WO2013105737A1 - Thermal stabilizer-free thermoplastic resin composition and method for manufacturing same - Google Patents

Thermal stabilizer-free thermoplastic resin composition and method for manufacturing same Download PDF

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Publication number
WO2013105737A1
WO2013105737A1 PCT/KR2012/010548 KR2012010548W WO2013105737A1 WO 2013105737 A1 WO2013105737 A1 WO 2013105737A1 KR 2012010548 W KR2012010548 W KR 2012010548W WO 2013105737 A1 WO2013105737 A1 WO 2013105737A1
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weight
parts
thermoplastic resin
resin composition
rubber
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PCT/KR2012/010548
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French (fr)
Korean (ko)
Inventor
안봉근
박은선
유근훈
채주병
정유성
한원덕
전태영
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(주)엘지화학
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Priority claimed from KR1020120140020A external-priority patent/KR101534378B1/en
Application filed by (주)엘지화학 filed Critical (주)엘지화학
Priority to US14/115,707 priority Critical patent/US9006330B2/en
Priority to CN201280027229.3A priority patent/CN103582673B/en
Publication of WO2013105737A1 publication Critical patent/WO2013105737A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a thermal stabilizer free thermoplastic resin composition and a method of manufacturing the same.
  • a method for improving the thermal stability and surface gloss of ABS copolymer resin or similar resin is to increase the amount of thermal stabilizer or to remove residual monomer by applying stripping process to ABS copolymer latex, residual emulsifier In order to minimize the content of the method of adding additional water during aggregation / dehydration has been applied.
  • rubber reinforcement resins such as ABS (acrylonitrile-butadiene-styrene), MBS (methacrylate-butadiene-styrene), and ASA (acrylonitrile-styrene-acrylate) are generally rubbers through emulsion polymerization. After reinforcement resin is made, it is agglomerated / dried to make powder, and then, it is put into an extruder together with resins such as styrene-acrylonitrile (hereinafter referred to as SAN) and polycarbonate (PC) and processed into pellets. It is manufactured through the steps. In this case, it is common to inject a rubber-reinforced resin having a moisture content of less than 1% into the extruder. In some cases, the first process is a continuous process of kneading powder with SAN and PC in the extruder, which contains about 30% of the water content after dehydration without the drying process. It causes a problem of deterioration.
  • ABS acrylonit
  • the present invention relates to a heat stabilizer-free thermoplastic resin composition and a method of manufacturing the same, and an object of the present invention is to improve thermal stability and surface gloss without using a heat stabilizer, and at the same time, to provide excellent impact resistance and impact impact strength. It is to provide a resin composition.
  • Another object of the present invention is to provide a manufacturing method capable of maintaining high productivity without undergoing a drying step in the preparation of the thermoplastic resin composition.
  • the heat stabilizer free thermoplastic resin composition of the present invention comprises a) a rubber reinforced resin and b) a matrix resin,
  • the a) rubber reinforcement resin is an ABS-based thermoplastic resin obtained by graft copolymerization comprising a large diameter rubbery polymer latex, an aromatic vinyl compound, a vinyl cyan compound and a reactive surfactant as an active ingredient.
  • the present invention comprises the steps of: a) preparing the ABS-based thermoplastic resin as a rubber-reinforced resin as a heat stabilizer pre-grafted copolymer latex having a water content of 45 to 70%;
  • thermoplastic resin composition characterized in that the graft copolymer latex to adjust the moisture content to 2 to 20% and then kneading the matrix resin and the lubricant.
  • the thermoplastic resin composition is excellent in impact resistance, dropping impact, gloss without using a heat stabilizer, and in particular, it is characterized by increasing the production efficiency when applied to the compression dehydrator without undergoing a drying process during manufacturing.
  • the heat stabilizer free thermoplastic resin composition of this invention consists of a) rubber reinforced resin and b) matrix resin.
  • stabilizer free thermoplastic resin composition refers to a thermoplastic resin composition that does not include a heat stabilizer, unless otherwise specified.
  • the a) rubber-reinforced resin corresponds to an ABS-based thermoplastic resin obtained by graft copolymerization including an rubbery polymer latex, an aromatic vinyl compound, a vinyl cyan compound, and a reactive emulsifier as an active ingredient.
  • the rubbery polymer may be a large-diameter rubbery latex obtained by preparing a small-diameter rubbery latex and then enlarging particles using an acid.
  • the small-diameter rubber latex is 100 parts by weight of 1,3-butadiene, 1 to 4 parts by weight of emulsifier, 0.1 to 0.6 parts by weight of polymerization initiator, 0.1 to 1 parts by weight of electrolyte, 0.1 to 0.5 parts by weight of molecular weight modifier, and 90 to ion exchanged water. 130 parts by weight of the batch is reacted at 50 to 65 °C for 7 to 12 hours, and then 0.05 to 1.2 parts by weight of a batch of the molecular weight regulator is prepared by reacting at 55 to 70 °C for 5 to 15 hours.
  • the small-diameter rubbery latex thus obtained has an average particle diameter of 600 to 1500 mm 3 and a gel content of 85 to 99% by weight.
  • the gel content range corresponds to a range in which graft copolymerization is effectively formed on the outside of the rubber particles to impart excellent impact strength and thermal stability.
  • Acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid or polymer flocculant is added in an amount of 1 to 4 parts by weight as 0.1 to 5 parts by weight of the small-diameter rubbery latex, and gradually added for 1 hour as another example. To enlarge the particles.
  • the large-diameter rubbery polymer latex obtained by particle enlargement has a particle size specifically in the range of 2500 to 5000 mm 3, more specifically in the range of 2500 to 3800 mm 3, and the gel content to satisfy the range of 85 to 99 wt%.
  • the particle diameter may be an average particle diameter or a number average particle diameter.
  • Such large diameter rubbery polymer latex is included in an amount of 60 to 75 parts by weight based on a total of 100 parts by weight of the monomer for rubber reinforced resin to provide a rubber reinforced resin.
  • the aromatic vinyl compound used in the present invention is not limited thereto, but styrene, ⁇ -methylstyrene, p-methylstyrene, vinyl toluene, t-butyl styrene, chlorostyrene, or a substituent thereof and the like, or a mixture of two or more thereof.
  • Based on 100 parts by weight of the total amount of monomers for rubber reinforcement resin may be specifically used in the range of 18 to 28 parts by weight, more specifically 21 to 25 parts by weight.
  • acrylonitrile, methacrylonitrile, or a substituent thereof or the like may be mixed alone or in combination of two or more thereof, specifically 5 to 15 parts by weight based on a total of 100 parts by weight of the monomer for rubber-reinforced resins. More specifically, it can be used in 9 to 10 parts by weight.
  • Reactive emulsifiers used in the present invention can be included in the rubber reinforcement resin to minimize residual emulsifier content in the rubber reinforcement resin to play a role of improving thermal stability and surface gloss without the addition of a heat stabilizer, as well as later
  • the compatibility with the matrix resin to be blended is also enhanced to serve to provide an ABS-based thermoplastic resin excellent in impact resistance and falling impact strength.
  • an emulsifier including at least one functional group selected from the group consisting of carbonate, sulfonate, sulfate, and the like, but is not limited thereto.
  • alkenyl C16-18 di-succinate di- potassium salt alken
  • the reactive emulsifier is included within the range of 0.001 to 2 parts by weight based on a total of 100 parts by weight of the monomer for rubber-reinforced resin, which is not easy to ensure the polymerization stability at a content of less than 0.001, the residual emulsifier content is higher than 2 parts by weight This is because the resin thermal stability deteriorates.
  • the appropriate residual emulsifier content range in the present invention is not limited to this, but 19,000 ppm or less (in terms of the amount of emulsifier used, for example, about 65% by weight or less based on 100% by weight of the total amount of emulsifier added), or 1 to 19,000 ppm, as another example, 17,500 ppm or less (in terms of the amount of emulsifier used, about 55% by weight or less based on 100% by weight of the total amount of emulsifier added), or 1 to 17,500 ppm is preferable.
  • the rubber reinforcement resin may include mercaptans as the molecular weight regulator, specifically n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and the like or Can be used in combination of two or more, the amount may be used in 0.1 to 1 parts by weight based on a total of 100 parts by weight of the monomer for rubber reinforced resin.
  • the rubber-reinforced resin is a fat-soluble peroxide type such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, paramethane hydroperoxide or benzoyl peroxide as a polymerization initiator.
  • Oxidation consisting of polysaccharide dihydroxyacetone or polyamines such as dextrose, glucose, and plotose as the polymerization initiator and metal salts such as iron (II), iron (III), cobalt (II) or cerium (IV)
  • metal salts such as iron (II), iron (III), cobalt (II) or cerium (IV)
  • One or more types of reducing-type polymerization initiators may be used, and the amount of the reducing agent may be used in an amount of 0.05 to 0.5 parts by weight based on 100 parts by weight of the total monomers for rubber-reinforced resins.
  • thermoplastic resin composition 20 to 40 parts by weight of such a) rubber reinforced resin b) 60 to 80 parts by weight of one or more matrix resins selected from styrene-acrylonitrile copolymers and polycarbonate resins as matrix resins, and the thermal stabilizer free of the present invention
  • the thermoplastic resin composition is completed.
  • the weight average molecular weight is in the range of 60,000 to 200,000 g / mol, and the acrylonitrile content is 15 to 40 weight in the styrene-acrylonitrile copolymer. It is preferably included in%.
  • the weight average molecular weight is less than 60,000 g / mol, the mechanical properties of the resin is lowered, when the weight average molecular weight is more than 200,000 g / mol, the compatibility with the ABS resin is not good, the surface properties are lowered, acrylonitrile content is 15% by weight If it is less than the impact resistance and chemical resistance is lowered, because when the acrylonitrile content is more than 40% by weight yellowing (yellowish).
  • Comparative Example 2 using an Irganox-based heat stabilizer such as IR1076 confirms the effect of improving the thermal stability to a similar degree as when not using the heat stabilizer of the present invention could.
  • thermoplastic resin composition using the heat stabilizer-free thermoplastic resin composition thus provided as follows:
  • thermoplastic resin as a) rubber reinforced resin described above is prepared as a heat stabilizer pregrafted copolymer latex having a water content of 45 to 70%.
  • the graft copolymerization monomer mixture may be used in a continuous input, batch input, or a mixture of the continuous input and the batch input may be optionally used, and is not particularly limited, but 5 to 40% by weight of the total monomer mixture at the initial stage of the reaction and the rest Continuous addition of the monomer mixture is preferred in view of the reaction efficiency.
  • the reactive emulsifier it is preferable to continuously add the polymerization conversion in the range of 65 to 75%. In this case, the polymerization stability is not lowered, so that the amount of coagulum generated is small (see Example 1-4 below). .
  • the graft polymerization time is preferably within 3 hours, the polymerization conversion after the reaction is 98.5% or more, the weight average molecular weight (Mw) of the polymer is preferably in the range of 50,000 to 150,000 g / mol.
  • the heat stabilizer pre-grafted copolymer latex obtained is then subjected to antioxidant treatment and flocculation to obtain a graft copolymer latex having a water content of 45 to 70%.
  • the amount in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the graft rubber latex.
  • the agglomeration process refers to a process in which a metal salt or an acid is added to the graft rubber latex and then aged.
  • the coagulant used herein includes MgSO 4 , CaCl 2 , Al 2 (SO 4 ) 3 , sulfuric acid, phosphoric acid, or the like.
  • Hydrochloric acid, a polymer flocculant, or the like may be used in an amount of 1 to 4 parts by weight based on 100 parts by weight of the graft rubber latex.
  • graft rubber latex having a water content of 20 to 40% has a water content of 2 to 20%, more specifically 2 to 10%, and then a styrene-acrylonitrile copolymer and poly as a matrix resin.
  • One of the carbonate resins is kneaded with a lubricant and a post process such as extrusion and / or injection molding is performed. In the case of having such a water content range, the drying process may be omitted.
