KR20150015899A - Method for preparing rubber reinforced thermoplastic high transparent resin - Google Patents

Abstract

The present invention relates to a manufacturing method of a rubber-reinforced thermoplastic resin with high transparency. According to the present invention, provided is a method for efficiently manufacturing rubber-reinforced thermoplastic resin of high transparency which improves the degree of light diffusion, light transmittance and yellow index and secures low-temperate whitening. More specifically, in the present invention, provided is a manufacturing method of a thermoplastic resin with reinforced rubber and high transparency whose color is close to high transparency and natural colors without using sodium formaldehyde sulfoxylate (SFS) and iron ions. In the present invention, the manufacturing method comprises a step of obtaining acrylate-based copolymers by mixing 50-80 wt % of alkyl ether monomers with 20-50 wt% of aromatic vinyl monomers.

Description

TECHNICAL FIELD [0001] The present invention relates to a rubber-reinforced thermoplastic high-transparency resin,

The present invention relates to a process for producing a rubber-reinforced thermoplastic high-transparency resin, and more particularly, to a process for producing a rubber-reinforced thermoplastic high-transparency resin, which comprises the step of adding an oil-soluble polymerization initiator and a 2-hydroxy-2-sulfinatoacetic acid- And a method for producing a rubber-reinforced thermoplastic high-transparency resin capable of securing a 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.

Thus, techniques for imparting transparency by introducing an alkyl acrylate or methacrylate alkyl ester monomer into an acrylonitrile-butadiene-styrene resin excellent in impact resistance, chemical resistance and processability have been developed (Korean Patent No. 0360987, 0423873).

For example, a transparent resin is prepared by graft copolymerizing methyl methacrylate-styrene-acrylonitrile on a diene rubber. However, transparency resins using diene rubbers have a disadvantage in that transparency is reduced when the rubber content exceeds 5%, and thus haze values are higher than those of polycarbonate resin or impact resistant polymethylmethacrylate resin. In addition, there is a limitation in that the color is adjusted by using a colorant in the process of extrusion due to a color defect, but the color is not close to natural color.

As another example, a redox system can be used to achieve high conversion rates at low polymerization temperatures. The redox system includes an addition method by colloidal dispersion of Fe 2+, a reducing sugar addition method such as fructose, and an application method of sodium formaldehyde sulfoxylate (SFS).

For reference, when iron ions remain in the product, the color of the product is discolored and the thermal stability is lowered. However, when the iron ion is not used in the polymerization, the polymerization conversion rate is remarkably lowered and the yield of the product is lowered and the residual monomer content in the product is also increased And adversely affect the physical properties of the product.

Sodium formaldehyde sulfoxylate (SFS) is used for the purpose of reducing the iron ion content as much as possible. However, in this case, it also decomposes into sodium sulfinate and formaldehyde during the reaction, resulting in the formation of formaldehyde in the post treatment of the product.

Therefore, there is a need to develop a thermoplastic transparent resin manufacturing technology capable of achieving a color effect close to high transparency and natural color without using sodium formaldehyde sulfoxylate (SFS) and iron ions.

The present invention overcomes the problems of the prior art and efficiently manufactures a rubber-reinforced thermoplastic high-transparency resin so as to achieve a color effect close to transparency and natural color without using sodium formaldehyde sulfoxylate (SFS) and iron ions The present invention provides a method for providing a plurality of data streams.

In order to achieve the above object, according to the present invention,

To the rubber latex, (meth) acrylic acid alkyl ester monomer, aromatic vinyl monomer; Vinyl cyan monomers; An oil-soluble polymerization initiator; And a 2-hydroxy-2-sulfinatoacetic acid-based additive are subjected to graft-emulsion polymerization under an emulsifier selected from at least one of compounds represented by the following formulas 1 to 3 to obtain a graft copolymer; Simultaneously or sequentially, 50 to 80% by weight of an alkyl (meth) acrylate monomer and 20 to 50% by weight of an aromatic vinyl monomer to obtain an acrylate-based copolymer; And

10 to 90% by weight of the graft copolymer; And 90 to 10% by weight of the acrylate-based copolymer, based on the total weight of the rubber-reinforced thermoplastic high-transparency resin.

