KR101072037B1 - Low-gloss thermoplastic resin composition having excellent impact resistance and heat resistance - Google Patents

Abstract

The present invention relates to a low-gloss thermoplastic resin composition, and more specifically, (a) 10 to 40 parts by weight of a copolymer formed by graft polymerization of an acrylonitrile monomer and a styrene derivative on a butadiene rubber, (b) maleimide 5 to 20 parts by weight of the system heat resistant copolymer, (c) 0.1 to 10 parts by weight of the acrylonitrile copolymer for low gloss filler, and (d) 40 to 85 parts by weight of the styrene / acrylonitrile copolymer, The present invention relates to a thermoplastic resin composition having excellent heat resistance and excellent low glossiness.

Low gloss, thermoplastic resin, ABS copolymer, maleimide heat resistant copolymer, low gloss filler, SAN copolymer, impact resistance, heat resistance

Description

LOW-GLOSS THERMOPLASTIC RESIN COMPOSITION HAVING EXCELLENT IMPACT RESISTANCE AND HEAT RESISTANCE}

The present invention relates to a low gloss thermoplastic resin composition, and more particularly, to a thermoplastic resin composition excellent in impact resistance and heat resistance and at the same time excellent in low gloss.

Acrylonitrile / butadiene / styrene copolymer (hereinafter referred to as ABS), methylmethacrylate / butadiene / styrene copolymer (MBS), acrylate / styrene / acrylonitrile copolymer (ASA), acrylic impact prepared through emulsion polymerization Reinforcing agent (AIM) resin and the like is excellent in physical properties such as impact resistance, rigidity, fluidity, etc., widely used as a modifier of various plastics.

In particular, ABS resin has been widely used in materials such as monitor housings, game machine housings, home appliances, office equipment, automobile lamp housings, etc., because of excellent dimensional stability, processability, and chemical resistance. In addition, in recent years, a lot of researches have been conducted to provide heat resistance to ABS resin having excellent impact resistance, chemical resistance, and processability as the necessity of automobile weight reduction, and to use it as an automotive interior material.

In addition, as users' emotional quality level increases in recent years, the demand for low-gloss resins is increasing to create a more elegant atmosphere. Also, as environmental problems arise, low-gloss coatings or pads are omitted and low-gloss resins are omitted. The trend is to use it directly.

The main principle applied to produce such a low gloss resin is to adjust the smoothness of the surface of the resin to be larger than the visible light region to scatter incident light to exert a low light effect. As a specific method, there is a method of improving the ABS resin to produce and use 1 µm or more large-diameter rubber particles. However, the resin produced by this method is low in gloss effect and poor in impact strength and heat resistance. Another method is to add a matte filler having a particle size of 5 µm or more to the resin. The resin produced by this method shows excellent moldability, but low glossiness, and particularly, the impact strength is severely reduced.

Conventional low gloss resin manufacturing method has a method of embossing the surface of the resin or coating with a low gloss material, there is a problem that increases the processing cost and the low gloss effect due to abrasion during processing.

On the other hand, the conventional method for imparting heat resistance to the resin is a method for preparing α-methylstyrene / acrylonitrile heat-resistant copolymer and kneading with the resin, US Patent Nos. 3,010,936 and 4,659,790 Disclosed is a method of partially or totally replacing styrene with α-methylstyrene in preparation. However, the resin produced by this method has a problem that the heat resistance is excellent, the impact strength is severely lowered, and the colorability is lowered due to the color of the heat resistant copolymer itself.

In addition, a low gloss filler is added in order to exhibit low glossiness, which is also required to add a large amount in order to exhibit low glossiness, resulting in a drop in impact strength and an increase in production cost.

Therefore, there is a demand for a resin that satisfies the existing impact resistance and heat resistance and imparts low gloss characteristics.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a thermoplastic resin composition which is excellent in impact resistance and heat resistance and at the same time excellent in low gloss.

These and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention

(a) 10 to 40 parts by weight of a copolymer formed by graft polymerization of an acrylonitrile monomer and a styrene derivative on a butadiene rubber;

(b) 5 to 20 parts by weight of the maleimide heat resistant copolymer;

(c) 0.1 to 10 parts by weight of acrylonitrile copolymer for low gloss filler; And

(d) 40 to 85 parts by weight of styrene-acrylonitrile copolymer;

It provides a low gloss thermoplastic resin composition comprising a.

