KR101484370B1 - Rubber reinforced graft copolymer and thermoplastic resin composition for reducing TVOCs - Google Patents

Abstract

The present invention relates to a rubber-reinforced graft copolymer and a thermoplastic resin composition for reducing total volatile organic compounds. More specifically, the present invention relates to a thermoplastic resin composition for reinforcing a rubber content in a graft copolymer contained in a thermoplastic resin composition, , It is possible to reduce residual emulsifier content and solidified solid content in the kneaded state with the matrix resin while providing excellent impact resistance while reducing gas generation and odor of the total volatile organic compounds (VOCs) during processing of the thermoplastic resin composition , It is possible to provide thermal stability and surface gloss without using a separate heat stabilizer.

Description

TECHNICAL FIELD [0001] The present invention relates to a rubber-reinforced graft copolymer and a thermoplastic resin composition for reducing total volatile organic compounds (rubber reinforced graft copolymer and thermoplastic resin composition for reducing TVOCs)

The present invention relates to a rubber-reinforced graft copolymer and a thermoplastic resin composition for reducing total volatile organic compounds. More specifically, the present invention relates to a thermoplastic resin composition for reinforcing a rubber content in a graft copolymer contained in a thermoplastic resin composition, , It is possible to reduce residual emulsifier content and solidified solid content in the kneaded state with the matrix resin while providing excellent impact resistance while reducing gas generation and odor of the total volatile organic compounds (VOCs) during processing of the thermoplastic resin composition A rubber-reinforced graft copolymer capable of providing thermal stability without using a separate heat stabilizer, and a thermoplastic resin composition for reducing total volatile organic compounds.

In general, as a method for improving the thermal stability and the surface gloss of the ABS copolymer resin or the like resin, a method of increasing the amount of the heat stabilizer or applying a stripping process to the ABS copolymer latex to remove the residual monomer, A method of additionally adding water at the time of flocculation / dehydration is applied to minimize the content of water.

Further, in order to improve the impact resistance and the impact strength of the drop impact, a method of increasing the rubber component and a method of increasing the acrylonitrile content in the ABS copolymer production are usually applied. At this time, when the content of the rubber component is increased, the impact resistance and whiteness are improved, but the coloring property is deteriorated due to the reduction of the molecular weight and graft ratio of the resin. In addition, when the acrylonitrile content is increased, the impact resistance and colorability are excellent, but the whiteness of the resin is reduced.

In general, rubber reinforcing resins such as ABS (acrylonitrile-butadiene-styrene), MBS (methacrylate-butadiene-styrene) and ASA (acrylonitrile-styrene- acrylate) A step of preparing a reinforced resin and coagulating / drying the same to prepare a powder, adding the resin to a extruder together with a resin such as styrene-acrylonitrile (hereinafter, referred to as SAN) and polycarbonate (PC) ≪ / RTI > At this time, rubber-reinforced resin having a moisture content of less than 1% is generally put into an extruder. Depending on the case, after the dewatering process, the powder containing about 30% of the water content may be subjected to a primary processing step by continuous kneading with SAN and PC in the extruder, where the high water content causes the physical deviation and productivity Causing a problem of degradation.

Therefore, when the powder containing water is introduced into the extruder without drying, minimizing the moisture content is an important factor for maintaining productivity and quality. The conventional centrifugal dehydrator is limited in reducing the moisture content.

Such a problem can be overcome by using a press-type dehydrator. However, the problem of the thermal stability and the deformation of the resin can be caused by the high-temperature and high-pressure processing in the compression-type dehydration process.

Accordingly, it is an object of the present invention to overcome the problems of the prior art as described above, to enhance the rubber content in the graft copolymer included in the thermoplastic resin composition, to use the volatile molecular weight modifier, to control the amount of residual emulsifier And solid coagulation, and it is possible to provide excellent impact resistance while reducing gas generation and odor of total volatile organic compounds (VOCs) when processing a thermoplastic resin composition, and to provide thermal stability without using a separate heat stabilizer It is an object of the present invention to provide a rubber-reinforced graft copolymer and a thermoplastic resin composition for reducing total volatile organic compounds.

