KR102165690B1 - Thermoplastic resin composition, method for preparing the resin composition and molded product comprising the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article including the same, and more particularly, a first comprising a hard core having a refractive index of 1.53 to 1.59, a crosslinked rubber layer having an average thickness of 30 to 80 nm, and a non-crosslinked hard shell. A thermoplastic resin and an aromatic vinyl compound having a refractive index of 1.51 to 1.56-a vinyl cyan compound-an alkyl (meth) acrylate compound copolymer (SAMMA resin) and an aromatic vinyl compound having a refractive index of 1.53 to 1.59-a vinyl cyan compound copolymer (SAN The present invention relates to a thermoplastic resin composition comprising a second thermoplastic resin including a system resin), a method for producing the same, and a molded article including the same. According to the present invention, by mixing SAMMA-based resins and SAN-based resins having different refractive indexes and applying them as matrix resins, the heat resistance, surface gloss, impact resistance, and tensile strength are excellent, while light transmittance is greatly improved, so that the colorability of the resin is excellent. .

Description

Thermoplastic resin composition, manufacturing method thereof, and molded article including the same TECHNICAL FIELD [THERMOPLASTIC RESIN COMPOSITION, METHOD FOR PREPARING THE RESIN COMPOSITION AND MOLDED PRODUCT COMPRISING THE SAME}

The present invention relates to a thermoplastic resin composition, a method of manufacturing the same, and a molded article including the same, and more particularly, a thermoplastic resin characterized in that it has excellent weather resistance, heat resistance, fluidity and impact resistance, and excellent surface gloss, light transmittance, and colorability. It relates to a composition and a method for preparing the same.

ABS resin is an acrylonitrile-butadiene-styrene terpolymer and has excellent impact resistance, stiffness, chemical resistance, and processability, so it is used in various fields such as electric and electronic, construction, and automobiles. However, since ABS resins use diene-based monomers containing chemically unsaturated unsaturated bonds such as butadiene, the rubber polymer is easily aged by ultraviolet rays, and the weather resistance is weak, so it is not suitable as an outdoor material.

Therefore, when it is desired to obtain a thermoplastic resin having excellent physical properties and excellent weather resistance and aging resistance, an ethylenically unsaturated polymer that causes aging due to ultraviolet rays should not be present in the graft copolymer.

In order to improve the weather resistance and aging resistance problems as described above, a technology using a chemically more stable crosslinked alkyl acrylate polymer has been proposed instead of a diene polymer. These resins are typically acrylate-styrene-acrylonitrile (Acrylate-Styrene-Acrylonitrile, ASA) resin. The ASA resin has excellent weather resistance and aging resistance, and is used in various fields such as automobiles, ships, leisure goods, construction materials, and horticulture, and various studies are being conducted in order to manufacture ASA-based resins having more improved physical properties.

For example, a method of using a crosslinked large-diameter acrylate rubber latex containing a rubber core having an average particle diameter of 150 to 800 nm and having a narrow particle size distribution has been proposed in order to prepare an ASA-based resin having excellent weather resistance and aging resistance. Compared to the case of using the late rubber latex, the notch impact strength and the like are improved, but it is difficult to color because it is manufactured in a pale pastel color, and its use is limited in the manufacture of colored molded articles with high saturation.

In another example, a first graft copolymer obtained by grafting a styrene-acrylonitrile copolymer to a crosslinked alkyl acrylate rubber polymer having a small average particle diameter and a crosslinked alkyl acrylate polymer having a large average particle diameter is styrene-acrylonitrile. A technique has been proposed to improve the weather resistance and mechanical strength of the thermoplastic resin as well as the colorability of the resin by mixing and using the second graft copolymer grafted with the copolymer, but this is due to the refractive index of the crosslinked alkyl acrylate polymer. There is a disadvantage in that the difference from the refractive index of the grafted styrene-acrylonitrile copolymer is large, so that light scattering occurs a lot, and it is difficult to implement a vivid color during coloring.

In addition, a method of lowering the refractive index of the matrix by using a ternary copolymer consisting of an alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound, an alkyl methacrylate polymer alone or a mixture thereof as a rigid thermoplastic resin forming a matrix phase has been proposed. .

However, the resin prepared by the above-described method still does not have sufficient light transmittance, so that the colorability is not satisfactory, and there is no disclosed method for improving gloss, so a technology related to a thermoplastic resin capable of solving the problems of the prior art There is still a need for development.

Korean Patent Registration No. 10-0815995

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 having very excellent weather resistance, heat resistance, fluidity, impact resistance, surface gloss, light transmittance and colorability, and a method for manufacturing the same.

In addition, an object of the present invention is to provide a technology for a thermoplastic resin molded article manufactured by injecting the thermoplastic resin composition according to the above manufacturing method.

All of the above 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 is a hard core having a refractive index of 1.53 to 1.59, a polymerized crosslinked rubber layer including an alkyl (meth)acrylate compound and a crosslinking agent surrounding the hard core, and an aromatic vinyl wrapped around the crosslinked rubber layer. A first thermoplastic resin comprising a polymerized non-crosslinked hard shell including a compound and a vinyl cyan compound; And a second thermoplastic resin comprising an aromatic vinyl compound having a refractive index of 1.51 to 1.56-vinyl cyan compound-alkyl (meth)acrylate compound copolymer and an aromatic vinyl compound having a refractive index of 1.53 to 1.59-vinyl cyan compound copolymer. It provides a thermoplastic resin composition, characterized in that.

In addition, the present invention includes a hard core having a refractive index of 1.53 to 1.59, a polymerized crosslinked rubber layer surrounding the hard core and including an alkyl (meth)acrylate compound and a crosslinking agent, and an aromatic vinyl compound and a vinyl cyanide compound surrounding the crosslinked rubber layer. The first thermoplastic resin comprising a polymerized non-crosslinked hard shell and an aromatic vinyl compound having a refractive index of 1.51 to 1.56-vinyl cyan compound-alkyl (meth)acrylate compound copolymer and an aromatic vinyl compound having a refractive index of 1.53 to 1.59-vinyl It provides a method for producing a thermoplastic resin composition comprising the step of kneading and extruding a thermoplastic resin composition comprising a second thermoplastic resin containing a cyan compound copolymer.

In addition, the present invention provides a molded article, characterized in that manufactured by injecting the thermoplastic resin composition manufactured according to the manufacturing method.

