KR101489558B1 - Rubber reinforced thermoplastic transparent resin composition and thermoplastic high transparent resin - Google Patents

Abstract

The present invention relates to a rubber-reinforced thermoplastic transparent resin composition and a thermoplastic high-transparency resin. More specifically, the present invention relates to a rubber-reinforced thermoplastic transparent resin composition and a thermoplastic high-transparency resin which are excellent in the rubber content in the graft copolymer contained in the resin composition, Light transmittance, yellow index, and even improved low temperature whiteness.
In particular, the rubber-reinforced thermoplastic transparent resin composition and the thermoplastic high-transparency resin according to the present invention are excellent in transparency regardless of the rubber content of the product, and can provide a thermoplastic high transparency resin having a Haze value of 1.0 or less and a yellowing index improved, have.

Description

[0001] The present invention relates to a rubber-reinforced thermoplastic transparent resin composition and a thermoplastic high-

The present invention relates to a rubber-reinforced thermoplastic transparent resin composition and a thermoplastic high-transparency resin. More specifically, the present invention relates to a rubber-reinforced thermoplastic transparent resin composition and a thermoplastic high-transparency resin which are excellent in the rubber content in the graft copolymer contained in the resin composition, To a rubber-reinforced thermoplastic transparent resin composition and a thermoplastic high-transparency resin capable of improving light transmittance, yellow index and providing improved low temperature whitening property.

Recently, as the industry has advanced and actively promoted differentiation of products, many changes have occurred in product design, and color diversification and transparent design are also attracting much attention. Material changes are required according to the change of design, and therefore research on the development of transparent materials is actively being carried out.

For this purpose, many techniques for imparting transparency by introducing an alkyl acrylate or methacrylate alkyl ester into an acrylonitrile-butadiene-styrene (ABS) resin excellent in impact resistance, chemical resistance and processability have been developed 0360987, 0423873).

As an example of the above-mentioned technique, a transparent resin is prepared by graft-copolymerizing methyl methacrylate-styrene-acrylonitrile with a conjugated diene rubber to make it transparent. However, transparency using a conjugated diene-based rubber has a limit of transparency, and transparency is excellent at a very low rubber content of 5% or less in the rubber content, but transparency becomes worse when it exceeds 5% It has a high haze value.

In addition, although the color is adjusted using a colorant in a pressure injection process due to poor color, there is a limitation in use because it can not give a color close to natural color.

Accordingly, it is an object of the present invention to overcome the problems of the prior art as described above, and to provide a thermoplastic high transparency resin product having an excellent transparency regardless of the rubber content of the product and having a haze value of 1.0 or less and being close to natural color.

That is, an object of the present invention is to provide a rubber-reinforced thermoplastic transparent resin composition and a thermoplastic high-transparency resin which are excellent in transparency and color even when the rubber content of the product is enhanced.

In order to achieve the above object, the rubber-reinforced thermoplastic transparent resin composition of the present invention,

(Meth) acrylic acid alkyl ester compound and a rubber-reinforced graft copolymer resin in which an aromatic vinyl compound is graft-emulsion-polymerized under one or more emulsifying agents represented by the following formulas (1) to (3), wherein the emulsifier comprises And a haze value of 1.0 or less and a yellow index of 2.0 or less based on 100 parts by weight of the total monomers constituting the graft copolymer.
[Chemical Formula 1]
_{(RO- (CH 2 CH 2 O} ) n) x-PO- (OX) y
(2)
(RC ₆ H ₄ -O- (CH ₂ CH ₂ On) x) -PO- (OX) y
(3)
(RO) x-PO- (OX) y
R is an alkyl group having 1 to 20 carbon atoms, an alkylaryl group having 5 to 25 carbon atoms, or an aryl group having 6 to 30 carbon atoms, n is an integer of 2 to 20, X is H, K or Na, x and y are each 1 or 2, and x + y = 3.