[Chemical Formula 1]

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

(2)

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

(3)

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

Wherein R is independently selected from an alkyl group having 1 to 20 carbon atoms, an alkylaryl group having 5 to 25 carbon atoms, and an aryl group having 6 to 30 carbon atoms, n is an integer of 2 to 20, X is independently H , K, and Na, where y is 2 if x is 1 and y is 1 if x is 2.)

Hereinafter, the present invention will be described in more detail.

In the present invention, a rubber latex is used as a graft copolymer, a (meth) acrylic acid alkyl ester monomer, an aromatic vinyl monomer; Vinyl cyan monomers; An oil-soluble polymerization initiator; (Meth) acrylic acid alkyl ester monomer and an aromatic vinyl monomer as an acrylate-based copolymer are obtained simultaneously or sequentially from the step of graft-emulsion-polymerizing a 2-hydroxy-2-sulfinatoacetic acid- And then mixing them in an appropriate range to provide a rubber-reinforced thermoplastic high-transparency resin.

As a specific example,

First, to the rubber latex, a (meth) acrylic acid alkyl ester monomer, an aromatic vinyl monomer; Vinyl cyan monomers; An oil-soluble polymerization initiator; And 2-hydroxy-2-sulfinatoacetic acid-based additive are subjected to graft emulsion polymerization under a specific emulsifier to obtain a graft copolymer.

At the same time or sequentially, 50 to 80% by weight of an alkyl (meth) acrylate monomer and 20 to 50% by weight of an aromatic vinyl monomer are polymerized to obtain an acrylate-based copolymer.

10 to 90% by weight of the graft copolymer; And 90 to 10% by weight of the acrylate-based copolymer.

For reference, the term " rubber-reinforced thermoplastic high-transparency resin "includes a graft copolymer having a content of 30 to 65% by weight of rubber latex (based on solid content) The haze value at room temperature by ASTM D1003 (3 mm sheet) is 1.0 or less and the difference ( Δ Haze) between the room temperature light diffusivity and the low temperature light diffusivity (-40 ° C., room temperature after storage for 8 hours) ≪ / RTI > or less.

The term "2-hydroxy-2-sulfinatoacetic acid-based additive" refers to 2-hydroxy-2-sulfinatoacetic acid and its alkali metal salts Quot; refers to at least one selected.

In the present invention, the emulsifier used for preparing the graft copolymer by emulsion polymerization may be at least one selected from the compounds represented by the following formulas 1 to 3, for example.

[Chemical Formula 1]

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

(2)

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

(3)

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

Wherein R is independently selected from an alkyl group having 1 to 20 carbon atoms, an alkylaryl group having 5 to 25 carbon atoms, and an aryl group having 6 to 30 carbon atoms, n is an integer of 2 to 20, X is independently H , K, and Na, where y is 2 if x is 1 and y is 1 if x is 2.)

As specific examples, in the above formulas (1) to (3), R may be independently selected from an alkyl group having 8 to 16 carbon atoms, an alkylaryl group having 8 to 16 carbon atoms, or an aryl group having 8 to 16 carbon atoms.

As a specific example, n may be 3 to 8, 4 to 7, or 5 to 6. As a specific example, X may be Na or H.

As another example, the emulsifier may be used in combination with the formula (1) and the formula (2), or two or more types of the formula (3) may be used.

As another example, the emulsifier may be selected from C ₁₂ H ₂₅ -O- (CH ₂ CH ₂ O) ₆ -PO- (OH) ₂ and C ₁₂ H ₂₅ -O- (CH ₂ CH ₂ O) ₆ ) ₂ -PO- (OH) may be mixed in a molar ratio of 1: 1 to 1: 3 or a molar ratio of 1: 1 to 1: 2.

As another example, the emulsifier may be prepared by mixing the RO-PO- (OH) ₂ type and the (RO) ₂ -PO- (OH) type in the molar ratio of 1: 1 to 1: : 2 molar ratio. Wherein R may be an alkyl group having from 8 to 16 carbon atoms.

The rubber latex may have an average particle diameter of 50 to 200 nm or 100 to 150 nm, and may be suitable for providing low temperature whitening property and light diffusibility within the above range. The gel content of the diene rubber core may be 70 to 95%, or 88 to 90%.