As described above, according to the present invention, there is an effect of providing a thermoplastic resin composition excellent in impact resistance and heat resistance and at the same time excellent in low gloss.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention, when using a maleimide-based copolymer as a heat-resistant copolymer with ABS resin, the maleimide-based heat-resistant copolymer is excellent in heat resistance can be given heat resistance even at a small content during kneading, impact strength decreases It is also not severe, and the kneading property between the matrix and the maleimide resin is less deteriorated depending on the content of the maleimide, and it is confirmed that the maleimide resin can form a domain between the matrix to obtain a low gloss effect. It was completed.

The low-gloss thermoplastic resin composition of the present invention is a copolymer formed by graft polymerization of an acrylonitrile monomer and a styrene derivative on a butadiene rubber, a maleimide heat resistant copolymer, an acrylonitrile copolymer for low gloss fillers, and styrene-acrylo Nitrile (SAN) copolymers.

(a) ABS  Preparation of Copolymer

In the present invention, a method for producing a copolymer in which an acrylonitrile monomer and a styrene derivative are formed by graft polymerization on butadiene rubber will be described as an example.

The particle size and gel content of the conjugated diene rubber latex used in the production of ABS copolymer have a great influence on the impact strength and workability of the resin. Generally, the smaller the particle size of the rubber latex, the better the glossiness, but the impact resistance and workability are lowered. The larger the particle size, the better the impact resistance but the glossiness is lowered. The lower the gel content, the more polymerized in the state in which the monomer is swelled in the rubber latex and the larger the apparent particle size, the higher the impact strength and the lower the gloss.

In addition, when the graft ABS polymer is manufactured, the graft ratio greatly affects the physical properties. When the graft ratio is lowered, there are many rubber grafts that are not grafted, and thus the thermal stability is lowered. In addition, the higher the content of the rubber latex and the larger the particle size, the lower the graft rate.

Therefore, a method for producing a conjugated diene rubber latex having an appropriate particle size and gel content is important, and a method of increasing the graft rate when grafting a styrene derivative and a vinyl cyan monomer to a large diameter rubber latex is important.

In consideration of the above points, in the present invention, in order to prepare a graft ABS polymer, a conjugated diene-based polymer has a particle diameter of 600 to 1,500 mm 3, a gel content of 70 to 95%, and a swelling index of 12 to 30 After the caliber rubber latex is prepared, the small-diameter rubber latex is associated to prepare a large-diameter rubber latex having a particle size of 2,500 to 5,000 mm 3, and grafting it.

In particular, the gel content of the small-diameter rubber latex is 70 to 95% because the impact strength is lowered when the gel content is greater than 95%, the thermal stability is lowered when the gel content is less than 70%, and the particle diameter of the large-diameter rubber latex Silver is an important factor in imparting high impact to the thermoplastic resin, and the particle size satisfying the physical properties of the present invention is 2,500 to 5,000 mm 3.

① Manufacture of small-diameter rubber latex

100 parts by weight of conjugated diene rubber latex, 1 to 4 parts by weight of emulsifier, 0.1 to 0.6 parts by weight of polymerization initiator, 0.1 to 1.0 parts by weight of electrolyte, 0.1 to 0.5 parts by weight of molecular weight regulator, 90 to 130 parts by weight of ion-exchanged water After the reaction, the reaction was carried out for 7 to 12 hours at a temperature of 50 to 65 ℃, 0.05 to 1.2 parts by weight of a molecular weight regulator was added to react for 5 to 15 hours at a temperature of 55 to 70 ℃, the average particle diameter is 600 to 1,500 Å, gel A small diameter conjugated diene rubber latex having a content of 70 to 95% and a swelling index of 12 to 30 is prepared.

As the conjugated diene rubber latex, an aliphatic conjugated diene compound or a mixture of aliphatic conjugated diene compound and an ethylenically unsaturated compound may be selected and used.

The emulsifier may be selected from one or more selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, alkali salts of rosin acid, and the like.