  • the moisture content is controlled to remove water using a dehydrator, more specifically, a compression dehydrator, separated into solids having a water content of 20 to 40%, and then manufactured in a powder form dried using a hot air drying method, followed by an extruder. It may be added or added to the extruder as a solid content in the water-containing state and then adjusted to a water content of 2 to 20% through the dehydration and water evaporation process in the extruder.
  • thermoplastic resin composition by blending 60 to 80 parts by weight of the matrix resin to 20 to 40 parts by weight of the graft copolymer having a water content of 2 to 20%
  • productivity during subsequent processing such as extrusion molding and / or injection molding is improved. It is preferable because it can improve.
  • the molded article obtained by extrusion molding or injection molding the thermoplastic resin composition by the method of the present invention was excellent in both thermal stability and gloss, impact resistance and impact impact strength as described in the following examples.
  • the lubricant may be ethylene bissteramide (EBA), magnesium stearate, or the like, and the amount of the lubricant may be 0.1 to 5 parts by weight based on 100 parts by weight of the graft copolymer and the matrix resin.
  • EBA ethylene bissteramide
  • magnesium stearate magnesium stearate
  • the rubber content is maximized and the reactive emulsifier is applied during the ABS graft copolymerization to minimize the residual emulsifier content in the ABS resin, thereby improving thermal stability and surface gloss without adding a thermal stabilizer.
  • improved compatibility with the styrene-acrylonitrile copolymer it was possible to produce a thermoplastic resin composition excellent in impact resistance and falling ball impact strength.
  • the particle diameter and the particle diameter distribution is measured by using a Nicomp 370HPL device (manufactured by Nicomp, USA) by the dynamic laser light scattering method.
  • the gel content of the rubber latex solidified with dilute acid or metal salt washed, dried in a vacuum oven at 60 °C for 24 hours, finely chopped the obtained rubber mass, and then put the 1g rubber section into 100g of toluene for 48 hours It is stored in a dark room at room temperature and then separated into a sol and a gel, the gel content is measured using the following formula.
  • the solid coagulation content is measured using the following formula.
  • Solid coagulation (%) [weight of coagulum produced in the reactor (g) / weight of total rubber and monomer (g)] x 100
  • the graft rate (%) of the graft polymer is obtained by coagulating, washing and drying the graft polymer latex to obtain a powder form, adding 2 g of this powder to 300 ml of acetone and stirring for 24 hours, and then using the ultracentrifuge for the solution. The separated acetone solution is dropped into methanol to obtain an grafted portion. It is dried to measure the weight and then calculated according to the following equation.
  • Graft Rate (%) Weight of Grafted Monomer (g) / Rubber Weight (g) x 100
  • the glossiness may be lowered, which may be unfavorable.
  • the residual emulsifier content (ppm) in the graft copolymer is 0.2g graft copolymer powder accurately taken in 50 ml vials, 10 ml of acetone is added and sonicated for 2 hours to dissolve the sample, and slowly added 30 ml of methanol Precipitate the polymer. After sonication for 1 hour to extract the additives, the supernatant was taken out, filtered and the residual emulsifier content (ppm) was measured using HPLC / DAD / MSD (Agilent 1100 system).
  • the water content of the graft rubber latex was in the range of 50 to 60%.
  • thermoplastic resin composition
  • the powdered graft copolymer having a water content of 30% was first made to have a water content of 5% in a compression dehydrator.
  • graft rubber latex of Example 1 70 parts by weight of the polybutadiene rubber latex (based on solids), 140 parts by weight of ion-exchanged water, 4.2 parts by weight of styrene, and 1.8 parts by weight of acrylonitrile were added to the reactor. 0.05 parts by weight of cumene hydroperoxide, 0.09 parts by weight of sodium pyrophosphate, 0.12 parts by weight of dextrose, and 0.002 parts by weight of ferrous sulfide were collectively added while maintaining the temperature at 50 ° C.
  • Example 1 Except that 0.03 parts by weight of IR1076 as a heat stabilizer according to the prior art in Example 1 was repeated the same experiment as in Example 1 and compounded through a drying process.
  • MI Melt flow index
  • Tensile strength measured by ASTM D638 method.
  • Example 3 using a reactive emulsifier, but with different timings, it was also worse than Example 1-6 in the field of measurement of impact strength, fluidity, surface gloss, whiteness, falling impact strength, etc. I could confirm it.

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Abstract

The present invention relates to a thermal stabilizer-free thermoplastic resin composition and to a method for manufacturing same. The thermal stabilizer-free thermoplastic resin composition according to the present invention has superior impact resistance, falling ball impact resistance, and gloss without using a separate thermal stabilizer. Particularly, when the thermal stabilizer-free thermoplastic resin composition is applied to a squeezing hydroextractor, production efficiency may be improved because a drying process is not performed during manufacture.

Description

열 안정화제 프리 열가소성 수지 조성물 및 그 제조방법Heat stabilizer-free thermoplastic resin composition and preparation method thereof
본 발명은 열 안정화제 프리(thermalstabilizer free) 열가소성 수지 조성물 및 그 제조방법에 관한 것이다.The present invention relates to a thermal stabilizer free thermoplastic resin composition and a method of manufacturing the same.
일반적으로 ABS 공중합체 수지 혹은 유사 수지의 열 안정성 및 표면 광택을 향상시키기 위한 방법으로는 열 안정제의 투입 량을 증가시키거나 ABS 공중합체 라텍스에 스트리핑 공정을 적용하여 잔류 모노머를 제거시키는 방법, 잔류 유화제의 함량을 최소화시키기 위해 응집/탈수 시 추가로 물을 투입하는 방법 등이 적용되고 있다. In general, a method for improving the thermal stability and surface gloss of ABS copolymer resin or similar resin is to increase the amount of thermal stabilizer or to remove residual monomer by applying stripping process to ABS copolymer latex, residual emulsifier In order to minimize the content of the method of adding additional water during aggregation / dehydration has been applied.
또한, 내충격성 및 낙구 충격강도를 향상시키기 위해서는 고무 성분을 증가시키는 방법 및 ABS 공중합체 제조시 아크릴로니트릴 함량을 증가시키는 방법이 통상적으로 적용된다. 이때 고무 성분 함량을 증가시키는 경우 내충격성 및 백색도는 향상되나 수지의 분자량 및 그라프트율 감소로 착색성이 저하되는 단점이 있다. 아울러 아크릴로니트릴 함량을 증가시킬 경우 내충격성 및 착색성은 우수하나 수지 백색도가 감소하는 단점을 갖는다. In addition, in order to improve impact resistance and impact resistance, a method of increasing the rubber component and a method of increasing the acrylonitrile content in the production of the ABS copolymer are commonly applied. In this case, when the rubber component content is increased, the impact resistance and the whiteness are improved, but there is a disadvantage that the colorability is lowered due to the decrease in the molecular weight and the graft ratio of the resin. In addition, when the acrylonitrile content is increased, the impact resistance and colorability are excellent, but the resin whiteness is reduced.
또한, 일반적으로 ABS(아크릴로니트릴-부타디엔-스티렌), MBS(메타크릴레이트-부타디엔-스티렌), ASA(아크릴로니트릴-스티렌-아크릴레이트)와 같은 고무 강화 수지는 통상적으로 유화 중합을 통해 고무강화 수지를 만들고, 이를 응집/건조하여 파우더로 제조한 후, 이를 스티렌-아크릴로니트릴(이하, SAN이라고도 칭함) 및 폴리카보네이트(PC) 등의 수지와 함께 압출기에 투입하여 펠렛 형태로 1차 가공하는 단계를 거쳐 제조되게 된다. 이때 수분 함량 1% 미만의 고무 강화 수지를 압출기에 투입하는 것이 일반적이다. 경우에 따라 건조 공정 없이 탈수 후 수분 함량이 30% 정도 함유하고 있는 파우더를 압출기 내에서 SAN 및 PC와 혼련하는 연속 공정으로 1차 가공과정을 거치기도 하는데, 이때 높은 수분함량은 물성편차와 생산성을 저하시키는 문제를 야기하게 된다. In addition, rubber reinforcement resins such as ABS (acrylonitrile-butadiene-styrene), MBS (methacrylate-butadiene-styrene), and ASA (acrylonitrile-styrene-acrylate) are generally rubbers through emulsion polymerization. After reinforcement resin is made, it is agglomerated / dried to make powder, and then, it is put into an extruder together with resins such as styrene-acrylonitrile (hereinafter referred to as SAN) and polycarbonate (PC) and processed into pellets. It is manufactured through the steps. In this case, it is common to inject a rubber-reinforced resin having a moisture content of less than 1% into the extruder. In some cases, the first process is a continuous process of kneading powder with SAN and PC in the extruder, which contains about 30% of the water content after dehydration without the drying process. It causes a problem of deterioration.
따라서, 건조공정 없이 수분을 포함한 파우더를 압출기에 투입할 경우 수분 함량을 최소화하는 것이 생산성 및 품질을 유지함에 있어 중요한 인자가 된다. 이 같은 수분 함량을 감소시킴에 있어 기존의 원심 탈수기로는 한계를 갖는다. Therefore, minimizing the moisture content is an important factor in maintaining the productivity and quality when the powder containing water without the drying process into the extruder. There is a limit to the conventional centrifugal dehydrator in reducing such moisture content.
이러한 문제는 압착식 탈수기를 사용함으로써 극복가능하지만, 이 같은 압착식 탈수 과정에서는 고온, 고압의 가공 공정을 거치게 되므로, 열 안정성 및 수지의 변형을 유발할 수 있다는 문제점을 또한 고려하여야 한다. This problem can be overcome by using a pressurized dehydrator. However, such a pressurized dehydration process requires high temperature and high pressure to be processed. Therefore, the problem of thermal stability and deformation of the resin may also be considered.
본 발명의 목적은 열 안정화제 프리 열가소성 수지 조성물 및 그 제조방법에 관한 것으로, 구체적인 발명의 목적은 열 안정제를 사용하지 않고도 열 안정성 및 표면 광택을 향상시키고, 동시에 내충격성 및 낙구 충격강도가 우수한 열가소성 수지 조성물을 제공하려는데 있다.SUMMARY OF THE INVENTION The present invention relates to a heat stabilizer-free thermoplastic resin composition and a method of manufacturing the same, and an object of the present invention is to improve thermal stability and surface gloss without using a heat stabilizer, and at the same time, to provide excellent impact resistance and impact impact strength. It is to provide a resin composition.
본 발명의 다른 목적은 상기 열가소성 수지 조성물 제조시 건조 공정을 거치지 않고도 높은 생산성을 유지할 수 있는 제조방법을 제공하려는데 있다. Another object of the present invention is to provide a manufacturing method capable of maintaining high productivity without undergoing a drying step in the preparation of the thermoplastic resin composition.
상기의 목적을 달성하기 위하여, In order to achieve the above object,
본 발명의 열 안정화제 프리 열가소성 수지 조성물은 a)고무 강화 수지와 b) 매트릭스 수지를 포함하되, The heat stabilizer free thermoplastic resin composition of the present invention comprises a) a rubber reinforced resin and b) a matrix resin,
상기 a)고무 강화 수지는 대구경 고무질 중합체 라텍스, 방향족 비닐 화합물, 비닐시안 화합물 및 반응형 유화제(reactive surfactant)를 유효 성분으로 포함하고 그라프트 공중합에 의해 수득되는 ABS계 열가소성 수지인 것을 특징으로 한다. The a) rubber reinforcement resin is an ABS-based thermoplastic resin obtained by graft copolymerization comprising a large diameter rubbery polymer latex, an aromatic vinyl compound, a vinyl cyan compound and a reactive surfactant as an active ingredient.
