KR100385721B1 - Non-glossy thermoplastic resin having heat resistance and method for preparing the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin and a method for producing the same, and more particularly, to a matt heat-resistant thermoplastic resin having excellent impact resistance, workability, and the like prepared by kneading a graft ABS polymer with a matte graft copolymer filler and a heat resistant copolymer, and It relates to a manufacturing method.

The present invention comprises a) 20 to 60 parts by weight of a) i) aromatic vinyl monomers; Ii) 5 to 20 parts by weight of a vinyl cyan compound; And iii) 6 to 12 parts by weight of an α, β-unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and crawltonic acid, to form a matt graft air. 5 to 15 parts by weight of coalescing filler; b) 10 to 90 parts by weight of graft ABS copolymer or graft ASA copolymer; And c) 10 to 90 parts by weight of a heat resistant SAN (styrene-acrylonitinile) copolymer.

Since the matte heat resistant thermoplastic resin composition of the present invention is a graft copolymer obtained by emulsion-polymerizing a matte filler, its surface gloss is less than 25 at an angle of 45 ° of ASTM D-523, but has excellent heat and weather resistance. Impact and workability are also excellent.

Description

Matte heat-resistant thermoplastic resin composition and manufacturing method thereof {NON-GLOSSY THERMOPLASTIC RESIN HAVING HEAT RESISTANCE AND METHOD FOR PREPARING THE SAME}

[Industrial use]

The present invention relates to a thermoplastic resin and a method for producing the same, and more particularly, to a matt heat-resistant thermoplastic resin having excellent impact resistance, workability, and the like prepared by kneading a graft ABS polymer with a matte graft copolymer filler and a heat resistant copolymer, and It relates to a manufacturing method.

[Prior art]

Generally, thermoplastic resins such as acrylonitrile-butadiene-styrene (ABS) and acrylonitrile-acryl-styrene (ASA) resins are rapidly used in a wide range of parts from daily necessities to automobile interiors, office equipment, and building materials. Is increasing. However, in recent years, users have increased the demand for matte resins to create a more elegant atmosphere with higher levels of emotional quality.In addition, due to environmental problems, the use of matte resins and pads has been omitted, and the use of matte resins has been made. That's the trend.

In order to produce a matte effect, a method of controlling the flatness of the resin surface to be larger than the visible light area to scatter incident light and producing a matte effect is used. In particular, in the method of improving acrylonitrile-butadiene-styrene resin The following three methods are widely used.

The first method is bulk polymerization to use large-diameter rubber particles of 2 µm or more, the second method is to introduce a matte filler having a particle size of 5 µm or more into resin, and the third method is an emulsion polymerization method. Graft polymerization of a monomer such as ethylene-unsaturated carboxylic acid with a modifier to an acryronitrile-butadiene-styrene polymer produced by the above.

However, in the first method, it is difficult to obtain an excellent low gloss effect, and when the limited low gloss effect is exhibited, the impact strength and the thermal deformation temperature are severely reduced.

In addition, while the second method is excellent in formability, the low glossiness is insufficient, and the impact strength is particularly low.

In addition, the third method is widely used to increase the matte effect of the resin because of its excellent low gloss, good impact strength and various physical properties. However, the third method lacks the heat resistance to produce a super heat-resistant thermoplastic resin. When applied to this increasing weather resistant resin (acrylonitrile-styrene-acrylate resin), there is a limit that the weather resistance is lowered.

Therefore, in view of the problems of the prior art, the present invention not only exhibits a remarkable matte effect, but also provides a matte heat-resistant thermoplastic resin composition excellent in heat resistance, heat deformation temperature and weather resistance, and excellent in impact resistance and workability. For the purpose of

[Means for solving the problem]

The present invention to achieve the above object,

In the thermoplastic resin composition excellent in heat resistance, weather resistance and matte effect,

a) 20 to 60 parts by weight of an aromatic vinyl monomer;

Ii) 5 to 20 parts by weight of a vinyl cyan compound; And

Iii) a group consisting of acrylic acid, methacrylic acid, itaconic acid, and crawltonic acid;

6 to 12 parts by weight of α, β-unsaturated carboxylic acid selected from

Matte graft copolymer prepared by emulsion polymerization of a composition comprising a

5 to 15 parts by weight of filler;

b) 10 to 90 parts by weight of graft ABS copolymer or graft ASA copolymer; And

c) 10 to 90 parts by weight of heat-resistant SAN (styrene-acrylonitinile) copolymer

It provides a matt heat-resistant thermoplastic resin composition comprising a.