According to the present invention, in the thermoplastic resin composition, excellent physical properties such as weather resistance, heat resistance, aging resistance, fluidity, impact resistance, and tensile strength are excellent, and there is an effect of providing improved surface gloss, light transmittance and coloring properties.

Hereinafter, the thermoplastic resin composition of the present disclosure, a method of manufacturing the same, and a molded article including the same will be described in detail.

The present inventors are an aromatic vinyl compound having a refractive index of 1.51 to 1.56 as a matrix and a thermoplastic resin comprising a hard core having a refractive index of 1.53 to 1.59, a crosslinked rubber layer surrounding the hard core, and a non-crosslinked hard shell surrounding the crosslinked rubber layer. -The thermoplastic resin composition prepared by mixing an alkyl (meth)acrylate compound copolymer and an aromatic vinyl compound having a refractive index of 1.53 to 1.59 and a vinyl cyan compound copolymer has excellent weather resistance, aging resistance, and impact resistance, which are the properties of ASA-based resins. It was confirmed that the light transmittance and colorability are greatly improved while showing glossiness, etc., and the present invention was completed based on this.

In the present description, the hard core refers to a polymer core having a glass transition temperature of room temperature or higher, specifically 20°C or higher.

In the present description, the non-crosslinked hard shell refers to a polymer that does not contain a crosslinking agent, that is, a polymer polymerized without including a crosslinking agent.

In the present description, the alkyl (meth)acrylate compound refers to an alkyl acrylate compound, an alkyl methacrylate compound, or a mixture thereof.

The thermoplastic resin composition of the present invention comprises A) a1) a hard core having a refractive index of 1.53 to 1.59, a2) a polymerized crosslinked rubber layer covering the hard core and having a thickness of 30 to 80 nm and comprising an alkyl (meth)acrylate compound and a crosslinking agent, and a3) The first thermoplastic resin covering the crosslinked rubber layer and comprising a non-crosslinked hard shell polymerized including an aromatic vinyl compound and a vinyl cyan compound is a matrix resin B) b1) an aromatic vinyl compound having a refractive index of 1.51 to 1.56-vinyl cyanide It may be characterized in that it is dispersed in a second thermoplastic resin comprising a compound-alkyl (meth)acrylate compound copolymer and an aromatic vinyl compound having a refractive index of 1.53 to 1.59-vinyl cyan compound copolymer.

The first thermoplastic resin of the present invention is a graft copolymer in which a hard core, a crosslinked rubber layer, and a non-crosslinked hard shell are sequentially polymerized to form a multilayer structure as described above, and the thickness of the crosslinked rubber layer is smaller than the wavelength range of light. Is minimized, thereby improving light transmittance, and finally, it can be characterized in that the colorability is excellent.

As described above, although the thickness of the crosslinked rubber layer is thin, the first thermoplastic resin having a multilayer structure including a hard core, a crosslinked rubber layer, and a non-crosslinked hard shell has an average particle diameter of 150 to 550 nm, so a thermoplastic resin composition in which a large-diameter rubber polymer is dispersed. It has the advantage of being able to show a level of impact resistance similar to that of.

Hereinafter, the thermoplastic resin composition of the present invention will be described in detail for each component.

A) first thermoplastic resin

a1) hard core

In the present invention, the hard core may have a refractive index of 1.53 to 1.59, and the transparency of the resin is improved within this range, thereby improving the colorability of the final molded article.

In the present invention, the hard core may be characterized by having a glass transition temperature (Tg) of 20° C. or higher, preferably 20 to 140° C., and more preferably 40 to 140° C.. When the glass transition temperature of the hard core is within the above-described range, physical properties such as surface gloss and impact strength are excellent.

In the present invention, the hard core may be a polymerized crosslinked polymer including a monomer for forming a hard core and a crosslinking agent.

The hard core-forming monomer may preferably be used in an amount of 5 to 40 parts by weight, 10 to 30 parts by weight, or 15 to 25 parts by weight based on a total of 100 parts by weight of the monomers used to prepare the first thermoplastic resin, and within this range. The resin's colorability and impact strength are excellent.

The crosslinking agent may be preferably contained in an amount of 0.01 to 0.5 parts by weight based on a total of 100 parts by weight of the monomers used to prepare the first thermoplastic resin, more preferably 0.01 to 0.1 parts by weight. Within the above range, the final product has excellent coloring properties and impact strength.

As another example, the hard core may be a crosslinked polymer polymerized further including a grafting agent.

The grafting agent may preferably be included in an amount of 0.01 to 0.5 parts by weight, more preferably 0.01 to 0.1 parts by weight based on 100 parts by weight of the total monomers used in the production of the first thermoplastic resin. Within the above range, there is an advantage of excellent mechanical properties such as external appearance characteristics of the final molded product such as surface gloss and impact strength.

The monomer for forming the hard core may include an aromatic vinyl compound and a vinyl cyan compound as an example, and may optionally further include an alkyl (meth)acrylate compound.

Specifically, the monomer for forming a hard core may include 50 to 90 parts by weight of an aromatic vinyl compound and 10 to 50 parts by weight of a vinyl cyan compound, and optionally more than 0 to 30 parts by weight of an alkyl (meth)acrylate compound. .

In the present disclosure, the aromatic vinyl compound may include at least one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, and vinyl toluene, unless otherwise specified, but is not limited thereto.

In the present description, the vinyl cyan compound may include one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, unless otherwise specified, but is not limited thereto.

In the present description, the alkyl (meth)acrylate compound may be an alkyl (meth)acrylate including a chain alkyl or branched alkyl group having 1 to 10 carbon atoms unless otherwise specified, specifically methyl acrylate, ethyl acrylate , Propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate may be included, but are not limited thereto.

The crosslinking agent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol Dimethacrylate, trimethylolpropane trimethacrylate, and may be one or more selected from the group consisting of trimethylolethane triacrylate, but is not limited thereto.

The grafting agent may be at least one selected from the group consisting of allyl methacrylate, triallyl isocyanurate, triallylamine, and diallylamine, but is not limited thereto.

In a more specific example, the hard core of the present invention includes 5 to 40 parts by weight of the monomer for forming the hard core, 0.05 to 0.5 parts by weight of a crosslinking agent, 0.05 to 0.5 parts by weight of a grafting agent, based on a total of 100 parts by weight of the monomers used to prepare the first thermoplastic resin. It may be polymerized including 0.5 to 2.5 parts by weight of a polymerization initiator, and 0.01 to 1 part by weight of an electrolyte, and the polymerization may optionally further include more than 0 to 2 parts by weight of an emulsifier, but is not limited thereto.