또한, 본 발명은 상술한 a) 고무 강화 수지로서 ABS계 열가소성 수지를 수분 함량이 45 내지 70 %인 열 안정화제 프리 그라프트 공중합체 라텍스로서 제조하는 단계; In addition, the present invention comprises the steps of: a) preparing the ABS-based thermoplastic resin as a rubber-reinforced resin as a heat stabilizer pre-grafted copolymer latex having a water content of 45 to 70%;
상기 열 안정화제 프리 그라프트 공중합체 라텍스를 산화방지 처리, 응집 및 탈수시켜 수분 함량이 20 내지 40 %인 그라프트 공중합체 라텍스를 수득하는 단계; 및 Antioxidant treatment, agglomeration and dehydration of the heat stabilizer free graft copolymer latex to obtain a graft copolymer latex having a water content of 20 to 40%; And
상기 그라프트 공중합체 라텍스를 수분 함량을 2 내지 20 %로 조절한 다음 매트릭스 수지와 활제를 혼련하는 단계;를 특징으로 하는 열가소성 수지 조성물의 제조방법을 제공한다. It provides a method for producing a thermoplastic resin composition, characterized in that the graft copolymer latex to adjust the moisture content to 2 to 20% and then kneading the matrix resin and the lubricant.
이하, 본 발명에 대하여 상세하게 설명한다. EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명에서는 열가소성 수지 조성물로서 열 안정제를 사용하지 않고도 내충격성, 낙구 충격, 광택성이 우수하며, 특히 제조 도중 건조 공정을 거치지 않아 압착 탈수기에 적용시 생산 효율성을 증가시키는 것을 기술적 특징으로 한다. In the present invention, the thermoplastic resin composition is excellent in impact resistance, dropping impact, gloss without using a heat stabilizer, and in particular, it is characterized by increasing the production efficiency when applied to the compression dehydrator without undergoing a drying process during manufacturing.
우선, 본 발명의 열 안정화제 프리 열가소성 수지 조성물은 a)고무 강화 수지와 b) 매트릭스 수지로 이루어진다. First, the heat stabilizer free thermoplastic resin composition of this invention consists of a) rubber reinforced resin and b) matrix resin.
본 발명에서 사용하는 용어 안정화제 프리(thermalstabilizer free) 열가소성 수지 조성물은 특별히 언급되지 않는 한, 열 안정화제를 포함하지 않고 구성된 열가소성 수지 조성물을 지칭한다. As used herein, the term stabilizer free thermoplastic resin composition refers to a thermoplastic resin composition that does not include a heat stabilizer, unless otherwise specified.
상기 a)고무 강화 수지는 고무질 중합체 라텍스, 방향족 비닐 화합물, 비닐시안 화합물 및 반응형 유화제를 유효 성분으로 포함하고 그라프트 공중합에 의해 수득되는 ABS계 열가소성 수지에 해당한다. The a) rubber-reinforced resin corresponds to an ABS-based thermoplastic resin obtained by graft copolymerization including an rubbery polymer latex, an aromatic vinyl compound, a vinyl cyan compound, and a reactive emulsifier as an active ingredient.
구체적으로 상기 고무질 중합체는 이에 한정하는 것은 아니나 소구경 고무질 라텍스를 제조한 다음 산을 이용하여 입자 비대화시켜 수득한 대구경 고무질 라텍스일 수 있다. Specifically, the rubbery polymer may be a large-diameter rubbery latex obtained by preparing a small-diameter rubbery latex and then enlarging particles using an acid.
이때 소구경 고무질 라텍스는 1,3-부타디엔 100 중량부, 유화제 1 내지 4 중량부, 중합개시제 0.1 내지 0.6 중량부, 전해질 0.1 내지 1 중량부, 분자량 조절제 0.1 내지 0.5 중량부 및 이온 교환수 90 내지 130 중량부를 일괄 투여하여 7 내지 12시간 동안 50 내지 65 ℃에서 반응시킨 다음 추가로 분자량 조절제를 0.05 내지 1.2 중량부 일괄 투여하여 5 내지 15시간 동안 55 내지 70 ℃에서 반응시켜 제조한다. In this case, the small-diameter rubber latex is 100 parts by weight of 1,3-butadiene, 1 to 4 parts by weight of emulsifier, 0.1 to 0.6 parts by weight of polymerization initiator, 0.1 to 1 parts by weight of electrolyte, 0.1 to 0.5 parts by weight of molecular weight modifier, and 90 to ion exchanged water. 130 parts by weight of the batch is reacted at 50 to 65 ℃ for 7 to 12 hours, and then 0.05 to 1.2 parts by weight of a batch of the molecular weight regulator is prepared by reacting at 55 to 70 ℃ for 5 to 15 hours.
이와 같이 수득된 소구경 고무질 라텍스는 평균 입자경이 600 내지 1500 Å이고 겔 함량은 85 내지 99 중량% 범위를 만족하게 된다. 상기 겔 함량 범위는 고무 입자 외부에 그라프트 공중합이 효과적으로 형성되어 우수한 충격강도 및 열 안정성을 부여할 수 있는 범위에 해당한다. The small-diameter rubbery latex thus obtained has an average particle diameter of 600 to 1500 mm 3 and a gel content of 85 to 99% by weight. The gel content range corresponds to a range in which graft copolymerization is effectively formed on the outside of the rubber particles to impart excellent impact strength and thermal stability.
상기 소구경 고무질 라텍스 100 중량부에 비대화용 산으로서 아세트산, 인산, 황산, 염산 혹은 고분자 응집제를 1 내지 4 중량부 함량으로 0.1 내지 5시간 혹은 0.5 내지 2시간, 또 다른 일례로 1시간 동안 서서히 투입하여 입자를 비대화하게 된다. Acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid or polymer flocculant is added in an amount of 1 to 4 parts by weight as 0.1 to 5 parts by weight of the small-diameter rubbery latex, and gradually added for 1 hour as another example. To enlarge the particles.
입자 비대화에 의해 얻어진 대구경 고무질 중합체 라텍스는 입자경이 구체적으로는 2500 내지 5000 Å 범위, 보다 구체적으로는 2500 내지 3800 Å 범위 내이고, 겔 함량은 85 내지 99 중량% 범위를 만족하게 된다. 상기 입자경은 평균 입자경 혹은 수평균 입자경일 수 있다. The large-diameter rubbery polymer latex obtained by particle enlargement has a particle size specifically in the range of 2500 to 5000 mm 3, more specifically in the range of 2500 to 3800 mm 3, and the gel content to satisfy the range of 85 to 99 wt%. The particle diameter may be an average particle diameter or a number average particle diameter.
이 같은 대구경 고무질 중합체 라텍스는 고무 강화 수지용 단량체 총 100 중량부 기준으로 60 내지 75 중량부로 포함되어 고무 강화된 수지를 제공한다. 이같이 고무 함량을 극대화함으로써 압착식 탈수 과정을 거친 수지의 압출기에 투입되는 양을 최소화하는 효과를 부여할 수 있다.Such large diameter rubbery polymer latex is included in an amount of 60 to 75 parts by weight based on a total of 100 parts by weight of the monomer for rubber reinforced resin to provide a rubber reinforced resin. By maximizing the rubber content in this way it can be given the effect of minimizing the amount of the resin is subjected to the extruded dehydration process.
본 발명에 사용되는 방향족 비닐 화합물로는 이에 한정하는 것은 아니나, 스티렌, α-메틸스티렌, p-메틸스티렌, 비닐 톨루엔, t-부틸 스티렌, 클로로스티렌 또는 이들의 치환체 등을 단독 또는 2종 이상 혼합하여 고무 강화 수지용 단량체 총 100 중량부 기준으로 구체적으로는 18 내지 28 중량부, 보다 구체적으로는 21 내지 25 중량부 범위 내로 사용할 수 있다. The aromatic vinyl compound used in the present invention is not limited thereto, but styrene, α-methylstyrene, p-methylstyrene, vinyl toluene, t-butyl styrene, chlorostyrene, or a substituent thereof and the like, or a mixture of two or more thereof. Based on 100 parts by weight of the total amount of monomers for rubber reinforcement resin may be specifically used in the range of 18 to 28 parts by weight, more specifically 21 to 25 parts by weight.
특히, 중합 안정성 확보 및 적절한 셀 형성을 통한 기계적 물성의 최적화, 열 안정성 확보를 위해, 하기 실시예에서 규명된 바와 같이, 중합 온도 승온 전후에 각각 분할 투입하는 것이 보다 바람직하다. Particularly, in order to secure polymerization stability, optimize mechanical properties through proper cell formation, and ensure thermal stability, it is more preferable to separately add each of the mixtures before and after the polymerization temperature is elevated as described in the following Examples.
본 발명에 사용되는 비닐시안화 화합물로는 아크릴로니트릴, 메타크릴로니트릴 또는 이들의 치환체 등을 단독 또는 2종 이상 혼합하여 고무 강화 수지용 단량체 총 100 중량부 기준으로 구체적으로는 5 내지 15 중량부, 보다 구체적으로는 9 내지 10 중량부로 사용할 수 있다. As the vinyl cyanide compound used in the present invention, acrylonitrile, methacrylonitrile, or a substituent thereof or the like may be mixed alone or in combination of two or more thereof, specifically 5 to 15 parts by weight based on a total of 100 parts by weight of the monomer for rubber-reinforced resins. More specifically, it can be used in 9 to 10 parts by weight.
특히, 중합 안정성 확보 및 적절한 셀 형성을 통한 기계적 물성의 최적화, 열 안정성 확보를 위해, 하기 실시예에서 규명된 바와 같이, 중합 온도 승온 전후 각각 분할하여 투입하는 것이 보다 바람직하다. Particularly, in order to secure polymerization stability, optimize mechanical properties through proper cell formation, and secure thermal stability, it is more preferable to divide each of the mixtures before and after the polymerization temperature is increased as described in the following Examples.
본 발명에 사용되는 반응형 유화제는 고무 강화 수지에 포함됨으로써 고무 강화 수지 내 잔류 유화제 함량을 최소화하여 열 안정제의 추가 투입 없이 열 안정성 및 표면 광택을 향상시키는 역할을 수행할 수 있으며, 이뿐 아니라 추후에 배합되는 매트릭스 수지와의 상용성 또한 높여 내충격성 및 낙구 충격강도가 우수한 ABS계 열가소성 수지를 제공할 수 있는 역할을 수행할 수 있다. Reactive emulsifiers used in the present invention can be included in the rubber reinforcement resin to minimize residual emulsifier content in the rubber reinforcement resin to play a role of improving thermal stability and surface gloss without the addition of a heat stabilizer, as well as later The compatibility with the matrix resin to be blended is also enhanced to serve to provide an ABS-based thermoplastic resin excellent in impact resistance and falling impact strength.
이와 같은 역할을 수행하기 위하여는 카보네이트, 술포네이트, 및 술페이트 등으로 이루어진 그룹으로부터 1종 이상 선택된 작용기를 포함하는 유화제를 사용하는 것이 바람직한 것으로, 이에 한정하는 것은 아니나, 예를 들어 술포에틸 메타크릴레이트(sulfoethyl methacrylate), 2-아크릴아미도-2-메틸프로판 술폰산(2-acrylamido-2-methylpropane sulfonic acid), 소디움 스티렌 술포네이트(sodium styrene sulfonate), 소디움 도데실 알릴 술포숙시네이트(sodium dodectyl allyl sulfosuccinate), 스티렌과 소디움 도데실 알릴 술포숙시네이트 공중합체, 폴리옥시에틸렌 알킬페닐 에테르 암모늄 술페이트류(polyoxyethylene alkylphenyl ether ammonium sulfate), 알케닐 C16-18 숙신산 디-포타슘염(alkenyl C16-18 succinic acid, di-potassium salt) 및 소디움 메트알릴 술포네이트(sodium methallyl sulfonate) 중에서 선택된 1종 이상을 사용할 수 있다. In order to perform such a role, it is preferable to use an emulsifier including at least one functional group selected from the group consisting of carbonate, sulfonate, sulfate, and the like, but is not limited thereto. For example, sulfoethyl methacryl Sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, sodium styrene sulfonate, sodium dodecyl allyl sulfosuccinate allyl sulfosuccinate), styrene and sodium dodecyl allyl sulfosuccinate copolymer, polyoxyethylene alkylphenyl ether ammonium sulfate, alkenyl C16-18 di-succinate di- potassium salt (alkenyl C16-18) one selected from succinic acid, di-potassium salt) and sodium methallyl sulfonate The can be used.