In addition, the present invention is a method for producing a heat-resistant thermoplastic resin composition excellent in heat resistance, weather resistance and matte effect,

a) 20 to 60 parts by weight of an aromatic vinyl monomer;

Ii) 5 to 20 parts by weight of a vinyl cyan compound;

Iii) a group consisting of acrylic acid, methacrylic acid, itaconic acid, and crawltonic acid;

6-12 parts by weight of an α, β-unsaturated carboxylic acid selected from one or more species;

Viii) 0.1 to 2 parts by weight of emulsifier

V) 0.1 to 0.5 parts by weight of initiator; And

Iii) 0.1-1 part by weight of molecular weight regulator

Emulsion polymerization of the composition comprising a matte graft having a conversion rate of 98% or more

Preparing a copolymer filler; And

b) iii) 5 to 15 matte graft copolymer fillers prepared in step a).

Parts by weight

Ii) 10 to 90 parts by weight of graft ABS copolymer or graft ASA copolymer;

And

Iii) 10 to 90 parts by weight of heat resistant SAN copolymer

Step of kneading

It provides a method for producing a matte heat resistant thermoplastic resin composition comprising a.

In the above composition and production method, the aromatic vinyl compound is preferably selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, O-ethylstyrene and p-ethylstyrene.

In addition, the vinyl cyan compound is preferably selected from the group consisting of acrylonitrile and methacrylonitrile.

In addition, the graft ratio of the graft ABS copolymer or the graft ASA copolymer is preferably 25% or more.

In addition, the heat-resistant SAN copolymer is 5% by weight of styrene, 69% by weight of α-methylstyrene, 26% by weight of acrylonitrile, SAN, and 38% by weight of n-phenylmaleimide, 53% by weight of styrene, It is preferable to select at least 1 type from the group which consists of n-phenylmaleimide type heat resistant SAN of the terpolymer consisting of 9 weight% of acrylonitrile. In the heat resistant SAN copolymer, maleimide heat resistant SAN is preferably prepared by bulk polymerization.

In addition, the composition may further comprise up to 50 parts by weight of the general SAN.

Hereinafter, the present invention will be described in detail.

[Action]

The present invention is a vinyl aromatic compound such as styrene, α-methylstyrene, vinyl cyanide compound such as acrylonitrile or methacrylonitrile copolymerizable with this, at least one α selected from acrylic acid, methacrylic acid, itaconic acid and crotonic acid Using a β-unsaturated carboxylic acid, a polymer having a conversion rate of 98% or more is prepared by emulsion polymerization, and then heat-resistant ABS (acrylonitrile-butadiene-styrene) resin, ASA (acrylonitrile-acryl-styrene) resin, and the like. It is produced by kneading and mixing with a thermoplastic resin, the surface gloss of which is less than 25 at an angle 45 ° of ASTM D-523, to provide a thermoplastic resin composition excellent in heat resistance and weather resistance, and a method for producing the same.

Hereinafter, the present invention will be described in detail for each manufacturing process.

A) Preparation of Matte Graft Copolymer Filler

First, 20 to 60 parts by weight of an aromatic vinyl monomer selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, O-ethylstyrene, and ρ-ethylstyrene and acrylonitrile or methacrylonitrile 5 to 20 parts by weight of vinyl cyan compounds, such as 6 to 12 parts by weight of at least one α, β-unsaturated carboxylic acid selected from acrylic acid, methacrylic acid, itaconic acid, and crontonic acid, and 0.1 to 2 parts by weight of an emulsifier. 0.1-0.5 weight part of initiator, and 0.1-1 weight part of molecular weight modifiers are put, and emulsion polymerization is performed.