In the present description, the polymerization initiator is sodium persulfate, potassium persulfate, ammodium persulfate, potassium persulfate, hydrogen peroxide, t-butyl peroxide, cumene hydroperoxide, p-methane hydroperoxide, di- unless otherwise specified. t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, diisopropylbenzene hydroperoxide, 3,5,5-trimethylhexanol per Peroxidation initiators such as oxide and t-butyl peroxy isobutylate, and azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (butyric acid) It may be one or more selected from azo-based initiators such as methyl, but is not limited thereto.

In addition, the polymerization initiator can be used in combination with an oxidation-reduction catalyst, and the oxidation-reduction catalyst is sodium pyrophosphate, dextrose, ferrous sulfide, sodium sulfite, sodium formaldehyde sulfoxylate, sodium ethylenediamine It may be one or more selected from among tetraacetates, but is not limited thereto.

In the present description, the electrolyte is KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , Na ₄ P ₂ O ₇ , unless otherwise specified. It may be at least one selected from K ₃ PO ₄ , Na ₃ PO _{4 ,} K ₂ HPO ₄ , Na ₂ HPO ₄ , KOH, NaOH, Na ₂ S ₂ O ₇ , but is not limited thereto.

Unless otherwise specified, the emulsifiers in the present disclosure include alkyl sulfosulfonic acid metal salts having 12 to 18 carbon atoms, alkyl sulfuric acid ester metal salts having 12 to 20 carbon atoms, alkyl sulfonic acid metal salts having 12 to 20 carbon atoms, fatty acid salts, rosin acid salts, and It should be noted that it may be one or more selected from the derivatives, but is not limited thereto.

In the present description, a derivative refers to a compound in which one or more hydrogen or functional groups of the original compound are substituted with other organic or inorganic groups.

In the present invention, the hard core may have an average particle diameter of 100 to 250 nm as an example, and more preferably 150 to 200 nm. Within the above range, there is an effect of improving mechanical properties such as surface gloss and impact strength.

a2) crosslinked rubber layer

In the present invention, the crosslinked rubber layer surrounds the hard core and may have an average thickness of 30 to 80 nm. When the average thickness of the crosslinked rubber layer is within the above-described range, light transmittance may be improved as the light scattering is minimized, which is smaller than the wavelength range of light, and ultimately, the colorability of the final resin may be improved.

The average thickness of the crosslinked rubber layer may be, for example, 30 to 80 nm, 30 to 70 nm, or 35 to 60 nm, and within this range, both coloring properties and impact strength of the final molded product are excellent.

In the present invention, the crosslinked rubber layer may have a glass transition temperature (Tg) of -70 to -20°C, more preferably -50 to -25°C. Within this range, the resin has excellent effects such as surface gloss and impact strength.

In the present invention, the crosslinked rubber layer may be polymerized by including a monomer alkyl (meth)acrylate compound and a crosslinking agent.

The alkyl (meth)acrylate compound may be preferably used in an amount of 30 to 55 parts by weight or 35 to 50 parts by weight based on a total of 100 parts by weight of the monomers used to prepare the first thermoplastic resin, and within this range, colorability and impact There is an advantage that both strength is excellent.

The alkyl (meth)acrylate compound is, for example, an alkyl (meth)acrylate having 2 to 8 carbon atoms or 4 to 8 carbon atoms in the alkyl portion.

In a specific example, the alkyl (meth)acrylate compound may be one or more of butyl acrylate, ethyl hexyl acrylate, butyl methacrylate, or ethylhexyl methacrylate, but is not limited thereto.

The crosslinking agent may be used in an amount of 0.1 to 1 parts by weight or 0.1 to 0.5 parts by weight based on a total of 100 parts by weight of the monomer (alkyl (meth) acrylate compound) used in preparing the first thermoplastic resin, and within this range, surface gloss and impact There is an advantage of excellent physical properties such as strength.

The crosslinking agent may be one or more of the crosslinking agents that can be used to manufacture the hard core, for example.

In another example, the crosslinked rubber layer may be polymerized by further comprising a grafting agent.

The grafting agent is preferably used in an amount of 0.1 to 1 parts by weight or 0.1 to 0.5 parts by weight based on a total of 100 parts by weight of a monomer (alkyl (meth) acrylate compound) used in preparing the first thermoplastic resin, and within this range It has the advantage of excellent physical properties such as gloss and complexation and impact strength.

The grafting agent may be one or more of grafting agents that can be used to manufacture the hard core, for example.

In a more specific example, the crosslinked rubber layer of the present invention comprises 20 to 70 parts by weight of an alkyl (meth)acrylate compound as a monomer, 0.1 to 70 parts by weight of a monomer, based on a total of 100 parts by weight of the monomers used to prepare the first thermoplastic resin in the presence of the hard core latex. 1 part by weight, 0.1 to 1 part by weight of a grafting agent, 0.1 to 2.5 parts by weight of an emulsifier, and 0.01 to 2 parts by weight of a polymerization initiator may be included in the polymerization, but the present disclosure is not limited thereto.

In addition, the polymerization may be performed at 30 to 85°C or 50 to 80°C for 1 to 7 hours or 1 to 3 hours, but is not limited thereto.

a3) non-crosslinked hard shell

In the present invention, the non-crosslinked hard shell may be characterized in that it surrounds the crosslinked rubber layer and is polymerized including an aromatic vinyl compound and a vinyl cyan compound as monomers.

The monomer (including an aromatic vinyl compound and a vinyl cyan compound) used in the preparation of the non-crosslinked hard shell is preferably 30 to 50 parts by weight or 35 to 45 parts by weight based on a total of 100 parts by weight of the monomers used for preparing the first thermoplastic resin. It can be, and within this range, there is an advantage of excellent colorability and impact strength.

More specifically, the non-crosslinked hard shell is 5 to 30 parts by weight of an aromatic vinyl compound, 2 to 25 parts by weight of a vinyl cyan compound, 0.5 to 3 parts by weight of an emulsifier in the presence of a polymer latex obtained by graft polymerization of the crosslinked rubber layer on the hard core. , Including 0.05 to 2 parts by weight of a polymerization initiator, and 0.02 to 2 parts by weight of a molecular weight modifier, it may be polymerized, but is not limited thereto.