The thermoplastic high-transparency resin of the present invention is a thermoplastic resin obtained by extruding and extruding the above-mentioned rubber-reinforced thermoplastic transparent resin composition, and has a total transmittance of 91 (measured by ASTM D1003 at room temperature on the basis of 3 mm sheet) , A haze value of 1.0 or less, and a yellowing index (YI) of 2.0 or less as measured by Color Quest II.

Hereinafter, the rubber-reinforced thermoplastic transparent resin composition according to the present invention will be described, and then the thermoplastic high transparent resin obtained therefrom will be specifically described.

First, in the present invention, a rubber-reinforced graft copolymer resin in which a (meth) acrylic acid alkyl ester compound and an aromatic vinyl compound are graft-polymerized in a diene rubber core, has a haze value of 1.0 or less and a yellowing index (yellow index) of not more than 2.0. The present invention also provides a rubber-reinforced thermoplastic transparent resin composition having a yellow index of not more than 2.0.

For reference, the rubber-reinforced thermoplastic transparent resin composition can be used alone as a rubber-reinforced graft copolymer in which a (meth) acrylic acid alkyl ester compound and an aromatic vinyl compound are graft polymerized in a diene rubber core (hereinafter referred to as Graf (Hereinafter referred to as "copolymer resin"), a (meth) acrylic acid alkyl ester compound, and an aromatic vinyl compound copolymerized therewith (hereinafter referred to as an additional copolymer resin).

Specifically, the composition of the rubber-reinforced thermoplastic transparent resin is 5 to 40 parts by weight of a diene rubber, 20 to 75 parts by weight of a (meth) acrylic acid alkyl ester compound, 10 to 50 parts by weight of an aromatic vinyl compound, 0 to 5 parts by weight of a rubber-reinforced copolymer. The resin of the graft copolymer is obtained by polymerizing 20 to 75 parts by weight of a (meth) acrylic acid alkyl ester compound, 5-50 parts by weight of an aromatic vinyl compound, and 0-10 parts by weight of a vinyl cyan compound in 5-70 parts by weight of a diene rubber latex, And is a copolymerized rubber-reinforced copolymer. The additional copolymer resin is characterized by copolymerizing 20-75 parts by weight of a (meth) acrylic acid alkyl ester compound, 10-50 parts by weight of an aromatic vinyl compound, and 0-10 parts by weight of a vinyl cyan compound.

The graft copolymer resin may be prepared by emulsion polymerization by graft-polymerizing a (meth) acrylic acid alkyl ester compound and an aromatic vinyl compound onto a diene rubber core, for example.

The above-mentioned additional copolymer resin is, for example, a copolymer prepared by bulk polymerization, solution polymerization or suspension polymerization of a (meth) acrylic acid alkyl ester compound and an aromatic vinyl compound. The copolymer is blended with the above-mentioned graft copolymer resin, Can be used as a copolymer composition.

The graft copolymer resin is used in an amount of 10 to 90% by weight, preferably 20 to 60% by weight, and the additional copolymer resin is used in an amount of 90 to 90% by weight based on the total weight of the copolymer of the graft copolymer resin and the additional copolymer. 10% by weight, preferably 80 to 40% by weight.

When the graft copolymer resin is less than 10% by weight, the impact strength remarkably decreases. When the graft copolymer resin is more than 90% by weight, fluidity of the resin is poor, and if the workability is poor, colorability and scratch resistance are deteriorated.

The diene-based rubber core in the graft copolymer resin may be, but is not limited to, butadiene rubber latex, styrene-butadiene copolymer latex, butadiene-acrylonitrile copolymer latex, ethylene-propylene copolymer latex or rubber derived therefrom Latex, for example, butadiene rubber latex or styrene-butadiene copolymer latex.

Such a technique of enhancing the rubber content can be achieved by controlling the content of the diene rubber core constituting the graft copolymer resin. In particular, in the present invention, transparency is obtained in PC or impact resistant PMMA even when the rubber content is increased. And has technical characteristics to express a color close to a natural color without using a colorant separately.