상기 반응형 유화제는 고무 강화 수지용 단량체 총 100 중량부 기준으로 0.001 내지 2 중량부 범위 내로 포함되는데, 이는 0.001 미만의 함량에서는 중합 안정성 확보가 용이하지 않고, 2 중량부 초과 함량에서는 잔류 유화제 함량이 높아 수지 열 안정성이 악화되기 때문이다. The reactive emulsifier is included within the range of 0.001 to 2 parts by weight based on a total of 100 parts by weight of the monomer for rubber-reinforced resin, which is not easy to ensure the polymerization stability at a content of less than 0.001, the residual emulsifier content is higher than 2 parts by weight This is because the resin thermal stability deteriorates.
참고로, 본 발명에서 적절한 잔류 유화제 함량 범위는 이에 한정하는 것은 아니나, 19,000 ppm 이하(유화제 사용량 기준으로 환산시, 일례로 투입된 유화제 총 100 중량% 기준으로 약 65 중량% 이하), 혹은 1 내지 19,000 ppm, 또 다른 일례로서, 17,500 ppm 이하(유화제 사용량 기준으로 환산시, 일례로 투입된 유화제 총 100 중량% 기준으로 약 55 중량% 이하), 혹은 1 내지 17,500 ppm인 것이 바람직하다. For reference, the appropriate residual emulsifier content range in the present invention is not limited to this, but 19,000 ppm or less (in terms of the amount of emulsifier used, for example, about 65% by weight or less based on 100% by weight of the total amount of emulsifier added), or 1 to 19,000 ppm, as another example, 17,500 ppm or less (in terms of the amount of emulsifier used, about 55% by weight or less based on 100% by weight of the total amount of emulsifier added), or 1 to 17,500 ppm is preferable.
또한, 본 발명에서 (a) 고무 강화수지는 분자량 조절제로서 메르캅탄류를 포함할 수 있으며, 구체적으로는 n-옥틸메르캅탄, n-도데실메르캅탄, t-도데실메르캅탄 등을 단독 또는 2종 이상 혼합 사용할 수 있는 것으로, 사용량은 고무 강화 수지용 단량체 총 100 중량부 기준으로 0.1 내지 1 중량부로 사용될 수 있다. In addition, in the present invention (a) the rubber reinforcement resin may include mercaptans as the molecular weight regulator, specifically n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and the like or Can be used in combination of two or more, the amount may be used in 0.1 to 1 parts by weight based on a total of 100 parts by weight of the monomer for rubber reinforced resin.
나아가, 본 발명에서 (a) 고무 강화수지는 중합 개시제로서 큐멘하이드로 퍼옥사이드, 디이소프로필벤젠하이드로퍼옥사이드, 3급부틸 하이드로퍼옥사이드, 파라메탄 하이드로퍼옥사이드 또는 벤조일 퍼옥사이드 등의 지용성 퍼옥사이드계 중합 개시제와 금속염류로 철(II), 철(III), 코발트(II) 또는 세륨(IV), 환원제로는 덱스트로스, 글루코스, 플로토스 등의 다당류 디하이드록시아세톤 또는 폴리아민류 등으로 구성된 산화-환원계 중합 개시제 중에서 1종 이상을 사용할 수 있으며, 사용량은 고무 강화 수지용 단량체 총 100 중량부 기준으로 0.05 내지 0.5 중량부로 사용될 수 있다. Furthermore, in the present invention, (a) the rubber-reinforced resin is a fat-soluble peroxide type such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, paramethane hydroperoxide or benzoyl peroxide as a polymerization initiator. Oxidation consisting of polysaccharide dihydroxyacetone or polyamines such as dextrose, glucose, and plotose as the polymerization initiator and metal salts such as iron (II), iron (III), cobalt (II) or cerium (IV) One or more types of reducing-type polymerization initiators may be used, and the amount of the reducing agent may be used in an amount of 0.05 to 0.5 parts by weight based on 100 parts by weight of the total monomers for rubber-reinforced resins.
이와 같은 a) 고무 강화 수지 20 내지 40 중량부에 b) 매트릭스 수지로서 스티렌-아크릴로니트릴 공중합체 및 폴리카보네이트 수지 중에서 선택된 1종 이상의 매트릭스 수지 60 내지 80 중량부를 배합하여 본 발명의 열 안정화제 프리 열가소성 수지 조성물을 완성하게 된다. 20 to 40 parts by weight of such a) rubber reinforced resin b) 60 to 80 parts by weight of one or more matrix resins selected from styrene-acrylonitrile copolymers and polycarbonate resins as matrix resins, and the thermal stabilizer free of the present invention The thermoplastic resin composition is completed.
특히, 상기 b) 매트릭스 수지로서 스티렌-아크릴로니트릴 공중합체를 사용할 경우 중량평균 분자량은 60,000 내지 200,000 g/mol 범위 내이고, 아크릴로니트릴 함량은 상기 스티렌-아크릴로니트릴 공중합체 내에 15 내지 40 중량%로 포함되는 것이 바람직하다. 이는 중량평균 분자량이 60,000 g/mol 미만에서는 수지의 기계적 물성이 저하되며, 200,000 g/mol 초과시에는 ABS계 수지와의 상용성이 좋지 않아 표면 물성이 저하되며, 아울러 아크릴로니트릴 함량이 15 중량% 미만인 경우 내충격성 및 내화학성이 저하되며, 아크릴로니트릴 함량이 40 중량% 초과시에는 수지가 황변(yellowish)하기 때문이다. In particular, when the styrene-acrylonitrile copolymer is used as the b) matrix resin, the weight average molecular weight is in the range of 60,000 to 200,000 g / mol, and the acrylonitrile content is 15 to 40 weight in the styrene-acrylonitrile copolymer. It is preferably included in%. When the weight average molecular weight is less than 60,000 g / mol, the mechanical properties of the resin is lowered, when the weight average molecular weight is more than 200,000 g / mol, the compatibility with the ABS resin is not good, the surface properties are lowered, acrylonitrile content is 15% by weight If it is less than the impact resistance and chemical resistance is lowered, because when the acrylonitrile content is more than 40% by weight yellowing (yellowish).
본 발명에 따르면, 하기 실시예에서 살펴본 바와 같이, IR1076와 같은 Irganox 계열의 열 안정화제를 사용한 비교예 2의 경우 본 발명의 열 안정화제를 사용하지 않은 경우와 유사한 정도의 열 안정성 개선 효과를 확인할 수 있었다. According to the present invention, as seen in the following examples, Comparative Example 2 using an Irganox-based heat stabilizer such as IR1076 confirms the effect of improving the thermal stability to a similar degree as when not using the heat stabilizer of the present invention Could.
이같이 제공되는 열 안정화제 프리 열가소성 수지 조성물을 이용하여 열가소성 수지 조성물의 제조방법을 구체적으로 살펴보면 다음과 같다:Looking at the manufacturing method of the thermoplastic resin composition using the heat stabilizer-free thermoplastic resin composition thus provided as follows:
우선, 상술한 a) 고무 강화 수지로서 ABS계 열가소성 수지를 수분 함량이 45 내지 70%인 열 안정화제 프리 그라프트 공중합체 라텍스로서 제조하게 된다. First, the a) thermoplastic resin as a) rubber reinforced resin described above is prepared as a heat stabilizer pregrafted copolymer latex having a water content of 45 to 70%.
이때 그라프트 공중합 시 단량체 혼합물은 연속 투입, 일괄 투입, 또는 연속 투입과 일괄 투입을 선택적으로 혼용하여 사용할 수 있으며, 특별히 제한되지 않으나 총 단량체 혼합물의 5 내지 40중량%를 반응 초기에 일괄 투입하고 나머지 단량체 혼합물을 연속 투입하는 것이 반응 효율성 측면을 감안할 때 바람직하다. At this time, the graft copolymerization monomer mixture may be used in a continuous input, batch input, or a mixture of the continuous input and the batch input may be optionally used, and is not particularly limited, but 5 to 40% by weight of the total monomer mixture at the initial stage of the reaction and the rest Continuous addition of the monomer mixture is preferred in view of the reaction efficiency.
이는 하기 실시예에서도 규명된 것으로, 즉, 고무 강화 수지를 구성하는 전체 단량체 중 방향족 비닐 화합물과 비닐시안화 화합물의 경우 각각 5 중량부와 2 중량부가 우선 투입된 다음 승온 조건하에 각각 20 중량부와 8 중량부가 투입될 수 있다.This is also shown in the following examples, that is, in the case of the aromatic vinyl compound and the vinyl cyanide compound of the total monomers constituting the rubber-reinforced resin, 5 parts by weight and 2 parts by weight, respectively, are first introduced, and then 20 parts by weight and 8 parts by weight under the elevated temperature conditions, respectively. An addition can be made.
상기 반응형 유화제의 경우 중합 전환율 65 내지 75% 범위 내에서 연속 투입하는 것이 바람직한데, 이 경우 중합 안정성이 저하되지 않아 응고물(coagulum) 발생량이 적은 효과가 있다(하기 실시예 1-4 참조). In the case of the reactive emulsifier, it is preferable to continuously add the polymerization conversion in the range of 65 to 75%. In this case, the polymerization stability is not lowered, so that the amount of coagulum generated is small (see Example 1-4 below). .
상기 그라프트 중합반응 시간은 3시간 이내인 것이 바람직하며, 반응 후 중합 전환율은 98.5% 이상이며, 중합체의 중량평균 분자량(Mw)은 50,000 내지 150,000 g/mol 범위내인 것이 바람직하다. The graft polymerization time is preferably within 3 hours, the polymerization conversion after the reaction is 98.5% or more, the weight average molecular weight (Mw) of the polymer is preferably in the range of 50,000 to 150,000 g / mol.
그런 다음 수득된 열 안정화제 프리 그라프트 공중합체 라텍스를 산화방지 처리 및 응집시켜 수분 함량이 45 내지 70%인 그라프트 공중합체 라텍스를 수득하게 된다.The heat stabilizer pre-grafted copolymer latex obtained is then subjected to antioxidant treatment and flocculation to obtain a graft copolymer latex having a water content of 45 to 70%.
상기 산화방지 처리 공정은 입경이 0.5 내지 2 ㎛로 유화된 페놀계 산화방지제, 인계 또는 황계 산화방지제를 40 내지 80 ℃의 그라프트 고무 라텍스에 서서히 투입하여 응집 공정 이전까지 연속 교반하여 주는 것이 효과적이다. In the anti-oxidation process, it is effective to gradually add phenol-based antioxidants, phosphorus-based, or sulfur-based antioxidants emulsified with a particle diameter of 0.5 to 2 μm into a graft rubber latex of 40 to 80 ° C., and to continuously stir until the coagulation process. .
그 사용량으로는 그라프트 고무 라텍스 100 중량부에 대하여 0.1 내지 2 중량부로 사용하면 충분하다. It is sufficient to use the amount in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the graft rubber latex.
또한 상기 응집 공정은 그라프트 고무 라텍스에 금속 염 혹은 산을 투입한 후 숙성시키는 공정을 의미하는 것으로, 이때 사용되는 응집제로는 MgSO4, CaCl2, Al2(SO4)3, 황산, 인산 또는 염산, 고분자 응집제 등을 그라프트 고무 라텍스 100 중량부에 대하여 1 내지 4 중량부로 사용할 수 있다. In addition, the agglomeration process refers to a process in which a metal salt or an acid is added to the graft rubber latex and then aged. The coagulant used herein includes MgSO 4 , CaCl 2 , Al 2 (SO 4 ) 3 , sulfuric acid, phosphoric acid, or the like. Hydrochloric acid, a polymer flocculant, or the like may be used in an amount of 1 to 4 parts by weight based on 100 parts by weight of the graft rubber latex.
이같이 하여 수분 함량이 20 내지 40%인 그라프트 고무 라텍스는 수분 함량을 구체적으로는 2 내지 20%, 보다 구체적으로는 2 내지 10%로 조절한 다음 매트릭스 수지로서 스티렌-아크릴로니트릴 공중합체 및 폴리카보네이트 수지 중 1종의 수지와 활제와 혼련하고 압출 성형 및/또는 사출 성형과 같은 후 공정을 수행하게 된다. 이 같은 수분 함량 범위를 갖는 경우 본 발명에서 목적으로 하는 건조 공정을 생략할 수 있다. Thus, graft rubber latex having a water content of 20 to 40% has a water content of 2 to 20%, more specifically 2 to 10%, and then a styrene-acrylonitrile copolymer and poly as a matrix resin. One of the carbonate resins is kneaded with a lubricant and a post process such as extrusion and / or injection molding is performed. In the case of having such a water content range, the drying process may be omitted.