As an example, the molecular weight modifier may be a mercaptan compound including tertiary dodecyl mercaptan.

In addition, the polymerization may be performed at a temperature of 50 to 85°C or 60 to 80°C over 2 to 7 hours or 2 to 5 hours, but is not limited thereto.

As an example, the aromatic vinyl compound may be one or more of aromatic vinyl compounds that can be used to prepare the hard core.

As an example, the vinyl cyan compound may be one or more of vinyl cyan compounds that can be used to prepare the hard core.

The first thermoplastic resin including the hard core, the crosslinked rubber layer and the non-crosslinked hard shell may have an average particle diameter of 150 to 550 nm, 200 to 450 nm or 250 to 450 nm, for example, and within this range, colorability, impact strength, fluidity, There is an advantage that both physical properties such as surface gloss are excellent.

As an example, the first thermoplastic resin may include 5 to 40% by weight of the hard core, 20 to 60% by weight of the crosslinked rubber layer, and 20 to 60% by weight of the non-crosslinked hard shell, within this range It has excellent effects in light transmittance and mechanical strength.

In another example, the first thermoplastic resin may include 5 to 40% by weight of the hard core, 20 to 60% by weight of the crosslinked rubber layer, and 20 to 60% by weight of the non-crosslinked hard shell, and the final The resin composition has excellent light transmittance and mechanical strength.

The first thermoplastic resin is manufactured in the form of latex, and the solid content in the latex may be 40 to 60% by weight or 45 to 55% by weight, and the stability of the latex is excellent within this range to maximize the productivity of the resin composition. There is an effect.

In the present description, the solid content may be calculated by drying 2 g of latex in a convection oven at 150° C. for 10 minutes to volatilize the reaction medium and unreacted monomers, and the mass fraction of the remaining solids relative to the initial latex.

The first thermoplastic resin latex may be obtained in a powder form through conventional processes such as agglomeration, washing, and drying. Specifically, the first thermoplastic resin latex may be agglomerated at atmospheric pressure of 60 to 100°C by adding sulfuric acid, magnesium sulfate, calcium chloride, aluminum sulfate, etc., which are known coagulants, and through aging, washing, dehydration, and drying processes It may be obtained as, but is not limited thereto, and is not particularly limited and may be selected and carried out if it is within the range commonly practiced in the technical field to which the present invention belongs.

B) Second thermoplastic resin

In the present invention, the second thermoplastic resin is a matrix resin in which the first thermoplastic resin is dispersed, and its refractive index may preferably be 1.52 to 1.56 or 1.53 to 1.55, and the light transmittance within this range is excellent, so that the colorability of the final product is large. There is an improvement effect.

In the present invention, in order to control the refractive index of the second thermoplastic resin to 1.52 to 1.56, an aromatic vinyl compound having a different refractive index-a vinyl cyan compound-an alkyl (meth) acrylate compound copolymer and an aromatic vinyl compound-a vinyl cyan compound copolymer are mixed. It is characterized by using.

For example, the second thermoplastic resin is an aromatic vinyl compound having a refractive index of 1.51 to 1.56 or 1.51 to 1.54-a vinyl cyan compound-alkyl (meth) acrylate compound copolymer and an aromatic vinyl compound having a refractive index of 1.53 to 1.59 or 1.55 to 1.59 -A vinyl cyan compound copolymer may be included, and as such, an aromatic vinyl compound having a different refractive index-vinyl cyan compound-alkyl (meth)acrylate compound copolymer and an aromatic vinyl compound-vinyl cyan compound copolymer are mixed to form a matrix resin. Depending on the application, the light transmittance, colorability and mechanical properties of the final product are all excellent.

The second thermoplastic resin may be characterized in that the glass transition temperature (Tg) is 60 to 140°C or 80 to 130°C, and within this range, it has excellent effects in surface gloss, mechanical strength, impact resistance and fluidity. .

b1) Aromatic vinyl compound-vinyl cyan compound-alkyl (meth)acrylate compound copolymer

In the present invention, the aromatic vinyl compound-vinyl cyan compound-alkyl (meth)acrylate copolymer is, for example, 20 to 60% by weight of an aromatic vinyl compound, 5 to 15% by weight of a vinylcyan compound, and 30 to 30 to an alkyl (meth)acrylate compound. It may be polymerized, including 75% by weight, and within this range, there are excellent effects in physical properties such as colorability and impact strength.

In another example, the aromatic vinyl compound-vinyl cyan compound-alkyl (meth)acrylate copolymer is an aromatic vinyl compound 20 to 50% by weight, a vinyl cyan compound 5 to 10% by weight, and an alkyl (meth)acrylate compound 45 to 70 It may be polymerized, including weight percent, and within this range, there is an excellent effect of physical properties such as colorability and impact strength.

The alkyl (meth)acrylate compound is, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethyl hexyl methacrylate, decyl methacrylate, methyl acrylate, ethyl acrylic It may be one or more selected from the group consisting of acrylate, propyl acrylate, butyl acrylate, and ethylhexyl acrylate, but preferably methyl methacrylate.

The aromatic vinyl compound-vinyl cyan compound-alkyl (meth)acrylate copolymer may, for example, have a weight average molecular weight (Mw) of 50,000 to 150,000 g/mol, 50,000 to 100,000 g/mol, or 110,000 to 150,000 g/mol, and In this range, both the fluidity and impact strength of the resin are excellent.

In addition, the aromatic vinyl compound-vinyl cyan compound-alkyl (meth)acrylate copolymer may optionally further include an antioxidant as needed, and the antioxidant is an aromatic vinyl compound-vinyl cyan compound-alkyl (meth) It may be preferable to use 0.05 to 1 parts by weight or 0.05 to 0.5 parts by weight based on the total 100 parts by weight of the monomers used in the preparation of the acrylate copolymer.

In addition, the polymerization method of the aromatic vinyl compound-vinyl cyan compound-alkyl (meth)acrylate copolymer is not particularly limited, and suspension polymerization, block polymerization or continuous block polymerization may be possible.

b2) Aromatic vinyl compound-vinyl cyan compound copolymer

In the present invention, the aromatic vinyl compound-vinyl cyan compound copolymer may be, for example, a copolymer in which 75 to 85% by weight of an aromatic vinyl compound and 15 to 25% by weight of a vinyl cyanide compound are copolymerized, and within this range, colorability and impact strength There are advantages such as excellent physical properties.