If the rubber latex is contained in an amount of less than 5 parts by weight, the thermoplastic transparent resin may be inferior in impact resistance and fragile. If the amount is more than 70 parts by weight, processing becomes difficult and transparency becomes poor.

Further, in the present invention, the diene rubber core preferably has an average particle size of 50 to 200 nm in terms of low-temperature whitening property and light diffusion, as described in the following examples. The average particle size of the diene rubber core corresponds to a factor greatly affecting the impact strength and workability of the final product resin. Generally, the smaller the particle size of the rubber polymer is, the lower the impact strength and processability are. .

On the other hand, when the content of the rubbery polymer is large and the particle size is large, the grafting rate is lowered. The graft rate greatly affects the physical properties of the graft copolymer. If the graft rate is lowered, the rubber stability improves because there are many ungrafted rubbery polymers. Therefore, it is important to prepare a conjugated diene-based rubbery polymer having an appropriate particle diameter. When the (meth) acrylic acid alkyl ester compound, the aromatic vinyl monomer, and the vinylcyanide monomer are grafted onto the conjugated diene rubbery polymer, It is important to do.

The rubber latex having an average particle diameter of less than 50 nm is difficult to produce and the efficiency of the rubber is poor, and when it exceeds 200 nm, the haze increases. It was also confirmed by the following examples that the use of a conjugated diene rubber latex having an average particle size of 50 to 200 nm improves the low temperature whitening phenomenon in which whitening occurs at a low temperature.

The (meth) acrylic acid alkyl ester compound is preferably selected from the group consisting of (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, Acrylic acid ester and lauryl acrylate ester.

If the (meth) acrylic acid alkyl ester compound is less than 20 parts by weight or more than 75 parts by weight based on 100 parts by weight of the total monomers constituting the copolymer, a difference in refractive index between the core diene rubber and the grafted copolymerization occurs, the haze is increased, which is not preferable.

The aromatic vinyl compound may be at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, and vinyltoluene.

The amount of the aromatic vinyl monomer is preferably 5 to 50 parts by weight based on 100 parts by weight of the total monomers constituting the copolymer. When the amount of the aromatic vinyl monomer is less than 5 parts by weight, the viscosity of the reactant is high and the processability and fluidity of the produced product deteriorate. When the amount is more than 100 parts by weight, the refractive index increases and transparency lowers.

The vinyl cyan compound may be acrylonitrile, methacrylonitrile, ethacrylonitrile, or a mixture thereof. When the amount of the vinyl cyan compound is more than 10 parts by weight based on the total monomers constituting the copolymer, the vinyl cyan compound may yellowishly affect the color of the final product. Which is not preferable.

The graft emulsion polymerization may be carried out by adding 0.1 to 2 parts by weight of at least one emulsifier represented by the following formulas 1 to 3 based on 100 parts by weight of the total monomers constituting the graft copolymer.

[Chemical Formula 1]

_{(RO- (CH 2 CH 2 O} ) n) x-PO- (OX) y

(2)

(RC ₆ H ₄ -O- (CH ₂ CH ₂ On) x) -PO- (OX) y

(3)

(R-O) x-PO- (OX) y

R is an alkyl group having 1 to 20 carbon atoms, an alkylaryl group having 5 to 25 carbon atoms, or an aryl group having 6 to 30 carbon atoms, n is an integer of 2 to 20, X is H, K or Na, x and y are each 1 or 2, and x + y = 3.

When the emulsifier is used, inherent properties of the latex maintain the stability of the latex while enhancing the thermal stability and enhancing the color of the resin.

For example, the emulsifier is a compound represented by the general formula (1) wherein R = C8-16 alkyl group, X = H, n = 6, x = 1 and y = , X = H, n = 6, x = 2, y = 1, or in a molar ratio of 2: 1 to 1: 2.

