KR20240039838A - Thermoplastic resin composition and molded product therefrom - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom. According to the present invention, there is an effect of providing a thermoplastic resin composition with excellent transparency and excellent impact strength, processability and scratch resistance, and a transparent resin molded article manufactured therefrom. there is.

Description

Thermoplastic resin composition and molded article manufactured therefrom {THERMOPLASTIC RESIN COMPOSITION AND MOLDED PRODUCT THEREFROM}

The present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom. More specifically, the present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom, and more specifically, to a thermoplastic resin composition containing a liquid silicone-based compound with different refractive index and a molecular weight modifier, yet having excellent transparency, and further excellent impact strength, processability, and scratch resistance. It relates to a resin composition and a transparent resin molded article manufactured therefrom.

Recently, transparent design products have been in the spotlight. Changes in design require changes in materials, and transparent materials are being actively developed.

Vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer represented by Acrylonitrile-Butadiene-Styrene (hereinafter referred to as 'ABS') resin (hereinafter referred to as 'ABS resin') ) is widely used in electrical/electronic products, toy products, and office equipment due to its balance of physical properties such as the rigidity and chemical resistance of acrylonitrile, processability, mechanical strength, and colorability of butadiene and styrene, and its beautiful appearance, but is opaque. Application to transparent products is limited.

Transparent materials include polycarbonate (hereinafter referred to as ‘PC’), polymethyl methacrylate (hereinafter referred to as ‘PMMA’), and polystyrene (hereinafter referred to as ‘PS’).

The PC has the advantage of excellent impact strength and transparency, but has problems with low processability and scratch resistance, and the PMMA has excellent optical properties and scratch resistance, but has poor impact resistance and chemical resistance.

Accordingly, transparent ABS materials that provide transparency to ABS, which has excellent rigidity, processability, impact strength, and colorability, are being actively researched.

Transparent ABS resin achieves transparency by keeping the difference in refractive index between the base resin and matrix resin within 0.005.

Transparent ABS resin can be applied to electrical and electronic fields, OA equipment, miscellaneous goods, and construction materials, and contains various additives to improve processability and mechanical properties.

However, because the refractive index of additives also affects the transparency of the final transparent ABS resin, it is very difficult to improve the properties without reducing transparency. As an example, there has been an attempt to improve impact resistance by adding liquid silicone additives or elastomers to transparent ABS resin. However, as the content of liquid silicone additives increases, the transparency of the product may decrease, so there is a limit to the amount of use, and the use of elastomers is limited. As the content increases, fluidity decreases, resulting in poor processability, and transparency and scratch resistance also decrease.

Therefore, research is continuing to provide transparent ABS resin that maintains transparency while realizing impact resistance, fluidity, and scratch resistance.

Korean Public Patent No. 2022-0006469

The purpose of the present invention is to provide a thermoplastic transparent resin composition that balances the physical properties of impact resistance, fluidity, and scratch resistance while maintaining transparency.

Additionally, the present invention aims to provide a molded article manufactured from the above thermoplastic transparent resin composition.

The above and other objects of the present invention can all be achieved by the present invention described below.

In order to achieve the above object, the present invention

A first copolymer comprising an alkyl (meth)acrylate monomer, an aromatic vinyl monomer, a vinyl cyan monomer, and a liquid silicone compound having a refractive index (25°C) of 1.401 to 1.418; and

Provided is a thermoplastic transparent resin composition comprising a second copolymer comprising a conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, a vinyl cyan-based monomer, and a silane-based molecular weight regulator.

The silane-based molecular weight regulator may be a compound containing one thiolalkyl group (-R'SH) and one or more alkoxy groups.

The silane-based molecular weight regulator may further include one or more alkyl groups.

The alkyl may be a linear or branched alkyl having 1 to 10 carbon atoms.

The silane-based molecular weight regulator may be selected from one or more compounds represented by the following formulas 3-1 to 3-4.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

The silane-based molecular weight regulator is 0.1 to 2 parts by weight based on a total of 100 parts by weight of all components (conjugated diene-based polymer, alkyl (meth)acrylate-based monomer, aromatic vinyl-based monomer and vinyl cyanide-based monomer) constituting the second copolymer. It may be included by weight.

The liquid silicone-based compound may be silicone oil with a viscosity (25°C) of 5 to 200 mm ² /s.

The liquid silicone-based compound may have a structure represented by Chemical Formula 1 below.

[Formula 1]

(In the above formula, n is an integer of 1 or more, and the terminal organic group is and R is alkyl with 1 to 10 carbon atoms or aryl with 6 to 12 carbon atoms.)

The alkyl may be a linear or branched alkyl having 1 to 10 carbon atoms.

The difference in refractive index between the first copolymer and the second copolymer may be 0.001 to 0.005.

The thermoplastic transparent resin composition contains 60 to 85% by weight of the first copolymer; And it may include 15 to 40% by weight of the second copolymer.

The first copolymer contains 30 to 85% by weight of the alkyl (meth)acrylate monomer; 10 to 45% by weight of the aromatic vinyl monomer; 1 to 20% by weight of the vinyl cyanide monomer; and 0.1 to 10% by weight of the liquid silicone-based compound.

The second copolymer contains 30 to 70% by weight of the conjugated diene polymer; 10 to 50% by weight of the alkyl (meth)acrylate monomer; 5 to 30% by weight of the aromatic vinyl monomer; and 1 to 20% by weight of the vinyl cyanide monomer.

The second copolymer may have a weight average molecular weight of 60,000 g/mol or more.

Additionally, the present invention provides a molded article made from the above-described thermoplastic transparent resin composition.

The molded article may have a transparency (haze) of 2.0 or less according to ASTM D-1003 at room temperature for a 3 mm specimen manufactured from the thermoplastic transparent resin composition.

The molded article may have an impact strength (Notched Izod) of 11 kg.cm/cm or more as measured according to ASTM D-256 for a 1/4" specimen manufactured from the thermoplastic transparent resin composition.

The molded article may have a fluidity index (220°C, 10kg load) of 10 g/10min or more as measured in accordance with ASTM D-1238 for a specimen manufactured from the thermoplastic transparent resin composition.

The molded article may have a pencil hardness of H or higher when visually observed under a load of 500 g using a pencil hardness meter from JUNGDO TESTING INSTRUMENT for a 3 mm specimen manufactured from the thermoplastic transparent resin composition.

