WO2015030415A1

WO2015030415A1 - Transparent abs resin and transparent abs resin composition

Info

Publication number: WO2015030415A1
Application number: PCT/KR2014/007745
Authority: WO
Inventors: 장석구; 박상후; 이루다; 이원석; 최정수; 유근훈
Original assignee: (주) 엘지화학
Priority date: 2013-08-29
Filing date: 2014-08-21
Publication date: 2015-03-05

Abstract

The present invention relates to a transparent ABS resin and a transparent ABS resin composition. According to the present invention, it is possible to provide a transparent ABS resin and a transparent ABS resin composition having excellent transparency, and, furthermore, impact resistance, through a formation of an effective graft shell by minimizing the amount of styrene-based monomers infiltrating into a polybutadiene-based rubber latex, and, instead, leading the styrene-based monomer into the shell. In particular, according to the present invention, it is possible to provide a transparent ABS resin composition having high transparency and impact resistance while applying, to an ABS resin, a reducing agent and iron ions which have an effect of lowering the transparency of the ABS resin in the conventional technique.

Description

Transparent AS resin and transparent AS resin composition

The present invention relates to a transparent ABS resin and a transparent ABS resin composition, specifically, to minimize the penetration of the styrene monomer to the polybutadiene-based rubber latex, instead of inducing styrene monomer into the shell transparency through the formation of an effective graft shell And further it relates to a transparent ABS resin and a transparent ABS resin composition excellent in impact resistance.

As the industry has advanced recently and actively promoted product differentiation, many changes have been made in product design, and the diversification of colors and transparent designs are also in the spotlight. As the design changes, the change of materials is required, and thus, the research on the development of transparent materials is actively conducted.

To this end, a lot of technologies have been developed to introduce transparency by introducing acrylic acid alkyl esters or methacrylic acid alkyl ester compounds to acrylonitrile-butadiene-styrene (ABS) resins having excellent impact resistance, chemical resistance, and processability. 0360987, 0423873).

As an example of the said technique, the transparent resin which makes a methacrylate-styrene-acrylonitrile graft copolymerized with conjugated diene rubber and makes it transparent is produced. However, the transparent resin using conjugated diene rubber has a limit of its transparency, and the rubber content is excellent at very low rubber content of 5% or less, but when it exceeds 5%, the transparency is worsened than PC or impact-resistant PMMA. It has a high Haze value.

In addition, although the color is bad, color adjustment is performed using a colorant during the extrusion process, but there is a limit in use because it does not produce a color close to the natural color.

On the other hand, the redox system is mainly used to obtain high conversion at low reaction temperature during polymerization. The redox system is a method of adding Fe2 + as a colloidal dispersion, a method of adding reducing sugars (fructose, etc.), sodium formaldehyde. Three methods of using sulfoxylate (SFS) are representative.

Dual sodium formaldehyde sulfoxylate (SFS) is mainly used because it can reduce the amount of iron ions relatively compared to other systems.

For reference, if iron ions remain in the product, the color of the product is discolored and thermal stability is lowered. However, if the iron ion is not used during the polymerization, the polymerization conversion is significantly lowered and the product yield is lowered, and the residual monomer content in the product is also increased, which adversely affects the physical properties of the product.

Accordingly, the present invention overcomes the problems of the prior art as described above to minimize the penetration of styrene-based monomers into the polybutadiene-based rubber latex and instead guide the styrene-based monomers into the shell to form an effective graft shell, thereby providing transparency and impact resistance. It is an object to provide this excellent transparent ABS resin and transparent ABS resin composition.

In order to achieve the above object, the transparent ABS resin of the present invention,

50 to 60 wt% polybutadiene-based rubber latex; And

Methyl methacrylate monomer, 50 to 40% by weight of the total amount of the styrene monomer and acrylonitrile monomer; and the permeation amount of the styrene monomer to the polybutadiene rubber latex is characterized in that less than 0.005. .