The emulsifiers used in the emulsion polymerization are sulfone-based, sulfate-based, sulfosuccinate-based, and in particular, 0.1 to 2 parts by weight of alkylbenzenesulfonate is used. In addition, the initiator uses 0.1 to 0.5 parts by weight of an oxidation-reduction catalyst of cumene hydroperoxide, diisopropylbenzene hydroperoxide and a reducing agent. In addition, the molecular weight regulator uses mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan, and its amount is preferably 0.1 to 1 parts by weight.

As a method of administering the monomers, a whole quantity continuous method is preferable. That is, all monomers are collectively administered at the beginning of the reaction, and the mixed monomers and the initiator are continuously administered over 3 to 4 hours while the temperature of the reactor is raised to 70 ° C or higher.

After the reaction is completed, the latex is agglomerated with calcium chloride, washed and dried to obtain a powder.

B) Graft ABS polymer manufacturing process

The particle diameter and gel content of the conjugated diene rubber latex used in the manufacture of graft ABS polymer have a great influence on the impact strength and processability of the resin. In general, the smaller the particle diameter of the rubber latex is excellent glossiness, but the impact resistance and workability is lowered, the larger the particle diameter is excellent impact resistance but the glossiness is lowered. The lower the gel content, the more monomers swell in the rubber latex and the polymerization takes place, thereby increasing the apparent particle size, thereby improving impact strength and lowering glossiness.

In addition, the graft rate greatly affects the physical properties of the graft ABS polymer, but when the graft rate is lowered, there is a lot of naked rubber latex without grafting, and thus the gloss is degraded. In addition, the higher the content of the rubber latex and the larger the particle size, the lower the graft rate, thus limiting the improvement of glossiness.

Therefore, the method of producing conjugated diene rubber latex having proper particle size and gel content is important, and the method of increasing the graft rate is important when grafting aromatic vinyl compound and vinyl cyanide compound to large diameter rubber latex.

Hereinafter, the process of preparing the graft ABS copolymer will be described in detail.

a) Manufacture of small diameter rubber latex

The small-diameter rubber latex used in the present invention is a conjugated diene polymer, preferably a particle diameter of 600 to 1500 Pa, a gel content of 70 to 95%, and a swelling index of 12 to 30. If the gel content is 95% or more, the impact strength is lowered. If the gel content is 70% or less, the glossiness is degraded.

The small-diameter rubber latex manufacturing process is as follows.

100 parts by weight of conjugated diene, 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, The reaction was carried out at 50 to 65 DEG C for an hour, and then 0.05 to 1.2 parts by weight of a molecular weight modifier was further added in a batch to react at 55 to 70 DEG C for 5 to 15 hours to have an average particle diameter of about 600 to 1500 Pa and a gel content of 70 to 95. A small diameter conjugated diene rubber latex having a swelling index of about 12 to 30% is prepared.

The emulsifiers used in the preparation of the small-diameter conjugated diene rubber latex are alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, alkali salts of rosin acid, and the like. Do.

A water-soluble persulfate or a peroxy compound can be used as the polymerization initiator, and an oxidation-reduction system can also be used. The most suitable water-soluble persulfates are sodium and potassium persulfates, and fat-soluble polymerization initiators include cumenehydro peroxide, diisopropyl benzenehydroperoxide, azobis isobutylnitrile, tertiary butyl hydroperoxide and paramethane hydroperoxide. , Benzoyl peroxide and the like can be used alone or as a mixture of two or more thereof.

The electrolyte may be KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO 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 , It is possible to use Na ₂ HPO ₄ and the like alone or in mixture of two or more thereof. Mercaptans are mainly used as a molecular weight regulator.

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.

b) Manufacture of large diameter rubber latex (fusion of small diameter rubber latex)

In general, since the large-diameter rubber latex particle diameter imparts high impact to the thermoplastic resin, its preparation is very important, and the particle diameter required to satisfy the physical properties in the present invention is about 2500 to 5000 mm 3.