The thermoplastic transparent resin composition according to the present invention has excellent transparency by controlling the refractive index of the materials included in the matrix area to an appropriate level, and the refractive index control allows the addition of an excessive amount of aromatic vinyl monomer with a high refractive index, thereby improving fluidity and processability. can be improved, and by introducing silane at the end of the ABS resin, compatibility with the resin contained in the matrix area can be improved, thereby improving impact strength and scratch resistance.

That is, the thermoplastic transparent resin composition according to the present invention and the molded article manufactured therefrom have excellent impact resistance, scratch resistance, and processability while maintaining excellent transparency.

Therefore, the thermoplastic resin composition and its molded article according to the present invention can be widely applied to various industrial fields that require it.

Hereinafter, the present invention will be described in more detail to facilitate understanding of the present invention.

Terms and words used in this specification and claims should not be construed as limited to their common or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain the invention in the best way. Therefore, it should be interpreted with meaning and concept consistent with the technical idea of the present invention.

In the present invention, the average particle diameter of the conjugated diene polymer can be measured using a dynamic light scattering method, and in detail, it can be measured using a Nicomp 380 equipment (product name, manufacturer PSS).

In this specification, the average particle diameter may mean the arithmetic average particle diameter in the particle size distribution measured by the dynamic light scattering method, that is, the average particle diameter of the scattering intensity (Intensity Distribution).

In this specification, the weight average molecular weight can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent, and in detail, the gel This is the value obtained by calculating the polystyrene conversion weight average molecular weight (Mw) by permeation chromatography (GPC: PL GPC220, Agilent Technologies).

Specifically, in this description, unless otherwise defined, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze). As a specific example, GPC (Gel Permeation Chromatography) is performed using THF (tetrahydrofuran) as an eluent. It can be measured relative to a standard PS (standard polystyrene) sample through chromatography and waters breeze. At this time, as a specific measurement example, solvent: THF, column temperature: 40℃, flow rate: 0.3ml/min, sample concentration: 20mg/ml, injection volume: 5㎕, column model: 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), Equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI Temperature: 35℃, Data processing: Agilent ChemStation S/W, test method (Mn, Mw and PDI): Can be measured under OECD TG 118 conditions.

The present inventors were continuing their research to solve the problem of lowering the transparency of transparent ABS resin as the content of liquid silicone-based additives used to improve impact strength when manufacturing transparent ABS resin increases. When a liquid silicone monomer with a low refractive index is included in a copolymer containing a monomer (hereinafter referred to as 'first copolymer'), the content of aromatic vinyl compounds included in the copolymer can be increased, thereby maintaining transparency. Processability and impact strength can be improved, and compatibility between the matrix resin and the graft resin is improved when silane is introduced at the end of a copolymer containing a conjugated diene polymer (hereinafter referred to as 'second copolymer'). After confirming that improved scratch resistance was achieved, the present invention was completed.

The thermoplastic transparent resin composition of the present invention is a first copolymer comprising an alkyl (meth)acrylate monomer, an aromatic vinyl monomer, a vinyl cyan monomer, and a liquid silicone compound having a refractive index (25° C.) of 1.401 to 1.418; And it may include a second copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer, a vinyl cyan-based monomer, and a silane-based molecular weight regulator.

The first molecular weight regulator is not limited to this, but it is preferable to use a type with a refractive index (20°C) in the range of, for example, 1.3 to 1.5, or 1.4 to 1.5, as it does not adversely affect the above-mentioned compatibility and scratch resistance.

In the present invention, the refractive index can be measured using an Abbe refractometer.

The liquid silicone-based compound may be a silicone oil with a viscosity (25°C) of, for example, 5 mm ² /s or more, or 5 to 200 mm ² /s, and can provide a balance of physical properties between transparency, impact resistance and fluidity within this range. .

The difference in refractive index between the first copolymer and the second copolymer may be, for example, 0.005 or less, preferably 0.001 to 0.005, more preferably 0.001 to 0.004, more preferably 0.001 to 0.003, or 0.001 or less, Transparency is excellent within the scope.

The thermoplastic transparent resin composition of the present invention includes, for example, 60 to 85% by weight, preferably 70 to 85% by weight, and more preferably 75 to 85% by weight of the first copolymer, and the second copolymer For example, it may contain 15 to 40% by weight, preferably 15 to 30% by weight, more preferably 15 to 25% by weight, and within this range, the physical property balance between mechanical strength, processability, transparency and scratch resistance is maintained. It has excellent effects.

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

first copolymer

The first copolymer may include, for example, an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, a vinyl cyan-based monomer, and a liquid silicone-based compound.

The first copolymer can provide excellent impact resistance, rigidity, and transparency to the thermoplastic transparent resin composition.

The first copolymer may have a refractive index of, for example, 1.510 to 1.530, preferably 1.515 to 1.530, more preferably 1.515 to 1.525, and most preferably 1.515 to 1.520. If the above-mentioned range is satisfied, the transparency of the molded article provided with the thermoplastic resin composition can be maintained.

The alkyl (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, and lauryl. It may be one or more types selected from (meth)acrylates, of which methyl methacrylate is preferable.

The alkyl (meth)acrylate monomer is based on 100% by weight of all components (alkyl (meth)acrylate monomer, aromatic vinyl monomer, vinyl cyanide monomer, and liquid silicone compound) constituting the first copolymer. For example, it may be included in an amount of 30 to 85% by weight, specifically 40 to 80% by weight, preferably 50 to 70% by weight, more preferably 60 to 70% by weight, and within the above range, the transparency, rigidity and Scratch resistance can be improved.

The aromatic vinyl monomer may be one or more selected from styrene, α-methylstyrene, α-ethylstyrene, and vinyl toluene, of which styrene is preferred.

The aromatic vinyl monomer is, for example, 10 to 100% by weight of all components (alkyl (meth)acrylate monomer, aromatic vinyl monomer, vinyl cyanide monomer, and liquid silicone compound) constituting the first copolymer. It may be included at 45% by weight, specifically 20 to 40% by weight, preferably 20 to 30% by weight, more preferably 25 to 30% by weight, and within the above range, the rigidity and processability of the copolymer are improved, and thermoplasticity is improved. The transparency of the transparent resin composition can be improved.

