KR100199090B1 - Thermoplastic resins and preparation thereof - Google Patents

Thermoplastic resins and preparation thereof Download PDF

Info

Publication number
KR100199090B1
KR100199090B1 KR1019950041089A KR19950041089A KR100199090B1 KR 100199090 B1 KR100199090 B1 KR 100199090B1 KR 1019950041089 A KR1019950041089 A KR 1019950041089A KR 19950041089 A KR19950041089 A KR 19950041089A KR 100199090 B1 KR100199090 B1 KR 100199090B1
Authority
KR
South Korea
Prior art keywords
weight
rubbery polymer
thermoplastic resin
particle diameter
polymerization
Prior art date
Application number
KR1019950041089A
Other languages
Korean (ko)
Other versions
KR970027131A (en
Inventor
최장현
김광윤
박상훈
이기호
임동수
Original Assignee
사공수영
금호케미칼주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 사공수영, 금호케미칼주식회사 filed Critical 사공수영
Priority to KR1019950041089A priority Critical patent/KR100199090B1/en
Publication of KR970027131A publication Critical patent/KR970027131A/en
Application granted granted Critical
Publication of KR100199090B1 publication Critical patent/KR100199090B1/en

Links

Classifications

    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Abstract

본 발명은 열가소성수지와 이의 제조방법에 관한 것으로서, 더욱 상세하게는 평균입경이 서로 다른 고무질 중합체 혼합물을 그라프트 본체로 하고 여기에 방향족 비닐화합물, 비닐시안화 화합물 및 아크릴계 화합물 등의 단량체를 그라프트 중합시켜 고충격성 등의 물리적 성질이 우수하면서도 백색도 및 광택도가 우수한 열가소성수지와 이의 제조방법에 관한 것이다.The present invention relates to a thermoplastic resin and a method for producing the same, and more particularly, to a graft main body of a rubbery polymer mixture having a different average particle diameter, and graft polymerization of monomers such as aromatic vinyl compounds, vinyl cyanide compounds, and acrylic compounds. The present invention relates to a thermoplastic resin having excellent physical properties such as high impact properties and excellent whiteness and glossiness, and a method of manufacturing the same.

Description

열가소성수지와 이의 제조방법Thermoplastic and its manufacturing method

본 발명은 열가소성수지와 이의 제조방법에 관한 것으로서, 더욱 상세하게는 평균입경이 서로 다른 고무질 중합체 혼합물을 그라프트 본체로 하고 여기에 방향족 비닐화합물, 비닐시안화 화합물 및 아크릴계 화합물 등의 단량체를 그라프트 중합시켜 고충격성 등의 물리적 성질이 우수하면서도 백색도 및 광택도가 우수한 열가소성수지와 이의 제조방법에 관한 것이다.The present invention relates to a thermoplastic resin and a method for producing the same, and more particularly, to a graft main body of a rubbery polymer mixture having a different average particle diameter, and graft polymerization of monomers such as aromatic vinyl compounds, vinyl cyanide compounds, and acrylic compounds. The present invention relates to a thermoplastic resin having excellent physical properties such as high impact properties and excellent whiteness and glossiness, and a method of manufacturing the same.

일반적으로, 가정용 전기제품의 하우징이나 자동차 부품분야에서는 내충격성과 함께 표면광택으로 대표되는 양호한 외관 등을 갖는 수지가 요구되는 바, 이러한 대표적인 수지로서 ABS 수지(아크릴로니트릴-부타디엔-스티렌)가 적용되고 있다.In general, in the housing or automotive parts of household appliances, a resin having a good appearance such as surface gloss and impact resistance is required. As such a representative resin, ABS resin (acrylonitrile-butadiene-styrene) is applied. have.

최근에는 용도의 다양화 및 복잡한 형상의 성형폼이 사용되어지면서 고급스런 제품에서는 고백색도(高白色度) 및 선명성이 요구되고 있다. 백색도 향상을 위하여 컬러링(coloring)을 하지 않은 자연색 수지에 백색안료를 첨가할 경우 백색수지는 얻을 수 있으나, 무기안료의 과량첨강 따른 물성저하가 발생하고 또한 안료 과다첨가에 따른 선명성이 저하된다.In recent years, as a variety of applications and molding foams of complex shapes are used, high-quality whiteness and sharpness are required in high-quality products. When white pigment is added to natural color resin without coloring to improve whiteness, white resin can be obtained. However, deterioration of physical properties occurs due to excessive addition of inorganic pigments, and the sharpness of pigments is excessively reduced.