The rubber latex may be at least one selected from among butadiene rubber latex, styrene-butadiene copolymer latex, butadiene-acrylonitrile copolymer latex, ethylene-propylene copolymer latex or rubber latex derived therefrom.

Examples of the alkyl (meth) acrylate monomer include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, 2-ethylhexyl (meth) acrylate, (Meth) acrylate and lauryl (meth) acrylate.

The aromatic vinyl monomer may be at least one selected from styrene,? -Methylstyrene, p-methylstyrene, and vinyltoluene.

The vinyl cyan monomer may be at least one selected from acrylonitrile, methacrylonitrile, and ethacrylonitrile.

Examples of the oil-soluble polymerization initiator include diisopropylbenzene hydroperoxide, t-hexylhydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, dicumyl peroxide, t-butyl cumyl 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, (4-t-butylcyclohexyl) peroxydicarbonate.

The above-mentioned oil-soluble polymerization initiator may be a rubber latex; (Meth) acrylic acid alkyl ester monomers; Aromatic vinyl monomers; And vinyl cyan monomers in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total amount.

In the present invention, the activator selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, and sodium sulfite, which is commonly used in combination with the above- There are other technical features to omit.

The 2-hydroxy-2-sulfinatoacetic acid-based additive can replace the activator described above, and includes rubber latex; (Meth) acrylic acid alkyl ester monomers; Aromatic vinyl monomers; 0.01 to 0.5 parts by weight, or 0.01 to 0.3 parts by weight, based on 100 parts by weight of the total of the vinyl cyan monomer and the vinyl cyan monomer.

Within this range, the polymerization conversion may not be lowered, the residual monomer content in the product may not be increased, and the haze of the product may not be generated.

Examples of the 2-hydroxy-2-sulfinatoacetic acid-based additive include 2-hydroxy-2-sulfinatoacetic acid, disodium salt of 2-hydroxy-2-sulfinatoacetic acid, Dipotassium salt of Roxy-2-sulfinatoacetic acid Or more.

The emulsifier may be a rubber latex; (Meth) acrylic acid alkyl ester monomers; Aromatic vinyl monomers; 0.1 to 2 parts by weight, or 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of the vinyl monomer and the vinyl cyan monomer. Within the above range, not only the emulsion stability is sufficiently ensured but also the occurrence of haze can be prevented.

Wherein the rubber latex; (Meth) acrylic acid alkyl ester monomers; Aromatic vinyl monomers; And vinyl cyan monomers are, for example, 30 to 65% by weight of rubber latex and 20 to 60% by weight of (meth) acrylic acid alkyl ester monomer; 5 to 45% by weight of an aromatic vinyl monomer; And 1 to 10% by weight of a vinyl cyan monomer.

The rubber latex may be, for example, 35 to 60% by weight or 40 to 55% by weight.

The (meth) acrylic acid alkyl ester monomer can prevent an increase in haze due to a difference in refractive index between the diene rubber core and the grafted outer skin layer within the above range. Specifically, 30 to 50% by weight, 40% by weight.

The aromatic vinyl monomer can prevent the degradation of transparency due to an increase in refractive index and workability of the product due to viscosity increase within the above range. Specifically, the aromatic vinyl monomer can be 5 to 35% by weight or 10 to 25% by weight .

The vinyl cyan monomer is capable of preventing yellowing within the above range, and may be, for example, 1 to 10% by weight, or 2 to 5% by weight.

As the molecular weight regulator, mercaptans such as dodecyl mercaptan can be included in a range of usually used.

As required, there can be used, for example, divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, aryl methacrylate, Butylene glycol diacrylate, and 3-butylene glycol diacrylate.

The graft-type emulsion polymerization can be carried out under ordinary reaction conditions, for example, in the range of 40 to 80 ° C for 3 to 8 hours.

The obtained graft copolymer may have a refractive index difference of 0.005 or less with respect to the diene rubber latex.

The graft copolymer is recovered as powder by carrying out a coagulation, dehydration and drying process; As shown in FIG. The coagulation, dehydration and drying may be carried out under ordinary reaction conditions. For example, the coagulation may be performed using an acidic substance or a polymeric substance such as calcium chloride, magnesium sulfate, aluminum sulfate, salt, sulfuric acid, nitric acid, have.