The vinyl cyanide monomer may be one or more selected from acrylonitrile, methacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, of which acrylonitrile is preferable.

The vinyl cyanide monomer is, for example, 1 to 100% by weight of all components (alkyl (meth)acrylate monomer, aromatic vinyl monomer, vinyl cyanide monomer, and liquid silicone compound) constituting the first copolymer. It may be included at 20% by weight, specifically 2 to 17% by weight, preferably 2 to 15% by weight, more preferably 3 to 10% by weight, and within the above range, the impact resistance of the copolymer can be further improved. , which is preferable because it does not affect the color of the thermoplastic transparent resin composition. For reference, if the above range is exceeded, the yellow index of the copolymer may increase, which may adversely affect the color of the thermoplastic transparent resin composition.

The liquid silicone-based compound may have a refractive index (25°C) of, for example, 1.401 to 1.418, specifically 1.403 to 1.418, and preferably 1.405 to 1.418. If the above-mentioned range is satisfied, it can provide a balance of physical properties of mechanical strength, processability, transparency, and scratch resistance when included in the first copolymer providing the matrix region.

In this description, the liquid phase means the liquid state at room temperature, i.e., 22 to 23° C., and atmospheric pressure, i.e., 1 atm.

For example, the liquid silicone-based compound may be silicone oil having a viscosity (25°C) of 5 to 200 mm ² /s, specifically 10 to 200 mm ² /s, and preferably 10 to 150 mm ² /s.

The viscosity can be measured using a Brookfield instrument under the following setting conditions.

For example, the setting conditions for the Brookfield device are as follows:

Spindle type (Cone type, product name CPA-52Z), cone angle (3°), cone radius (1.2cm), gap (13㎛ or less), measured shear rate (10 to 20/sec), measurement temperature (25℃).

For example, the liquid silicone-based compound preferably has a structure represented by the following formula (1).

[Formula 1]

In the above formula, n may be an integer of 1 or more, preferably an integer of 1 to 3, and in this case, it can provide a balance of physical properties of mechanical strength, processability, transparency, and scratch resistance.

In the above formula, R may be, for example, alkyl with 1 to 10 carbon atoms or aryl with 6 to 12 carbon atoms, preferably alkyl with 1 to 5 carbon atoms or aryl with 6 to 12 carbon atoms.

The liquid silicone-based compound can be a commercially available material as long as it follows the definition of the present invention. Examples include one or more types selected from Shin-Etsu's product names: X22-174ASX, X22-174BX, KF-2012, X-22-2426, and X-22-2404.

The liquid silicone-based compound is, for example, 0.1 to 10% by weight out of 100% by weight of all components (alkyl (meth)acrylate-based monomer, aromatic vinyl-based monomer, vinyl cyanide-based monomer, and liquid silicone-based compound) constituting the first copolymer. %, specifically 0.2 to 7% by weight, preferably 0.5 to 5% by weight, more preferably 1 to 5% by weight, and within this range, the physical properties of mechanical strength, processability, transparency and scratch resistance are balanced. can be provided.

The first copolymer can be prepared by polymerizing an alkyl (meth)acrylate monomer, an aromatic vinyl monomer, a vinyl cyan monomer, and a liquid silicone compound using a method selected from emulsion polymerization, suspension polymerization, and bulk polymerization.

For example, when manufactured by bulk polymerization, manufacturing costs are reduced and mechanical properties are excellent.

A molecular weight regulator may be used in the polymerization, and it is preferable to use a molecular weight regulator that does not impair compatibility between the components constituting the first copolymer.

The molecular weight regulator used in the above-described first copolymer may be, for example, a carbon compound containing an alkyl group and a thiol group, and as a specific example, may be a carbon compound containing one or more alkyl groups and one or more thiol groups.

The molecular weight regulator is one or more selected from the compounds represented by the following formulas 2-1 to 2-3 without reducing compatibility between the components constituting the first copolymer and without affecting the transparency of the thermoplastic resin composition. It is not desirable.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

The molecular weight regulator is, for example, 3 parts by weight or less based on 100 parts by weight of all components (alkyl (meth)acrylate monomer, aromatic vinyl monomer, vinyl cyanide monomer, and liquid silicone compound) constituting the first copolymer, Specifically, it may be included in an amount of 0.001 to 3 parts by weight, preferably 0.01 to 2 parts by weight, and is preferably contained within this range as it does not adversely affect compatibility, scratch resistance, etc.

For reference, since additives such as emulsifiers and suspending agents are not added to bulk polymerization, a high-purity copolymer with minimal impurity content can be produced.

Therefore, it is preferable that the first copolymer includes a copolymer prepared by bulk polymerization to maintain transparency.

For example, the bulk polymerization may be a method of polymerizing a monomer mixture by adding an organic solvent as a reaction medium and, if necessary, additives including a molecular weight regulator and a polymerization initiator.

As a specific example, the method for producing the first copolymer includes 30 to 85% by weight of an alkyl (meth)acrylate monomer; 10 to 45% by weight of aromatic vinyl monomer; 1 to 20% by weight of vinyl cyanide monomer; and 100 parts by weight of a monomer mixture containing 0.1 to 10% by weight of a liquid silicone compound, mixed with 20 to 40 parts by weight of a reaction medium and 0.05 to 0.5 parts by weight of a molecular weight regulator, and maintained at a reaction temperature of 130 to 170°C for 2 to 4 hours. It may include a polymerization reaction step.

The reaction medium is not particularly limited as long as it is a solvent commonly used in this technical field, and may be, for example, an aromatic hydrocarbon-based compound such as ethylbenzene, benzene, toluene, or xylene.

The method for producing the first copolymer includes, for example, a raw material introduction pump, a continuous stirring tank into which reaction raw materials are continuously introduced, a preheating tank for preliminarily heating the polymer solution discharged from the continuous stirring tank, unreacted monomers, and/or It can be performed in a continuous process consisting of a volatilization tank that volatilizes the reaction medium, a polymer transfer pump, and an extrusion processor that produces the polymer in the form of pellets.

At this time, the extrusion processing conditions may be, for example, 210 to 240°C, but are not limited thereto.