In order to achieve the above object, the rubber-reinforced graft copolymer of the present invention is a rubber-

An aromatic vinyl compound and a vinyl cyan compound are graft-emulsion-polymerized with a reactive emulsifier, a volatile molecular weight modifier, and an oil-soluble polymerization initiator,

Is rubber-reinforced and has a moisture content in the range of 2 to 10%.

Further, the thermoplastic resin composition for reducing total volatile organic compounds of the present invention,

At least one resin (b) selected from the above-mentioned rubber-reinforced graft copolymer (a) and a copolymer of an aromatic vinyl compound and a vinyl cyan compound, polyvinyl chloride and polycarbonate, and the residual emulsifier content Is not more than 17500 占 퐂 / g.

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

First, in the present invention, an aromatic vinyl compound and a vinyl cyan compound are graft-emulsion-polymerized with a reactive emulsifier, a volatile molecular weight modifier, and an oil-soluble polymerization initiator in a diene rubber core, Reinforced < / RTI > graft copolymers.

The diene rubber core may be prepared by reacting butadiene rubber latex, styrene-butadiene copolymer latex, butadiene-acrylonitrile copolymer latex, ethylene-propylene copolymer latex or rubber latex having an average particle size of 600 to 1500 A derived therefrom with acetic acid, And cured.

Specifically, the rubber latex having an average particle diameter of 600 to 1,500 angstrom is prepared by mixing 100 parts by weight of butadiene rubber latex, 1 to 4 parts by weight of a non-reactive emulsifier, 0.01 to 1 part by weight of a reactive emulsifier, 0.1 to 0.6 parts by weight of a polymerization initiator, 0.1 to 0.5 parts by weight of a molecular weight regulator and 90 to 130 parts by weight of ion exchange water are added to the mixture at a temperature of 50 to 65 ° C for 7 to 12 hours and then 0.05 to 1.2 parts by weight of a molecular weight modifier For 5 to 15 hours at 55 to 70 < 0 > C.

1 to 4 parts by weight of an acetic acid aqueous solution may be slowly added to 100 parts by weight of the rubber latex thus prepared for 1 hour to enlarge the particles to an average particle diameter of 2500 to 3800 ANGSTROM. The rubber latex having an average particle diameter of less than 2500 Å is difficult to produce and the efficiency of the rubber is inferior. When the average particle diameter exceeds 3800 Å, the grafting efficiency is lowered and the gloss is lowered and the haze is increased.

The gel content of the diene rubber core before and after the non-enlargement is preferably 85 to 99% by weight, because graft copolymerization is effectively formed on the outside of the rubber particle, which is preferable in terms of impact strength and thermal stability. For reference, the gel content (%) corresponds to the percentage of the insoluble content (gel) divided by the weight of the sample.

The graft ratio of the graft copolymer according to the present invention is 20% or more, and the residual solid solid content is 0.05% or less.

For reference, there is a problem that the graft ratio decreases as the content of the rubber core is large and the particle size is large. The graft ratio greatly affects the physical properties of the graft copolymer. If the graft ratio is low, the rubber grains are not grafted, and the thermal stability is poor. Therefore, it is important to prepare a diene rubber core having an appropriate particle diameter and gel content, and it is important that the aromatic vinyl monomer and the vinylcyanide monomer are appropriately grafted to the diene rubber core.

For reference, the graft rate (%) corresponds to the percentage of the weight (g) of the grafted monomer divided by the rubber weight (g). In the present invention, when the graft rate is 20% or less, the gloss is lowered, which is not preferable.

Also, the solidified solid content (%) corresponds to the percentage of the weight (g) of the solidified solid in the reaction tank divided by the total weight (g) of the rubber and the monomer. In the present invention, when the solid solid content exceeds 0.5%, the latex stability is extremely low and it is difficult to obtain a suitable graft copolymer due to a large amount of solidification product.