The polymerization initiators include water-soluble persulfates such as sodium persulfate and potassium persulfate, peroxy compounds, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, textrose, sodium pyrrolate and sodium sulfite. Redox-based compounds or cumene hydroperoxides, diisopyrophyll benzenehydroperoxide, azobis isobutylnitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, benzoyl peroxide, One or more selected fat-soluble polymerization initiators can be selected from the group consisting of persulfates.

As the electrolyte, KCl, NaCl, KHCO ₃ , NaHCO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ , Na ₂ HPO It can select and use 1 or more types from the group which consists of _four .

As the molecular weight modifier, mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan can be used.

The polymerization temperature is very important for adjusting the gel content and swelling index of the rubber latex, and the selection of the initiator should also be considered.

② Manufacturing large diameter rubber latex

In general, since the large-diameter rubber latex particle diameter imparts a high impact to the thermoplastic resin, its preparation is very important, and the particle size required to satisfy the physical properties in the present invention is about 2,500 to 5,000 mm 3.

2.5 to 4.5 parts by weight of acetic acid aqueous solution was slowly added to 100 parts by weight of the small-diameter rubber latex prepared in ① for 1 hour to agitate to enlarge the particles, and then the stirring was stopped to have a particle diameter of 2,500 to 5,000 kPa and a gel content of 70 to 95% and a large diameter rubber latex is produced by associating with a swelling index of 12 to 30.

③ Preparation of graft ABS copolymer

40 to 70 parts by weight of the large diameter conjugated diene rubber latex prepared by the above method 15 to 40 parts by weight of styrene derivative, 5 to 20 parts by weight of vinyl cyanide monomer, 0.2 to 0.6 parts by weight of emulsifier, 0.2 to 0.6 parts by weight of molecular weight regulator, polymerization Graft copolymerization is carried out using 0.1 to 0.5 parts by weight of an initiator or the like. At this time, the polymerization temperature is 45 to 80 ℃, the polymerization time is preferably 3 to 5 hours.

Examples of the method of adding each component in the graft polymerization include a method of collectively administering each component, a method of dividing the components into multiple stages, and a method of continuously administering the components, but in order to improve the graft rate and minimize the formation of coagulated substances, the method of multicomponent division is performed. Administration method or continuous administration method is preferable.

As the styrene derivative, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, or the like may be used.

Acrylonitrile, methacrylonitrile or ethacrylonitrile may be used as the vinyl cyan monomer.

The emulsifier may be selected from one or more selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, alkali salts of rosin acid, and the like.

The polymerization initiators include water-soluble persulfates such as sodium persulfate and potassium persulfate, peroxy compounds, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, textrose, sodium pyrrolate and sodium sulfite Redox compounds or cumene hydroperoxides, diisopyrophyll benzenehydroperoxides, azobis isobutylnitriles, tertiary butyl hydroperoxides, paramethane hydroperoxides, benzoyl peroxides in admixture with reducing agents such as , From the group consisting of persulfates, one or more selected fat-soluble polymerization initiators can be selected and used.

As the molecular weight modifier, mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan can be used.

The polymerization conversion rate of the latex obtained after the completion of the polymerization was 96% or more. An antioxidant and a stabilizer were administered to the latex to coagulate with an aqueous sulfuric acid solution at a temperature of 80 ° C. or higher, followed by dehydration and drying to obtain an ABS copolymer powder.

The stability of the graft copolymer latex prepared above is determined by measuring the solid coagulation content (%) according to Equation 1 below. When the solid coagulation content is 70% or more, the latex stability is extremely lowered to a large amount of coagulum. Due to this, it is not suitable for the present invention.

Solid coagulation (%) = (weight of coagulant in the reactor) / total rubber and monomer weight) * 100

The graft rate of the graft copolymer is obtained by coagulating, washing and drying the graft copolymer latex to obtain a powder form. The solution obtained by stirring 2 g of this powder in 300 ml of acetone and stirring for 24 hours is separated by a centrifugal separator. The solution was dropped in methanol to obtain an grafted portion, dried, and weighed to measure the weight. At this time, if the graft ratio is 25% or less, the thermal stability is lowered and is not suitable for the present invention.