Moreover, the manufacturing method of the transparent ABS resin of this invention,

A first step of preparing a polybutadiene-based rubber latex having a gel content of 85 to 94% by separately adding butadiene-based monomers; And

50 to 60% by weight of the polybutadiene-based rubber latex graft under a reactive emulsifier and an oil-soluble polymerization initiator while continuously adding a methyl methacrylate monomer, a styrene monomer and an acrylonitrile monomer in a total amount of 50 to 40% by weight. A second step of polymerizing to prepare a transparent ABS resin; Characterized in that it comprises a.

Moreover, the transparent ABS resin composition of this invention is transparent ABS resin; And SAN or MSAN resin; comprising, the transparent ABS resin,

50 to 60 wt% polybutadiene-based rubber latex; And a total amount of methyl methacrylate monomer, a styrene monomer and a total amount of the acrylonitrile monomer in a total amount of 50 to 40 wt%; wherein the amount of the styrene monomer penetrating into the polybutadiene rubber latex is 0.005 or less. do.

Furthermore, the thermoplastic transparent resin of the present invention is a thermoplastic resin obtained by extruding and injecting the transparent ABS resin composition described above, and has a total transmittance of 90.5 or more measured using ASTM D1003 at room temperature based on a 3 mm sheet. And Haze value of 2.0 or less, and Izod impact strength measured using ASTM D256 (1/4 ") is characterized in that 15 or more.

Hereinafter, the transparent ABS resin according to the present invention will be described in detail with respect to the transparent ABS resin composition and the thermoplastic transparent resin including the same.

First, in the present invention, 50 to 60% by weight of polybutadiene-based rubber latex; And a total amount of methyl methacrylate monomer, a styrene monomer and a total amount of the acrylonitrile monomer in a total amount of 50 to 40 wt%, wherein the amount of penetration of the styrene monomer into the polybutadiene rubber latex is 0.005 or less. To provide a technical feature.

For reference, in the present invention, unless otherwise specified, the term "penetration amount of styrene monomer to polybutadiene-based rubber latex" refers to a methyl methacrylate monomer, a styrene monomer and an acrylonitrile-based monomer in a polybutadiene rubber latex. The graft refers to the difference in refractive index between the polybutadiene-based rubber latex and the graft copolymer.

For reference, the refractive index of the graft copolymer can be calculated by the following equation:

WtA x RIA + WtS x RIS + WtM x RIM

Wherein WtA is the weight percent of the vinyl cyan compound, RIA is the refractive index of the vinyl cyan polymer, WtS is the weight percent of the aromatic vinyl compound, RIS is the refractive index of the aromatic vinyl compound, and WtM is an alkyl methacrylate or alkyl acrylate. By weight percent of the ester compound, RIM represents the refractive index of the methacrylic acid alkyl ester compound or the acrylic acid alkyl ester compound.)

As a specific example, the transparent ABS resin of the present invention may have a penetration amount of the styrene monomer into the polybutadiene rubber latex 0.005 or less, or 0 to 0.005.

Specifically, the polybutadiene-based rubber latex may have a gel content of 85 to 94%, or 86 to 87%.

The polybutadiene-based rubber latex may have an average particle diameter of 2500 to 4000 mm 3, or 2900 to 3300 mm 3.

Examples of the methyl methacrylate monomer include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid decyl ester, and ( It may be in the range of 27 to 36% by weight, as one or more monomers selected from meth) acrylic acid lauryl ester.

The styrene-based monomer may be, for example, in the range of 10 to 13% by weight as one or more monomers selected from styrene, α-methylstyrene, p-methylstyrene, and vinyl toluene.

The acrylonitrile-based monomer may be, for example, in the range of 2 to 6% by weight as one or more monomers selected from acrylonitrile, methacrylonitrile, and ethacrylonitrile.