Wherein the graft copolymer is a rubber-reinforced graft copolymer obtained by graft-emulsion-polymerizing 60 to 75 parts by weight of butadiene rubber latex or styrene-butadiene copolymer latex, 18 to 28 parts by weight of an aromatic vinyl compound, and 5 to 15 parts by weight of a vinyl cyan compound Lt; / RTI >

When the rubber latex is contained in an amount of less than 60 parts by weight, the polymerization time becomes longer due to the increase of the graft monomer and the reaction heat control becomes difficult. When the amount exceeds 75 parts by weight, the graft ratio is lowered, It is difficult to work and the gloss becomes worse.

The aromatic vinyl compound may be used alone or in admixture of two or more of styrene,? -Methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene or substituents thereof.

The aromatic vinyl compound is preferably 18 to 28 parts by weight based on 100 parts by weight of the total monomers constituting the copolymer. When the amount is less than 18 parts by weight, the reactivity 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 amount of acrylonitrile to be injected is decreased, and the chemical resistance is lowered.

The vinyl cyan compound may be used alone or as a mixture of two or more of acrylonitrile, methacrylonitrile, ethacrylonitrile, and their substituents. When the amount of the vinyl cyan compound exceeds 15 parts by weight based on the total monomers constituting the copolymer, The color of the final product may be adversely affected, and if it is less than 5 parts by weight, the chemical resistance may be deteriorated.

The emulsifiers used in the graft emulsion polymerization in the present invention include, but are not limited to, sulfoethyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, sodium styrene sulfonate, sodium dodecyl allyl sulfosuccinate TREM LF-40 copolymer, styrene and TREM LF-40 copolymer, polyoxyethylene alkylphenyl ether ammonium sulfate, HITENOL-BC series, sodium polyoxyethylene alkyl ether sulfosuccinate, alkenyl C16 -18 succinic acid, di-potassium salt (Latemul ASK, ELOPLA AS100 series) and sodium methallylsulfonate.

The content of the monomer is preferably within the range of 0.001 to 2 parts by weight based on 100 parts by weight of the monomers constituting the rubber-reinforced graft copolymer. When the amount of the emulsifier is less than 0.001 parts by weight, the stability of emulsification becomes poor. When the amount of the emulsifier is more than 2 parts by weight, the content of the residual emulsifier increases and the surface sharpness decreases.

In the present invention, the molecular weight regulator used in the graft-emulsion polymerization may be, but is not limited to, ethyl 2-mercaptoethylpropionate, 2-mercaptoethylpropionate, 2-mercaptoethanol, And acetic acid is preferable because it is possible to reduce the total volatile organic compound content.

The volatile molecular weight modifier may further include at least one member selected from n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan. The total amount of the graft copolymer may be rubber- The amount of the volatile organic compounds (TVOCs) is reduced as the amount of the mercaptans used is reduced.

Further, in the present invention, the polymerization initiator used in the graft emulsion polymerization may include, but is not limited to, diisopropylbenzene hydroperoxide, t-hexylhydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide , Dicumyl peroxide, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, Di (t-butylperoxy) 3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, t-butylperoxybenzoate, t-butylperoxybenzoate, -Butyl peroxy-2-ethylhexanoate, and bis (4-t-butylcyclohexyl) peroxydicarbonate.

It is preferable that the content thereof is within the range of 0.05 to 0.5 parts by weight based on 100 parts by weight of the monomers constituting the rubber-reinforced graft copolymer.

Further, it is preferable that the above-mentioned oil-soluble polymerization initiator is used together with at least one activator selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate and sodium sulfite And may be contained in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the total amount of monomers constituting the rubber-reinforced graft copolymer.

Further, the graft copolymer may be selected from the group consisting of divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, aryl methacryl And at least one crosslinking monomer selected from the group consisting of 1,3-butylene glycol diacrylate, and the like in an amount of 5 parts by weight or less.

In the graft copolymerization, the monomer mixture may be used in such a manner that the monomer mixture may be continuously introduced, batchwise introduced, or a mixture of the continuous introduction and the batch introduction, and is not particularly limited. Preferably, 5-40% It is preferable to batchwise add the remaining monomer mixture continuously.

The graft polymerization reaction time is preferably within 4 hours, and the polymerization conversion ratio after the reaction is 98.5% or more and the weight average molecular weight (Mw) is 50,000 to 150,000 g / mol.