 Graft Rate (%) = (Weight of Grafted Monomer) / (Rubber Weight) * 100

(b) Maleimide  Preparation of Heat Resistant Copolymer

The maleimide heat resistant copolymer of the present invention is a copolymer prepared by polymerizing 0 to 70 parts by weight of styrene derivative, 0 to 20 parts by weight of vinyl cyan monomer, and 10 to 60 parts by weight of maleimide compound based on 100 parts by weight of the total content. to be.

As the styrene derivative, styrene, α-methylstyrene, p-methylstyrene, vinyl toluene, or the like may be used. Preferably, styrene is used.

Acrylonitrile or methacrylonitrile may be used as the vinyl cyan monomer.

Although the kind is not specifically limited as said maleimide type compound, It is preferable to use N-substituted maleimide defined by following General formula (1). Specifically, N-cyclohexyl maleimide, N-phenylmaleimide, N-methyl maleimide, N-ethyl maleimide, N-isopropyl maleimide, Nt-butyl maleimide, N-lauryl maleimide, N- It is preferable to use benzyl maleimide or N-tribromophenyl maleimide and the like, and more preferably N-cyclohexyl maleimide or the like in consideration of transparency, low colorability, heat resistance, etc. N-phenylmaleimide is used.

In Formula 1, R is hydrogen or an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group or an aryl group.

The maleimide compound is preferably used in 10 to 60 parts by weight based on 100 parts by weight of the maleimide-based heat resistant copolymer. When the content is 10 to 60 parts by weight, while ensuring the polymerization stability, there is an effect that easy color control and heat resistance increase.

Such components may be polymerized by suspension polymerization or bulk polymerization, and the suspension polymerization method is preferable in terms of color of the heat resistant copolymer.

The produced maleimide heat resistant copolymer preferably has a weight average molecular weight of 60,000 to 300,000, and at this time, the molecular weight may be adjusted using a molecular weight regulator. When the weight average molecular weight is 60,000 to 300,000, the fluidity is good and the workability is improved, and the impact strength of the final thermoplastic resin is improved. As said molecular weight regulator, mercaptans, such as n-octyl mercaptan, t-dodecyl mercaptan, or n-dodecyl mercaptan, can be used.

In addition, the maleimide heat-resistant copolymer is preferably a glass transition temperature of 130 to 200 ℃.

The maleimide heat-resistant copolymer is preferably contained in 5 to 20 parts by weight in the low-gloss thermoplastic resin composition of the present invention.

(c) Low gloss For filler Acrylonitrile  Preparation of Copolymer

The acrylonitrile copolymer of the present invention is used as a low gloss filler and is a copolymer prepared by adding a diepoxide, which is an epoxide-based electrolyte, to the acrylonitrile monomer and polymerizing it.

The diepoxide may be prepared by catalytic esterification of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylates. It may be represented by the following formula (2).

In Formula 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are each independently or simultaneously in the same formula, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Preferred diepoxide structures are those in which the total number of carbon atoms contained in the alkyl group does not exceed 12, and more preferred structures are R ₁ to R ₆ Is composed of a hydrogen atom and a methyl group.

More details on the acrylonitrile copolymer for low gloss fillers discussed above are in accordance with the method disclosed in US Pat. No. 5,536,780.

The acrylonitrile copolymer may be one containing 5 to 30 parts by weight of an unsaturated nitrile monomer such as acrylonitrile, methacrylonitrile or fumaronitrile based on 100 parts by weight of the total content.

Such components may be polymerized by emulsion polymerization, block polymerization, suspension polymerization, block-suspension polymerization or solution polymerization.

The acrylonitrile copolymer is preferably included in the low-gloss thermoplastic resin composition of the present invention 0.1 to 10 parts by weight.

(d) SAN  Preparation of Copolymer

The SAN copolymer of the present invention is composed of a hard polymer-forming monomer having a glass transition temperature of at least 60 ° C. or higher, and may be prepared by copolymerizing vinyl cyan monomer with styrene monomer and acrylonitrile monomer, and derived from methyl methacrylate. It can be prepared by including a compound containing a single unit, a compound capable of forming a polycarbonate polymer and the like alone or two or more.

The SAN copolymer has an acrylonitrile content of 24 to 28 parts by weight based on the total weight of the SAN copolymer, and preferably a weight average molecular weight of 80,000 to 120,000.