The first copolymer is, for example, 60 to 85% by weight, preferably 60 to 85% by weight, based on the total weight of all components (first copolymer and second copolymer) constituting the thermoplastic transparent resin composition. It may preferably be contained at 70 to 85% by weight, more preferably at 75 to 85% by weight, and most preferably at 77 to 82% by weight. If the above-mentioned range is satisfied, the thermoplastic transparent resin composition has an excellent balance of physical properties of mechanical strength, processability, transparency, and scratch resistance.

second copolymer

The second copolymer includes a conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer.

The second copolymer not only provides excellent processability to the thermoplastic transparent resin composition, but can also serve as an impact modifier in the thermoplastic transparent resin molded product.

The second copolymer may have a refractive index of, for example, 1.510 to 1.530, preferably 1.515 to 1.530, more preferably 1.515 to 1.525, and most preferably 1.515 to 1.520. If the above-mentioned range is satisfied, the refractive index between the first copolymer and the second copolymer can be more easily adjusted, and a thermoplastic transparent resin molded product having physical property balance in processability and transparency can be manufactured.

The second copolymer is produced by graft polymerizing (shell formation) an alkyl (meth)acrylate monomer, an aromatic vinyl monomer, and a vinyl cyan monomer to a conjugated diene polymer (core) prepared by polymerizing a conjugated diene monomer. can be manufactured.

For example, the conjugated diene monomer may be one or more selected from 1,3-butadiene, isoprene, chloroprene, and piperylene, of which 1,3-butadiene is preferable.

The conjugated diene-based polymer may have an average particle diameter of, for example, 0.1 to 0.5 ㎛, preferably 0.1 to 0.4 ㎛, more preferably 0.1 to 0.3 ㎛, and within the above range, the impact resistance of the copolymer can be further improved. there is.

The conjugated diene-based polymer is, for example, based on a total of 100% by weight of all components (conjugated diene-based polymer, alkyl (meth)acrylate-based monomer, aromatic vinyl-based monomer, and vinyl cyan-based monomer) constituting the second copolymer. It may be included in 20 to 70% by weight, preferably 30 to 60% by weight, more preferably 35 to 60% by weight, and even more preferably 40 to 55% by weight. Within the above range, the impact resistance of the copolymer and the processability and transparency of the thermoplastic transparent resin composition can be improved.

The alkyl (meth)acrylate monomer is as described in the description of the first copolymer.

The alkyl (meth)acrylate monomer is added to 100% by weight of all components (conjugated diene polymer, alkyl (meth)acrylate monomer, aromatic vinyl monomer, and vinyl cyanide monomer) constituting the second copolymer. For example, it may be included in an amount of 10 to 50% by weight, preferably 10 to 45% by weight, more preferably 15 to 45% by weight, even more preferably 15 to 40% by weight, and most preferably 20 to 40% by weight. Within the above range, the impact resistance of the copolymer and the processability and transparency of the thermoplastic transparent resin composition can be improved.

The aromatic vinyl monomer is as described in the description of the first copolymer.

The aromatic vinyl monomer is, for example, based on 100% by weight of all components (conjugated diene polymer, alkyl (meth)acrylate monomer, aromatic vinyl monomer, and vinyl cyanide monomer) constituting the second copolymer. It may be included in an amount of 5 to 30% by weight, preferably 5 to 25% by weight, more preferably 5 to 20% by weight, even more preferably 7 to 20% by weight, and most preferably 7 to 18% by weight. Within this range, the rigidity and processability of the copolymer and the transparency of the thermoplastic transparent resin composition can be improved.

The vinyl cyan-based monomer is as described in the description of the first copolymer.

The vinyl cyan monomer is, for example, based on 100% by weight of all components (conjugated diene polymer, alkyl (meth)acrylate monomer, aromatic vinyl monomer, and vinyl cyan monomer) constituting the second copolymer. It may be included in an amount of 1 to 20% by weight, preferably 1 to 15% by weight, more preferably 3 to 15% by weight, even more preferably 3 to 10% by weight, and most preferably 3 to 8% by weight. If the above range is exceeded, the yellow index of the copolymer may increase, which may adversely affect the color of the thermoplastic transparent resin composition. Therefore, within the above range, the chemical resistance and impact resistance of the copolymer are improved and it is preferable because it does not affect the transparency of the thermoplastic transparent resin composition.

The shell of the copolymer may include an alkyl (meth)acrylate monomer, an aromatic vinyl monomer, and a vinyl cyan monomer graft polymerized to the conjugated diene polymer (core).

The copolymer can be prepared by polymerizing an alkyl (meth)acrylate monomer, an aromatic vinyl monomer, and a vinyl cyan monomer in the presence of a conjugated diene polymer by one or more methods selected from emulsion polymerization, suspension polymerization, and bulk polymerization. , among these, it is preferable to produce it by emulsion polymerization.

The emulsion polymerization may be graft emulsion polymerization, and for example, may be performed at a polymerization temperature of 50 to 85°C, preferably 60 to 80°C.

The emulsion polymerization may use molecular weight regulators, initiators, and emulsifiers.

The molecular weight regulator used in the second copolymer is preferably one with a refractive index (20°C) of 1.334 to 1.451 because it does not adversely affect the compatibility and scratch resistance of the thermoplastic resin composition, and is especially effective at the ends of the matrix resin. It is preferable to use a silane compound capable of introducing a silane group because it can improve the compatibility of the thermoplastic resin composition.

For example, the molecular weight regulator may be a silane compound substituted with one thiol alkyl group and one or more alkoxy groups, and may further include one or more alkyl groups. In this case, compatibility with the above-described first copolymer can be improved and scratch resistance can be improved.

As a specific example, the molecular weight regulator may be selected from one or more compounds represented by the following formulas 3-1 to 3-4.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

The molecular weight regulator is, for example, 0.1 to 0.1 parts by weight based on a total of 100 parts by weight of all components (conjugated diene polymer, alkyl (meth)acrylate monomer, aromatic vinyl monomer, and vinyl cyanide monomer) constituting the second copolymer. It may be added in an amount of 2 parts by weight, preferably 0.27 to 1.6 parts by weight, more preferably 0.28 to 1.5 parts by weight, more preferably 0.3 to 1.3 parts by weight, and most preferably 0.5 to 1.2 parts by weight. In this case, not only can it provide a balance of physical properties between transparency, impact resistance, and fluidity, but it can also improve compatibility between the matrix area and the transparent graft resin and further improve scratch resistance.