The graft copolymer prepared as described above may further contain an antioxidant to prevent oxidation during processing. The antioxidant may be a phenol-based antioxidant, a phosphorus-based or a sulfur-based antioxidant, and is preferably contained in an amount of 0.1 to 2 parts by weight per 100 parts by weight of the graft copolymer emulsified with a particle size of 0.5 to 2 μm. It is preferable that the antioxidant is gradually added to the graft copolymer at 40 to 80 캜 and continuously stirred until the coagulation process.

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.

After the agglomeration and agglomeration, the solid type having a water content of 20 to 40% is subjected to hot-air drying or extrusion, followed by dehydration by compression and water evaporation by dehydration to obtain a water content of the graft copolymer of 2 to 10%, preferably 2 to 5 %. ≪ / RTI > The pressurized dehydrator used for this purpose requires a high temperature of 130 to 150 DEG C and a high pressure of about 50 to 110 kgf.

In addition, if the moisture content is within the range, the drying process can be omitted, and at the same time, the extrusion productivity can be improved.

In the present invention, at least one resin (b) selected from the above-mentioned rubber-reinforced graft copolymer (a) and a copolymer of an aromatic vinyl compound and a vinyl cyan compound, polyvinyl chloride and polycarbonate, It is possible to provide a thermoplastic resin composition for reducing total volatile organic compounds having a residual emulsifier content of not more than 17500 占 퐂 / g.

The amount used may be 20 to 40 wt% of the graft copolymer (a) and 60 to 80 wt% of the resin (b), based on the total weight of the components (a) and (b).

When the amount of the graft copolymer is less than 20% by weight, the impact strength is remarkably decreased. When the graft copolymer is more than 40% by weight, the flowability of the resin is not good, and if there is a problem in workability, colorability and scratch resistance are deteriorated.

In particular, the aromatic vinyl compound and the vinyl cyan compound in the copolymer (b) are obtained by polymerizing 60 to 85 parts by weight of an aromatic vinyl compound and 15 to 40 parts by weight of a vinyl cyan compound and having a weight average molecular weight (Mw) g / mol. The above-mentioned graft copolymer-related types may be used for the aromatic vinyl compound and the vinyl cyan compound.

The aromatic vinyl monomer is preferably used in an amount of 60 to 85 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 60 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 acrylonitrile content is reduced and the chemical resistance is reduced.

If the amount of the vinyl cyan compound is greater than 40 parts by weight based on the total monomers constituting the copolymer, the color of the vinyl cyan compound may be yellowed to adversely affect the color of the final product. If the amount is less than 15 parts by weight, the chemical resistance may be deteriorated.

The composition was prepared by equilibrating the pellet obtained by extruding the thermoplastic resin composition using a Static Head Space Sampler at 60 DEG C and then measuring the volatile components of the total volatile organic compounds (TVOCs) measured by GC / MS using toluene as a reference material ) Is 700 占 퐂 / g or less. Examples of the total volatile organic compounds include acrylonitrile, toluene, ethylbenzene, styrene,? -Methylstyrene, acetophenone, and TDDM, as shown in the following examples.

Particularly, as described in the following examples, the content of acrylonitrile in the total volatile organic compounds (TVOCs) is not more than 1 占 퐂 / g.

The thermoplastic resin composition of the present invention composed of the above-described components may be suitably used in the form of a lubricant, an antioxidant, an antistatic agent, a releasing agent, a heat stabilizer, a releasing agent, a dispersant, a dropping inhibitor, a weathering stabilizer, an inorganic filler, Can be prepared by adding selected additives.

The double lubricant may be selected from ethylene bis stearamide, oxidized polyethylene wax, and magnesium stearate, and the amount thereof is in the range of 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, per 100 parts by weight of the thermoplastic resin composition .

The antioxidant may be a phenolic antioxidant such as IR1076. The amount of the antioxidant is 0.5 to 2 parts by weight based on 100 parts by weight of the thermoplastic resin composition.

The thermoplastic resin composition as described above 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. After passing through a water bath and cutting, a resin in the form of pellets is obtained.