The SAN copolymer is preferably included in the low-gloss thermoplastic resin composition of the present invention 40 to 85 parts by weight.

The low-gloss thermoplastic resin composition comprising the above components (a) to (d) is a dye, pigment, lubricant, antioxidant, ultraviolet stabilizer, thermal stabilizer, reinforcing agent, filler, flame retardant, foaming agent, It may further include additives such as a plasticizer or a low gloss agent.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

[Example]

(a) ABS  Preparation of Copolymer

① Manufacture of small-diameter rubber latex

A polymerization reactor in which nitrogen was removed to remove oxygen, 100 parts by weight of ion-exchanged water, 100 parts by weight of 1,3-butadiene, 1.2 parts by weight of potassium rosin salt as an emulsifier, 1.5 parts by weight of potassium oleate salt, and sodium carbonate as an electrolyte 0.1 parts by weight, 0.5 parts by weight of potassium hydrogen carbonate and 0.3 parts by weight of tertiary dodecyl mercaptan as a molecular weight modifier were collectively administered, and the reaction temperature was adjusted to 55 ° C., and then 0.3 parts by weight of potassium persulfate as an initiator was reacted for 10 hours. . After the reaction, 0.05 parts by weight of tertiary dodecyl mercaptan was further administered to increase the reaction temperature to 65 ° C., and then reacted for 8 hours to prepare a small diameter rubber latex. The rubber latex produced had a particle diameter of 1000 GPa, a gel content of 90%, and an swelling index of 18.

② Manufacturing large diameter rubber latex

100 parts by weight of the small-diameter rubber latex prepared in ① was added to the reaction tank, while 3.0 parts by weight of a 7% acetic acid aqueous solution was slowly added for 1 hour while stirring at a temperature of 30 ° C. at 10 rpm, and then the stirring was stopped and left for 30 minutes. A large diameter conjugated diene rubber latex was prepared by associating a small diameter rubber latex. The particle diameter of the prepared large-diameter rubber latex was 3100 mm 3, the gel content was 90%, and the swelling index was 17.

③ Preparation of graft ABS copolymer

50 parts by weight of large diameter rubber latex prepared in ②, 65 parts by weight of ion-exchanged water, 0.35 parts by weight of potassium rosinate emulsifier, 0.1 parts by weight of sodium ethylenediaminetetraacetate, ferrous sulfate 0.005 parts by weight and 0.23 parts by weight of formaldehyde sodium sulfoxylate were administered in a batch and the temperature was raised to 70 ° C. And 50 parts by weight of ion-exchanged water, 0.62 parts by weight of potassium rosinate, 35 parts by weight of styrene, 15 parts by weight of acrylonitrile, 0.4 parts by weight of t-dodecyl mercaptan, and 0.4 parts by weight of diisopropylene hydroperoxide. After continuous injection for an hour, the temperature was raised to 80 ° C., and further aged for 1 hour to terminate the reaction to prepare a graft ABS copolymer. The polymerization conversion rate of the prepared graft ABS copolymer was 97.5%, solid coagulation content was 0.2%, graft rate was 37%. This graft ABS copolymer was coagulated with an aqueous sulfuric acid solution and washed to obtain a powder.

( b1 ) Maleimide  Preparation of Heat Resistant Copolymer

49 parts by weight of styrene, 6 parts by weight of acrylonitrile, 0.1 part by weight of initiator 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 0.2 part by weight of t-butyl peroxybenzoate, 0.15 parts by weight of n-octyl mercaptan as a molecular weight regulator and 0.05 parts by weight of 2,6-di-t-butyl-p-cresol as an antioxidant were prepared. 30% by weight of this mixed solution was added to a reactor containing 100 parts by weight of water and 2 parts by weight of 10% solution of sodium sulfate, followed by stirring for 20 minutes. The reactor was then heated to 100 ° C. for 1 hour. After 20 minutes of holding at 100 ° C, 2.5 parts by weight of acrylic acid and a 2-ethylhexyl acrylate copolymer 2% solution were added as a dispersant. Starting at 25 ° C. for 25 minutes, 45 parts by weight of N-phenylmaleimide was dissolved in 70% by weight of the mixed solution, followed by continuous addition for 3 hours and 30 minutes. After the continuous dosing was completed, it was maintained for 30 minutes, the temperature was raised to 120 ℃ for 1 hour and maintained for 3 hours, and then cooled to 40 ℃ for 1 hour. The prepared product was dehydrated and dried to obtain a final heat resistant copolymer.