Meanwhile, the step of preparing the acrylate copolymer of the present invention can be obtained by polymerizing 50 to 80% by weight of an alkyl (meth) acrylate monomer and 20 to 50% by weight of an aromatic vinyl monomer. The polymerization may be carried out in one or more ways selected, for example, from bulk polymerization, solution polymerization and suspension polymerization.

Specifically, the acrylate-based copolymer may be prepared by subjecting 50 to 80% by weight or 60 to 80% by weight of an alkyl (meth) acrylate monomer and 50 to 20% by weight or 40 to 20% by weight of an aromatic vinyl monomer, Solution polymerization or suspension polymerization. It is possible not only to increase the viscosity but also to prevent yellowing without causing a refractive index difference with the graft copolymer within each of the above ranges.

The vinyl cyan monomer may be polymerized in an amount of 0.01 to 25 parts by weight or 2 to 25 parts by weight based on 100 parts by weight of the total of the (meth) acrylic acid alkyl ester monomer and the aromatic vinyl monomer.

The (meth) acrylic acid alkyl ester monomer, the aromatic vinyl monomer, and the vinyl cyan monomer may be those described in relation to the graft copolymer, and may also include the above-mentioned molecular weight regulator.

The graft copolymer and the acrylate-based copolymer may have a refractive index difference of 0.005 or less.

10 to 90% by weight of the graft copolymer; And 90 to 10% by weight of the acrylate-based copolymer. If the amount of the graft copolymer is less than 10% by weight, the impact strength may be significantly reduced. If the graft copolymer is more than 90% by weight, the resin flowability may be poor and the processability, colorability and scratch resistance may be reduced.

In another example, the rubber-reinforced thermoplastic high-transparency resin may be composed of 20 to 60% by weight of the graft copolymer and 80 to 40% by weight of the acrylate-based copolymer.

In the compounding step, one or more additives selected from a lubricant, an antioxidant, an antistatic agent, a release agent and a UV stabilizer may be added according to the application. As a specific example, the lubricant may be selected from ethylene bis stearamide, oxidized polyethylene wax, metal stearate, various silicone oils, and may be 0 to 5 parts by weight, or 0.1 to 2 parts by weight, based on 100 parts by weight of the rubber-reinforced thermoplastic high- .

Then, the compounded product can be homogeneously dispersed to prepare a high-transparency resin. The homogeneous dispersion can be performed using, for example, at least one of a uniaxial extruder, a twin-screw extruder, and a Banbury mixer. As a specific example, a uniformly dispersed material is uniformly dispersed using a uniaxial extruder, a twin-screw extruder, or a Banbury mixer, and then the material is passed through a water tank and cut to provide a highly transparent resin in the form of a pellet.

The resultant rubber-reinforced thermoplastic high-transparency resin may have a haze value of 1.0 or less, 0.5 to 1.0, or 0.6 to 0.7 at room temperature by a press release ASTM D1003 (3 mm sheet), and the room temperature light diffusivity and the low temperature ( DELTA Haze) of light diffusivity (-40 ° C, measured at room temperature after being stored for 8 hours) is 0.7 or less, 0.3 to 0.7, or 0.3 to 0.4.

According to the present invention, it is possible to enhance the rubber content but to provide transparency up to the level of haze by polycarbonate resin or polymethylmethacrylate resin, as well as to provide a color that is close to natural color even when a colorant is not used A method of producing a rubber-reinforced thermoplastic high-resolution resin can be provided. In particular, the use of specific additives and emulsifiers can provide effects of enhancing thermal stability and color of the resin while maintaining the stability of latex.

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 1)

50 parts by weight (based on the rubber content) of a polybutadiene rubber latex having an average particle diameter of 150 nm and a gel content of 88% as measured by a Submicron Particle Sizer, NICOMP 380 manufactured by PPS (Particle Sizing Systems) as a diene rubber latex, , 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 parts by weight of tertiary dodecylmercaptan, 0.1 parts by weight of disodium sodium 2-sulfo-2-sulfatoacetate, and 0.04 part by weight of cumene hydroperoxide were successively administered at 75 캜 for 5 hours and reacted. The polymerization conversion was 98.3%.