The initiator may include inorganic peroxides including sodium persulfate, potassium persulfate, ammonium persulfate, potassium superphosphate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide oxides, organic peroxides including 3,5,5-trimethylhexanol peroxide and t-butylperoxy isobutyrate; One or more radical initiators selected from azo compounds including azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobis cyclohexanecarbonylnitrile, and azobismethyl azobutyrate (butyrate) can be used. there is.

The initiator is, for example, 0.001 to 1 part by weight based on a total of 100 parts by weight of all components (conjugated diene-based polymer, alkyl (meth)acrylate-based monomer, aromatic vinyl-based monomer, and vinylcyan-based monomer) constituting the second copolymer. It may be added in parts by weight, preferably 0.01 to 0.5 parts by weight, and more preferably 0.02 to 0.1 parts by weight. Within the above range, emulsion polymerization can be easily performed and the initiator content remaining in the copolymer can be minimized to tens of ppm.

If necessary, an activator may be added to promote the initiation reaction by the initiator.

For example, the activator may be one or more selected from sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrose sulfate, dextrose, sodium pyrophosphate, sodium pyrophosphate anhydrose, and sodium sulfate.

The activator is, for example, 0.001 to 0.001 parts by weight based on a total of 100 parts by weight of all components (conjugated diene-based polymer, alkyl (meth)acrylate-based monomer, aromatic vinyl-based monomer and vinyl cyanide-based monomer) constituting the second copolymer. It may be added in an amount of 1 part by weight, preferably 0.001 to 0.5 part by weight, more preferably 0.001 to 0.1 part by weight. Within the above range, emulsion polymerization can be easily performed and the initiator content remaining in the copolymer can be minimized to tens of ppm.

The emulsifier is, for example, a potassium compound of alkylbenzenesulfonate, a sodium compound of alkylbenzenesulfonate, a potassium compound of alkyl carboxylate, a sodium compound of alkyl carboxylate, a potassium compound of oleic acid, a sodium compound of oleic acid, and a potassium compound of alkyl sulfate. , sodium compounds of alkyl sulfates, potassium compounds of alkyl dicarboxylates, sodium compounds of alkyl dicarboxylates, potassium compounds of alkyl ether sulfonates, sodium compounds of alkyl ether sulfonates and allyloxynonylphenoxypropan-2-yloxy. It may be one or more types selected from ammonium compounds of methylsulfonate, of which sodium dodecylbenzenesulfonate is preferable.

The emulsifier is used in an amount of, for example, 0.15 to 2.0 parts by weight based on a total of 100 parts by weight of all components constituting the second copolymer (conjugated diene polymer, alkyl (meth)acrylate monomer, aromatic vinyl monomer, and vinyl cyanide monomer). It can be added in parts by weight, preferably 0.3 to 1.5 parts by weight, more preferably 0.5 to 1.2 parts by weight, and emulsion polymerization can be easily performed within the above range.

The emulsion polymerization may be started after adding monomers, etc. to the reactor in batches, or some of the monomers, etc. may be added to the reactor before starting the emulsion polymerization, and the remainder may be continuously added after starting, or the emulsion polymerization may be performed while continuously adding monomers, etc. for a certain period of time. You can.

The second copolymer obtained in this way is in the form of latex and can be recovered in the form of dry powder through the processes of coagulation, dehydration and drying.

The coagulant used for the coagulation may be salts such as calcium chloride, magnesium sulfate, aluminum sulfate, acidic substances such as sulfuric acid, nitric acid, hydrochloric acid, or mixtures thereof.

The second copolymer has a weight average molecular weight of, for example, 60,000 g/mol or more, preferably 70,000 g/mol or more, more preferably 80,000 g/mol or more, and even more preferably 83,000 g/mol or more. It may be 200,000 g/mol or less, preferably 180,000 g/mol or less, more preferably 160,000 g/mol or less, and even more preferably 140,000 g/mol or less. If the above-mentioned range is satisfied, the thermoplastic transparent resin composition has an excellent balance of physical properties of mechanical strength, processability, transparency, and scratch resistance.

The second copolymer is, for example, 15 to 40% by weight, preferably 15 to 30% by weight, based on 100% by weight of all components (first copolymer and second copolymer) constituting the thermoplastic transparent resin composition. More preferably, it may be included in 15 to 25% by weight. If the above-mentioned range is satisfied, the thermoplastic transparent resin composition has an excellent balance of physical properties of mechanical strength, processability, transparency, and scratch resistance.

Thermoplastic transparent resin composition

The difference in refractive index between the first copolymer and the second copolymer constituting the thermoplastic transparent resin composition of the present invention may be, for example, 0.005 or less, preferably 0.001 to 0.004, more preferably 0.001 to 0.003, or 0.001 or less, and Transparency is excellent within the scope. Here, the first copolymer may provide a matrix region, and the second copolymer may provide an impact reinforcement region.

For example, the thermoplastic transparent resin composition may further include one or more additives selected from heat stabilizers, UV stabilizers, lubricants, antioxidants, processing aids, pigments, and colorants.

For example, the additive may be 0.01 to 5 parts by weight, preferably 0.5 to 2 parts by weight, more preferably 1 to 2 parts by weight, based on a total of 100 parts by weight of the first copolymer and the second copolymer. It may be included, and within this range, the inherent properties of the additive can be expressed without affecting the physical properties of the thermoplastic transparent resin composition.

As another example, the additive may include 0.1 to 2 parts by weight of a lubricant, preferably 0.5 to 1.5 parts by weight, and 0.1 to 1 part by weight of an antioxidant, preferably 0.1 to 0.5 parts by weight, and within this range, the thermoplastic transparent It has the effect of expressing the natural properties of the lubricant and antioxidant without affecting the physical properties of the resin composition.

The method for producing a thermoplastic transparent resin composition of the present invention is a first atom comprising an alkyl (meth)acrylate monomer, an aromatic vinyl monomer, a vinyl cyan monomer, and a liquid silicone compound having a refractive index (25° C.) of 1.401 to 1.418. coalescence; And a second copolymer comprising a conjugated diene polymer, an aromatic vinyl monomer, a vinyl cyanide monomer, and a silane-based molecular weight regulator having a refractive index (20°C) of 1.334 to 1.451 is put into an extruder and melt-kneaded at 190 to 240°C. It includes steps to:

At this time, the above-mentioned additives can be added together.