The produced maleimide heat resistant copolymer had a weight average molecular weight of 150,000 and a glass transition temperature of 175 ° C.

( b2 ) Maleimide  Preparation of Heat Resistant Copolymer

(B1) In the preparation of the maleimide heat-resistant copolymer, 35 parts by weight instead of 49 parts by weight of styrene, 5 parts by weight instead of 6 parts by weight of acrylonitrile, and 60 parts by weight instead of 45 parts by weight of phenylmaleimide, except that b1) It carried out by the method similar to manufacture of a maleimide type heat resistant copolymer.

The prepared maleimide heat resistant copolymer had a weight average molecular weight of 160,000 and a glass transition temperature of 197 ° C.

(c) Low gloss For filler Acrylonitrile  Copolymer

As an acrylonitrile copolymer for low gloss fillers, an acrylonitrile resin matrix (B MAT, manufactured by GE), which is a light yellow powder containing no butadiene, was used.

(d) SAN  Copolymer

As the SAN copolymer, a styrene / acrylonitrile copolymer (92HR, manufactured by LG Chemical) was used.

< Low gloss  Manufacture of thermoplastic resin composition>

Example  One

30 parts by weight of the prepared (a) ABS copolymer, (b1) 10 parts by weight of the maleimide-based heat-resistant copolymer, (c) 3 parts by weight of the acrylonitrile copolymer, and (d) 60 parts by weight of the SAN copolymer After adding 1 part by weight of lubricant and 0.5 parts by weight of antioxidant, the resultant was prepared in pellet form using a 40 pie extrusion kneader at a cylinder temperature of 220 ° C., and the pellet was injected to prepare a physical specimen.

Example  2, Comparative example  1 to 3

In Example 1, except that (a) to (d) component was added in the composition shown in Table 1 below was carried out in the same manner as in Example 1.

TABLE 1

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 (a) ABS copolymer 30 30 30 30 30 (b) imide
Heat resistant copolymer b1 10 - - - 30 b2 - 7 - - - (c) acrylonitrile copolymer 3 3 3 7 3 (d) SAN copolymer 60 73 70 70 40 Lubricant One One One One One Antioxidant 0.5 0.5 0.5 0.5 0.5

[Test Example]

The physical properties of the thermoplastic resin composition specimens prepared in Examples 1 to 2 and Comparative Examples 1 to 3 were measured by the following method, and the results are shown in Table 2 below.

* Impact strength (1/4 "notched at 23 ℃, kg · cm / ㎝)-measured according to ASTM D256.

* Tensile Strength (kg / cm ² )-It was measured according to ASTM D638.

* Flowability (g / cm ² )-measured according to ASTM D1238.

* Heat deflection temperature (1/4 ", ℃)-measured according to ASTM D648.

* Glossiness (45 °)-measured according to ASTM D523.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Impact strength
(1/4 ", kg cm / cm) 25.4 25.9 26.1 19.8 13.1 Tensile Strength (㎏ / ㎝ ² ) 497 492 487 512 534 Fluidity (g / cm ² ) 10.5 10.7 15.3 14.6 8.4 Heat deflection temperature
(1/4 ", ℃) 95 94 86 86 101 Glossiness (45 °) 8 10 16 9 8

As shown in Table 2, it was confirmed that the low-gloss thermoplastic resin composition of Examples 1 to 2 prepared according to the present invention was excellent in impact resistance and heat resistance, but excellent in the low-gloss effect.

On the other hand, Comparative Example 1, which does not include the maleimide-based heat-resistant copolymer, has a low heat resistance, increased gloss, and a low gloss property. Although the low gloss effect was improved by including many fillers compared with the comparative example 1, impact strength fell. In addition, Comparative Example 3 containing an excessive amount of the maleimide-based heat-resistant copolymer was very excellent in heat resistance, it was confirmed that the fluidity and impact resistance is reduced.

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.