After the reaction, the temperature was raised to 80 ° C., aged for 1 hour, and the reaction was terminated. The reaction was terminated by coagulation with an aqueous solution of calcium chloride to obtain a powdery graft copolymer.

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

The structure of the emulsifier is as follows:

Structure 1) C ₁₂ H ₂₅ -O- (CH ₂ CH ₂ O) ₆ -PO- (OH) ₂

Structure 2) C ₁₂ H ₂₅ -O- (CH ₂ CH ₂ O) ₆ ) ₂ -PO- (OH)

The molar ratio of structure 1) to structure 2) was 1: 2.

Manufacturing example  2( Graft  Copolymer 2)

Except that polybutadiene rubber latex was replaced with polybutadiene rubber latex having an average particle size of 100 nm and a gel content of 90% in the preparation example 1 and 1.0 part by weight of an emulsifier having the following structure (3, 4) as an emulsifier, 1 was repeated. The polymerization conversion was 98.1%.

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.

Manufacturing example  3 ( Graft  Copolymer 3)

The same process was repeated except that the polybutadiene rubber latex was replaced with a polybutadiene rubber latex having an average particle diameter of 300 nm and a gel content of 65%. The polymerization conversion was 98.2%.

Manufacturing example  4( Graft  Copolymer 4)

The same procedure as in Production Example 2 was repeated, except that 50 parts by weight of the polybutadiene rubber latex was replaced with 1.2 parts by weight of the emulsifier sodium dodecylsulfonate. The polymerization conversion was 97.5%.

Manufacturing example  5 ( Graft  Copolymer 5)

In Production Example 1, 0.002 parts by weight of ferrous sulfate, and sodium ethylenediaminetetraacetate The same process was repeated except that 0.012 parts by weight was added. The polymerization conversion was 98.3%.

Manufacturing example  6 ( Graft  Copolymer 6)

The same procedure was repeated except that the disodium salt of 2-hydroxy-2-sulfinatoacetic acid in Preparation Example 1 was replaced with 0.1 part by weight of sodium formaldehyde sulfoxylate (SFS). The polymerization conversion was 93%.

Manufacturing example  7 ( Graft  Copolymer 7)

In Production Example 6, 0.002 parts by weight of ferrous sulfate, and sodium ethylenediaminetetraacetate The same process was repeated except that 0.012 parts by weight was added. The polymerization conversion was 97.5%.

Manufacturing example  8( Acrylate series  Copolymer 1)

A reaction tank was charged with 73 parts by weight of methyl methacrylate, 25 parts by weight of styrene, 2 parts by weight of acrylonitrile, and 30 parts by weight of toluene and 0.15 part by weight of tertiary dodecyl mercaptan, The reaction temperature was maintained at 148 占 폚.

The polymerized liquid discharged from the reactor was heated in a preheater and volatilized unreacted monomers in a volatilization tank, and then a polymer in the form of pellets was prepared using a polymer transfer pump extrusion machine at a temperature of 210 ° C.

Manufacturing example  9 ( Acrylate series  Copolymer 2)

The same procedure as in Production Example 8 was repeated, except that 74 parts by weight of methyl methacrylate was used in Production Example 8, 26 parts by weight of styrene was used, and acrylonitrile was not used.

Manufacturing example  10 ( Acrylate series  Copolymer 3)

The same procedure as in Production Example 8 was repeated, except that 60 parts by weight of methyl methacrylate was used in Production Example 8, 20 parts by weight of styrene was used, and 20 parts by weight of acrylonitrile was used.

< Example  1-3 and Comparative Example  1-5>

The graft copolymer of Preparation Example 1-7 and the acrylate copolymer of Preparation Example 8-10 were mixed in the composition shown in the following table, and 0.1 part by weight of the lubricant and 0.1 part by weight of the antioxidant were mixed, and 2 Extruding kneader to prepare pellets.

division Graft copolymer
(Production Example No.) Acrylate-based copolymer
(Production Example No.) One 2 3 4 5 6 7 8 9 Example 1 20 80 Example 2 40 60 Example 3 60 40 Comparative Example 1 20 80 Comparative Example 2 40 60 Comparative Example 3 40 60 Comparative Example 4 40 60 Comparative Example 5 40 60

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

<Property Test>

Haze and Light Transmittance (%): The haze value and the light transmittance (%) of a 3 mm sheet were measured at room temperature using ASTM D-1003.