These resins reduce the generation of total volatile organic compounds (TVOCs) gas and odor during processing and have impact resistance. Examples of the total volatile organic compound include acrylonitrile, toluene, ethylbenzene, styrene,? -Methylstyrene, acetophenone, and TDDM.

The rubber-reinforced graft copolymer and the thermoplastic resin composition for reducing total volatile organic compounds according to the present invention reduce residual emulsifier content and solidified coagulation and improve the gas generation and odor of total volatile organic compounds (VOCs) during the processing of the thermoplastic resin composition It is possible to provide excellent impact resistance while reducing wastage, and it is possible to provide thermal stability and surface gloss without using a separate heat stabilizer.

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.

Example  One

Graft  Preparation of Copolymer

3 parts by weight of an acetic acid aqueous solution was gradually added to 100 parts by weight of a small-diameter rubbery latex polymer having a rubber particle diameter of 1,000 Å and a gel content of 97% for 1 hour to obtain a polybutadiene rubber latex having a rubber particle diameter of 3,400 Å and a gel content of 97% Respectively.

65 parts by weight (based on solid content) of the polybutadiene rubber latex, 140 parts by weight of ion-exchanged water, 5 parts by weight of styrene and 2 parts by weight of acrylonitrile were fed into a nitrogen-substituted polymerization reactor (autoclave) , 0.05 part by weight of cumene hydroperoxide and 0.09 part by weight of sodium pyrophosphate, 0.12 part by weight of dextrose and 0.002 part by weight of ferrous sulphate were added all at once.

Subsequently, 20 parts by weight of styrene, 8 parts by weight of acrylonitrile, 0.25 parts by weight of ethyl 2-mercaptoethylpropionate as a molecular weight modifier and 0.12 parts by weight of cumene hydroperoxide were continuously added thereto while being heated to 75 DEG C over 2 hours. In parallel with this, 0.2 parts by weight (based on solid content, 28% aqueous solution) of alkenyl C16-18 succinate potassium salt (ELOPLA AS100) as a reactive emulsifier was continuously added for 2 hours.

After the continuous introduction, 0.06 part by weight of cumene hydroperoxide, 0.04 part by weight of sodium pyrophosphate, 0.06 part by weight of dextrose and 0.001 part by weight of iron sulfide were added, and the mixture was heated to 80 ° C. for 30 minutes, Lt; / RTI > The polymerization conversion was 99%, the coagulated content was 0.03%, the grafting rate was 32%, and the residual emulsifier content was 17000 ㎍ / g.

Wherein the moisture content of the graft copolymer was in the range of 50 to 65%.

Graft  Coagulation of copolymer

0.5 part by weight of an antioxidant (winstay-L / IR1076 = 0.8 / 0.2) emulsion having an average particle diameter of 0.9 탆 was added to the above-mentioned graft copolymer, and then primary coagulation was carried out at 85 캜 in the presence of 1.3 parts by weight of MgSO 4, To obtain a powdery graft polymer having a water content of 30% level after secondary aging.

Preparation of thermoplastic resin composition

The powdery graft copolymer having a water content of 30% obtained was first subjected to a moisture content of 5% by using a crimping dehydrator at a temperature of 130 to 150 DEG C and a pressure of 50 to 110 kgf.

To 25 parts by weight of these, 75 parts by weight of a styrene-acrylonitrile (SAN) copolymer having a weight average molecular weight of 140,000 and an acrylonitrile content of 24% by weight and 1.5 parts by weight of ethylene bisstereamide (EBA) The specimens were molded to have a final rubber content of 15%, and physical properties were measured and summarized in Table 1 below.

Example  2

The same procedure as in Example 1 was repeated except that 0.2 parts by weight of HITENOL KH-10 as a reactive emulsifier was continuously injected for 2 hours in the step of preparing the graft copolymer in Example 1.

Example  3

The same procedure as in Example 1 was repeated except that sodium dodecyl allyl sulfosuccinate (TREM LF-40) was used as a reactive emulsifier in the step of preparing the graft copolymer in Example 1.

Example  4

The procedure of Example 1 was repeated except that 0.15 part by weight of ethyl 2-mercaptoethylpropionate and 0.1 part by weight of tertiary dodecyl mercaptan were used as a molecular weight regulator in the step of preparing the graft copolymer in Example 1. [ The same process was repeated.