Alternatively, the emulsifier may be a compound represented by the general formula (2) wherein R = C8-16 alkyl, X = Na, n = 4, x = 2, y = 4, x = 1, y = 2, or a compound represented by the formula 2: 1 to 1: 2 in molar ratio.

Alternatively, the emulsifier may be prepared by reacting a compound represented by the general formula (3), R = C8-C16 alkyl group, X = H, x = y = 1 or a compound represented by y = 1 in a molar ratio of 2: 1 to 1: 2.

When the amount of the emulsifier is less than 0.1 parts by weight or exceeds 2.0 parts by weight, the emulsion stability is deteriorated and haze is generated.

The graft emulsion polymerization may be carried out in the presence of a base such as diisopropylbenzene hydroperoxide, t-hexylhydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, dicumyl peroxide, Methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, 1,1- (Peroxy) cyclohexane, 1,1-di (t-butylperoxy) 3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, t- butylperoxy 2-ethylhexanoate, 0.1 to 5 parts by weight of at least one oil-soluble polymerization initiator selected from the group consisting of (4-t-butylcyclohexyl) peroxydicarbonate and sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, Roll acid may be carried out in sodium sulfite and one or more of the active range of 0.1 to 1 part by weight, selected from the group consisting of In.

Further, as the molecular weight regulator, mercaptans such as dodecyl mercaptan can be included.

Further, the graft copolymer may include 0.05 to 5 parts by weight of at least one monomer represented by the following formula (4).

 [Chemical Formula 4]

A 'represents a hydrogen group, an alkyl group having 1 to 30 carbon atoms or an arylalkyl group having 5 to 24 carbon atoms, or an arylamine group having 5 to 24 carbon atoms, wherein A is independently a vinyl group-containing substituent or a (meth) acrylate group, Or an aryl group having 6 to 30 carbon atoms,

R is independently an ethyl group or a propyl group,

and n is an integer of 5 to 15.)

The monomer represented by the formula (4) includes, but is not limited to, divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol di Methacrylate, aryl methacrylate, and 1,3-butylene glycol diacrylate.

In the present invention, the graft copolymer resin is characterized in that the refractive index difference from the diene rubber latex is within 0.005 to maintain transparency.

The graft copolymer thus prepared is in the form of a latex, and can be recovered in the form of a powder by a process of coagulation, dehydration and drying. As the coagulant, there may be used salts such as calcium chloride, magnesium sulfate and aluminum sulfate, and acidic substances and mixtures such as sulfuric acid, nitric acid and hydrochloric acid.

The additional copolymer resin is characterized by 20 to 75 parts by weight of a (meth) acrylic acid alkyl ester compound, 10 to 50 parts by weight of an aromatic vinyl compound, and 0 to 10 parts by weight of a vinyl cyanide compound by bulk polymerization, solution polymerization or suspension polymerization .

(Meth) acrylic acid alkyl ester compound, an aromatic vinyl compound, and a vinyl cyan compound may be used as the above described graft copolymer-related types .

If the amount of the (meth) acrylic acid alkyl ester compound is less than 20 parts by weight based on 100 parts by weight of the total monomers constituting the copolymer, or when the amount exceeds 75 parts by weight, a difference in refractive index with respect to the copolymer 1 will occur and haze will increase Which is undesirable.

The amount of the aromatic vinyl monomer is preferably 10 to 50 parts by weight based on 100 parts by weight of the total monomers constituting the copolymer. When the amount of the aromatic vinyl monomer is less than 10 parts by weight, the viscosity of the reactant is high and the processability and fluidity of the produced product deteriorate. When the amount is more than 100 parts by weight, the refractive index increases and transparency lowers.

When the vinyl cyanide compound is used in an amount of more than 10 parts by weight based on the total monomers constituting the copolymer, the vinyl cyanide compound may be yellowed and adversely affect the color of the final product.

Such an additional copolymer resin may be contained in an amount of 10 to 90% by weight based on the total thermoplastic resin composition. When the amount exceeds 90% by weight, the impact strength is lowered. When the amount is less than 10% by weight, scratch resistance and rigidity There is a falling problem.