이때 수분 함량의 조절은 탈수기, 보다 구체적으로는 압착 탈수기를 사용하여 수분을 제거하여 20 내지 40%의 함수율을 갖는 고형분으로 분리된 후 열풍 건조 방식을 이용하여 건조된 파우더 형태로 제조한 뒤 압출기에 투입하거나, 수분이 함유된 상태의 고형분으로 압출기에 투입한 다음 압출기에서 탈수 및 수분 증발 과정을 거쳐 수분 함량 2 내지 20%로 조절할 수 있다. At this time, the moisture content is controlled to remove water using a dehydrator, more specifically, a compression dehydrator, separated into solids having a water content of 20 to 40%, and then manufactured in a powder form dried using a hot air drying method, followed by an extruder. It may be added or added to the extruder as a solid content in the water-containing state and then adjusted to a water content of 2 to 20% through the dehydration and water evaporation process in the extruder.
이때 수분 함량이 2 내지 20%인 그라프트 공중합체 20 내지 40 중량부에 매트릭스 수지 60 내지 80 중량부로 배합하여 열가소성 수지 조성물을 수득하는 것이 이후 압출 성형 및/또는 사출 성형 등의 후 공정시 생산성을 개선시킬 수 있어 바람직하다. 일례로, 본 발명의 방법에 의해 열가소성 수지 조성물을 압출 성형 또는 사출 성형시켜 수득된 성형품의 경우 하기 실시예에서 기재된 바와 같이, 열 안정성과 광택, 내충격성 및 낙구 충격강도가 모두 우수하였다. At this time, to obtain a thermoplastic resin composition by blending 60 to 80 parts by weight of the matrix resin to 20 to 40 parts by weight of the graft copolymer having a water content of 2 to 20%, the productivity during subsequent processing such as extrusion molding and / or injection molding is improved. It is preferable because it can improve. In one example, the molded article obtained by extrusion molding or injection molding the thermoplastic resin composition by the method of the present invention was excellent in both thermal stability and gloss, impact resistance and impact impact strength as described in the following examples.
이때 활제로는 에틸렌비스스테라마이드(EBA), 마그네슘 스테아레이트 등을 사용할 수 있으며, 그 사용량은 상기 그라프트 공중합체와 매트릭스 수지 총 100 중량부에 대하여 0.1 내지 5 중량부일 수 있다.In this case, the lubricant may be ethylene bissteramide (EBA), magnesium stearate, or the like, and the amount of the lubricant may be 0.1 to 5 parts by weight based on 100 parts by weight of the graft copolymer and the matrix resin.
상기에서 살펴본 바와 같이, 본 발명에 따라 고무 함량을 극대화하고 반응형 유화제를 ABS 그라프트 공중합시 적용하여 ABS 수지 내 잔류 유화제 함량을 최소화하여 열 안정화제의 추가투입 없이도 열 안정성 및 표면 광택을 향상시키고, 스티렌-아크릴로니트릴 공중합체와의 상용성을 높여 내충격성 및 낙구 충격강도가 우수한 열가소성 수지 조성물을 제조할 수 있었다.As described above, according to the present invention, the rubber content is maximized and the reactive emulsifier is applied during the ABS graft copolymerization to minimize the residual emulsifier content in the ABS resin, thereby improving thermal stability and surface gloss without adding a thermal stabilizer. , And improved compatibility with the styrene-acrylonitrile copolymer, it was possible to produce a thermoplastic resin composition excellent in impact resistance and falling ball impact strength.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술상 범위 내에서 다양한 변경 및 수정 가능함은 당업자에게 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다. Hereinafter, preferred examples are provided to help the understanding of the present invention, but the following examples are only for exemplifying the present invention, and various changes and modifications within the scope and technical scope of the present invention will be apparent to those skilled in the art. Naturally, the modifications belong to the appended claims.
실시예 1Example 1
그라프트 고무 라텍스의 제조Preparation of Graft Rubber Latex
우선, 고무 입자경이 1,000 Å이고 겔 함량이 97중량%인 소구경 고무질 라텍스 중합체 100 중량부에 아세트산 수용액 3 중량부를 1시간 동안 서서히 첨가하여 고무 입자경이 3,400 Å이고 겔 함량이 97중량%인 폴리부타디엔 고무 라텍스를 수득하였다. First, 3 parts by weight of an aqueous acetic acid solution was slowly added to 100 parts by weight of a small diameter rubbery latex polymer having a rubber particle diameter of 1,000 mm 3 and a gel content of 97% by weight for 1 hour, and a polybutadiene having a rubber particle diameter of 3,400 mm 3 and a gel content of 97% by weight Rubber latex was obtained.
참고로, 상기 입자경 및 입자경 분포는 다이나믹 레이져라이트 스케트링법으로 Nicomp 370HPL 기기(미국, Nicomp사 제품)를 이용하여 측정한 것이다. For reference, the particle diameter and the particle diameter distribution is measured by using a Nicomp 370HPL device (manufactured by Nicomp, USA) by the dynamic laser light scattering method.
또한 상기 겔 함량은 고무 라텍스를 묽은 산이나 금속염을 사용하여 응고한 다음 세척하여 60 ℃의 진공 오븐에서 24시간 동안 건조한 다음 얻어진 고무 덩어리를 잘게 자른 다음 1g의 고무 절편을 톨루엔 100g에 넣고 48 시간 동안 실온의 암실에서 보관한 다음 졸과 겔로 분리하고, 하기 식을 이용하여 겔 함량을 측정한 것이다. In addition, the gel content of the rubber latex solidified with dilute acid or metal salt and then washed, dried in a vacuum oven at 60 ℃ for 24 hours, finely chopped the obtained rubber mass, and then put the 1g rubber section into 100g of toluene for 48 hours It is stored in a dark room at room temperature and then separated into a sol and a gel, the gel content is measured using the following formula.
[식 1][Equation 1]
겔 함량(%) = 불용분(겔)의 무게/시료의 무게 x 100 Gel content (%) = weight of insolubles (gel) / weight of sample x 100
그런 다음 질소 치환된 중합 반응기(오토크레이브)에 상기 폴리부타디엔 고무 라텍스 65 중량부(고형분 기준)와 이온교환수 140 중량부, 스티렌 5 중량부, 및 아크릴로니트릴 2 중량부를 투입한 다음 반응기 온도를 50 ℃로 유지한 채 큐멘 하이드로 퍼옥사이드 0.05 중량부 및 피로인산 나트륨 0.09 중량부, 덱스트로스 0.12 중량부, 및 황화제1철 0.002 중량부를 일괄 투입하였다. Then, 65 parts by weight of the polybutadiene rubber latex (based on solids), 140 parts by weight of ion-exchanged water, 5 parts by weight of styrene, and 2 parts by weight of acrylonitrile were added to a nitrogen-substituted polymerization reactor (autoclave). 0.05 parts by weight of cumene hydroperoxide, 0.09 parts by weight of sodium pyrophosphate, 0.12 parts by weight of dextrose, and 0.002 parts by weight of ferrous sulfide were added at a constant temperature of 50 ° C.
이어서 스티렌 20 중량부와 아크릴로니트릴 8 중량부, 3급 도데실메르캅탄 0.4 중량부와 큐멘 하이드로퍼옥사이드 0.12 중량부의 혼합액을 2시간 동안 75 ℃까지 승온하면서 연속 투입하였다. 2시간 경과 후 중합 전환율은 93%에 도달하였다. Subsequently, a mixture of 20 parts by weight of styrene, 8 parts by weight of acrylonitrile, 0.4 part by weight of tertiary dodecyl mercaptan and 0.12 part by weight of cumene hydroperoxide was continuously added while raising the temperature to 75 ° C for 2 hours. After 2 hours the polymerization conversion reached 93%.
이중 연속 투입 시작 30분 후(중합 전환율 65 내지 75% 시점) 반응형 유화제로 2-아크릴아미도-2-메틸프로판 술폰산(2-acrylamido-2-methylpropane sulfonic acid) 0.3 중량부(고형분 기준, 20% 수용액, pH 9(NaOH 처리))를 1시간 30분 동안 연속 투입하였다. 30 minutes after the start of continuous dosing (at a conversion rate of 65 to 75%) 0.3 part by weight of 2-acrylamido-2-methylpropane sulfonic acid as a reactive emulsifier (based on solids, 20 % Aqueous solution, pH 9 (treated with NaOH) was continuously added for 1 hour 30 minutes.
상기 연속 투입이 끝난 후(중합 전환율 93% 시점)에 큐멘 하이드로퍼옥사이드 0.06 중량부, 피로인산나트륨 0.04 중량부, 덱스트로스 0.06 중량부 및 황화제1철 0.001 중량부를 투입하고 80 ℃로 30분간 승온한 다음 30분간 유지하고 반응을 종료하였다. 이때 중합 전환율은 99%이었고, 고형 응고분(그라프트 공중합체 라텍스의 안정성 평가 척도) 함량은 0.03%, 그라프트율은 27%이었고 잔류 유화제 함량은 18000 ppm이었다. After completion of the continuous addition (at a polymerization conversion rate of 93%), 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 ferrous sulfide were heated to 80 ° C. for 30 minutes. The mixture was then held for 30 minutes and the reaction was terminated. At this time, the polymerization conversion rate was 99%, the solid coagulation content (scalability evaluation scale of the graft copolymer latex) was 0.03%, the graft rate was 27%, and the residual emulsifier content was 18000 ppm.
참고로, 상기 고형 응고분 함량은 하기 식을 이용하여 측정한 것이다.For reference, the solid coagulation content is measured using the following formula.
[식 2][Equation 2]
고형 응고분(%) = [반응조내 생성 응고물 무게(g)/총 고무 및 단량체의 무게(g)] x 100Solid coagulation (%) = [weight of coagulum produced in the reactor (g) / weight of total rubber and monomer (g)] x 100
상기 고형 응고분이 0.5% 이상일 때는 라텍스 안정성이 극히 떨어지며 다량의 응고물로 인해 본 발명에 적합한 그라프트 중합체를 얻기 어려운 것으로 판단할 수 있다. When the solidified solid content is more than 0.5%, latex stability is extremely low and it may be determined that graft polymer suitable for the present invention is difficult to obtain due to a large amount of coagulum.
또한, 상기 그라프트 중합체의 그라프트율(%)은 그라프트 중합체 라텍스를 응고, 세척 및 건조하여 분말 형태를 얻고, 이 분말 2g을 아세톤 300 ml에 넣고 24시간 동안 교반한 다음 용액을 초원심분리기를 이용하여 분리하고 분리된 아세톤 용액을 메탄올에 떨어뜨려 그라프트되지 않은 부분을 얻는다. 이를 건조시켜 무게를 측정한 다음 하기 식에 따라 계산하게 된다. In addition, the graft rate (%) of the graft polymer is obtained by coagulating, washing and drying the graft polymer latex to obtain a powder form, adding 2 g of this powder to 300 ml of acetone and stirring for 24 hours, and then using the ultracentrifuge for the solution. The separated acetone solution is dropped into methanol to obtain an grafted portion. It is dried to measure the weight and then calculated according to the following equation.
[식 3][Equation 3]
그라프트율(%) = 그라프트된 단량체의 무게(g)/고무질 무게(g) x 100Graft Rate (%) = Weight of Grafted Monomer (g) / Rubber Weight (g) x 100
이때 그라프트율이 20% 이하이면 광택성이 저하되어 바람직하지 않은 것으로 평할 수 있다. At this time, if the graft ratio is 20% or less, the glossiness may be lowered, which may be unfavorable.