As another example, the method for producing the thermoplastic transparent resin composition includes mixing the first copolymer and the second copolymer, uniformly dispersing and extruding using a single-screw extruder, twin-screw extruder, or Banbury mixer, and then placing the extruded product in a water bath. It may include the step of passing it through and cutting it to produce pellets.

For example, the thermoplastic resin composition pellets can be manufactured into injection molded products using an injection machine at an injection barrel temperature of 190 to 240°C.

Thermoplastic transparent resin molded products

According to another embodiment of the present invention, a molded article manufactured from the above-described thermoplastic transparent resin composition can be provided.

The molded article may have a transparency (haze) of, for example, 2.0 or less, preferably 1.5 or less, based on ASTM D-1003 under room temperature conditions for a 3 mm specimen manufactured from the thermoplastic transparent resin composition.

For example, the molded product has an impact strength (Notched Izod) of 11 kg.cm/cm or more, preferably 13 kg, as measured according to ASTM D-256 for a 1/4" specimen made from the thermoplastic transparent resin composition. It may be more than cm/cm.

The molded article may have a fluidity index (220°C, 10kg load) measured according to ASTM D-1238 for a specimen made from the thermoplastic transparent resin composition, for example, 10 g/10min or more, preferably 12 g/10min or more. there is.

The molded article may have a pencil hardness of, for example, H or higher when visually observed under a load of 500 g using a pencil hardness meter from JUNGDO TESTING INSTRUMENT for a 3 mm specimen manufactured from the thermoplastic transparent resin composition.

In describing the thermoplastic transparent resin composition, its manufacturing method, and molded article of this material, other conditions or equipment not explicitly described can be appropriately selected within the range commonly practiced in the industry, and are not particularly limited. Specify.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice it. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[Example]

Preparation Example 1: Preparation of the first copolymer

66.8 parts by weight of methyl methacrylate, 26.2 parts by weight of styrene, 5 parts by weight of acrylonitrile, liquid silicone compound (Shin-Etsu Corporation, KF-2012, compound represented by the above-mentioned formula 1, R = methyl, n = 1, refractive index 1.407, Viscosity (25°C, 1.407) 2 parts by weight, 30 parts by weight of toluene as a solvent, and 0.15 parts by weight of t-dodecyl mercaptan as a molecular weight regulator were added continuously into the reaction tank so that the average reaction time was 3 hours, and the reaction temperature was adjusted. It was maintained at 148°C.

The polymer liquid discharged from the reaction tank was heated in a preheating tank, and unreacted monomers were volatilized in a volatilization tank.

Next, a copolymer in the form of a pellet was manufactured using a polymer transfer pump extrusion machine while maintaining a temperature of 210°C. The refractive index of the copolymer prepared in this way was 1.5162, and the weight average molecular weight was 130,000 g/mol.

Preparation Example 2: Preparation of the first copolymer

62.3 parts by weight of methyl methacrylate, 28.2 parts by weight of styrene, 5 parts by weight of acrylonitrile, liquid silicone compound (Shin-Etsu Corporation, KF-2012, compound represented by the above-mentioned formula 1, R = methyl, n = 1, refractive index 1.407, The raw materials containing 4.5 parts by weight of viscosity (25°C, 1.407), 30 parts by weight of toluene as a solvent, and 0.15 parts by weight of t-dodecyl mercaptan as a molecular weight regulator were continuously added to the reaction tank so that the average reaction time was 3 hours, and the reaction temperature was adjusted. It was maintained at 148°C.

The polymer liquid discharged from the reaction tank was heated in a preheating tank, and unreacted monomers were volatilized in a volatilization tank.

Next, a copolymer in the form of a pellet was manufactured using a polymer transfer pump extrusion machine while maintaining a temperature of 210°C. The refractive index of the copolymer prepared in this way was 1.5160.

Preparation Example 3: Preparation of the first copolymer

56.8 parts by weight of methyl methacrylate, 30.7 parts by weight of styrene, 5 parts by weight of acrylonitrile, liquid silicone compound (Shin-Etsu Corporation, KF-2012, compound represented by the above-mentioned formula 1, R = methyl, n = 1, refractive index 1.407, viscosity (25℃, 1.407) 7.5 parts by weight, a mixture of 30 parts by weight of toluene as a solvent and 0.15 parts by weight of t-dodecyl mercaptan as a molecular weight regulator were continuously added to the reaction tank so that the average reaction time was 3 hours, and the reaction temperature was raised to 148. It was maintained at ℃.

The polymer liquid discharged from the reaction tank was heated in a preheating tank, and unreacted monomers were volatilized in a volatilization tank.

Next, a copolymer in the form of a pellet was manufactured using a polymer transfer pump extrusion machine while maintaining a temperature of 210°C. The refractive index of the copolymer prepared in this way was 1.5161.

Preparation Example 4: Preparation of the first copolymer

The raw materials were mixed with 70.4 parts by weight of methyl methacrylate, 24.6 parts by weight of styrene, 5 parts by weight of acrylonitrile, 30 parts by weight of toluene as a solvent, and 0.15 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, with an average reaction time of 3 hours. The reaction temperature was maintained at 148°C while continuously adding to the reaction tank as much as possible.

The polymer liquid discharged from the reaction tank was heated in a preheating tank, and unreacted monomers were volatilized in a volatilization tank.

Next, a copolymer in the form of a pellet was manufactured using a polymer transfer pump extrusion machine while maintaining a temperature of 210°C. The refractive index of the copolymer prepared in this way was 1.5162.

Preparation Example 5: Preparation of the second copolymer

Butadiene polymer latex (solvent-insoluble gel content of 90% by weight) with an average particle diameter of 0.15㎛ was prepared.

50 parts by weight of the butadiene polymer latex (based on solid content, 90% by weight of gel content insoluble in solvents), 33.6 parts by weight of methyl methacrylate, 11.4 parts by weight of styrene, 5 parts by weight of acrylonitrile, and a molecular weight regulator (3-mercapto) Propyl) 1.0 parts by weight of trimethoxysilane, 1 part by weight of sodium dodecylbenzenesulfonate as an emulsifier, 0.04 parts by weight of cumene hydroperoxide as an initiator, 0.048 parts by weight of sodium formaldehyde sulfoxylate, 0.015 parts by weight of sodium ethylenediamine tetraacetate as an activator. A mixture containing 0.001 parts by weight of ferrous sulfate and 100 parts by weight of ion-exchanged water was polymerized by continuously adding it at a constant rate for 3 hours at 75°C.