The additional copolymer resin is characterized in that the refractive index difference with respect to the graft copolymer is within 0.005 to maintain transparency.

The thermoplastic resin composition of the present invention may be prepared by adding additives selected from a lubricant, an antioxidant, an antistatic agent, a release agent, and a UV stabilizer.

The double lubricant may be selected from, for example, ethylene bis stearamide, oxidized polyethylene wax, metal stearate and various silicone oils. The amount of the double lubricant used is 0 to 5 parts by weight, more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin composition. 2 parts by weight.

The rubber-reinforced thermoplastic transparent resin composition according to the above-mentioned method is kneaded to finally produce a thermoplastic transparent resin.

The above composition is uniformly dispersed by using a single screw extruder, a twin screw extruder or a Banbury mixer. Then, after passing through a water bath and cutting, a highly transparent resin in the form of pellets is obtained.

Such a high-transparency resin has a light transmittance of 91 or more and a haze value of 1.0 or less as measured using ASTM D1003 at room temperature on the basis of a 3 mm sheet, and a yellowing index (YI ) 2.0 or less.

When the light diffusivity is represented by (A), and the light diffusivity measured at room temperature after storage at -40 ° C for 4 hours is (B), the difference ( Δ Haze) between (A) and (B) .

The rubber-reinforced thermoplastic transparent resin composition and the thermoplastic high-transparency resin according to the present invention can improve the rubber content in the graft copolymer contained in the resin composition, and also have a haze value, a light transmittance ), Improve the Yellow Index and provide improved low temperature whiteness.

In particular, the transparency is very excellent regardless of the rubber content of the product, and the haze value is 1.0 or less and the yellowing index is improved, so that a thermoplastic high transparency resin close to natural color can be provided.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Manufacturing example  One( Graft  Copolymer Resin 1)

A polybutadiene rubber latex having an average particle diameter of 150 nm and a gel content of 88% was used as the diene rubber latex. For reference, the refractive index of latex was 1.516.

To 50 parts by weight of the polybutadiene rubber latex were added 100 parts by weight of ion-exchanged water, 0.8 parts by weight of an emulsifier having the following structures (1 and 2), 35 parts by weight of methyl methacrylate, 12 parts by weight of styrene, 3 parts by weight of acrylonitrile, 0.5 part by weight of tert-dodecylmercaptan, 0.048 part by weight of sodium formaldehyde sulfoxylate, 0.012 part by weight of sodium ethylenediaminetetraesterate, 0.001 part by weight of iron sulfide and 0.04 part by weight of cumene hydroperoxide were added at 75 DEG C for 5 hours Lt; / RTI >

After the reaction, the temperature was raised to 80 ° C, and the reaction was terminated by aging for 1 hour. Then, it was coagulated with an aqueous solution of calcium chloride and washed to obtain a powdery thermoplastic transparent resin.

The structure of the emulsifier is as follows:

Structure 1) RO- (CH ₂ CH ₂ O) ₆ -PO- (OH) ₂

Structure 2) (RO- (CH ₂ CH ₂ O) ₆ ) ₂ -PO- (OH)

In the structures 1) and 2), R is a C8-16 alkyl group, and the molar ratio is 1: 2.

For reference, the refractive index of the graft copolymer resin 1 was 1.516.

Manufacturing example  2( Graft  Copolymer resin 2)

As the diene rubber latex, a polybutadiene rubber latex having an average particle diameter of 100 nm and a gel content of 90% was used. For reference, the refractive index of latex was 1.516.

The same process was repeated except that the polybutadiene rubber latex was replaced with 1.0 part by weight of an emulsifier having the following structure (3, 4) as an emulsifier.

The structure of the emulsifier is as follows:

Structure 3) RO-PO- (OH) ₂

Structure 4) (RO) _2- PO- (OH)

In Structure 3) and Structure 4), R is a C8-16 alkyl group, and the molar ratio of Structure 3) to Structure 4) was 1: 2.