Method for producing a transparent ABS resin of the present invention, for example, the first step of preparing a polybutadiene-based rubber latex having a gel content of 85 to 94% by dividing the butadiene-based monomer; And

50 to 60% by weight of the polybutadiene-based rubber latex graft under a reactive emulsifier and an oil-soluble polymerization initiator while continuously adding a methyl methacrylate monomer, a styrene monomer and an acrylonitrile monomer in a total amount of 50 to 40% by weight. A second step of polymerizing to prepare a transparent ABS resin; It may be configured to include.

As a specific example, the butadiene-based monomer may be to be continuously divided into 60 to 80% of the polymerization conversion rate of the first step.

As another example, the butadiene-based monomer 10 to 20, or 10 to 15 parts by weight of butadiene 10 to 60 minutes, or 15 to 25 minutes at the polymerization conversion rate of 50 to 60%, or 55 to 60% of the first step Continuous injection, and then heated to 40 ℃ to 55 ℃ 40 to 60 parts by weight of butadiene, or 50 to 55 parts by weight may be continuously added for 7 to 9 hours to reach a polymerization conversion of 80%.

The polybutadiene-based rubber latex may be, for example, polybutadiene rubber latex, styrene-butadiene copolymer rubber latex, butadiene-acrylonitrile copolymer rubber latex, ethylene-propylene copolymer rubber latex or rubber latex derived therefrom.

The polymerization conversion rate is raised to 70 to 80 ℃, or 70 to 75 ℃ at 80% point, the final polymerization conversion may be 95 to 99%, or 97 to 98%.

At the beginning of the first step, divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, aryl methacrylate and 1,3-butylene glycol diacrylate One or more crosslinking agents selected from polyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate are used in the first step. Butadiene monomer may be included in the range of 0.1 to 5 parts by weight, 0.1 to 5 parts by weight, or 0.1 to 1 parts by weight based on a total of 100 parts by weight.

The reactive emulsifiers include, for example, sodium dodecyl allylsulfosuccinate (TREM LF-40), C16-C18 alkenyl succinate dipotassium salt (Latemul ASK series), sodium acrylamide stearate (NaAAS) and sodium 3-sulfo At least one of propyl tetradodecyl maleate (M14) may be included in the range of 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 latex used in the second step and the total monomers. have.

The emulsifier maintains latex stability, which is an inherent characteristic of latex, while also reinforcing thermal stability and reinforcing color of the resin.

The oil-soluble polymerization initiator may be, for example, diisopropylbenzene hydroperoxide, t-hexyl hydroperoxide, 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-di (t-butyl Peroxy) cyclohexane, 1,1-di (t-butyl peroxy) 3,3,5-trimethylcyclohexane, t-butyl peroxybenzoate, t-butyl peroxy 2-ethyl hexanoate, and bis One or more selected from (4-t-butylcyclohexyl) peroxydicarbonate, 0.01 to 5 parts by weight, or 0.01 to 1 part by weight based on a total of 100 parts by weight of the latex used in the second step and the total monomers You can include it inside.

The oil-soluble polymerization initiator may be used in combination with one or more activators selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylene diamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, and sodium sulfite.

Unless specified, the anionic adsorptive emulsifier is an anionic adsorptive emulsifier selected from at least one selected from potassium rosin, potassium fatty acid, sodium lauryl sulfonate and sodium alkylbenzene sulfonate, molecular weight modifiers such as tertiary dodecyl mercaptan, Reducing agents such as sodium formaldehyde sulfoxylate can be added in the content ranges commonly used in the art.

The first step may have a total reaction time of 18 to 20 hours, or 18 to 19 hours.

In the present invention, the swelling index of the polybutadiene-based rubber latex may be 10 to 20, 10 to 18, 14 to 20, or 16 to 18, the monomer absorption within the above range is reduced and occlusion during grafting ), And as a result, the penetration of styrene monomer into polybutadiene-based rubber latex can be reduced.