또한 상기 그라프트 공중합체 내 잔류 유화제 함량(ppm)은 0.2g의 그라프트 공중합체 분말을 50 ml 바이알에 정확히 취하고 아세톤 10ml를 가한 다음 2시간 동안 초음파처리하여 시료를 용해시키고, 메탄올 30ml를 천천히 가하여 고분자 침전시킨다. 이후 1시간 동안 초음파 처리하여 첨가제를 추출하고, 상등액을 취출한 다음 여과하고 HPLC/DAD/MSD(Agilent 1100 system)을 사용하여 잔류 유화제 함량(ppm)을 측정한 것이다.In addition, the residual emulsifier content (ppm) in the graft copolymer is 0.2g graft copolymer powder accurately taken in 50 ml vials, 10 ml of acetone is added and sonicated for 2 hours to dissolve the sample, and slowly added 30 ml of methanol Precipitate the polymer. After sonication for 1 hour to extract the additives, the supernatant was taken out, filtered and the residual emulsifier content (ppm) was measured using HPLC / DAD / MSD (Agilent 1100 system).
이때 그라프트 고무 라텍스의 수분 함량은 50 내지 60% 범위 내이었다.At this time, the water content of the graft rubber latex was in the range of 50 to 60%.
그라프트 고무 라텍스의 응집Agglomeration of Graft Rubber Latex
상기 반응 종료된 그라프트 고무 라텍스에서 평균 입자경이 0.9 ㎛인 산화방지제(winstay-L/IR1076=0.8/0.2) 유화액 0.5 중량부를 투입한 다음 85 ℃, MgSO4 1.3 중량부 존재하에 1차 응집시키고 97 ℃에서 2차 숙성한 후 수분 함량이 30% 수준인 분말상의 그라프트 중합체를 수득하였다. 0.5 parts by weight of an antioxidant (winstay-L / IR1076 = 0.8 / 0.2) emulsion having an average particle diameter of 0.9 μm was added to the finished graft rubber latex, followed by primary aggregation in the presence of 1.3 parts by weight of 85 ° C. and MgSO 4. After secondary aging at 占 폚, a powdery graft polymer with 30% moisture content was obtained.
열가소성 수지 조성물 제조Manufacture of thermoplastic resin composition
상기 수득된 수분 함량이 30%인 분말상 그라프트 공중합체를 압착 탈수기에서 1차적으로 수분 함량이 5% 수준이 되도록 하였다. The powdered graft copolymer having a water content of 30% was first made to have a water content of 5% in a compression dehydrator.
이 수분함량이 5% 수준인 그라프트 공중합체 25 중량부에, 중량평균 분자량이 140,000 g/mol이고 아크릴로니트릴 함량이 24중량%인 스티렌-아크릴로니트릴 공중합체 75 중량부와 활제로서 에틸렌비스스테라마이드(EBA) 1.5 중량부를 첨가하고 혼련한 다음 압출 성형하여 최종 고무 함량이 15%가 되도록 시편을 제작한 후 물성들을 측정하고 하기 표 1에 함께 정리하였다. 25 parts by weight of the graft copolymer having a water content of 5%, 75 parts by weight of a styrene-acrylonitrile copolymer having a weight average molecular weight of 140,000 g / mol and an acrylonitrile content of 24% by weight, and ethylene bis as a lubricant. 1.5 parts by weight of steamide (EBA) was added, kneaded, and extruded to prepare a specimen to have a final rubber content of 15%. The physical properties were measured and summarized together in Table 1 below.
실시예 2Example 2
상기 실시예 1중 그라프트 고무 라텍스의 제조 단계에서 2-아크릴아미도-2-메틸프로판 술폰산(2-acrylamido-2-methylpropane sulfonic acid) 대신 폴리옥시에틸렌 알킬페닐 에테르 암모늄 술페이트(polyoxyethylene alkylphenyl ether ammonium sulfate, 제품명: HITENOL-BC)를 사용한 것을 제외하고는 동일한 공정을 반복하였다. Polyoxyethylene alkylphenyl ether ammonium instead of 2-acrylamido-2-methylpropane sulfonic acid in the manufacturing step of the graft rubber latex of Example 1 The same process was repeated except that sulfate, product name: HITENOL-BC) was used.
실시예 3 Example 3
상기 실시예 1 중 그라프트 고무 라텍스의 제조 단계에서 2-아크릴아미도-2-메틸프로판 술폰산(2-acrylamido-2-methylpropane sulfonic acid) 대신 알케닐 C16-18 숙신산 디-포타슘염(alkenyl C16-18 succinic acid, di-potassium salt, 제품명: Latemul ASK)를 사용한 것을 제외하고는 동일한 공정을 반복하였다. Alkenyl C16-18 succinic acid di-potassium salt (alkenyl C16-) instead of 2-acrylamido-2-methylpropane sulfonic acid in the step of preparing graft rubber latex in Example 1 The same process was repeated except that 18 succinic acid, di-potassium salt, product name: Latemul ASK) was used.
실시예 4Example 4
상기 실시예 1중 그라프트 고무 라텍스의 제조 단계에서, 상기 폴리부타디엔 고무 라텍스 70 중량부(고형분 기준)와 이온교환수 140 중량부, 스티렌 4.2 중량부, 및 아크릴로니트릴 1.8 중량부를 투입한 다음 반응기 온도를 50 ℃로 유지한 채 큐멘 하이드로 퍼옥사이드 0.05 중량부 및 피로인산 나트륨 0.09 중량부, 덱스트로스 0.12 중량부, 및 황화제1철 0.002 중량부를 일괄 투입하였다. In the manufacturing step of the graft rubber latex of Example 1, 70 parts by weight of the polybutadiene rubber latex (based on solids), 140 parts by weight of ion-exchanged water, 4.2 parts by weight of styrene, and 1.8 parts by weight of acrylonitrile were added to the reactor. 0.05 parts by weight of cumene hydroperoxide, 0.09 parts by weight of sodium pyrophosphate, 0.12 parts by weight of dextrose, and 0.002 parts by weight of ferrous sulfide were collectively added while maintaining the temperature at 50 ° C.
이어서 스티렌 16.8 중량부와 아크릴로니트릴 7.2 중량부, 3급 도데실메르캅탄 0.4 중량부와 큐멘 하이드로퍼옥사이드 0.12 중량부의 혼합액을 1시간 40분간 75 ℃까지 승온하면서 연속 투입하였다. 1시간 40분 경과 후 중합 전환율은 90 %에 도달하였다,Subsequently, a mixture of 16.8 parts by weight of styrene, 7.2 parts by weight of acrylonitrile, 0.4 part by weight of tertiary dodecyl mercaptan and 0.12 part by weight of cumene hydroperoxide was continuously added while raising the temperature to 75 ° C. for 1 hour and 40 minutes. After 1 hour and 40 minutes, the polymerization conversion reached 90%,
이중 연속 투입 시작 30분 후(중합 전환율 65 내지 75% 시점) 반응형 유화제로 2-아크릴아미도-2-메틸프로판 술폰산(2-acrylamido-2-methylpropane sulfonic acid) 0.3 중량부(고형분 기준, 20% 수용액, pH 9(NaOH 처리))를 1시간 10분 동안 연속 투입(1시간 10분 경과한 시점에 중합 전환율은 70 내지 80%)한 것을 제외하고는 실시예 1과 동일한 공정을 반복하였다. 30 minutes after the start of continuous dosing (at a conversion rate of 65 to 75%) 0.3 part by weight of 2-acrylamido-2-methylpropane sulfonic acid as a reactive emulsifier (based on solids, 20 The same process as in Example 1 was repeated except that the aqueous solution of%, pH 9 (NaOH treatment)) was continuously added for 1 hour and 10 minutes (polymerization conversion was 70 to 80% after 1 hour and 10 minutes).
실시예 5Example 5
상기 실시예 1중 그라프트 고무 라텍스의 제조 단계에서, 연속 투입 시작 30분 후(중합 전환율 65 내지 75% 시점) 반응형 유화제로 2-아크릴아미도-2-메틸프로판 술폰산(2-acrylamido-2-methylpropane sulfonic acid)을 0.3 중량부(고형분 기준, 20% 수용액, pH 9(NaOH 처리))를 0.001 중량부로 대체한 것을 제외하고는 실시예 1과 동일한 공정을 반복하였다. In the manufacturing step of the graft rubber latex of Example 1, 30 minutes after the start of continuous dosing (time of polymerization conversion 65 to 75%) 2-acrylamido-2-methylpropane sulfonic acid (2-acrylamido-2) as a reactive emulsifier The same process as in Example 1 was repeated except that 0.3 parts by weight (based on solids, 20% aqueous solution, pH 9 (NaOH treatment)) was replaced with 0.001 parts by weight of -methylpropane sulfonic acid).
실시예 6Example 6
상기 실시예 1중 그라프트 고무 라텍스의 제조 단계에서, 연속 투입 시작 30분 후(중합 전환율 65 내지 75% 시점) 반응형 유화제로 2-아크릴아미도-2-메틸프로판 술폰산(2-acrylamido-2-methylpropane sulfonic acid)을 0.3 중량부(고형분 기준, 20% 수용액, pH 9(NaOH 처리))를 2 중량부로 대체한 것을 제외하고는 실시예 1과 동일한 공정을 반복하였다. In the manufacturing step of the graft rubber latex of Example 1, 30 minutes after the start of continuous dosing (time of polymerization conversion 65 to 75%) 2-acrylamido-2-methylpropane sulfonic acid (2-acrylamido-2) as a reactive emulsifier The same process as in Example 1 was repeated except that 0.3 parts by weight (based on solids, 20% aqueous solution, pH 9 (NaOH treatment)) was replaced with 2 parts by weight of -methylpropane sulfonic acid).
비교예 1Comparative Example 1
상기 실시에 1 중 그라프트 고무 라텍스의 제조 단계에서 2-아크릴아미도-2-메틸프로판 술폰산(2-acrylamido-2-methylpropane sulfonic acid) 대신 비반응형 유화제로서 지방산 비누 0.6 중량부를 1시간 30분 동안 연속 주입한 것을 제외하고는 동일한 공정을 반복하였다. 0.6 parts by weight of fatty acid soap as a non-reactive emulsifier instead of 2-acrylamido-2-methylpropane sulfonic acid in the step of preparing graft rubber latex in Example 1 for 1 hour 30 minutes The same process was repeated except that it was continuously injected.
비교예 2Comparative Example 2
상기 실시예 1에 종래 기술에 따른 열 안정화제로서 IR1076 0.03 중량부를 투입한 것을 제외하고는 실시예 1과 동일한 실험을 반복하고 건조 공정을 거쳐 컴파운딩하였다. Except that 0.03 parts by weight of IR1076 as a heat stabilizer according to the prior art in Example 1 was repeated the same experiment as in Example 1 and compounded through a drying process.
비교예 3Comparative Example 3
상기 실시예 1 중 그라프트 고무 라텍스의 제조 단계에서 2-아크릴아미도-2-메틸프로판 술폰산(2-acrylamido-2-methylpropane sulfonic acid)를 승온 후 30분 이후부터 투입하는 대신 승온 전 반응온도 50 ℃인 시점부터 투입시킨 것을 제외하고는 실시예 1과 동일한 공정을 반복하였다. 2-acrylamido-2-methylpropane sulfonic acid in the manufacturing step of the graft rubber latex in Example 1 after the temperature increase 30 minutes after the addition of the reaction temperature before the temperature rise 50 The same process as in Example 1 was repeated except that it was added at the time of ℃.
[측정항목][Metric]
상기 실시예 1-6 및 비교예 1-3에서 제조한 ABS 시편의 물성을 하기와 같은 방법으로 측정하였다. Physical properties of the ABS specimens prepared in Examples 1-6 and Comparative Examples 1-3 were measured in the following manner.
*아이조드 충격강도: 시편의 두께를 1/4" inch로 하여 ASTM D256 방법으로 측정하였다. * Izod impact strength : The thickness of the specimen was measured by ASTM D256 method to 1/4 "inch.
*유동지수(MI: melt flow index): 220 ℃/10kg 하에 ASTM D1238 방법으로 측정하였다. * Melt flow index (MI): measured by ASTM D1238 under 220 ° C / 10kg.