Example  5

In the production step of the graft copolymer in Example 1, 60 parts by weight of styrene as a monomer and 2.8 parts by weight of acrylonitrile were used as a monomer instead of 65 parts by weight of polybutadiene rubber latex, and 21.6 parts by weight of styrene , 8.4 parts by weight of acrylonitrile, 0.3 parts by weight of ethyl 2-mercaptoethyl propionate and 0.12 parts by weight of cumene hydroperoxide was continuously introduced for 2 hours and 30 minutes while being heated to 75 ° C., Except that 0.3 parts by weight of a ketyl C16-18 succinate potassium salt (ELOPLA AS100) was continuously added for 2 hours and 30 minutes.

Example  6

In the step of preparing the graft copolymer in Example 1, 70 parts by weight of styrene was used instead of 65 parts by weight of polybutadiene rubber latex, 2.1 parts by weight of acrylonitrile was added as a monomer, and 16.56 parts by weight , 6.44 parts by weight of acrylonitrile, 0.2 parts by weight of ethyl 2-mercaptoethyl propionate and 0.12 parts by weight of cumene hydroperoxide was continuously introduced while being heated to 75 ° C. for 1 hour and 30 minutes, The same processes as in Example 1 were repeated except that 0.1 part by weight of a Cayenne C16-18 succinate potassium salt (ELOPLA AS100) was continuously added for 1 hour 30 minutes.

Comparative Example  One

The procedure of Example 1 was repeated except that 0.6 part by weight of a fatty acid soap was used instead of the reactive emulsifier and 0.4 part by weight of tertiary dodecylmercaptan was used as a molecular weight regulator in the step of preparing the graft copolymer in Example 1 for 3 hours. . ≪ / RTI > After the continuous introduction, 0.06 part by weight of cumene hydroperoxide, 0.04 part by weight of sodium pyrophosphate, 0.06 part by weight of dextrose and 0.001 part by weight of iron sulfide were added, and the mixture was heated at 80 DEG C for 30 minutes and maintained for 30 minutes. Terminated.

Comparative Example  2

The same experiment as in Example 1 was repeated, except that 0.03 part by weight of IR1076 was added as the heat stabilizer according to the prior art in Example 1, followed by compounding after drying.

Comparative Example  3

The same experiment as in Example 1 was repeated, except that a graft copolymer having a water content of 20% obtained by compression dewatering in Example 1 was used, and compounding was carried out through a drying process.

[Measures]

The physical properties of the ABS specimens prepared in Examples 1-6 and 1-3 were measured by the following methods.

* Izod Impact Strength : The ASTM D256 method was used to measure the thickness of the specimen at 1/4 inch.

* Flow Index ( MI : melt flow index : 220 占 폚 / 10 kg by the ASTM D1238 method.

It was measured by ASTM D638 method: - tensile strength.

* Surface gloss: measured by the ASTM D528 method at a 45 ° angle.

* Residence gloss: The pellets obtained from the extruder were placed in an extruder and allowed to stand for 15 minutes at 270 ° C to obtain glossy specimens. The specimens were extruded at 200 ° C without retention, and 45 ° gloss was measured. . The smaller the measured value, the better the staying gloss.

* Residual discoloration ( ΔE ) : L, a, and b values of the specimen obtained before and after retention were obtained for the glossy specimens obtained by the same method as the method for measuring the residence luster, Respectively.

[Formula 1]