In another example, the aromatic vinyl compound-vinyl cyan compound copolymer may be a copolymer in which 76 to 82% by weight of an aromatic vinyl compound and 18 to 24% by weight of a vinylcyan compound are copolymerized, and within this range, colorability and impact strength, etc. There is an effect of excellent physical properties.

The aromatic vinyl compound-vinyl cyan compound copolymer may have, for example, a weight average molecular weight (Mw) of 100,000 to 150,000 g/mol or 110,000 to 150,000 g/mol, and has excellent fluidity and impact strength within this range. have.

In addition, the polymerization of the aromatic vinyl compound-vinyl cyan compound copolymer may optionally further include an antioxidant, and the antioxidant may be 0.05 to 1 parts by weight based on a total of 100 parts by weight of monomers used for preparing the copolymer or It may be desirable to use 0.05 to 0.5 parts by weight.

In addition, the polymerization method of the aromatic vinyl compound-vinyl cyan compound copolymer is not particularly limited, and suspension polymerization, block polymerization or continuous block polymerization may be possible.

Thermoplastic resin composition

The thermoplastic resin composition of the present invention may be prepared by kneading the first thermoplastic resin and the second thermoplastic resin, and then extruding.

As an example, the thermoplastic resin composition of the present invention comprises A) 20 to 50% by weight of the first thermoplastic resin, B) b1) 20 to 55% by weight of the aromatic vinyl compound-vinyl cyan compound-alkyl (meth)acrylate compound copolymer And b2) 20 to 55% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer, and within this range, the resin composition has excellent properties such as light transmittance and impact strength.

In another example, the thermoplastic resin composition of the present invention is A) 20 to 40% by weight of the first thermoplastic resin, B) b1) 30 to 50% by weight of the aromatic vinyl compound-vinyl cyan compound-alkyl (meth)acrylate compound copolymer % And b2) The aromatic vinyl compound-vinyl cyan compound copolymer may contain 20 to 40% by weight, and within this range, both light transmittance and mechanical properties are excellent.

The thermoplastic resin composition of the present invention may optionally further include additives as needed, and the additive may be at least one selected from among lubricants, antioxidants, light stabilizers, and pigments, but is not limited thereto.

As an example, the additive may be included in an amount of 0.1 to 5 parts by weight or 0.2 to 2.5 parts by weight based on a total of 100 parts by weight of the first thermoplastic resin and the second thermoplastic resin. Within this range, the processability and physical property balance are more excellent. have.

The kneading may be performed under conditions of 180 to 250°C and 100 to 200 rpm, for example, and there is an advantage in that the processability of the resin is excellent within this range.

In addition, the difference between the refractive index of the first thermoplastic resin and the second thermoplastic resin may preferably be 1 or less, and more preferably 0.03 or less. Within this range, there is an advantage that the transparency of the thermoplastic resin composition is more excellent.

The thermoplastic resin composition of the present invention may be characterized in that, for example, light transmittance is 35% or more, more preferably 45% or more, 50% or more, 52% or more, or 55% or more, and thereby the colorability of the final product. It can be improved.

The thermoplastic resin composition of the present invention may be characterized in that, for example, the impact strength is 15 kg·cm/cm or more, or 15 to 25 kg·cm/cm or 20 to 25 kg·cm/cm, and the tensile strength is 400 kg/cm that ² or more, or from 400 to 450kg / cm ² may be characterized.

Further, it is possible to manufacture a thermoplastic resin molded article by injecting the thermoplastic resin composition of the present invention.

The injection may be performed under conditions of 190 to 260° C. and 20 to 60 bar, for example, but is not limited thereto.

The above-described thermoplastic resin composition of the present invention, its manufacturing method, and other conditions not explicitly described in relation to the molded article including the same are not particularly limited if they are within the range commonly practiced in the technical field to which the present invention belongs, and is necessary. It can be appropriately selected and implemented according to.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It is natural that such modifications and modifications fall within the appended claims.

[Example]

Example One

A) Preparation of the first thermoplastic resin

a1) Preparation of hard core

In the reactor, 15 parts by weight of styrene, 5 parts by weight of acrylonitrile, 0.2 parts by weight of di2-ethylhexyl sulfosuccinate sodium salt, 0.04 parts by weight of ethylene glycol dimethacrylate, 0.04 parts by weight of allyl methacrylate, sodium hydrogen carbonate 0.2 parts by weight and 40 parts by weight of distilled water were collectively administered, the temperature was raised to 70°C, and then 0.05 parts by weight of potassium persulfate was added to initiate the polymerization reaction. After that, polymerization was performed at 70° C. for 1 hour. The average particle diameter of the hard core on the latex obtained after the polymerization reaction was completed was 170 nm and the refractive index was confirmed to be 1.573.

a2) Preparation of crosslinked rubber layer

In the hard core latex prepared above, 40 parts by weight of butyl acrylate, 0.5 parts by weight of di 2-ethyl hexyl sulfosuccinate sodium salt, 0.2 parts by weight of ethylene glycol dimethacrylate, 0.2 parts by weight of allyl methacrylate, hydrogen carbonate A mixture of 0.1 parts by weight of sodium, 20 parts by weight of distilled water, and 0.05 parts by weight of potassium persulfate was continuously added at 70° C. for 3 hours, and polymerization was further carried out for 1 hour after completion of the addition. The average particle diameter of the latex-like rubber polymer obtained after the polymerization reaction was completed was 250 nm, and the thickness of the crosslinked rubber layer was 40 nm.

In the present description, the thickness of the crosslinked rubber layer is calculated from Equation 1 below.

[Equation 1]

Thickness of crosslinked rubber layer = [(average particle diameter of rubber polymer)-(average particle diameter of hard core)]/2

a3) Preparation of non-crosslinked hard shell

To the rubber polymer latex (hard core + crosslinked rubber layer) prepared above, 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 1.5 parts by weight of potassium rosinate, 0.1 parts by weight of potassium persulfate, 0.05 parts by weight of tertiary dodecyl mercaptan And a mixture mixed with 50 parts by weight of distilled water was continuously added at 70° C. for 3 hours to perform a polymerization reaction. In order to increase the polymerization conversion rate, the temperature was raised to 75° C. after the addition was completed, and the mixture was further reacted for 1 hour and then cooled to 60° C. The average particle diameter of the latex phase of the first thermoplastic resin, which is the final graft copolymer obtained after completion of the reaction, was confirmed to be 300 nm, and the total solid content in the latex was confirmed to be 48%.