*인장강도: ASTM D638 방법으로 측정하였다. Tensile strength : measured by ASTM D638 method.
*표면 광택: 45°각도에서 ASTM D528 방법으로 측정하였다. Surface gloss: measured by ASTM D528 method at a 45 ° angle.
*체류 광택: 압출기에서 얻어진 펠렛을 사출기에 넣고 270 ℃ 조건하에 15분간 체류시킨 후 광택 시편을 얻고, 이를 200 ℃에서 체류 없이 사출한 시편과 같이 45 ° 광택을 측정하고 이에 대한 편차를 측정하였다. 수치가 작을수록 체류광택이 우수한 것을 나타낸다. * Plant gloss: The pellet obtained from the extruder was placed in the injection machine and held for 15 minutes under the conditions of 270 ° C to obtain a gloss specimen, and 45 ° gloss was measured and the deviation thereof was measured like the specimen injected without staying at 200 ° C. Smaller values indicate better retention gloss.
*체류 변색( △ E): 체류 광택을 측정하는 방법과 동일한 방법으로 얻어진 광택 시편에 대하여 슈가 칼라 컴퓨터(Suga color computer)를 이용하여 체류 전후 시편에 대한 L,a,b 값을 구하고 하기 식에 의거하여 체류변색 정도를 구하였다.* Retention Discoloration ( △ E) : For the gloss specimen obtained by the same method as the method of measuring the retention gloss, L, a, b values for the specimens before and after the retention were obtained using a sugar color computer. Based on the degree of retention discoloration was obtained.
[식 4][Equation 4]
Figure PCTKR2012010548-appb-I000001
Figure PCTKR2012010548-appb-I000001
*낙구충격강도: ASTM D3783 방법으로 측정하였다. * Dropping impact strength: measured by ASTM D3783 method.
표 1
구분 실시예 비교예
1 2 1 2 3 4 5 6 1 2 3
고무라텍스 입경(Å)/겔 함량(중량%) 3400/97
함량(중량부) 65 65 65 70 65 65 65 65 65
단량체* 혼합물 투입방식 일괄(1단계)/연속(2단계) 7/28 7/28 7/28 6/24 7/28 7/28 7/28 7/28 7/28
(비)반응형유화제 중량부 0.3 0.3 0.3 0.3 0.001 2 0.6 0.3 0.3
중합결과 중합전환율(%) 99 98.9 98.9 99.2 98.5 99.1 97.5 98 97.5
고형응고분(%) 0.03 0.02 0.03 0.05 0.05 0.02 0.12 0.05 0.8
그라프트율(%) 27 26.5 27 25 26.5 27 19 26 22
잔류 유화제 함량(ppm) 18000 18500 19000 17500 17000 19000 23000 18500 18200
물성 충격강도(kg.cm/cm) 23.5 24.0 23.8 23.2 23.0 23.5 21.0 22.5 21.0
유동성(g/10min) 21 20.8 21.3 21.3 20 22 20 21 20
인장강도(kg/cm2) 515 512 510 508 510 516 515 513 505
표면광택 109.5 108.5 108.8 108.2 106.5 107.5 106.5 108.0 106.0
백색도 57 57 56 58 58 56 55 54 53
체류광택 2.5 2.6 2.8 2.1 2.5 4.0 5.5 3.8 2.7
체류열변색 3.5 3.6 3.8 3.3 3.4 3.8 6.2 4.0 3.8
낙구충격(F,N) 4020 4025 4030 4000 4030 3960 3880 3800 3750
낙구충격(E,J) 32 33 33 31 30 29 28 30 28
Table 1
division Example Comparative example
One 2 One 2 3 4 5 6 One 2 3
Rubber Latex Particle size / gel content (% by weight) 3400/97
Content (parts by weight) 65 65 65 70 65 65 65 65 65
Monomer * mixture Bulk (1st level) / Continuous (2nd level) 7/28 7/28 7/28 6/24 7/28 7/28 7/28 7/28 7/28
(Non) reactive emulsion Parts by weight 0.3 0.3 0.3 0.3 0.001 2 0.6 0.3 0.3
Polymerization Result Polymerization Conversion Rate (%) 99 98.9 98.9 99.2 98.5 99.1 97.5 98 97.5
Solid Coagulation (%) 0.03 0.02 0.03 0.05 0.05 0.02 0.12 0.05 0.8
Graft Rate (%) 27 26.5 27 25 26.5 27 19 26 22
Residual Emulsifier Content (ppm) 18000 18500 19000 17500 17000 19000 23000 18500 18200
Properties Impact Strength (kg.cm/cm) 23.5 24.0 23.8 23.2 23.0 23.5 21.0 22.5 21.0
Fluidity (g / 10min) 21 20.8 21.3 21.3 20 22 20 21 20
Tensile Strength (kg / cm 2 ) 515 512 510 508 510 516 515 513 505
Surface gloss 109.5 108.5 108.8 108.2 106.5 107.5 106.5 108.0 106.0
Whiteness 57 57 56 58 58 56 55 54 53
Staying gloss 2.5 2.6 2.8 2.1 2.5 4.0 5.5 3.8 2.7
Retention heat discoloration 3.5 3.6 3.8 3.3 3.4 3.8 6.2 4.0 3.8
Falling Shock (F, N) 4020 4025 4030 4000 4030 3960 3880 3800 3750
Falling impact (E, J) 32 33 33 31 30 29 28 30 28
*스티렌 및 아크릴로니트릴 합량* Total styrene and acrylonitrile
상기 표 1에서 보듯이, 본 발명에 따라 제조된 실시예 1-6의 경우 별도의 열 안정화제를 사용하지 않고도 열 안정성 및 광택이 우수할 뿐 아니라 제조 도중 건조 공정을 거치지 않아 ABS 수지의 내충격성 및 낙구 충격강도 등이 우수한 것을 확인할 수 있었다. As shown in Table 1, in the case of Examples 1-6 manufactured according to the present invention not only excellent thermal stability and gloss without using a separate heat stabilizer, but also the impact resistance of the ABS resin does not undergo a drying process during manufacturing And it was confirmed that falling impact strength and the like is excellent.
한편, 반응형 유화제가 아닌 비반응형 유화제를 사용한 비교예 1의 경우에는 충격강도, 유동성, 표면광택, 백색도, 체류광택, 체류 열변색, 낙구 충격강도 등 전 측정 분야에 걸쳐 실시예 1-6보다 불량한 결과를 확인할 수 있었다. On the other hand, in the case of Comparative Example 1 using a non-reactive emulsifier rather than a reactive emulsifier, Examples 1-6 throughout all measurement fields, such as impact strength, fluidity, surface gloss, whiteness, retention gloss, retention thermochromic, falling impact strength Better results could be confirmed.
또한, 종래 투입하던 열 안정제를 투입한 비교예 2의 경우 열 안정제를 별도로 투입하지 않은 실시예 1-6과 유사하거나 동등한 측정 물성을 보이는 것을 확인할 수 있었다. In addition, in the case of Comparative Example 2 in which the thermal stabilizer was added conventionally, it was confirmed that the measurement properties similar or equivalent to those of Example 1-6, in which the thermal stabilizer was not separately added.
나아가, 반응형 유화제를 사용하되, 투입 시기를 달리한 비교예 3의 경우에는 충격강도, 유동성, 표면광택, 백색도, 낙구 충격강도 등의 측정 분야에서 실시예 1-6 보다 불량한 결과를 갖는 것을 또한 확인할 수 있었다.Furthermore, in the case of Comparative Example 3 using a reactive emulsifier, but with different timings, it was also worse than Example 1-6 in the field of measurement of impact strength, fluidity, surface gloss, whiteness, falling impact strength, etc. I could confirm it.

Claims (20)

  1. a)고무 강화 수지와 b) 매트릭스 수지를 포함하되, a) rubber reinforced resins and b) matrix resins,
    상기 a)고무 강화 수지는 고무질 중합체 라텍스, 방향족 비닐 화합물, 비닐시안 화합물 및 반응형 유화제를 포함하고 그라프트 공중합에 의해 수득되는 ABS계 열가소성 수지인 것을 특징으로 하는 열 안정화제 프리 열가소성 수지 조성물.The a) rubber reinforcing resin is a heat stabilizer-free thermoplastic resin composition, characterized in that the ABS-based thermoplastic resin comprising a rubbery polymer latex, an aromatic vinyl compound, a vinyl cyan compound and a reactive emulsifier and obtained by graft copolymerization.
  2. 제1항에 있어서, The method of claim 1,
    상기 b) 매트릭스 수지는 스티렌-아크릴로니트릴 공중합체 및 폴리카보네이트 수지 중에서 선택된 1종 이상의 수지인 것을 특징으로 하는 열 안정화제 프리 열가소성 수지 조성물. The b) matrix resin is a heat stabilizer-free thermoplastic resin composition, characterized in that at least one resin selected from styrene-acrylonitrile copolymer and polycarbonate resin.
  3. 제2항에 있어서, The method of claim 2,
    상기 b) 매트릭스 수지는 중량평균 분자량은 60,000 내지 200,000 g/mol 범위이고, 아크릴로니트릴 함량이 15 내지 40중량%인 스티렌-아크릴로니트릴 공중합체를 사용하는 것을 특징으로 하는 열 안정화제 프리 열가소성 수지 조성물.The b) matrix resin is a heat stabilizer-free thermoplastic resin, characterized in that the weight average molecular weight is in the range of 60,000 to 200,000 g / mol, the styrene-acrylonitrile copolymer having an acrylonitrile content of 15 to 40% by weight Composition.
  4. 제1항에 있어서, The method of claim 1,
    상기 고무질 중합체는 입자경이 2500 내지 5000 Å이고, 겔 함량은 85 내지 99 중량%인 것으로, 고무 강화 수지용 단량체 총 100 중량부 기준으로 60 내지 75 중량부로 포함되는 것을 특징으로 하는 열 안정화제 프리 열가소성 수지 조성물.The rubbery polymer has a particle diameter of 2500 to 5000 mm 3 and a gel content of 85 to 99% by weight, based on a total of 100 parts by weight of the monomer for rubber-reinforced resin, heat stabilizer free thermoplastic, characterized in that Resin composition.
  5. 제1항에 있어서, The method of claim 1,
    상기 방향족 비닐 화합물은 스티렌, α-메틸스티렌, p-메틸스티렌, 비닐 톨루엔, t-부틸 스티렌, 클로로스티렌 또는 이들의 치환체 등을 단독 또는 2종 이상 혼합하여 고무 강화 수지용 단량체 총 100 중량부 기준으로 18 내지 28 중량부 범위 내로 사용하는 것을 특징으로 하는 열 안정화제 프리 열가소성 수지 조성물.The aromatic vinyl compound is based on a total of 100 parts by weight of monomers for rubber-reinforced resins by mixing styrene, α-methylstyrene, p-methylstyrene, vinyl toluene, t-butyl styrene, chlorostyrene, or a substituent thereof alone or in combination of two or more thereof. Heat stabilizer-free thermoplastic resin composition, characterized in that used within the range of 18 to 28 parts by weight.
  6. 제1항에 있어서, The method of claim 1,
    상기 비닐시안화 화합물로는 아크릴로니트릴, 메타크릴로니트릴 또는 이들의 치환체를 단독 또는 2종 이상 혼합하여 고무 강화 수지용 단량체 총 100 중량부 기준으로 5 내지 15 중량부 범위 내로 사용하는 것을 특징으로 하는 열 안정화제 프리 열가소성 수지 조성물.As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, or a substituent thereof may be used alone or in a mixture of two or more thereof, and used within a range of 5 to 15 parts by weight based on 100 parts by weight of the total monomers for rubber-reinforced resins. Heat stabilizer free thermoplastic resin composition.
  7. 제1항에 있어서, The method of claim 1,
    상기 반응형 유화제는 카보네이트, 술포네이트, 및 술페이트로 이루어진 그룹으로부터 선택된 작용기를 1종 이상 포함하는 유화제를 고무 강화 수지용 단량체 총 100 중량부 기준으로 0.001 내지 2 중량부 범위 내로 사용하는 것을 특징으로 하는 열 안정화제 프리 열가소성 수지 조성물.The reactive emulsifier is characterized in that for using an emulsifier comprising at least one functional group selected from the group consisting of carbonate, sulfonate, and sulfate in the range of 0.001 to 2 parts by weight based on a total of 100 parts by weight of monomer for rubber-reinforced resin. A heat stabilizer free thermoplastic resin composition.