The manufacturing process of large diameter rubber latex (small diameter rubber latex fusion process) is as follows.

2.5 to 4.5 parts by weight of an acetic acid aqueous solution was gradually administered to 100 parts by weight of the small-diameter rubber latex prepared by the above method for 1 hour to enlarge the particles, and then the stirring was stopped to obtain a particle diameter of 2500 to 5000 kPa, and a gel content of 70 to 95%. To prepare a large diameter conjugated diene rubber latex for grafting copolymerization by swelling so that the swelling index 12 to 30.

c) graft polymer preparation

40 to 70 parts by weight of large diameter conjugated diene rubber latex prepared by the above method, 15 to 40 parts by weight of aromatic vinyl compound, 5 to 20 parts by weight of vinyl cyan compound, 0.2 to 0.6 parts by weight of emulsifier, 0.2 to 0.6 parts by weight of molecular weight regulator, and polymerization It is graft copolymerized using 0.1-0.5 weight part of initiators, etc. At this time, the polymerization temperature is suitable 45 ~ 80 ℃ and the polymerization time is suitable 3 to 5 hours. The method of adding each component in graft polymerization may include a method of collectively administering each component, a multi-step divided administration method, or a continuous administration method. In order to improve graft ratio and minimize coagulation formation, a multi-step divided administration method or continuous The method of administration is preferred.

The emulsifiers used in the polymerization reaction are alkylaryl sulfonates, alkali methylalkyl sulfates, sulfonated alkyl esters, soaps of fatty acids, alkali salts of rosin acids, and the like, and these may be used alone or as a mixture of two or more thereof.

As the molecular weight control agent, tertiary dodecyl mercaptan is mainly used, and as polymerization initiator, peroxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, peranthate, sodium formaldehyde succilate, sodium ethylenediamine tetraacetate Redox catalyst systems made of a mixture with a reducing agent such as ferrous sulfate, dextrose, sodium pyrrolate, sodium sulfite and the like can be used.

The polymerization conversion rate of the latex obtained after the completion of the polymerization was 96% or more, and 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 a powder.

The stability of the graft copolymer latex prepared above is determined by measuring the solidified solid content (%) as shown in Equation 1 below.

[Equation 1]

When the solidified solid content was more than 0.7%, latex stability was extremely poor, and it was difficult to obtain a graft polymer suitable for the present invention due to the large amount of coagulum.

And the graft rate of the graft polymer is measured as follows. Coagulate graft polymer latex. wash. Dry to obtain a powder form, 2 g of this powder in 300 ml of acetone and stirred for 24 hours. The solution is separated using an ultracentrifuge, and the separated acetone solution is dropped in methanol to obtain an ungrafted portion, which is dried and weighed. From this, the graft ratio is measured by the following formula (2).

[Equation 2]

At this time, if the graft ratio is 25% or less, glossiness is lowered and is not suitable for the present invention.

This graft polymer applies equally to ASA copolymer as well as ABS copolymer.

C) kneading process

Heat-resistant SAN (S-1) (Styrene 5) to a graft ABS polymer or ASA resin (acrylonitrile-acryl-styrene) prepared by the method of (a) tertiary polymer consisting of%, α-methylstyrene 69%, acrylonitrile 26%), heat resistant SAN such as N-phenyl maleimide (PMI) SAN (S-2), in addition to lubricants, antioxidants, stabilizers, etc. After that, pellets are manufactured using a twin extruder in the range of 220 to 250 ° C. The pellet was injected again to measure its physical properties. Physical properties were measured by the ASTM method.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and is not limited only to these.