For reference, the refractive index of the graft copolymer resin 2 was 1.516.

Manufacturing example  3 ( Graft  Copolymer resin 3)

A polybutadiene rubber latex having an average particle size of 300 nm and a gel content of 65% was used as the diene rubber latex. For reference, the refractive index of latex was 1.517.

The same process was repeated except that the kind of polybutadiene rubber latex was replaced in Production Example 1.

For reference, the refractive index of the graft copolymer resin 3 was 1.516.

Manufacturing example  4( Graft  Copolymer resin 4)

The same procedure was repeated except that 1.2 parts by weight of sodium dodecylsulfonate was used as the emulsifier in Production Example 2. For reference, the refractive index of latex was 1.516.

For reference, the refractive index of the graft copolymer resin 4 was 1.516.

Manufacturing example  5 ( Graft  Copolymer resin 5)

The polybutadiene rubber latex used in Production Example 2 (refractive index of latex: 1.516)

Except for using, in 25 parts by weight of polybutadiene rubber latex, 0.7 parts by weight of an emulsifier having the following structure (5,6), 54.4 parts by weight of methyl methacrylate, 18.6 parts by weight of styrene, and 2 parts by weight of acrylonitrile The same process was repeated.

Structure 5) RC ₆ H ₄ -O- (CH ₂ CH ₂ O) ₄ ) ₂ -PO-ONa

Structure 6) RC ₆ H ₄ -O- (CH ₂ CH ₂ O) ₄ ) -PO- (ONa) ₂

In the structures 5) and 6), R is a C8-16 alkyl group, and the molar ratio is 1: 1.

For reference, the refractive index of the graft copolymer resin 5 was 1.516.

Manufacturing example  6 (additional copolymer resin-1)

A mixture of 73 parts by weight of methyl methacrylate, 25 parts by weight of styrene and 2 parts by weight of acrylonitrile was mixed with 30 parts by weight of toluene as a solvent and 0.15 part by weight of tertiary dodecylmercaptan as a molecular weight adjuster. And the reaction temperature was maintained at 148 占 폚. The polymer solution discharged from the reactor was heated in a preheating tank and the unreacted monomers were volatilized in the volatilization tank.

Next, a pellet type copolymer was prepared using a polymer transfer pump extrusion machine so as to be maintained at a temperature of 210 ° C.

Manufacturing example  7 (additional copolymer resin-2)

The same procedure as in Production Example 5 was repeated except that 74 parts by weight of methyl methacrylate was used, 26 parts by weight of styrene was used, and acrylonitrile was not used.

Manufacturing example  8 (additional copolymer resin-3)

The same processes as in Production Example 5 were repeated except that 60 parts by weight of methyl methacrylate was used, 20 parts by weight of styrene was used, and 20 parts by weight of acrylonitrile was used.

Manufacturing example  9 (additional copolymer resin-4)

The same processes as in Production Example 5 were repeated using 100 parts by weight of methyl methacrylate.

< Example  1-4 and Comparative Example  1-4>

The graft copolymer of Preparation Example 1-5 and the additional copolymer of Preparation Example 6-9 were mixed in the composition shown in the following table, 0.1 part by weight and 0.1 part by weight of the lubricant were added, and the mixture was subjected to 2-axis extrusion kneading Were prepared in the form of pellets.

division Rubber reinforced graft copolymer resin Additional copolymer resin Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Production Example 6 Production Example 7 Production Example 8 Production Example 9 Example 1 20 80 Example 2 40 60 Example 3 60 40 Example 4 100 Comparative Example 1 20 80 Comparative Example 2 40 60 Comparative Example 3 40 60 Comparative Example 4 20 80

The pellets were injected and the light diffusivity, light transmittance, yellowing index and low temperature whiteness degree were measured in the following manner, and the results are shown in Table 2.