The prepared transparent ABS resin may be recovered in powder form by a process of coagulation, dehydration and drying as a latex form. At this time, as the flocculant, salts such as calcium chloride, magnesium sulfate, aluminum sulfate, and acidic substances such as sulfuric acid, nitric acid, hydrochloric acid, and mixtures may be used.

The transparent ABS resin composition of the present invention is a transparent ABS resin; And SAN or MSAN resin, wherein the transparent ABS resin comprises: 50 to 60 wt% of a polybutadiene-based rubber latex; And a total amount of the methyl methacrylate monomer, the styrene monomer and the acrylonitrile monomer in a total amount of 50 to 40 wt%; and the penetration amount of the styrene monomer into the polybutadiene rubber latex may be 0.005 or less. .

The transparent ABS resin may be 5 to 25%, or 10 to 20% of the composition.

The SAN or MSAN resin is, for example, from 0 to 75 parts by weight of the (meth) acrylic acid alkyl ester monomer, 10 to 50 parts by weight of the styrene monomer, and 10 to 20 parts by weight of the acrylonitrile monomer, bulk polymerization, solution polymerization or suspension. It may be a polymerized resin.

The composition may be prepared by adding additives selected from a lubricant, an antioxidant, an antistatic agent, a mold release agent and an ultraviolet stabilizer according to the use.

The dual lubricant may be selected from, for example, ethylene bis stearamide, polyethylene oxide wax, metal stearate, and various silicone oils, and the amount thereof may be used in an amount of 0 to 5 parts by weight, more preferably 0.1 to about 100 parts by weight of the thermoplastic resin composition. It is in the range of 2 parts by weight.

The transparent ABS resin composition may be kneaded to finally prepare a thermoplastic transparent resin. The composition is uniformly dispersed using a single screw extruder, twin screw extruder or Banbury mixer or the like. The water bath is then passed through and cut to obtain a transparent resin in pellet form.

The thermoplastic transparent resin of the present invention is a thermoplastic resin obtained by extruding and injecting the above-mentioned transparent ABS resin composition, which has a total transmittance of 90.5 or more measured using ASTM D1003 at room temperature based on a 3 mm sheet, Haze value 2.0 or less, and the Izod impact strength measured using ASTM D256 (1/4 ") may be 15 or more.

According to the present invention, the transparent ABS resin and the transparent ABS resin excellent in transparency and further impact resistance through formation of an effective graft shell by minimizing the penetration of styrene monomer into the polybutadiene rubber latex and inducing the styrene monomer into the shell instead. A composition can be provided.

In particular, according to the present invention, it is possible to provide a transparent ABS resin composition having high transparency and impact resistance while applying a reducing agent and iron ions to the ABS resin, which previously affected the transparency inhibition of the ABS resin.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Preparation Example 1 Preparation of Polybutadiene Rubber Latex (A-1)

50 parts by weight of ion-exchanged water was added to a nitrogen-substituted polymerization reactor (autoclave), followed by stirring by adding 0.8 parts by weight of fatty acid potassium, 1.0 parts by weight of potassium rosinate, and 1.0 parts by weight of potassium carbonate at room temperature, followed by stirring. 30 parts by weight of butadiene, 0.3 parts by weight of tertiary dodecyl mercaptan, 0.8 parts by weight of polyethylene glycol diacrylate, 0.3 parts by weight of diisopropylbenzene hydroperoxide, and then the reaction temperature was raised to 40 ° C. for 6 hours. When the reaction polymerization conversion reached 60%, 15 parts by weight of 1,3-butadiene was additionally added over 20 minutes, and the reaction temperature was raised to 55 ° C.

Then, 55 parts by weight of 1,3-butadiene was continuously added over 8 hours, and the reaction temperature was raised to 75 ° C. at a reaction conversion rate of 80%.