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

* Low-temperature whitening degree ( △ Haze): The light diffusivity was measured at room temperature using ASTM D-1003 after storing at -40 ° C. for 8 hours, and the difference in light diffusivity measured at room temperature was calculated.

division Light transmittance Light diffusivity YI △ Haze Example 1 92.7 0.6 0.1 0.4 Example 2 92.8 0.6 0.2 0.4 Example 3 92.6 0.7 1.0 0.3 Comparative Example 1 91.0 1.7 0.9 6.5 Comparative Example 2 91.7 1.3 2.7 0.4 Comparative Example 3 91.8 0.6 3.2 0.5 Comparative Example 4 88.8 4.5 0.5 0.8 Comparative Example 5 91.7 0.8 3.3 0.5

As shown in Table 2, Examples 1 to 3 △ was a low temperature whitening based on the Haze value excellent, and the light diffusivity is very low, less than 0.7, a high light transmittance (Tt), Yellowness Index (b value) FIG. Respectively.

On the other hand, in Comparative Example 1 in which the average particle diameter of the rubber latex was out of the range, the low temperature whitening property was very poor and the light diffusivity (1.7) was not improved.

In addition, in Comparative Example 2 using a conventional emulsifier (sodium dodecylsulfonate), the light diffusivity and the YI value were high.

Further, in Comparative Example 4 using sodium formaldehyde sulfoxylate used in the conventional redox system, it was confirmed that the polymerization conversion ratio, the total light transmittance (Tt) and the transmittance (Haze) were both lowered.

Further, in Comparative Examples 3 and 5 in which the activator was added, it was confirmed that the color (YI) value was poor.

Further, in order to confirm the change of physical properties according to the vinyl cyan content of the acrylate copolymer, the following additional experimental examples were carried out.

<Add Experimental Example >

40 parts by weight of the graft copolymer of Preparation Example 1 and 60 parts by weight of the acrylate copolymer of Preparation Example 10 were mixed and 0.1 part by weight of the lubricant and 0.1 part by weight of the antioxidant were added thereto and the mixture was kneaded at a cylinder temperature of 220 캜 using a twin screw extrusion kneader Pellet form.

The light transmittance was 92.7%, the haze was 0.9, the yellowing index (YI) was 92.7%, and the yellowing index (YI) was 0.9, It is 5.5, and the low temperature bleaching is also (△ Haze) was 0.6.

As a result, it was confirmed that the color (YI value) of the vinyl cyan monomer in the acrylate-based copolymer was remarkably poor when used in excess.

Claims (17)

