 μm to 0.55 μm, or Different particle sizes mixed.