At this time, an emulsion consisting of 4 parts by weight of ion-exchanged water, 0.5 parts by weight of potassium rosinate and 0.3 parts by weight of tertiary butyl hydroperoxide was added over 6 hours at the same time as the start of continuous butadiene injection. Subsequently, 0.0003 parts by weight of ferrous sulfide, 0.05 parts by weight of dextrose, 0.04 parts by weight of sodium pyrrole phosphate, and 0.3 parts by weight of tertiary butyl hydroperoxide were further administered to sustain the reaction for 4 hours and terminate the reaction.

Preparation Example 2 Preparation of Polybutadiene Rubber Latex (A-2)

50 parts by weight of ion-exchanged water was added to a nitrogen-substituted polymerization reactor (autoclave), followed by stirring by adding 0.8 parts by weight of fatty acid potassium, 1.0 parts by weight of potassium rosinate, and 1.0 parts by weight of potassium carbonate at room temperature, followed by stirring. 40 parts by weight of butadiene, 0.3 parts by weight of tertiary dodecyl mercaptan, 0.8 parts by weight of polyethylene glycol diacrylate, 0.3 parts by weight of diisopropylbenzene hydroperoxide, and then the reaction temperature was raised to 40 ° C. for 6 hours. When the reaction polymerization conversion reached 60%, 15 parts by weight of 1,3-butadiene was additionally added over 20 minutes, and the reaction temperature was raised to 55 ° C. Then, 45 parts by weight of 1,3-butadiene was continuously added over 8 hours, and the reaction temperature was raised to 75 ° C. at a reaction conversion rate of 80%. At this time, an emulsion consisting of 4 parts by weight of ion-exchanged water, 0.5 part by weight of potassium rosinate and 0.3 part by weight of tertiary butyl hydroperoxide was added over 6 hours at the same time as the start of continuous butadiene injection. Subsequently, 0.0003 parts by weight of ferrous sulfide, 0.05 parts by weight of dextrose, 0.04 parts by weight of sodium pyrrole phosphate, and 0.3 parts by weight of tertiary butyl hydroperoxide were further administered to sustain the reaction for 4 hours and terminate the reaction.

Preparation Example 3 Preparation of Polybutadiene Rubber Latex (A-3)

50 parts by weight of ion-exchanged water was added to a nitrogen-substituted polymerization reactor (autoclave), followed by stirring by adding 0.8 parts by weight of fatty acid potassium, 1.0 parts by weight of potassium rosinate, and 1.0 parts by weight of potassium carbonate at room temperature, followed by stirring. When 40 parts by weight of butadiene, 0.3 parts by weight of tertiary dodecyl mercaptan, and 0.3 parts by weight of potassium persulfate were added all at once, and the reaction temperature was raised to 70 ° C. for 7 hours and the reaction polymerization conversion reached 60%. In addition, 30 parts by weight of 1,3-butadiene, 0.5 parts by weight of potassium rosinate, and 0.2 parts by weight of potassium persulfate were collectively added, followed by further 7 hours of reaction. Subsequently, 30 parts by weight of 1,3-butadiene, 0.5 parts by weight of potassium rosinate, and 0.2 parts by weight of potassium persulfate were collectively added, and further polymerization was performed for 4 hours while the temperature was raised to 80 ° C. Subsequently, 4 parts by weight of ion-exchanged water, 0.5 parts by weight of potassium rosinate, and 0.2 parts by weight of potassium persulfate were added at the reaction conversion rate of 85%, and the reaction was terminated for 4 hours at 80 ° C.

The polymerization conversion rate, gel content, average particle diameter, reaction time and swelling index of the polybutadiene-based rubber latex of Preparation Examples 1 to 3 are summarized in Table 1 below.

For reference, the rubbery polymer latex of Preparation Examples 1 to 3 was coagulated using dilute acid or metal salt, washed, dried in a vacuum oven at 60 ° C. for 24 hours, and finely chopped the obtained rubber mass with scissors and then 1 g of rubber. Sections were put in 100 g of toluene, stored in a dark room at room temperature for 48 hours, separated into sol and gel, and the gel content and swelling index were measured according to the following equations.