Then, the temperature was raised to 80°C, aged for 1 hour, and polymerization was completed.

It was coagulated with calcium chloride and then washed to obtain a powdery thermoplastic transparent resin. At this time, the polymerization conversion rate was 99%, the refractive index was 1.5160, and the weight average molecular weight was 90,000 g/mol.

Preparation Example 6: Preparation of the second copolymer

The same process as Preparation Example 5 was repeated, except that 0.5 parts by weight of (3-mercaptopropyl) trimethoxysilane was added.

At this time, the polymerization conversion rate was 99%, the refractive index was 1.5160, and the weight average molecular weight was 85,000 g/mol.

Preparation Example 7: Preparation of the second copolymer

The same process as Preparation Example 5 was repeated, except that 0.05 parts by weight of (3-mercaptopropyl) trimethoxysilane was added.

At this time, the polymerization conversion rate was 99%, the refractive index was 1.5160, and the weight average molecular weight was 120,000 g/mol.

Preparation Example 8: Preparation of the second copolymer

The same process as Preparation Example 5 was repeated, except that 2.2 parts by weight of (3-mercaptopropyl) trimethoxysilane was added.

At this time, the polymerization conversion rate was 99%, the refractive index was 1.5160, and the weight average molecular weight was 44,000 g/mol.

Preparation Example 9: Preparation of the second copolymer

The same process as Preparation Example 5 was repeated, except that (3-mercaptopropyl)trimethoxysilane was replaced with 0.5 parts by weight of t-dodecyl mercaptan.

At this time, the polymerization conversion rate was 99%, the refractive index was 1.5160, and the weight average molecular weight was 100,000 g/mol.

<Examples 1 to 4, and Comparative Examples 1 to 5>

The first copolymer of Preparation Examples 1 to 4 and the second copolymer of Preparation Examples 5 to 9 were mixed in the composition as shown in the table below, and 1.0 parts by weight of lubricant and 0.2 part by weight of antioxidant were added, and the mixture was mixed at a cylinder temperature of 220°C. It was manufactured in pellet form using a shaft extrusion kneader.

For reference, in Comparative Example 5, Dow Corning's XIAMETER ^™ PMX-200 (Silicone Fluid, Polydimethylsiloxane Fluid, refractive index 1.4009, viscosity 20 mm ² /s, basic structure of the following formula 4) was used as a non-reactive silicone-based oil.

[Formula 4]

division
(Unit wt%) First copolymer (Preparation Example 1) First copolymer (Production Example 2) First copolymer (Production Example 3) First copolymer (Production Example 4) second polymer
(Production Example 5) second polymer
(Production Example 6) second polymer
(Production Example 9) Non-reactive silicone-based oil* Example 1 80 - - - - 20 - - Example 2 80 - - - 20 - - - Example 3 - 80 - - - 20 - - Example 4 - 80 - - 20 - - - Comparative Example 1 - - - 80 - - 20 - Comparative example 2 - - - 80 - 20 - - Comparative example 3 80 - - - - - 20 - Comparative example 4 - 80 - - - - 20 - Comparative Example 5 - - - 80 - - 20 0.5

* The non-reactive silicone-based oil represents 100 parts by weight of the total of the first copolymer and the second copolymer.

Test example 1

The pellets prepared in Examples 1 to 4 and Comparative Examples 1 to 5 were similarly injected using an injection molding machine at an injection temperature of 230°C, and then the injected specimens were incubated at 25°C and a relative humidity of 50±5°C for 12 hours. After aging, physical properties were evaluated according to the method below, and the results are shown in Table 2 below.

*Transparency: The haze value (haze) of a 3mm sheet was measured at room temperature using ASTM D-1003.

*Notched Izod Impact Strength: Notched Izod impact strength was measured according to ASTM D-256. Measurements were made using a 1/4" specimen.

*Melt index: Liquidity was measured according to ASTM D-1238. Measurements were made at 220°C and 10 kg using extruded pellets.

*Pencil hardness: ASTM D-1003 transparency evaluation specimen was used, and a pencil hardness measuring instrument from JINGDO TESTING INSTRUMENT was used. Measurements were made using a Mitsubishi pencil, and the load at the time of measurement was 500 g. Pencil hardness was determined by visual inspection to determine whether scratches occurred.

division Liquid silicone compound conversion content** Non-reactive silicone oil equivalent content** transparency
(haze, a) impact strength
(kg.cm/cm, b) Liquidity Index (MI, g/10 min) pencil hardness Example 1 1.6 - 1.3 13.2 13.0 H Example 2 1.6 - 1.4 13.6 12.6 H Example 3 3.6 - 1.3 14.4 14.5 H Example 4 3.6 - 1.4 14.8 14.0 H Comparative Example 1 - - 1.3 9.5 8.1 B Comparative example 2 - - 1.3 9.8 8.9 F Comparative Example 3 1.6 - 1.3 12.7 12.2 B Comparative example 4 3.6 - 1.4 14.3 14.0 B Comparative Example 5 - 0.49 5.7 14.4 8.3 B

** The converted content corresponds to the value converted into weight percent of the monomer or oil based on the total weight of all components constituting the first copolymer and the second copolymer.

Referring to Tables 1 and 2, Examples 1 to 4, which include both a first copolymer containing a liquid silicone-based compound and a second copolymer using a mercaptosilane-based compound, have a haze of 1.3 to 1.4 and an impact strength of It was confirmed that the was 13.2 to 14.8 kg.cm/cm, the fluidity index was 12.6 to 14.5 g/10 min, and the pencil hardness was all H. From these results, it can be predicted that using the thermoplastic transparent resin composition of the present invention, it is possible to manufacture molded articles that realize a balance of physical properties such as processability, impact resistance, transparency, and scratch resistance. In particular, as the liquid silicone compound content increases, transparency becomes more and more important. It was found that it affects impact strength and fluidity.

In fact, in the case of Comparative Example 1, which contained neither a liquid silicone-based compound nor a mercaptosilane-based compound, and Comparative Example 2, which contained a mercaptosilane-based compound but did not use a liquid silicone-based compound, the impact strength and fluidity index were poor and scratch resistance was poor. It was confirmed that the performance was significantly reduced.