따라서 충격강도가 우수하면서 고백색도와 고광택특성을 갖는 수지를 제조하기 위한 각종 제조방법이 연구되고 있다. 일본특허출원공고 소62-59,726호 및 일본특허출원공개 소61-203,158호에서는 괴상중합방법을 도입하여 백색도를 개선하고자 하였으나, 이러한 방법에 의해서는 고무입자의 크기 조절이 어렵기 때문에 이에 의해 제조된 열가소성수지는 충격강도 및 광택도가 크게 저하되었다. 또한 일본특허출원공고 소50-17,227호에서는 충격강도를 향상시키기 위하여 유화중합 고무를 이용한 괴상중합을 시도하였으나, 충격강도는 약간 개선되었지만 일반 유화중합으로 인한 기타 물성이 저하되는 문제가 있다. 이밖에도 열안정성을 개선하고자 하는 일반적인 방법으로서 산화방지제를 압출전에 첨가하는 방법에 있으나 이는 근본적인 해결방법이 될 수 없었다.Therefore, various manufacturing methods for producing a resin having excellent impact strength and high whiteness and high gloss characteristics have been studied. Japanese Patent Application Publication No. 62-59,726 and Japanese Patent Application Publication No. 61-203,158 attempted to improve the whiteness by introducing a bulk polymerization method, but it was difficult to control the size of the rubber particles. Thermoplastic resins were greatly reduced in impact strength and gloss. In addition, Japanese Patent Application Publication No. 50-17,227 tried mass polymerization using an emulsion polymerization rubber to improve impact strength, but the impact strength is slightly improved, but there is a problem that other physical properties are lowered due to general emulsion polymerization. In addition, a general method for improving thermal stability is to add an antioxidant before extrusion, but this cannot be a fundamental solution.

이에 본 발명에서는 일단 단시간 중합공정을 거쳐 소입경 고무질 중합체를 제조하고 이것의 일부를 고분자 응집제, 산 또는 산염의 전해질 첨가에 의한 입자 비대화과정을 거쳐 제조한 대입경 고무질 중합체를 혼합한 고무질 중합체 혼합물을 그라프트 본체로하고, 여기에 방향족 비닐화합물 단량체와 비닐시안화 단량체 및 아크릴계 화합물 단량체 중에서 선택된 단량체 혼합물을 그라프트 중합시키되 고무질 중합체의 조성과 종류, 입경, 겔 함량 및 팽윤지수 등을 적절히 선택하고 단량체 혼합물의 첨가방법 등의 중합조건을 적절히 조절하여 물리적 특성이 우수하면서 자연색의 백색도 및 광택도가 대폭 개선되어 공업적으로 유리하게 사용될 수 있는 열가소성수지를 제조하므로써 본 발명을 완성하였다.Accordingly, in the present invention, a rubber polymer mixture is prepared by mixing a large particle rubber polymer prepared by producing a small particle rubbery polymer through a short-time polymerization process, and a part of which is obtained through a particle enlargement process by adding an electrolyte of a polymer flocculant, an acid or an acid salt. The graft body, and graft polymerization of a monomer mixture selected from an aromatic vinyl compound monomer, a vinyl cyanide monomer and an acrylic compound monomer, graft polymer composition, the appropriate composition and type of the rubbery polymer, particle size, gel content and swelling index, etc. The present invention has been completed by preparing a thermoplastic resin which can be used industrially advantageously by adjusting the polymerization conditions such as the method of addition, and having excellent physical properties while greatly improving the whiteness and gloss of natural colors.

따라서 본 발명은 내충격성을 비롯한 제반물성이 뛰어나면서 자연색의 백색도 및 광택특성이 우수한 열가소성수지를 제공하는 데 그 목적이 있다.Therefore, an object of the present invention is to provide a thermoplastic resin having excellent whiteness and gloss characteristics of natural colors while having excellent physical properties including impact resistance.

이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명은 중량 평균입경이 0.05~0.20㎛인 소입경 고무질 중합체 50~80 중량%(고형분 환산)와 중량 평균입경이 0.4~1.0㎛인 대입경 고무질 중합체 20~50 중량%(고형분 환산)로 이루어진 고무질 중합체 혼합물(A) 50~80 중량%와 비닐 방향족 화합물 단량체 60~80 중량% 및 비닐시안화 화합물과 아크릴계 화합물 중에서 선택된 1종 또는 2종 이상의 단량체 20~40 중량%로 이루어진 단량체 혼합물(B) 20~50 중량%가 그라프트 유화중합된 열가소성수지를 그 특징으로 한다.The present invention comprises 50 to 80% by weight (in terms of solids) of small particle rubbery polymers having a weight average particle diameter of 0.05 to 0.20 µm and 20 to 50% by weight (in terms of solids) of a large particle rubbery polymer having a weight average particle diameter of 0.4 to 1.0 µm. A monomer mixture (B) comprising 50 to 80% by weight of a rubbery polymer mixture (A), 60 to 80% by weight of a vinyl aromatic compound monomer and 20 to 40% by weight of one or two or more monomers selected from a vinyl cyanide compound and an acrylic compound. It is characterized by -50 wt% graft emulsion-polymerized thermoplastic resin.

이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.