  8. 제6항에 있어서, The method of claim 6,
    상기 반응형 유화제는 술포에틸 메타크릴레이트(sulfoethyl methacrylate), 2-아크릴아미도-2-메틸프로판 술폰산(2-acrylamido-2-methylpropane sulfonic acid), 소디움 스티렌 술포네이트(sodium styrene sulfonate), 소디움 도데실 알릴 술포숙시네이트(sodium dodectyl allyl sulfosuccinate), 스티렌과 소디움 도데실 알릴 술포숙시네이트 공중합체, 폴리옥시에틸렌 알킬페닐 에테르 암모늄 술페이트(polyoxyethylene alkylphenyl ether ammonium sulfate), 알케닐 C16-18 숙신산 디-포타슘염(alkenyl C16-18 succinic acid, di-potassium salt) 및 소디움 메트알릴 술포네이트(sodium methallyl sulfonate) 중에서 선택된 1종 이상인 것을 특징으로 하는 열 안정화제 프리 열가소성 수지 조성물.The reactive emulsifier is sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, sodium styrene sulfonate, sodium dode Sodium dodectyl allyl sulfosuccinate, styrene and sodium dodecyl allyl sulfosuccinate copolymer, polyoxyethylene alkylphenyl ether ammonium sulfate, alkenyl C16-18 succinic acid di Heat stabilizer-free thermoplastic resin composition, characterized in that at least one selected from potassium salt (alkenyl C16-18 succinic acid, di-potassium salt) and sodium methallyl sulfonate (sodium methallyl sulfonate).
  9. 제1항에 있어서,The method of claim 1,
    상기 a) 고무 강화 수지는 분자량 조절제를 고무 강화 수지용 단량체 총 100 중량부 기준으로 0.1 내지 1 중량부 범위 내로 포함하는 것을 특징으로 하는 열 안정화제 프리 열가소성 수지 조성물.The a) rubber reinforcing resin is a heat stabilizer-free thermoplastic resin composition comprising a molecular weight regulator in the range of 0.1 to 1 part by weight based on a total of 100 parts by weight of monomer for rubber reinforcing resin.
  10. 제1항에 있어서, The method of claim 1,
    상기 a) 고무 강화 수지는 중합 개시제를 고무 강화 수지용 단량체 총 100 중량부 기준으로 0.05 내지 0.5 중량부 범위 내로 포함하는 것을 특징으로 하는 열 안정화제 프리 열가소성 수지 조성물.The a) rubber reinforcing resin is a heat stabilizer-free thermoplastic resin composition comprising a polymerization initiator in the range of 0.05 to 0.5 parts by weight based on a total of 100 parts by weight of monomers for rubber reinforcing resin.
  11. 제1항에 있어서, The method of claim 1,
    상기 a) 고무 강화 수지 20 내지 40 중량부에, b) 매트릭스 수지 60 내지 80 중량부를 배합하는 것을 특징으로 하는 열 안정화제 프리 열가소성 수지 조성물.A thermal stabilizer-free thermoplastic resin composition comprising a) 20 to 40 parts by weight of a) rubber reinforcement resin, and b) 60 to 80 parts by weight of matrix resin.
  12. 제1항에 있어서, The method of claim 1,
    상기 a) 고무 강화 수지의 잔류 유화제 함량은 투입된 유화제 총 100 중량% 기준으로 65 중량% 이하인 것을 특징으로 하는 열 안정화제 프리 열가소성 수지 조성물.Residual emulsifier content of the a) rubber reinforced resin is a heat stabilizer-free thermoplastic resin composition, characterized in that 65% by weight or less based on the total 100% by weight of the emulsifier.
  13. a) 제1항 내지 제12항 중 어느 한 항의 열 안정화제 프리 열가소성 수지 조성물중 고무 강화 수지를 수분 함량이 45 내지 70%인 열 안정화제 프리 그라프트 공중합체 라텍스로서 제조하는 단계; a) preparing a rubber-reinforced resin in the heat stabilizer free thermoplastic resin composition of any one of claims 1 to 12 as a heat stabilizer free graft copolymer latex having a water content of 45 to 70%;
    b)상기 열 안정화제 프리 그라프트 공중합체 라텍스를 산화방지 처리 및 응집시켜 수분 함량이 20 내지 40%인 그라프트 공중합체 라텍스를 수득하는 단계; 및 b) antioxidant treatment and aggregation of the heat stabilizer free graft copolymer latex to obtain a graft copolymer latex having a water content of 20 to 40%; And
    c)상기 그라프트 공중합체 라텍스를 수분 함량을 2 내지 20 %로 조절한 다음 제1항의 열 안정화제 프리 열가소성 수지 조성물 중 매트릭스 수지와 활제를 혼련하는 단계;를 특징으로 하는 열가소성 수지 조성물의 제조방법.c) controlling the graft copolymer latex to a water content of 2 to 20%, and then kneading the matrix resin and the lubricant in the heat stabilizer-free thermoplastic resin composition of claim 1; .
  14. 제13항에 있어서, The method of claim 13,
    상기 a)단계는 상기 고무 강화 수지를 구성하는 전체 단량체의 5 내지 40 중량%를 반응 초기에 일괄 투입하고 나머지 잔부를 연속 투입하는 것을 특징으로 하는 열가소성 수지 조성물의 제조방법.Step a) is a method for producing a thermoplastic resin composition, characterized in that 5 to 40% by weight of all the monomers constituting the rubber-reinforced resin in a batch at the beginning of the reaction and the remainder is continuously added.
  15. 제13항에 있어서, The method of claim 13,
    상기 a)단계에 사용되는, 제1항의 열 안정화제 프리 열가소성 수지 조성물 중 반응형 유화제는 중합 전환율 65 내지 75%에서 연속 투입하는 것을 특징으로 하는 열가소성 수지 조성물의 제조방법.Reactive emulsifier in the heat stabilizer-free thermoplastic resin composition of claim 1, used in step a) is a method of producing a thermoplastic resin composition characterized in that the continuous conversion at a polymerization conversion of 65 to 75%.
  16. 제13항에 있어서, The method of claim 13,
    상기 b)단계에서 산화 방지 공정은 입경이 0.5 내지 2 ㎛로 유화된 페놀계 산화방지제, 인계 또는 황계 산화방지제를 그라프트 고무 라텍스 100 중량부에 대하여 0.1 내지 2 중량부 범위 내에서 40 내지 80 ℃의 그라프트 고무 라텍스에 서서히 투입하여 응집 공정 이전까지 연속 교반하는 것을 특징으로 하는 열가소성 수지 조성물의 제조방법.The antioxidant process in step b) is 40 to 80 ℃ within the range of 0.1 to 2 parts by weight of phenol-based antioxidant, phosphorus or sulfur-based antioxidant emulsified in the particle size of 0.5 to 2 ㎛ with respect to 100 parts by weight of the graft rubber latex A method of producing a thermoplastic resin composition, characterized in that the solution is gradually added to the graft rubber latex and continuously stirred until the aggregation process.
  17. 제13항에 있어서, The method of claim 13,
    상기 b) 단계에서 응집 공정은 그라프트 고무 라텍스에 MgSO4, CaCl2, Al2(SO4)3, 황산, 인산, 염산으로부터 선택된 1종 이상 또는 고분자 응집제를 그라프트 고무 라텍스 100 중량부 기준으로 1 내지 4 중량부 함량으로 투입한 후 숙성시키는 것을 특징으로 하는 열가소성 수지 조성물의 제조방법.In the b) step, the coagulation process is based on 100 parts by weight of the graft rubber latex or at least one polymer coagulant selected from MgSO 4 , CaCl 2 , Al 2 (SO 4 ) 3 , sulfuric acid, phosphoric acid and hydrochloric acid in the graft rubber latex Method of producing a thermoplastic resin composition, characterized in that the aging after adding to 1 to 4 parts by weight.
  18. 제13항에 있어서, The method of claim 13,
    상기 c) 단계에서 수분 함량 2 내지 20%로의 조절은 탈수 공정을 통해 수행되는 것을 특징으로 하는 열가소성 수지 조성물의 제조방법.The control method of the c 2 to 20% moisture content in the step c) is carried out through a dehydration process.
  19. 제13항에 있어서, The method of claim 13,
    상기 c)단계에서 수분 함량이 2 내지 20%로 조절된 그라프트 공중합체 20 내지 40 중량부에 매트릭스 수지 60 내지 80 중량부를 배합하는 것을 특징으로 하는 열가소성 수지 조성물의 제조방법.The method of producing a thermoplastic resin composition, characterized in that in the step c) blending 60 to 80 parts by weight of the matrix resin to 20 to 40 parts by weight of the graft copolymer having a water content of 2 to 20%.
  20. 제13항에 있어서, The method of claim 13,
    상기 c)단계에 투입되는 활제는 그라프트 공중합체와 매트릭스 수지의 총 100 중량부 기준으로 0.1 내지 5 중량부인 것을 특징으로 하는 열가소성 수지 조성물의 제조방법.The lubricant in step c) is 0.1 to 5 parts by weight based on a total of 100 parts by weight of the graft copolymer and the matrix resin.
PCT/KR2012/010548 2012-01-11 2012-12-06 Thermal stabilizer-free thermoplastic resin composition and method for manufacturing same WO2013105737A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105026491A (en) * 2013-08-02 2015-11-04 Lg化学株式会社 Production method for rubber-reinforced thermoplastic resin
US20160096957A1 (en) * 2013-06-28 2016-04-07 Lg Chem, Ltd. Method of preparing thermoplastic resin composition having superior surface clearness and gloss

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020003434A (en) * 2000-07-03 2002-01-12 노기호 Process for preparing thermoplastic resin having superior heat-stability
KR20040057408A (en) * 2002-12-26 2004-07-02 주식회사 엘지화학 Perparation of thermoplastic resin composition having excellent thermal stability and power properties
KR20040067424A (en) * 2003-01-23 2004-07-30 주식회사 엘지화학 Method for preparing of acrylonitrile-butadiene-styrene graft copolymer
KR20060042465A (en) * 2004-11-09 2006-05-15 주식회사 엘지화학 Method for producing thermoplastic resin
KR20080070399A (en) * 2007-01-26 2008-07-30 주식회사 엘지화학 Abs resin having good surface property, good colorability and heat resistance and a method for the preparation thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020003434A (en) * 2000-07-03 2002-01-12 노기호 Process for preparing thermoplastic resin having superior heat-stability
KR20040057408A (en) * 2002-12-26 2004-07-02 주식회사 엘지화학 Perparation of thermoplastic resin composition having excellent thermal stability and power properties
KR20040067424A (en) * 2003-01-23 2004-07-30 주식회사 엘지화학 Method for preparing of acrylonitrile-butadiene-styrene graft copolymer
KR20060042465A (en) * 2004-11-09 2006-05-15 주식회사 엘지화학 Method for producing thermoplastic resin
KR20080070399A (en) * 2007-01-26 2008-07-30 주식회사 엘지화학 Abs resin having good surface property, good colorability and heat resistance and a method for the preparation thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160096957A1 (en) * 2013-06-28 2016-04-07 Lg Chem, Ltd. Method of preparing thermoplastic resin composition having superior surface clearness and gloss
US9920153B2 (en) * 2013-06-28 2018-03-20 Lg Chem, Ltd. Method of preparing thermoplastic resin composition having superior surface clearness and gloss
CN105026491A (en) * 2013-08-02 2015-11-04 Lg化学株式会社 Production method for rubber-reinforced thermoplastic resin
CN105026491B (en) * 2013-08-02 2017-11-28 Lg化学株式会社 The preparation method of rubber reinforcement thermoplastic resin
US9932472B2 (en) 2013-08-02 2018-04-03 Lg Chem, Ltd. Production method for rubber-reinforced thermoplastic resin

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