The first thermoplastic resin latex obtained above is subjected to atmospheric pressure coagulation at 85° C. using an aqueous calcium chloride solution, then aged at 95° C., dehydrated and washed, and dried for 30 minutes with hot air at 90° C. The resin was obtained.

B) Preparation of the second thermoplastic resin

b1) SAMMA (styrene-acrylonitrile-methyl methacrylate) resin preparation

1,1-bis(t-butylperoxy)-3,3,5-trimethyl cyclohexane in a mixed solution in which 20 parts by weight of toluene, 24 parts by weight of styrene, 50 parts by weight of methyl methacrylate and 6 parts by weight of acrylonitrile are dissolved 0.02 parts by weight, 0.08 parts by weight of n-dodecyl mercaptan, and Ivgacure (1,3,5-tris(4-tertbutyl-3-hydroxy-2,6-dimethylbenzyl)-1,3 as a hindered phenolic antioxidant ,5-triazine-2,4,6-(1H,3H,5H)-trione) 0.1 parts by weight of a polymerization solution added to the 26L reactor at a rate of 14L/hr was added to the 26L reactor while polymerization at 140℃ in the first reactor. Then, the polymerization was carried out at a temperature of 150°C in the second reactor, and when the polymerization conversion rate was about 60% or more, unreacted monomers and reaction medium were removed at a temperature of 215°C in a volatilization tank to prepare a pellet-type SAMMA resin.

The weight average molecular weight of the prepared SAMMA resin was 90,000 g/mol, and the refractive index was confirmed to be 1.521.

b2) SAN resin manufacturing

1,1-bis(t-butylperoxy)-3,3,5-trimethyl cyclohexane 0.02 parts by weight, n-dodecyl in a mixed solution of 20 parts by weight of toluene, 64 parts by weight of styrene, and 16 parts by weight of acrylonitrile 0.08 parts by weight of mercaptan, and Ivgacure (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2 as a hindered phenolic antioxidant ,4,6-(1H,3H,5H)-trione) 0.1 parts by weight of the polymerization solution was added to the 26L reactor at a rate of 14L/hr, and polymerization was performed at a temperature of 140℃ in the first reactor, and 150 in the second reactor. When the polymerization was performed at a temperature of about 60% or more, the unreacted monomer and the reaction medium were removed in a volatilization tank at a temperature of 215°C to prepare a pellet-type SAN resin.

The prepared SAN resin had a weight average molecular weight of 130,000 g/mol, and a refractive index of 1.587.

Preparation of thermoplastic resin composition

(A) 30 parts by weight of the first thermoplastic resin powder and B) as the second thermoplastic resin, b1) 40 parts by weight of SAMMA resin and b2) 30 parts by weight of SAN resin, 1 part by weight of lubricant, 0.5 parts by weight of antioxidant , And 0.5 parts by weight of an ultraviolet stabilizer were added and mixed. This was melt-kneaded and extruded using a 40 pie extrusion kneader at a cylinder temperature of 220°C to prepare a thermoplastic resin composition in the form of a pellet, and then injected to prepare a specimen for measuring physical properties.

Specimens for evaluation of pigment colorability were prepared by melt-kneading and extrusion, further including 1 part by weight of carbon black in the process of preparing the thermoplastic resin composition.

Example 2

In the process of manufacturing the thermoplastic resin composition, (A) the first thermoplastic resin powder, b1) SAMMA resin, and b2) SAN resin prepared in the same manner as in Example 1 are used in 30 parts by weight, 30 parts by weight, and 40 parts by weight, respectively. Except for that, a specimen for measuring physical properties was prepared in the same manner as in Example 1.

Example 3

In the process of manufacturing the thermoplastic resin composition, (A) the first thermoplastic resin powder, b1) SAMMA resin, and b2) SAN resin prepared in the same manner as in Example 1 were used in 30 parts by weight, 50 parts by weight, and 20 parts by weight, respectively. Except for that, a specimen for measuring physical properties was prepared in the same manner as in Example 1.

Example 4

In the process of preparing the b1) SAMMA resin of Example 1, it was carried out in the same manner as in Example 1, except that 24 parts by weight of styrene, 48 parts by weight of methyl methacrylate, and 8 parts by weight of acrylonitrile were used.

Example 5

In the process of preparing the b1) SAMMA resin of Example 1, it was carried out in the same manner as in Example 1, except that 24 parts by weight of styrene, 52 parts by weight of methyl methacrylate, and 4 parts by weight of acrylonitrile were used.

Example 6

In the process of preparing the b2) SAN resin of Example 1, it was carried out in the same manner as in Example 1, except that 65 parts by weight of styrene and 15 parts by weight of acrylonitrile were used.

Example 7

In the process of preparing the b2) SAN resin of Example 1, it was carried out in the same manner as in Example 1, except that 61 parts by weight of styrene and 19 parts by weight of acrylonitrile were used.

Comparative example One

In the process of manufacturing the thermoplastic resin composition, (A) the first thermoplastic resin powder, b1) SAMMA resin, and b2) SAN resin prepared in the same manner as in Example 1 were used in 30 parts by weight, 60 parts by weight, and 10 parts by weight, respectively. Except for that, a specimen for measuring physical properties was prepared in the same manner as in Example 1.

Comparative example 2

In the process of manufacturing the thermoplastic resin composition, (A) the first thermoplastic resin powder, b1) SAMMA resin, and b2) SAN resin prepared in the same manner as in Example 1 were used in 30 parts by weight, 10 parts by weight, and 60 parts by weight, respectively. Except for that, a specimen for measuring physical properties was prepared in the same manner as in Example 1.

Comparative example 3

In the process of preparing the b1) SAMMA resin of Example 1, it was carried out in the same manner as in Example 1, except that 20 parts by weight of styrene, 40 parts by weight of methyl methacrylate, and 20 parts by weight of acrylonitrile were used.

Comparative example 4

In the process of preparing the b2) SAN resin of Example 1, it was carried out in the same manner as in Example 1, except that 56 parts by weight of styrene and 24 parts by weight of acrylonitrile were used.

Comparative example 5

In the process of manufacturing the thermoplastic resin composition, physical properties in the same manner as in Example 1 except that (A) 30 parts by weight of the first thermoplastic resin powder and b1) 70 parts by weight of the SAMMA resin prepared in the same manner as in Example 1 were used. A specimen was prepared for measurement.