Claims (18)

(a) 10 to 40 parts by weight of a copolymer formed by graft polymerization of an acrylonitrile monomer and a styrene derivative on a butadiene rubber; (b) 5 to 20 parts by weight of the maleimide heat resistant copolymer; (c) 0.1 to 10 parts by weight of acrylonitrile copolymer for low gloss filler; And (d) 40 to 85 parts by weight of styrene-acrylonitrile copolymer; Including the The maleimide heat resistant copolymer is prepared by polymerizing 0 to 70 parts by weight of styrene derivative, 0 to 20 parts by weight of vinyl cyanide monomer, and 10 to 60 parts by weight of maleimide compound based on 100 parts by weight of the total content, and glass transition temperature. Is 130 to 200 ° C, The low gloss filler acrylonitrile copolymer is prepared by adding a diepoxide to an acrylonitrile monomer and polymerizing it. Low gloss thermoplastic resin composition. The method of claim 1, The copolymer formed by graft polymerization of acrylonitrile monomer and styrene derivative on the butadiene rubber (Iii) a conjugated diene polymer having a particle size of 600 to 1,500 mm 3 and a gel content of 70 to 95%, (Ii) combining the small-diameter rubber latex to produce a large-diameter rubber latex having a particle diameter of 2,500 to 5,000 mm 3; (Iii) graft copolymerization of a styrene derivative and a vinyl cyan monomer to the large-diameter rubber latex; Low gloss thermoplastic resin composition. The method of claim 2, The graft copolymerization is characterized in that to polymerize the monomer mixture including 15 to 40 parts by weight of styrene derivatives, 5 to 20 parts by weight of vinyl cyanic monomers in 40 to 70 parts by weight of the prepared large diameter conjugated diene rubber latex. Low gloss thermoplastic resin composition. delete The method according to claim 1 or 3, The styrene derivative is at least one member selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene and vinyl toluene. Low gloss thermoplastic resin composition. The method according to claim 1 or 3, The vinyl cyan monomer is acrylonitrile or methacrylonitrile, characterized in that Low gloss thermoplastic resin composition. The method of claim 1, The maleimide compound is N-cyclohexyl maleimide, N-phenyl maleimide, N-methyl maleimide, N-ethyl maleimide, N-isopropyl maleimide, Nt-butyl maleimide, N-lauryl maleimide , N-benzyl maleimide and N-tribromophenyl maleimide, characterized in that at least one member selected from the group consisting of Low gloss thermoplastic resin composition. The method of claim 1, The maleimide-based heat-resistant copolymer is characterized in that the weight average molecular weight of 60,000 to 300,000 Low gloss thermoplastic resin composition. delete delete The method of claim 1, The diepoxide is characterized in that the compound represented by the formula (2) Low gloss thermoplastic resin composition.

In the above formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each independently or simultaneously in the same formula a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The method of claim 1, The acrylonitrile copolymer is selected from the group consisting of acrylonitrile, methacrylonitrile, and fumaronitrile based on 100 parts by weight of the total content of 5 to 30 parts by weight Low gloss thermoplastic resin composition.  The method of claim 1, The styrene-acrylonitrile copolymer is prepared by polymerizing a hard polymer-forming monomer having a glass transition temperature of at least 60 ℃. Low gloss thermoplastic resin composition. The method of claim 1, The styrene-acrylonitrile copolymer has an acrylonitrile content of 24 to 28 parts by weight based on 100 parts by weight of the styrene-acrylonitrile copolymer in total. Low gloss thermoplastic resin composition. The method according to claim 1 or 14, The styrene-acrylonitrile copolymer has a weight average molecular weight of 80,000 to 120,000 Low gloss thermoplastic resin composition. The method according to claim 2 or 3, Solidification of the graft copolymer latex prepared by the graft copolymer is characterized in that less than 70% Low gloss thermoplastic resin composition. The method according to claim 2 or 3, The graft ratio of the graft copolymer by the graft copolymer is characterized in that more than 25% Low gloss thermoplastic resin composition. The method of claim 1, The low gloss thermoplastic resin composition further comprises at least one additive selected from the group consisting of dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, plasticizers, and low gloss agents. doing Low gloss thermoplastic resin composition.