EXAMPLE

Example 1

a) Preparation of Matte Graft Copolymer Fillers

70 parts by weight of ion-exchanged water in one step, 15 parts by weight of styrene as an aromatic vinyl monomer, 8 parts by weight of α-methylstyrene, 7 parts by weight of acrylonitrile as a vinyl cyan compound, and methacryl to α, β-unsaturated carboxylic acid. 4 parts by weight of acid, 2 parts by weight of alkylbenzene sulfonate as emulsifier, 0.03 part by weight of t-dodecyl mercaptan as molecular weight modifier, 0.1 part by weight of cumene hydroperoxide as initiator, and sodium formaldehyde slaxate 0.2 as other additives By weight, 0.1 parts by weight of sodium ethylenediamine tetraacetate and 0.005 parts by weight of ferrous sulfate were collectively administered to the reactor, and the reaction temperature was raised to 70 ° C. while stirring to effect emulsion polymerization.

25 parts by weight of ion-exchanged water in the emulsion prepared in step 1, 15 parts by weight of styrene as an aromatic vinyl monomer and 7 parts by weight of α-methylstyrene, 7 parts by weight of acrylonitrile as a vinyl cyan compound, and -4 parts by weight of methacrylic acid as unsaturated carboxylic acid, 0.5 parts by weight of alkylbenzenesulfonate as emulsifier, 0.03 part by weight of t-dodecyl mercaptan as molecular weight modifier, and 0.1 part by weight of cumene hydroperoxide as an initiator to a reaction temperature of 70 deg. It was added continuously while maintaining and stirring.

20 parts by weight of ion-exchanged water in the emulsion prepared in step 2, 15 parts by weight of styrene as an aromatic vinyl monomer, 7 parts by weight of α-methylstyrene, 7 parts by weight of acrylonitrile as a vinyl cyan compound, and -4 parts by weight of methacrylic acid as unsaturated carboxylic acid, 0.5 parts by weight of alkylbenzenesulfonate as emulsifier, 0.03 part by weight of t-dodecyl mercaptan as molecular weight regulator, and 0.1 part by weight of cumene hydroperoxide as initiator at 70 ° C for 1 hour. During heating to 75 ° C. and continuous administration with stirring to prepare a matte graft copolymer filler.

b) graft ABS polymer preparation

(Manufacture of small diameter rubber latex)

In a nitrogen-substituted polymerization reactor (autoclave) 100 parts by weight of ion-exchanged water, 100 parts by weight of 1,3-butadiene as monomer, 1.2 parts by weight of potassium rosin salt as emulsifier, 1.5 parts by weight of potassium oleate salt, sodium carbonate as electrolyte ₂ CO ₃ ) 0.1 parts by weight, 0.5 parts by weight of potassium hydrogen carbonate (KHCO ₃ ), 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, the reaction temperature was raised to 55 ℃ and persulfate as an initiator 0.3 parts by weight of potassium was administered in a batch to initiate the reaction, and after reacting for 10 hours, 0.05 parts by weight of tertiary dodecylmercaptan was further administered again to react at 65 ° C. for 8 hours, and then the reaction was terminated. And the obtained rubber latex was analyzed. Rubber latex analysis method at this time is as follows.

The gel content and the swelling index were solidified by diluting the rubber latex with dilute acid or metal salt, washed, dried in a vacuum oven at 60 ° C. for 24 hours, and then chopped into pieces of rubber with scissors. After storage in a dark room at room temperature for 48 hours, the sol and gel were separated and the gel content and swelling index were measured according to Equations 3 and 4 below.

[Equation 3]

[Equation 4]

The particle size was measured using Nicomp 370 HPL by the dynamic laser light scattering method.

The rubber latex thus obtained had a particle size of 1000 GPa, a gel content of 90% and a swelling index of 18.

(Large Diameter Rubber Latex Manufacturing (Small Diameter Rubber Latex Fusion))

100 parts by weight of the small-diameter rubber latex prepared above was added to the reactor, the stirring speed was adjusted to 10 rpm, the temperature was adjusted to 30 ° C., and then 3.0 parts by weight of 7% acetic acid aqueous solution was gradually added for 1 hour, followed by stirring. A large diameter conjugated diene rubber latex was prepared by fusing the small diameter rubber latex by stopping and leaving it for 30 minutes. The large diameter rubber latex prepared by the fusion process was analyzed.