division Example Comparative Example One 2 3 4 5 6 One 2 3 Polymerization Conversion (%) 99.0 99.0 98.9 98.9 98.9 99.2 97.5 99.0 99.0 Solidification% (%) 0.03 0.03 0.02 0.02 0.03 0.05 0.12 0.03 0.03 Residual emulsifier content 17000 16000 16500 16500 17500 15000 23000 17000 19000 Graft rate (%) 32 32.5 31.5 31.5 34 30 30 32 32 Polymerization time (hr) 3 3 3 3 4 2.5 3.5 3 3 Impact strength
(kg.cm/cm) 24.0 23.5 23.4 23.8 24.0 23.2 21.0 23.8 20.5 Flowability (g / 10 min) 21.0 21.5 21.0 21.3 21.0 21.3 21.0 20.7 24.0 Tensile strength (kg / cm2) 510 512 513 511 509 513 515 512 530 Surface gloss 109.5 109.5 109.0 109.3 109.4 109.7 106.5 107.0 108.0 Whiteness 57 57 57 56 58 58 55 54 52 Stay polished 2.5 2.6 2.6 2.8 2.1 2.1 5.5 3.5 3.2 Staying heat discoloration 3.4 3.4 3.2 3.8 3.3 3.0 6.2 3.9 4.0 TVOCs Acrylonitrile 0.8 0.8 0.6 0.9 0.9. 0.8 2.5 0.6  3.5 toluene 45.6 45.0 44.2 44.0 45.2 44.8 50.5 45.0 45.5 Ethylbenzene 102.1 100.8 103.0 103.3 101.1 102.1 101.8 101.8 98.8 Styrene 450.7 448.6 449.0 449.3 451.3 450.3 900.5 440.5 700.5 alpha -methyl styrene 38.8 37.5 36.4 36.5 38.2 39.1 40.3 35.2 30.1 Acetophenone 22.0 21.5 21.6 21.8 22.5 21.4 23.5 22.3 20.5 TDDM 2.5 2.4 16.3 16.5 3.0 2.8 50.6 2.5 50.1 Total TVOCs 662.5 656.6 671.1 672.3 652.2 661.3 1169.7 647.9 949

As shown in Table 1, in the case of Example 1-6 prepared according to the present invention, the thermal stability and gloss were excellent without using a separate thermal stabilizer, and the ABS resin had no impact resistance And the generation of the total volatile organic compound gas is reduced, so that it is confirmed that the smell is also reduced.

On the other hand, in the case of Comparative Example 1 using the non-reactive emulsifier and the nonvolatile molecular weight modifier, all the measurements such as impact strength, fluidity, surface gloss, whiteness, staying gloss, staying heat discoloration, falloff impact and total volatile organic compounds The results were inferior to those in Examples 1-6 over the field.

In addition, it was confirmed that Comparative Example 2 in which a conventional heat stabilizer was added showed similar or equivalent measured properties to Example 1-6 in which no heat stabilizer was added.

Further, in Comparative Example 3 in which the water content was outside the appropriate range, the impact resistance was deteriorated and the content of total volatile organic compounds (TVOCs) was increased.

Claims (19)