Gel content (%) = weight of insolubles (gel) / weight of sample * 100

Swelling index = weight of swollen gel / weight of gel

Table 1

division	Preparation Example 1	Preparation Example 2	Preparation Example 3
% Polymerization conversion	98	97	90
Gel content (%)	87	86	80
Average particle size	3200	3100	2900
Response time (hr)	18	18	22
Swelling index	16	18	26

As shown in Table 1, in Preparation Examples 1 and 2 according to the present invention, a large diameter polybutadiene-based rubber latex having high conversion rate and gel content through effective particle diameter and polymerization heat control within a short reaction time compared to Preparation Example 3, which is a conventional method. Could get

Particularly, in the case of Preparation Examples 1 and 2, the swelling index was lower than that of Preparation Example 3, and in Preparation Examples 1 and 2, monomer absorption was low and occlusion was small during grafting. Small ones can also be seen.

Using the polybutadiene-based rubber latex of Preparation Examples 1 to 3, the transparent ABS resin of Examples 1-4 and Comparative Examples 1-3 was prepared as follows.

Example 1 Preparation of Transparent ABS Resin (B-1)

100 parts by weight of ion-exchanged water, 50 parts by weight of polybutadiene-based rubber latex of Preparation Example 1, 0.5 parts by weight of di-potassium salt of alkenyl C16-18 succinic acid (Latemul ASK, ELOPLA AS100 series), methyl methacrylate 34 Parts by weight, 13 parts by weight of styrene, 3 parts by weight of acrylonitrile, 0.5 part by weight of tertiary dodecyl mercaptan, 0.048 part by weight of sodium formaldehyde sulfoxylate, 0.012 part by weight of sodium ethylenediaminetetraacetic acid, ferrous sulfide 0.001 Parts by weight, and 0.04 parts by weight of tertiary butyl hydroperoxide were continuously administered at 75 ° C. for 5 hours and reacted. After the reaction, the temperature was raised to 80 ° C., and aged for 1 hour to terminate the reaction.

Example 2 Preparation of Transparent ABS Resin (B-2)

Except for using 55 parts by weight of polybutadiene-based rubber latex of Preparation Example 1 30 parts by weight of methyl methacrylate, 12 parts by weight of styrene, 3 parts by weight of acrylonitrile was prepared in the same manner as in Example 1.

Example 3 Preparation of Transparent ABS Resin (B-3)

60 parts by weight of polybutadiene-based rubber latex of Preparation Example 1 was prepared in the same manner as in Example 1 except that 27 parts by weight of methyl methacrylate, 10 parts by weight of styrene, and 3 parts by weight of acrylonitrile were used.

Example 4 Preparation of Transparent ABS Resin (B-4)

50 parts by weight of polybutadiene-based rubber latex of Preparation Example 2 was prepared in the same manner as in Example 1 except that 34 parts by weight of methyl methacrylate, 13 parts by weight of styrene, and 3 parts by weight of acrylonitrile were used.

Comparative Example 1 Preparation of Transparent ABS Resin Latex (B-5)

50 parts by weight of polybutadiene-based rubber latex of Preparation Example 3 was prepared in the same manner as in Example 1 except that 34 parts by weight of methyl methacrylate, 13 parts by weight of styrene, and 3 parts by weight of acrylonitrile were used.

Comparative Example 2 Preparation of Transparent ABS Resin Latex (B-6)

Except for using 55 parts by weight of polybutadiene-based rubber latex of Preparation Example 3 30 parts by weight of methyl methacrylate, 12 parts by weight of styrene, 3 parts by weight of acrylonitrile was prepared in the same manner as in Example 1.