The rubber latex obtained at this time had a particle diameter of 3100 mm 3, a gel content of 90% and a swelling index of 17.

(Graft polymer production)

50 parts by weight of large-diameter rubber latex prepared by the fusion method in a nitrogen-substituted polymerization reactor, 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, 0.005 parts by weight of ferrous sulfate And 0.23 parts by weight of formaldehyde sodium sulfoxylate were administered to a batch reactor, and the temperature was raised to 70 ° C. And 50 parts by weight of ion-exchanged water, 0.65 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.

At this time, the polymerization conversion rate was 97.5%, the solid coagulation content was 0.2%, and the graft rate was 37%. The latex was solidified with an aqueous sulfuric acid solution, washed, and then powdered.

c) kneading

8 parts by weight of the matt graft copolymer filler prepared as described in Table 1, 35 parts by weight of the graft ABS copolymer, heat resistant SAN (S-1) (5% by weight of styrene, 69% by weight of α-methylstyrene) 25 parts by weight of a terpolymer consisting of 26% by weight of acrylonitrile), 0.5 parts by weight of lubricant, 0.4 part by weight of antioxidant, and 0.3 part by weight of light stabilizer to 32 parts by weight of general SAN (S-3; LG Chem 80HF) After mixing uniformly in a Henschel mixer, pellets were prepared using a twin screw extruder at 230 to 250 ° C., and the pellets were injected again to measure physical properties, and the results are shown in Table 1 below.

Izod impact strength was measured by ASTM D256 method, heat deflection temperature by ASTM D648 method, fluidity by ASTM D1238 method, and gloss was produced by 75 ton injection molding machine in 8in × 8in × 1 / 8in size. The specimen appearance was visually determined after the measurement at 45 degrees.

Example 2

A matt thermoplastic resin composition was prepared in the same manner as in Example 1, except that 10 parts by weight of the matte graft copolymer filler was added in the kneading process and 30 parts by weight of the general SAN (S-3). Changed to wealth was added. The results are shown in Table 1.

When the matte graft copolymer filler is used in an amount of 5 parts by weight or less, it is difficult to expect a gloss of 25 or less on the basis of ASTM D523 45 degrees.

Examples 3 and 4

A matt thermoplastic resin composition was prepared in the same manner as in Example 1, but as shown in Table 1, n-phenylmaleimide heat resistant SAN (S-2; n-phenylmaleimide in the kneading process instead of heat resistant SAN (S-1)). Terpolymers consisting of 38% by weight, 53% by weight of styrene, 9% by weight of acrylonitrile), 25 parts by weight, and the amount of general SAN were changed to 30 and 32 parts by weight, respectively. The results are shown in Table 1.

Example 5

Prepare a matt thermoplastic resin composition in the same manner as in Example 1, but 50 parts by weight of ASA resin (acrylonitrile-acryl-styrene terpolymer) instead of ABS copolymer in the kneading process, as shown in Table 2, matt graft air 5 parts by weight of the coalescing filler and 45 parts by weight of the heat-resistant SAN (S-1) were changed and added.

The physical properties were measured in the same manner as in Example 1, and in order to further measure the weather resistance of the resin, 2,000 hours of testing was performed using an ATLAS WOM test apparatus using ASTM D4459 method, and the weathering resistance of the resin was measured using a color difference meter. Degree (ΔE) was measured and the results are shown in Table 2.

Example 6

To prepare a matt thermoplastic resin composition in the same manner as in Example 5, but in the kneading process as shown in Table 2 n-phenylmaleimide heat-resistant SAN (S-2; n-phenylmaleimide 38 weight instead of SAN (S-1) %, 53 parts by weight of styrene, 9 parts by weight of a terpolymer consisting of 9% by weight of acrylonitrile) and 25 parts by weight of general SAN (S-3), respectively. The results are shown in Table 2.