An aromatic vinyl compound and a vinyl cyan compound are graft-emulsion-polymerized with a reactive emulsifier, a volatile molecular weight modifier, and an oil-soluble polymerization initiator,
A rubber-reinforced graft copolymer, which is rubber reinforced and has a moisture content in the range of 2 to 10%.
The method according to claim 1,
Wherein the diene rubber core has an average particle diameter of 2500 to 3800 ANGSTROM and a gel content of 85 to 99 wt.%.
The method according to claim 1,
The diene rubber core may be prepared by reacting butadiene rubber latex, styrene-butadiene copolymer latex, butadiene-acrylonitrile copolymer latex, ethylene-propylene copolymer latex or rubber latex having an average particle size of 600 to 1500 A derived therefrom with acetic acid, Cured < / RTI > rubber-reinforced graft copolymer
The method according to claim 1,
Wherein the graft copolymer is obtained by graft-emulsion-polymerizing 60 to 75 parts by weight of butadiene rubber latex or styrene-butadiene copolymer latex, 18 to 28 parts by weight of an aromatic vinyl compound, and 5 to 15 parts by weight of a vinyl cyan compound Reinforced graft copolymer.
The method according to claim 1,
The reactive emulsifier may be selected from the group consisting of sulfoethyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, sodium styrene sulfonate, sodium dodecyl allyl sulfosuccinate (TREM LF-40), styrene and TREM LF- (HITENOL-BC series), sodium polyoxyethylene alkyl ether sulfosuccinate (HITENOL-KF series), alkenyl C16-18 succinic acid, di-potassium salt (Latemul ASK, ELOPLA AS100 series) and sodium methallylsulfonate in a range of 0.001 to 2 parts by weight based on 100 parts by weight of total monomers constituting the rubber-reinforced graft copolymer. Copolymer.
The method according to claim 1,
The volatile molecular weight modifier may be at least one selected from the group consisting of ethyl 2-mercaptoethylpropionate, 2-mercaptoethylpropionate, 2-mercaptoethanol, and mercaptoacetic acid as monomers constituting a rubber-reinforced graft copolymer By weight based on 100 parts by weight of the rubber-reinforced graft copolymer.
The method according to claim 6,
Wherein the volatile molecular weight modifier further comprises at least one member selected from n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan.
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, Butyl peroxide, peroxides such as peroxides, peroxides, peroxides, peroxides, peroxides, peroxides, peroxides such as peroxides, methyl isobutyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, Butylperoxybenzoate, t-butylperoxy 2-ethylhexanoate, and bis (4-tert-butylperoxy) t-butylcyclohexyl) peroxydicarbonate in the range of 0.05 to 0.5 parts by weight based on 100 parts by weight of the total of the monomers constituting the rubber-reinforced graft copolymer. Lt; / RTI >
9. The method of claim 8,
Wherein the oil-soluble polymerization initiator is at least one activator selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, and sodium sulfite, In the range of 0.1 to 1 part by weight based on 100 parts by weight of the total monomers to be combined.
The method according to claim 1,
Wherein the graft ratio of the graft copolymer is 20% or more, and the residual solid coagulation amount is 0.05% or less.
The method according to claim 1,
Wherein the polymerization conversion of the graft copolymer is 98.5% or more and the weight average molecular weight (Mw) is 50,000 to 150,000 g / mol.
The method according to claim 1,
The water content of the graft copolymer is obtained by hot-air drying or extruding a solid type having a water content of 20 to 40% by dehydration after latex agglomeration, followed by compression dewatering and moisture evaporation. The rubber-reinforced graft copolymer .
At least one resin (b) selected from the group consisting of a rubber-reinforced graft copolymer (a) of any one of claims 1 to 12, a copolymer of an aromatic vinyl compound and a vinyl cyan compound, a polyvinyl chloride and a polycarbonate, ; And the residual emulsifier content is not more than 17500 占 퐂 / g.
14. The method of claim 13,
Wherein the amount of the graft copolymer (a) is 20 to 40% by weight and the amount of the resin (b) is 60 to 80% by weight based on the total weight of the components (a) and (b) And a thermoplastic resin composition.
14. The method of claim 13,
The copolymer of aromatic vinyl compound and vinyl cyan compound in (b) above is obtained by polymerizing 60 to 85 parts by weight of an aromatic vinyl compound and 15 to 40 parts by weight of a vinyl cyan compound and has a weight average molecular weight (Mw) of 60,000 to 200,000 g / mol. < / RTI > The thermoplastic resin composition for reducing total volatile organic compounds according to claim 1,
14. The method of claim 13,
The composition was prepared by equilibrating the pellet obtained by extruding the thermoplastic resin composition using a Static Head Space Sampler at 60 DEG C and then measuring the volatile components of the total volatile organic compounds (TVOCs) measured by GC / MS using toluene as a reference material ) Is not more than 700 [mu] g / g. [7] The thermoplastic resin composition for reducing total volatile organic compounds according to claim 1,
17. The method of claim 16,
Wherein the content of acrylonitrile in the total volatile organic compounds (TVOCs) is not more than 1 占 퐂 / g.
14. The method of claim 13,
The composition is characterized by comprising at least one additive selected from the group consisting of a lubricant, an antioxidant, an antistatic agent, a releasing agent, a heat stabilizer, a releasing agent, a dispersant, an antistatic agent, a weathering stabilizer, an inorganic filler, an inorganic fiber, By weight based on the total weight of the thermoplastic resin composition.
A thermoplastic resin obtained by extruding and extruding the thermoplastic resin composition according to claim 13 as a thermoplastic resin having reduced volatile organic compound gas generation and odor during processing and improved thermal stability, impact resistance and surface gloss.