< Performance test >

* Light diffusivity and light transmittance: A using ASTM D-1003 haze value of 3mm sheets (haze value), and total light transmittance (light transmittance) were measured, respectively.

Yellow Index ( YI ): The YI value (b value) of a 3 mm sheet was measured using a Color Quest II machine. For reference, the higher the YI value, the closer to yellow, and the closer the YI value is to 0, the closer to natural color.

* Low-temperature whiteness degree ( △ Haze): The light diffusivity was measured at room temperature after storing at -40 ° C. for 4 hours, and the difference from the value measured at room temperature was calculated.

division Light transmittance Light diffusivity YI Low temperature whitening degree The difference in refractive index between the graft copolymer and the additional copolymer Example 1 92.7 0.6 0.1 0.8 0.001 Example 2 92.8 0.6 0.5 0.4 0.001 Example 3 92.6 0.7 1.5 0.3 0.001 Example 4 92.5 0.7 1.3 0.4 - Comparative Example 1 91.0 1.7 0.9 15.4 0.001 Comparative Example 2 92.7 1.5 3.7 0.5 0.001 Comparative Example 3 92.7 0.9 5.5 0.7 0.001 Comparative Example 4 85.2 45.2 1.2 0.4 0.026

As shown in Table 1, Examples 1 to 4 according to the present invention have excellent low-temperature whitening characteristics, extremely low light diffusivity of 1.0 or less, high total light transmittance (Tt) Respectively.

On the other hand, in the case of Comparative Example 1, 300 nm in which the average particle diameter of the rubber latex used deviates from the range of the present invention was applied. As a result, the low temperature whitening property was very poor and the light diffusivity was 1.7.

In the case of Comparative Example 2, when the emulsifier used was sodium dodecylsulfonate which was not the emulsifier represented by the formulas 1 to 3 shown in the present invention, the light transmittance was high, but the light diffusivity was high and the YI value was high I do not.

Further, in the case of Comparative Example 3, it was confirmed that the color (YI value) was very poor as a result of the use range of acrylonitrile of the additional copolymer resin resin exceeding the upper limit of 10 parts by weight.

In addition, in Comparative Example 4, since the composition of the additional copolymer was not suitable, the difference in refractive index with respect to the graft copolymer reached 0.026, indicating that transparency was not suitable for the present invention.

Claims (17)

(Meth) acrylic acid alkyl ester compound and a rubber-reinforced graft copolymer resin in which an aromatic vinyl compound is graft-emulsion-polymerized under one or more emulsifying agents represented by the following formulas (1) to (3), wherein the emulsifier comprises A rubber-reinforced thermoplastic transparent resin composition having a haze value of 1.0 or less and a yellow index of 2.0 or less, in a range of 0.1 to 2 parts by weight based on 100 parts by weight of the total monomers constituting the graft copolymer .
[Chemical Formula 1]
_{(RO- (CH 2 CH 2 O} ) n) x-PO- (OX) y
(2)
(RC ₆ H ₄ -O- (CH ₂ CH ₂ On) x) -PO- (OX) y
(3)
(RO) x-PO- (OX) y
R is an alkyl group having 1 to 20 carbon atoms, an alkylaryl group having 5 to 25 carbon atoms, or an aryl group having 6 to 30 carbon atoms, n is an integer of 2 to 20, X is H, K or Na, x and y are each 1 or 2, and x + y = 3.
The method according to claim 1,
Wherein the composition further comprises an (meth) acrylic acid alkyl ester compound and an aromatic vinyl compound copolymer, as an additional copolymer.
3. The method of claim 2,
Wherein the graft copolymer is 10 to 90% by weight, and the additional copolymer is 90 to 10% by weight based on the total weight of the copolymer of the graft copolymer and the additional copolymer. . The method of claim 3,
The diene rubber core is a butadiene rubber latex, a styrene-butadiene copolymer rubber latex, a butadiene-acrylonitrile copolymer latex, an ethylene-propylene copolymer rubber latex or a rubber latex having an average particle diameter of 50 to 200 nm derived therefrom Wherein the thermoplastic resin is a thermoplastic resin.
The method according to claim 1,
The graft copolymer is obtained by copolymerizing 5 to 70 parts by weight of butadiene rubber latex or styrene-butadiene copolymer latex, 20 to 75 parts by weight of a (meth) acrylic acid alkyl ester compound, 5 to 50 parts by weight of an aromatic vinyl compound, Wherein the rubber-reinforced thermoplastic transparent resin composition is a rubber-reinforced copolymer obtained by graft-emulsion-polymerizing 10 parts by weight of a thermoplastic resin.
delete The method according to claim 1,
The graft emulsion polymerization may be carried out in the presence of a base such as diisopropylbenzene hydroperoxide, t-hexylhydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, dicumyl peroxide, t-butyl cumyl peroxide, methyl ethyl But are not limited to, ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, ), Cyclohexane, 1,1-di (t-butylperoxy) 3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, t-butylperoxy 2-ethylhexanoate, 0.1 to 5 parts by weight of at least one oil-soluble polymerization initiator selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, pyrroline Sodium sulfite and activation of at least one member selected from the group consisting of 0.1 to 1 part by weight of the rubber-reinforced, characterized in that is carried out in the added thermoplastic transparent resin composition. The method according to claim 1,
Wherein the graft copolymer comprises 0.05 to 5 parts by weight of at least one monomer represented by the following formula (4).
[Chemical Formula 4]