Comparative Example 3 Preparation of Transparent ABS Resin Latex (B-7)

60 parts by weight of polybutadiene-based rubber latex of Preparation Example 3 was prepared in the same manner as in Example 1 except that 27 parts by weight of methyl methacrylate, 10 parts by weight of styrene, and 3 parts by weight of acrylonitrile were used.

The transparent ABS resin latex obtained in Examples 1-4 and Comparative Examples 1-3 was prepared as a powder through agglomeration and drying process, and mixed with MSAN (XT500, manufactured by LG Chem) so that the rubber content was 15%. To prepare the thermoplastic transparent resin in pellet form, 0.2 parts by weight of an antioxidant was administered and a twin screw extruder was kneaded at a cylinder temperature of 210 ° C.

Injection to the prepared pellets to prepare a 3mm specimen and measured in the physical properties shown in Table 2 below.

[Property evaluation]

1. Transparency (Haze): Measured according to ASTM D1003.

2. Permeability (Tt): Measured according to ASTM D1003.

3. Notched Izod Impact Strength: Impact strength was measured using 1/4 "specimens using ASTM D256.

TABLE 2

division	Example 1	Example 2	Example 3	Example 4	Comparative Example 1	Comparative Example 2	Comparative Example 3
Polybutadiene rubber latex	A-1	A-1	A-1	A-2	A-3	A-3	A-3
Polybutadiene rubber latex (wt%)	50	55	60	50	50	55	60
Haze	1.5	1.6	1.6	1.5	2.2	2.5	3.4
Transmittance	90.8	90.6	90.6	90.7	90.0	89.9	89.9
Impact strength	17	16	16	17	13	12	10

As shown in Table 2, in the case of Examples 1 to 4 according to the present invention, unlike the conventional Comparative Examples 1 to 3, the infiltration amount of the styrene monomer to the polybutadiene-based rubber latex is minimized and the styrene-based monomer is replaced with the shell Induction through effective formation of graft shell, total transmittance of 90.5 or more, Haze value of 2.0 or less, ASTM D256 (1 / It can be seen that the thermoplastic transparent resin having the excellent transparency and impact resistance of Izod impact strength measured using 4 ") can be produced.

Claims

50 to 60 wt% polybutadiene-based rubber latex; And

A total amount of methyl methacrylate monomer, styrene monomer and acrylonitrile monomer in total amount of 50 to 40% by weight;

Transparent ABS resin, characterized in that the penetrating amount of the styrene monomer to the polybutadiene rubber latex is 0.005 or less.
The transparent ABS resin of claim 1, wherein the polybutadiene-based rubber latex has a swelling index of 10 to 20.
The method of claim 1, wherein the polybutadiene-based rubber latex is a transparent ABS resin, characterized in that the gel content of 85 to 94%.
The transparent ABS resin according to claim 1, wherein the polybutadiene-based rubber latex has an average particle diameter of 2500 to 4000 mm.
According to claim 1, wherein the methyl methacrylate monomer is (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid decyl Transparent ABS resin, characterized in that in the range of 27 to 36% by weight, as one or more monomers selected from esters and (meth) acrylic acid lauryl ester.
The method of claim 1, wherein the styrene-based monomer is a transparent ABS resin, characterized in that in the range of 10 to 13% by weight of at least one monomer selected from styrene, α-methylstyrene, p-methylstyrene, and vinyl toluene.
The method of claim 1, wherein the acrylonitrile-based monomer is a transparent ABS resin, characterized in that in the range of 2 to 6% by weight as one or more monomers selected from acrylonitrile, methacrylonitrile, and ethacrylonitrile.
A first step of preparing a polybutadiene-based rubber latex having a gel content of 85 to 94% by separately adding butadiene-based monomers; and