Comparative Examples 1 and 2

A matt thermoplastic resin composition was prepared in the same manner as in Example 1, but as shown in Table 1, aromatics such as styrene and α-methylstyrene in the presence of the rubber polymer latex instead of the matte graft copolymer filler prepared above in the kneading process. A thermoplastic resin was prepared by adding 8 to 10 parts by weight of a matte filler (L-2; LG Chemical PW144) copolymerized with a vinyl compound, a vinyl cyan compound, and an α, β-unsaturated carboxylic acid in a general manner. Physical properties were measured in the same manner as 1. The results are shown in Table 1.

Comparative Examples 3 and 4

To prepare a matte thermoplastic resin composition in the same manner as in Comparative Examples 1 and 2, but as shown in Table 1 in the kneading process instead of the heat-resistant SAN (S-1) to 25 parts by weight of n-phenylmaleimide heat-resistant SAN (S-2) The change was added. The results are shown in Table 1.

Comparative Example 5

A matt thermoplastic resin composition was prepared in the same manner as in Example 5, but instead of the graft ABS copolymer (A-1) in the kneading process, the ASA copolymer (A-2) (acrylonitrile-acryl-styrene terpolymer, LG) Chemical SA911) was added into 50 parts by weight, heat resistant SAN (S-1) 45 parts by weight, and 5 parts by weight of the matte filler (L-2) used in Comparative Example 1. The results are shown in Table 2.

Comparative Example 6

A matt thermoplastic resin composition was prepared in the same manner as in Example 6, but was changed to 5 parts by weight of the matte filler (L-2) used in Comparative Example 1 instead of the matte graft copolymer filler in the kneading process. The results are shown in Table 2.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 combination ABS copolymer (A-1) 35 35 35 35 35 35 35 35 Heat Resistant SAN (S-1) 25 25 - - 25 25 - - Heat Resistant SAN (S-2) - - 25 25 - - 25 25 General SAN (S-3) 32 30 32 30 30 30 30 30 Matte Copolymer (L-1) 8 10 8 10 - - - - Matte Copolymer (L-2) - - - - 8 10 8 10 Properties Impact Strength (notched, 1/4 ", kgcm / cm) 15 13 10 9 24 26 19 21 Flow index (220 ℃, 10 kg) 9 8 10 10 7.5 7 8.5 8 Heat Deflection Temperature (18.5 kg / ㎠, 1/4 ") 94 95 98 99 91 90 96 95 Surface glossiness (ASTM D523, 45 °) 14 10 17 12 25 20 27 23 Surface condition (150 x 150 x 3 mm) ○ ○ ○ ○ ○ ○ ○ ○

division Example 5 Example 6 Comparative Example 5 Comparative Example 6 combination ASA Copolymer (A-2) 50 50 50 50 Heat Resistant SAN (S-1) 45 - 45 - Heat Resistant SAN (S-2) - 25 - 25 General SAN (S-3) - 25 - 25 Matte Copolymer (L-1) 5 5 - - Matte Copolymer (L-2) - - 5 5 Properties Impact Strength (notched, 1/4 ", kgcm / cm) 15 16 24 26 Flow index (220 ℃, 10 kg) 5 4.8 2.5 2.7 Heat Deflection Temperature (18.5 kg / ㎠, 1/4 ") 96 98 93 95 Surface glossiness (ASTM D523, 45 °) 14 16 25 28 Weathering Discoloration (ΔE) 2.3 2.1 6.7 6.3 Surface condition (150 x 150 x 3 mm) ○ ○ ○ ○

Since the matte heat resistant thermoplastic resin composition of the present invention is a graft copolymer obtained by emulsion-polymerizing a matte filler, its surface gloss is less than 25 at 45 ° of the angle of ASTM D-523, and it has excellent heat and weather resistance. Impact and workability are also excellent.