Comparative example 6

In the process of manufacturing the thermoplastic resin composition, physical properties in the same manner as in Example 1 except that (A) 30 parts by weight of the first thermoplastic resin powder and b2) 70 parts by weight of the SAN resin prepared in the same manner as in Example 1 were used. A specimen was prepared for measurement.

Comparative example 7

In the process of manufacturing the a1) hard core of Example 1, 15 parts by weight of styrene, 5 parts by weight of acrylonitrile, and 0.2 parts by weight of di 2-ethylhexyl sulfosuccinate sodium salt were replaced with 5 parts by weight of styrene and 1 part by weight of acrylonitrile. Parts, di 2-ethyl hexyl sulfosuccinate sodium salt 0.06 parts by weight, and a2) in the process of preparing the crosslinked rubber layer, except that butyl acrylate 54 parts by weight instead of 40 parts by weight was used. In the same manner, a first thermoplastic resin powder was obtained.

At this time, a1) the refractive index of the hard core latex was 1.571, and the average particle diameter was 170 nm. In addition, the average particle diameter of the rubber polymer latex (hard core + crosslinked rubber layer) was 360 nm, and the thickness of the crosslinked rubber layer (b) was 95 nm. In addition, the average particle diameter of the obtained first thermoplastic resin latex was 430 nm.

Except for the above process, a thermoplastic resin composition was prepared in the same manner as in Example 1, and then a specimen for measuring physical properties was prepared by injection.

Comparative example 8

In the process of manufacturing a1) hard core of Example 1, butyl acrylate 10 parts by weight, di 2-in place of styrene 15 parts by weight, acrylonitrile 5 parts by weight, di 2-ethylhexyl sulfosuccinate sodium salt 0.2 parts by weight 0.15 parts by weight of ethyl hexyl sulfosuccinate sodium salt is used, a2) 30 parts by weight of butyl acrylate is used instead of 40 parts by weight of butyl acrylate in the process of preparing a crosslinked rubber layer, a3) 30 parts by weight of styrene in the process of preparing a non-crosslinked hard shell Example 1, except that 45 parts by weight of styrene, 15 parts by weight of acrylonitrile, and 0.08 parts by weight of tertiary dodecyl mercaptan were used instead of 10 parts by weight of acrylonitrile and 0.05 parts by weight of tertiary dodecyl mercaptan. A first thermoplastic resin powder was obtained in the same manner as described above.

At this time, a1) the hard core latex had a refractive index of 1.473 and an average particle diameter of 180 nm. Further, the average particle diameter of the rubber polymer latex (hard core + crosslinked rubber layer) was 290 nm, and the average particle diameter of the finally obtained first thermoplastic resin latex was 400 nm.

Except for the above process, a thermoplastic resin composition was prepared in the same manner as in Example 1, and then a specimen for measuring physical properties was prepared by injection.

[Test Example]

The properties of the specimens prepared in Examples 1-7 and Comparative Examples 1-8 were measured by the following method, and the results are shown in Tables 1 and 2 below.

1) Flow index (g/10min): In accordance with ASTM D1238, it was measured under conditions of a temperature of 220°C and a load of 10 kg.

2) Light transmittance (%): It was measured using a specimen having a thickness of 3.2 mm according to ASTM D1003.

3) Glossiness (45°): It was measured using a specimen having a thickness of 3.2 mm according to ASTM D528.

4) Heat Distortion Temperature (HDT, ℃): According to ASTM D648, the heat distortion temperature of a specimen with a thickness of 1/4" was measured under the condition of a load of 18.6kg/cm ² .

5) Izod impact strength (kg·cm/cm): The impact strength of a 1/4" thick specimen was measured at 23°C according to ASTM D256.

6) Tensile strength (kg/cm ² ): According to ASTM D638, the specimen was pulled at a rate of 50 mm/min under the condition of 1/8" thickness, and the strength at the breaking point was measured.

7) Pigment colorability: The L value of a specimen to which 1/8" thick carbon black was added was measured using a color difference meter, and the lower the L value, the lower the brightness and the darker black color, indicating good pigment colorability.

8) Refractive index: It was measured using a refractive index meter Metricon 2010.

9) Average particle diameter: It was measured using a particle size analyzer NICOMP 380.

10) Weight average molecular weight: The sample was dissolved in tetrahydrofuran and measured using GPC.

11) Glass transition temperature: Measured using DSC Q100 manufactured by TA Instruments.

Example One 2 3 4 5 6 7 b1 ^* % by weight 40 30 50 40 40 40 40 b2 ^* % by weight 30 40 20 30 30 30 30 AN ^* wt% in b1 resin 7.5 7.5 7.5 10 5 7.5 7.5 weight% of AN in b2 resin 20 20 20 20 20 18.75 23.75 b1 refractive index 1.521 1.521 1.521 1.522 1.521 1.521 1.521 b2 refractive index 1.587 1.587 1.587 1.587 1.587 1.576 1.572 B refractive index 1.544 1.588 1.539 1.549 1.549 1.544 1.542 Flow index[g/10min] 14 39 42 38 40 40 39 Light transmittance[%] 57 55 60 59 58 58 57 Surface gloss 99 99 99 98 97 98 99 HDT[℃] 85 82 83 82 83 85 84 Impact strength[kg·cm/cm] 24 25 22 20 21 24 23 Tensile strength[kg/cm ² ] 430 440 420 430 410 430 420 Coloring (L) 24.07 25.05 24.55 24.89 25.10 24.51 24.31

(b1 ^* : SAMMA resin, b2 ^* : SAN resin, AN ^* : acrylonitrile)

Comparative example One 2 3 4 5 6 7 8 b1 wt% 60 10 40 40 70 - 40 40 b2 wt% 10 60 30 30 - 70 30 30 AN* wt% in b1 resin 7.5 7.5 25 7.5 7.5 - 7.5 7.5 weight% of AN in b2 resin 20 20 20 30 - 20 20 20 b1 refractive index 1.521 1.521 1.521 1.521 1.521 - 1.521 1.521 b2 refractive index 1.587 1.587 1.587 1.587 - 1.587 1.587 1.587 B refractive index 1.530 1.577 1.549 1.541 1.521 1.587 1.544 1.544 Flow index[g/10min] 39 35 35 31 35 24 42 39 Light transmittance[%] 51 32 43 44 30 25 8 7 Surface gloss 99 88 86 98 97 96 88 81 HDT[℃] 84 83 82 82 83 85 83 85 Impact strength[kg·cm/cm] 21 19 16 15 12 18 26 23 Tensile strength[kg/cm ² ] 400 410 430 440 430 410 370 360 Coloring (L) 25.00 25.94 25.84 27.01 26.50 27.10 27.01 27.00

As shown in Table 1, the thermoplastic resin composition having a controlled refractive index according to an embodiment of the present invention (Example 1-7) has excellent heat resistance, fluidity, surface gloss, impact strength, and tensile strength, and light transmittance. It can be seen that it is higher than 55% and improved colorability.