In addition, in the case of Comparative Examples 3 to 4, which contained a liquid silicone-based compound but did not use a mercaptosilane-based compound, it was confirmed that the impact strength and fluidity index were relatively improved, but the scratch resistance was poor.

In addition, in the case of Comparative Example 5 using non-reactive silicone oil, impact strength was excellent, but transparency, fluidity, and scratch resistance were poor.

<Reference Examples 1 to 4>

The first copolymer of Preparation Examples 1 to 4 and the second copolymer of Preparation Examples 5 to 9 were mixed in the composition as shown in the table below, and 1.0 parts by weight of lubricant and 0.2 part by weight of antioxidant were added, and the mixture was mixed at a cylinder temperature of 220°C. It was manufactured in pellet form using a shaft extrusion kneader.

division
(unit weight%) first copolymer
(Production Example 1) first copolymer
(Production Example 2) first copolymer
(Production Example 3) Second copolymer
(Production Example 6) second polymer
(Production Example 7) second polymer
(Production Example 8) second polymer
(Production Example 9) Reference example 1 80 - - - - 20 - Reference example 2 - - 80 20 - - - Reference example 3 - 80 - - 20 - - Reference example 4 - 40 - 60 - - -

Test example 2

After the pellets prepared in Reference Examples 1 to 4 were injected at the same injection temperature of 230°C using an injection machine, the injected specimens were aged for 12 hours at 25°C and a relative humidity of 50±5°C, and then subjected to the above-described method. Physical property evaluation was conducted based on and the results are shown in Table 4 below.

division Liquid silicone compound conversion content** Mercapto silane equivalent content ** transparency
(haze, a) impact strength
(kg.cm/cm, b) Liquidity Index (MI, g/10 min) pencil hardness Reference example 1 1.6 0.4 1.4 10.2 15.7 H Reference example 2 6.0 0.2 1.6 14.5 14.5 B Reference example 3 3.6 - 1.5 15.0 8.0 HB Reference example 4 1.8 0.6 2.9 23.1 5.6 2B

(** The converted content corresponds to the content (% by weight) of the monomer or oil relative to the total weight of all components constituting the first copolymer and the second copolymer.)

Referring to Tables 3 and 4, Reference Example 1, in which the mercaptosilane compound was used in excessive amounts outside the appropriate range, had excellent pencil hardness, but it was confirmed that the impact strength was not improved even when liquid silicone monomer was applied due to the low molecular weight of the resin. .

In addition, Reference Example 2, which contained both a liquid silicone-based compound and a mercaptosilane-based compound, but in which the liquid silicone-based compound was used in excess of the appropriate amount, had excellent impact strength and fluidity index, but the content of methyl methacrylate monomer in the overall resin was small, making it difficult to use. Hardness decreased.

In addition, Reference Example 3, in which the mercaptosilane compound was used in a small amount outside the appropriate range, had a minimal effect on improving pencil hardness.

In addition, Reference Example 4, in which the ratio of the first copolymer and the second copolymer was adjusted, had excellent impact strength but poor transparency, fluidity, and scratch resistance.

In conclusion, the thermoplastic transparent resin composition according to the present invention has excellent transparency because the refractive index of the materials included in the matrix region is controlled to an appropriate level, and the refractive index control allows the addition of an excessive amount of aromatic vinyl monomer with a high refractive index, thereby improving fluidity. , processability can be improved, and silane is introduced at the end of the ABS resin to improve compatibility with the resin contained in the matrix area, improving impact strength and scratch resistance, confirming that it is suitable for thermoplastic transparent resin molded products. .

Claims (11)

A first copolymer comprising an alkyl (meth)acrylate monomer, an aromatic vinyl monomer, a vinyl cyan monomer, and a liquid silicone compound having a refractive index (25°C) of 1.401 to 1.418; and
A thermoplastic transparent resin composition comprising a second copolymer comprising a conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, a vinyl cyan-based monomer, and a silane-based molecular weight regulator. According to paragraph 1,
A thermoplastic transparent resin composition, wherein the silane-based molecular weight regulator is a compound containing one thiolalkyl group (-R'SH) and one or more alkoxy groups. According to paragraph 1,
A thermoplastic transparent resin composition, wherein the silane-based molecular weight regulator is selected from one or more compounds represented by the following formulas 3-1 to 3-4.
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]
According to paragraph 1,
The silane-based molecular weight regulator is included in an amount of 0.1 to 2 parts by weight based on a total of 100 parts by weight of the conjugated diene-based polymer, alkyl (meth)acrylate-based monomer, aromatic vinyl-based monomer, and vinylcyan-based monomer components constituting the second copolymer. A thermoplastic transparent resin composition characterized in that. According to paragraph 1,
A thermoplastic transparent resin composition, wherein the liquid silicone-based compound is silicone oil with a viscosity (25°C) of 5 to 200 mm ² /s. According to paragraph 1,
The liquid silicone-based compound is a thermoplastic transparent resin composition characterized in that it has a structure represented by the following formula (1):
[Formula 1]

(In the above formula, n is an integer of 1 or more, and R is alkyl with 1 to 10 carbon atoms or aryl with 6 to 12 carbon atoms.) According to paragraph 1,
A thermoplastic transparent resin composition, characterized in that the difference in refractive index between the first copolymer and the second copolymer is 0.001 to 0.005. According to paragraph 1,
The thermoplastic transparent resin composition includes 60 to 85% by weight of the first copolymer; And a thermoplastic transparent resin composition comprising 15 to 40% by weight of the second copolymer. According to paragraph 1,
The first copolymer is
30 to 85% by weight of the alkyl (meth)acrylate monomer;
10 to 45% by weight of the aromatic vinyl monomer;
1 to 20% by weight of the vinyl cyanide monomer; and
A thermoplastic transparent resin composition comprising 0.1 to 10% by weight of the liquid silicone compound. According to paragraph 1,
The second copolymer is
30 to 70% by weight of the conjugated diene polymer;
10 to 50% by weight of the alkyl (meth)acrylate monomer;
5 to 30% by weight of the aromatic vinyl monomer; and
A thermoplastic transparent resin composition comprising 1 to 20% by weight of the vinyl cyanide monomer. A molded article manufactured from the thermoplastic transparent resin composition of any one of claims 1 to 10.