Claims (15)

In the matt heat-resistant thermoplastic resin composition, a) 20 to 60 parts by weight of an aromatic vinyl monomer; Ii) 5 to 20 parts by weight of a vinyl cyan compound; And Iii) a group consisting of acrylic acid, methacrylic acid, itaconic acid, and crawltonic acid; 6 to 12 parts by weight of α, β-unsaturated carboxylic acid selected from Matte graft copolymer prepared by emulsion polymerization of a composition comprising a 5 to 15 parts by weight of filler; b) 10 to 90 parts by weight of graft ABS copolymer or graft ASA copolymer; And c) 10 to 90 parts by weight of heat resistant SAN copolymer Matte heat resistant thermoplastic resin composition comprising a. The method of claim 1 Matte heat-resistant thermoplastic resin further comprises 50 parts by weight or less of the general SAN copolymer. The method according to claim 1 or 2, Matte heat-resistant thermoplastic resin composition wherein the aromatic vinyl monomer of a) iii) is selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, O-ethylstyrene, and ρ-ethylstyrene. The method according to claim 1 or 2, Matte heat-resistant thermoplastic resin composition wherein the vinyl cyan compound of a) ii) is selected from the group consisting of acrylonitrile, and methacrylonitrile. The method according to claim 1 or 2, Matte heat-resistant thermoplastic resin composition of the graft ABS copolymer or graft ASA copolymer of b) is 25% or more. The method according to claim 1 or 2, The heat-resistant SAN copolymer of c) is composed of 5% by weight of styrene, 69% by weight of α-methylstyrene, 26% by weight of acrylonitrile, and 30% by weight of SAN and n-phenylmaleimide. %, At least one member selected from the group consisting of n-phenylmaleimide heat-resistant SAN of the terpolymer consisting of 9% by weight of acrylonitrile. The method of claim 6, Matte heat-resistant thermoplastic resin composition wherein the maleimide heat-resistant SAN is produced by bulk polymerization. In the manufacturing method of the matte heat-resistant thermoplastic resin composition, a) 20 to 60 parts by weight of an aromatic vinyl monomer; Ii) 5 to 20 parts by weight of a vinyl cyan compound; Iii) a group consisting of acrylic acid, methacrylic acid, itaconic acid, and crawltonic acid; 6-12 parts by weight of an α, β-unsaturated carboxylic acid selected from one or more species; Viii) 0.1 to 2 parts by weight of emulsifier V) 0.1 to 0.5 parts by weight of initiator; And Iii) 0.1-1 part by weight of molecular weight regulator Emulsion polymerization of a composition comprising a matte graphene having a conversion rate of 98% or more Preparing a loft copolymer filler; And b) iii) 5 to 15 matte graft copolymer fillers prepared in step a). Parts by weight Ii) 10 to 90 parts by weight of graft ABS copolymer or graft ASA copolymer; And Iii) 10 to 90 parts by weight of heat resistant SAN copolymer Step of kneading Method of producing a matte heat resistant thermoplastic resin composition comprising a. The method of claim 8, Method for producing a matte heat-resistant thermoplastic resin composition of the a) the aromatic vinyl compound of step iii) is selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, O-ethylstyrene, ρ-ethylstyrene. The method of claim 8, The method of producing a matte heat resistant thermoplastic resin composition wherein the vinyl cyan compound of a) step ii) is selected from the group consisting of acrylonitrile and methacrylonitrile. The method of claim 8 Method for producing a matt heat-resistant thermoplastic resin composition of the emulsion polymerization temperature of step a) is 70 ℃ or more. The method of claim 8, Method for producing a matt heat-resistant thermoplastic resin composition of the graft ABS copolymer or graft ASA copolymer of step b) ii) is 25% or more. The method of claim 8, B) the heat-resistant SAN copolymer of step iii) is 5% by weight of styrene, 69% by weight of α-methylstyrene, 26% by weight of acrylonitrile, and 30% by weight of n-phenylmaleimide, A method for producing a matte heat resistant thermoplastic resin composition selected from the group consisting of n-phenylmaleimide heat resistant SANs of terpolymers composed of 53% by weight of styrene and 9% by weight of acrylonitrile. The method of claim 13, A method for producing a matte heat resistant thermoplastic resin composition wherein the maleimide heat resistant SAN is produced by bulk polymerization. The method of claim 8 Method for producing a matte heat-resistant thermoplastic resin composition is kneaded in step b) is further kneaded further comprising a general SAN 50 parts by weight or less.