A 'represents a hydrogen group, an alkyl group having 1 to 30 carbon atoms or an arylalkyl group having 5 to 24 carbon atoms, or an arylamine group having 5 to 24 carbon atoms, wherein A is independently a vinyl group-containing substituent or a (meth) acrylate group, Or an aryl group having 6 to 30 carbon atoms,
R is independently an ethyl group or a propyl group,
and n is an integer of 5 to 15.)
3. The method of claim 2,
Wherein the additional copolymer is obtained by bulk polymerization, solution polymerization or suspension polymerization of 20 to 75 parts by weight of a (meth) acrylic acid alkyl ester compound, 10 to 50 parts by weight of an aromatic vinyl compound, and 0 to 10 parts by weight of a vinyl cyan compound Reinforced thermoplastic transparent resin composition.
10. The method according to claim 5 or 9,
The (meth) acrylic acid alkyl ester compound is preferably selected from the group consisting of (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, Acrylate and lauryl acrylate, wherein the rubber-reinforced thermoplastic transparent resin composition is at least one selected from the group consisting of acrylic acid and lauryl acrylate.
10. The method according to claim 5 or 9,
Wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, and vinyltoluene.
10. The method according to claim 5 or 9,
Wherein the vinyl cyan compound is acrylonitrile, methacrylonitrile, ethacrylonitrile, or a mixture thereof.
The method according to claim 1,
The graft copolymer is characterized in that the refractive index difference with the diene rubber latex is within 0.005
Rubber reinforced thermoplastic transparent resin composition.
3. The method of claim 2,
Wherein the additional copolymer has a difference in refractive index between the graft copolymer and the rubber-reinforced thermoplastic resin is within 0.005.
The method according to claim 1,
Wherein the composition comprises at least one selected from a heat stabilizer, a UV stabilizer and a lubricant.
A thermoplastic resin obtained by extruding and extruding a rubber-reinforced thermoplastic transparent resin composition according to any one of claims 1 to 3, having a total transmittance of 91 or more as measured on a 3 mm sheet at room temperature using ASTM D1003, It has a haze value of 1.0 or less and a yellowing index (YI) of 2.0 or less as measured by Color Quest II Features,
Thermoplastic high transparency resin.
17. The method of claim 16,
When the light diffusivity is represented by (A), and the light diffusivity measured at room temperature after being stored at -40 ° C for 4 hours is (B), the difference ( Δ Haze) between (A) and (B) Thermoplastic high transparency resin.