To the rubber latex, (meth) acrylic acid alkyl ester monomer, aromatic vinyl monomer; Vinyl cyan monomers; An oil-soluble polymerization initiator; And a 2-hydroxy-2-sulfinatoacetic acid-based additive are subjected to graft-emulsion polymerization under an emulsifier selected from at least one of compounds represented by the following formulas 1 to 3 to obtain a graft copolymer; Simultaneously or sequentially, 50 to 80% by weight of an alkyl (meth) acrylate monomer and 20 to 50% by weight of an aromatic vinyl monomer to obtain an acrylate-based copolymer; And
10 to 90% by weight of the graft copolymer; And 90 to 10% by weight of the acrylate-based copolymer; and a process for producing a rubber-reinforced thermoplastic high-transparency resin
[Chemical Formula 1]
_{(RO- (CH 2 CH 2 O} ) n) x-PO- (OX) y
(2)
(RC ₆ H ₄ -O- (CH ₂ CH ₂ O) n) x-PO- (OX) y
(3)
(RO) x-PO- (OX) y
Wherein R is independently selected from an alkyl group having 1 to 20 carbon atoms, an alkylaryl group having 5 to 25 carbon atoms, and an aryl group having 6 to 30 carbon atoms, n is an integer of 2 to 20, X is independently H , K, and Na, where y is 2 if x is 1 and y is 1 if x is 2.)
The method according to claim 1,
The emulsifier is of the formula _{C 12 H 25 -O- (CH 2} CH 2 O) 6 -PO- (OH) 2, and general formula (2) of _{C 12 H 25 -O- (CH 2} CH 2 O) 6) ₂ -PO- (OH) _{2 in a} molar ratio of 1: 1 to 1: 3, based on the total weight of the rubber-reinforced thermoplastic high-transparency resin.
The method according to claim 1,
The emulsifier is a mixture of RO-PO- (OH) ₂ type of formula (3) and (RO) ₂ -PO- (OH) type at a molar ratio of 1: 1 to 1: 3, Lt; RTI ID = 0.0 &gt; of-16. &Lt; / RTI &gt;
The method according to claim 1,
Wherein the rubber latex has an average particle diameter of 50 to 200 nm.
The method according to claim 1,
The rubber latex is at least one selected from among butadiene rubber latex, styrene-butadiene copolymer latex, butadiene-acrylonitrile copolymer latex, ethylene-propylene copolymer latex or rubber latex derived therefrom. A method for producing a highly transparent resin.
The method according to claim 1,
The (meth) acrylic acid alkyl ester monomer may be at least one 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 lauryl ester. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
The method according to claim 1,
Wherein the aromatic vinyl monomer is at least one selected from styrene,? -Methylstyrene, p-methylstyrene, and vinyltoluene.
The method according to claim 1,
Wherein the vinyl cyan monomer is at least one selected from acrylonitrile, methacrylonitrile, and ethacrylonitrile. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
The method according to claim 1,
The oil-soluble polymerization initiator may be at least one member selected from the group consisting of diisopropylbenzene hydroperoxide, t-hexylhydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, dicumyl peroxide, t-butyl cumyl peroxide, 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, -t-butylcyclohexyl) peroxydicarbonate. The method for producing a rubber-reinforced thermoplastic high-transparency resin according to claim 1,
The method according to claim 1,
The 2-hydroxy-2-sulfinatoacetic acid-based additive is selected from the group consisting of 2-hydroxy-2-sulfinatoacetic acid, disodium salt of 2-hydroxy-2-sulfinatoacetic acid, - dipotassium salt of sulfinatoacetic acid Wherein the rubber-reinforced thermoplastic high-transparency resin is at least one selected from the group consisting of rubber-reinforced thermoplastic resins.
The method according to claim 1,
The above-mentioned oil-soluble polymerization initiator may be a rubber latex; (Meth) acrylic acid alkyl ester monomers; Aromatic vinyl monomers; And the vinyl cyan monomer is added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total weight of the rubber-reinforced thermoplastic high-transparency resin.
The method according to claim 1,
The 2-hydroxy-2-sulfinatoacet based additives include rubber latex; (Meth) acrylic acid alkyl ester monomers; Aromatic vinyl monomers; And the vinyl cyan monomer is added in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of the total weight of the rubber-reinforced thermoplastic high-transparency resin.
The method according to claim 1,
The emulsifier may be selected from the group consisting of rubber latex; (Meth) acrylic acid alkyl ester monomers; Aromatic vinyl monomers; And 0.1 to 2 parts by weight based on 100 parts by weight of the total amount of the vinyl cyan monomer and the vinyl cyan monomer.
14. The method according to any one of claims 11 to 13,
The rubber latex; (Meth) acrylic acid alkyl ester monomers; Aromatic vinyl monomers; And vinyl cyan monomers in an amount of 30 to 65% by weight of the rubber latex and 20 to 60% by weight of the alkyl (meth) acrylate monomer; 5 to 45% by weight of an aromatic vinyl monomer; And 1 to 10% by weight of a vinyl cyan monomer, based on the total weight of the rubber-reinforced thermoplastic high-transparency resin.
The method according to claim 1,
Wherein the polymerization of the (meth) acrylic acid alkyl ester monomer and the aromatic vinyl monomer is carried out in a manner selected from bulk polymerization, solution polymerization and suspension polymerization.
The method according to claim 1,
Wherein the acrylate-based copolymer comprises 0.01 to 25 parts by weight of a vinyl cyan monomer based on 100 parts by weight of the total of the alkyl (meth) acrylate monomer and the aromatic vinyl monomer .
The method according to claim 1,
Uniformly dispersing the compounded product to prepare a high-transparency resin; Wherein the rubber-reinforced thermoplastic high-transparency resin is a rubber-reinforced thermoplastic high-transparency resin.