50 to 60% by weight of the polybutadiene-based rubber latex graft under a reactive emulsifier and an oil-soluble polymerization initiator while continuously adding a methyl methacrylate monomer, a styrene monomer and an acrylonitrile monomer in a total amount of 50 to 40% by weight. A second step of polymerizing to prepare a transparent ABS resin; Method for producing a transparent ABS resin comprising a.
The method of claim 8, wherein the butadiene-based monomer is a method for producing a transparent ABS resin, characterized in that the continuous division into the polymerization conversion ratio of 60 to 80% of the first step.
According to claim 8, The butadiene-based monomer 10 to 20 parts by weight of continuous butadiene for 20 minutes at a polymerization conversion rate of 50 to 60% of the first step, the temperature is raised from 40 ℃ to 55 ℃ 40 to 60 parts by weight of butadiene Method for producing a transparent ABS resin, characterized in that continuously added for 7 to 9 hours and reaches a polymerization conversion rate of 80%.
The method for producing a transparent ABS resin according to claim 9 or 10, wherein the polymerization conversion rate is raised to 75 ° C at a point of 80% conversion, and the final polymerization conversion rate is 95 to 99%.
According to claim 8, Divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate at the beginning of the first step , At least one crosslinking agent selected from aryl methacrylate and 1,3-butylene glycol diacrylate polyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate. Method for producing a transparent ABS resin, characterized in that included in the range of 0.1 to 5 parts by weight based on a total of 100 parts by weight of the butadiene monomer used in the first step.
The method of claim 8, wherein the reactive emulsifier is sodium dodecyl allylsulfosuccinate (TREM LF-40), C16-C18 alkenyl disuccinate dipotassium salt (Latemul ASK series), sodium acrylamistearate (NaAAS) and At least one selected from sodium 3-sulfopropyl tetradodecyl maleate (M14) is used in the range of 0.1 to 2 parts by weight based on a total of 100 parts by weight of the latex used in the second step and the total monomers. Method for producing a transparent ABS resin.
The method of claim 8, wherein the oil-soluble polymerization initiator is diisopropylbenzene hydroperoxide, t-hexyl hydro peroxide, 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-di ( t-butyl peroxy) cyclohexane, 1,1-di (t-butyl peroxy) 3,3,5-trimethylcyclohexane, t-butyl peroxybenzoate, t-butyl peroxy 2-ethyl hexanoate And at least one selected from bis (4-t-butylcyclohexyl) peroxydicarbonate, latex used in the second step, and 0.01 to 5 parts by weight based on a total of 100 parts by weight of the total monomers. Transparent ABS resin Method.
The method of claim 8, wherein the first step has a total reaction time of 18 to 20 hours.
Transparent ABS resin; And

SAN or MSAN resin;

The transparent ABS resin, polybutadiene rubber latex 50 to 60% by weight; And

A total amount of methyl methacrylate monomer, styrene monomer and acrylonitrile monomer in total amount of 50 to 40% by weight;

Transparent ABS resin composition, characterized in that the penetrating amount of the styrene monomer to the polybutadiene-based rubber latex is 0.005 or less.
17. The transparent ABS resin composition of claim 16, wherein the polybutadiene-based rubber latex has a swelling index of 10 to 20.
The method of claim 16,

The transparent ABS resin is a transparent ABS resin composition, characterized in that 5 to 25% of the composition.
17. The method according to claim 16, wherein the SAN or MSAN resin is (meth) acrylic acid alkyl ester monomer 0 to 75 parts by weight, styrene monomer 10 to 50 parts by weight, acrylonitrile monomer 10 to 20 parts by weight bulk polymerization, solution It is superposition | polymerization or suspension polymerization resin, The transparent ABS resin composition characterized by the above-mentioned.
A thermoplastic resin obtained by extruding and injecting a transparent ABS resin composition according to claim 16, wherein the thermoplastic resin has a total transmittance of 90.5 or more and a light diffusivity (Haze value) measured using an ASTM D1003 at room temperature based on a 3 mm sheet. ) 2.0 or less, and an Izod impact strength measured using ASTM D256 (1/4 ") is 15 or more, The thermoplastic transparent resin.