Referring to Table 2, it was confirmed that the overall light transmittance of Comparative Example 1-8, which was not according to the present invention, was lower than that of Example 1-6, and the colorability and surface gloss were also poor. In addition, it can be seen that the resin composition of Comparative Example 1-8 exhibits inferior physical properties compared to Example 1-6 in terms of impact strength and fluidity.

In addition, as shown in Table 2, when the refractive index is not controlled by using only one of SAMMA resin or SAN resin as the matrix resin (Comparative Examples 5 and 6), it can be seen that the light transmittance is more poor.

In addition, it was confirmed that the thermoplastic resin composition of Comparative Example 7 having a thick crosslinked rubber layer of 95 nm had very poor light transmittance and colorability compared to the examples according to the present invention.

In addition, the same monomer (butyl acrylate) was used when manufacturing the hard core and the crosslinked rubber layer, and it was confirmed that the light transmittance and colorability were significantly lower than those of the examples according to the present invention even in Comparative Example 8, where the refractive index of the hard core was low at 1.473 Became.

Claims (20)

A rigid core having a refractive index of 1.53 to 1.59, a polymerized crosslinked rubber layer surrounding the hard core and including an alkyl (meth)acrylate compound and a crosslinking agent, and a polymerized ratio including an aromatic vinyl compound and a vinyl cyanide compound surrounding the crosslinked rubber layer 20 to 40% by weight of the first thermoplastic resin comprising a bridge hard shell; And 30 to 50% by weight of an aromatic vinyl compound having a refractive index of 1.51 to 1.56-vinyl cyan compound-alkyl (meth)acrylate compound copolymer and 20 to 40% by weight of an aromatic vinyl compound having a refractive index of 1.53 to 1.59-vinyl cyan compound copolymer. Including; a second thermoplastic resin comprising a,
The second thermoplastic resin has a refractive index of 1.53 to 1.55,
A thermoplastic resin composition, characterized in that the light transmittance is 55% or more. delete The method of claim 1,
The first thermoplastic resin, a thermoplastic resin composition comprising 5 to 40% by weight of the hard core, 20 to 60% by weight of the crosslinked rubber layer, and 20 to 60% by weight of the non-crosslinked hard shell. The method of claim 1,
The hard core is a thermoplastic resin composition, characterized in that the glass transition temperature (Tg) is 20 ℃ or more. The method of claim 1,
The hard core is a thermoplastic resin composition, characterized in that the polymerized crosslinked polymer containing an aromatic vinyl compound, a vinyl cyan compound, a crosslinking agent and a grafting agent. The method of claim 5,
The crosslinking agent is a thermoplastic resin composition, characterized in that contained in an amount of 0.01 to 0.5 parts by weight based on a total of 100 parts by weight of the monomers used to prepare the first thermoplastic resin. The method of claim 5,
The grafting agent is a thermoplastic resin composition, characterized in that contained in an amount of 0.01 to 0.5 parts by weight based on a total of 100 parts by weight of the monomers used in the production of the first thermoplastic resin. The method of claim 1,
The crosslinked rubber layer is a thermoplastic resin composition, characterized in that the average thickness of 30 to 80nm. The method of claim 1,
The crosslinked rubber layer has a glass transition temperature (Tg) of -70 to -20°C. The method of claim 1,
The crosslinked rubber layer is a thermoplastic resin composition, characterized in that the polymerized comprising an alkyl (meth)acrylate compound, a crosslinking agent and a grafting agent. The method of claim 10,
The crosslinking agent is a thermoplastic resin composition, characterized in that contained in an amount of 0.1 to 1 part by weight based on a total of 100 parts by weight of the monomers used to prepare the first thermoplastic resin. The method of claim 10,
The grafting agent is a thermoplastic resin composition, characterized in that contained in an amount of 0.1 to 1 part by weight based on a total of 100 parts by weight of the monomers used to prepare the first thermoplastic resin. The method of claim 1,
The first thermoplastic resin is a thermoplastic resin composition, characterized in that the average particle diameter of 150 to 550nm. The method of claim 1,
The second thermoplastic resin is a thermoplastic resin composition, characterized in that the glass transition temperature (Tg) is 60 to 140 ℃. delete The method of claim 1,
The aromatic vinyl compound-vinyl cyan compound-alkyl (meth)acrylate compound copolymer has a weight average molecular weight (Mw) of 50,000 to 150,000 g/mol. The method of claim 1,
The aromatic vinyl compound-vinyl cyan compound-alkyl (meth)acrylate compound copolymer comprises 20 to 60% by weight of an aromatic vinyl compound, 5 to 15% by weight of a vinylcyan compound, and 30 to 75% by weight of an alkyl (meth)acrylate compound. A thermoplastic resin composition comprising the polymerized. The method of claim 1,
The aromatic vinyl compound-vinyl cyan compound copolymer is a thermoplastic resin composition, characterized in that the polymerization containing 75 to 85% by weight of the aromatic vinyl compound and 15 to 25% by weight of the vinyl cyanide compound. delete A rigid core having a refractive index of 1.53 to 1.59, a polymerized crosslinked rubber layer surrounding the hard core and including an alkyl (meth)acrylate compound and a crosslinking agent, and a polymerized ratio including an aromatic vinyl compound and a vinyl cyanide compound surrounding the crosslinked rubber layer The first thermoplastic resin containing a bridge hard shell 20 to 40% by weight and a refractive index of 1.51 to 1.56 aromatic vinyl compound-vinyl cyan compound-alkyl (meth)acrylate compound copolymer 30 to 50% by weight and refractive index 1.53 to 1.59 Including the step of kneading and extruding a thermoplastic resin composition comprising a second thermoplastic resin comprising a phosphorus aromatic vinyl compound-vinyl cyanide copolymer 20 to 40% by weight,
The second thermoplastic resin has a refractive index of 1.53 to 1.55,
Method for producing a thermoplastic resin composition, characterized in that the light transmittance is 55% or more.