본 발명은 입경이 서로 다른 고무질 중합체 혼합물에 비닐 방향족 화합물 단량체, 비닐시안화 화합물 단량체 및 아크릴 화합물 단량체를 일정비율로 그라프트 중합시킴으로써 충격강도 및 인장강도를 비롯한 제반물성이 우수하면서도 백색도 및 광택도가 우수한 열가소성수지와 이의 제조방법에 관한 것이다.According to the present invention, graft polymerization of vinyl aromatic compound monomers, vinyl cyanide compound monomers, and acrylic compound monomers with rubber particles having different particle diameters at a predetermined ratio results in excellent physical properties including impact strength and tensile strength, and excellent whiteness and gloss. It relates to a thermoplastic resin and a method of manufacturing the same.

본 발명의 열가소성수지의 그라프트 본체로 사용되는 고무질 중합체는 1,3-부탄디엔을 70 중량% 이상 함유하는 부타디엔과 방향족 비닐화합물 단량체 예를 들면 스티렌, α-메틸스티렌, 비닐톨루엔 등을 포함하는 라텍스이며, 고무질 중합체의 입자크기에 따라 팽윤지수와 겔 함량은 변화되고 이로 인해 물리적 특성, 백색도 및 광택도 등은 변화된다.The rubbery polymer used as the graft body of the thermoplastic resin of the present invention includes butadiene containing at least 70% by weight of 1,3-butanediene and an aromatic vinyl compound monomer such as styrene, α-methylstyrene, vinyltoluene and the like. It is a latex, and the swelling index and the gel content are changed according to the particle size of the rubbery polymer, thereby changing physical properties, whiteness and glossiness.

본 발명에서는 고무질 중합체로서 중량 평균입경이 0.05~0.20㎛인 소입경 고무질 중합체 50~80 중량%와 중량 평균입경이 0.40~1.0㎛인 대입경 고무질 중합체 20~50 중량%를 혼합한 것을 사용하는데, 이는 먼저 소입경 고무질 중합체를 미리 제조하고 소입경 고무질 중합체중의 일부를 입자 비대화시켜 대입경 고무질 중합체를 제조하여 혼합한 것이다. 만약, 전체 고무질 중합체 혼합물중에 소입경 고무질 중합체가 60 중량% 미만 함유되면 광택도가 떨어지고, 80 중량%를 초과하여 함유되면 광택도는 우수하나 고충격강도를 얻을 수 없다. 상기와 같은 조성으로 이루어진 고무질 중합체 혼합물(A)은 중량 평균입경이 0.3~0.5㎛ 겔 함량 60~90% 그리고 팽윤지수 10~30을 갖게 되는데, 만약 고무질 중합체의 평균입경, 겔 함량과 팽윤지수가 상기의 범위를 벗어나면 그라프트 중합시 그라프트 효율이 저하됨은 물론 그라프트율의 제어가 곤란하게 되어 충격강도가 저하되고 고신율의 열가소성수지를 얻을 수 없다. 또한, 본 발명의 고무질 중합체 혼합물을 구성하고 있는 대입경 고무질 중합체는 소입경 고무질 중합체를 아크릴아미드, 메타크릴아미드, 아크릴레이트 또는 메타크릴레이트-아크릴아미드 등의 고분자 응집제, 황산, 염산 또는 아세트산 등의 산, 도는 황산마그네슘, 수산화암모늄 등의 산염을 사용하여 라텍스의 안정성을 떨어뜨려 비대화시키는 방법에 의해 짧은 시간에 입자를 비대화시켜 만든 것으로서, 장시간 중합에 의한 여련색을 방지하여 최종 제품인 열가소성수지가 자연색의 색상을 그대로 유지할 수 있도록 하였다.In the present invention, the rubber polymer is a mixture of 50 to 80% by weight of the small particle rubbery polymer having a weight average particle diameter of 0.05 to 0.20 µm and 20 to 50% by weight of the large particle rubbery polymer having a weight average particle diameter of 0.40 to 1.0 µm. This is prepared by first preparing a small particle rubbery polymer in advance and enlarging a part of the small particle rubbery polymer to produce a large particle rubbery polymer and mixing them. If the total rubbery polymer mixture contains less than 60% by weight of the small-size rubbery polymer, the gloss is inferior. If it is contained in excess of 80% by weight, the gloss is excellent but high impact strength cannot be obtained. The rubbery polymer mixture (A) having the above composition has a weight average particle diameter of 0.3-0.5 μm, a gel content of 60-90%, and a swelling index of 10-30, and if the average particle diameter, gel content and swelling index of the rubbery polymer are Outside the above range, the graft efficiency is lowered during the graft polymerization, as well as the control of the graft rate becomes difficult, so that the impact strength is lowered and a high elongation thermoplastic resin cannot be obtained. In addition, the large-diameter rubbery polymer constituting the rubbery polymer mixture of the present invention may be a small particle rubbery polymer such as polymer coagulant such as acrylamide, methacrylamide, acrylate or methacrylate-acrylamide, sulfuric acid, hydrochloric acid or acetic acid, and the like. It is made by making the particles enlarge in a short time by the method of reducing the stability of latex by using acidic acid, magnesium sulfate, ammonium hydroxide or other acid salts, and preventing the red color by long time polymerization. To keep the color as it is.

상기와 같이 고무질 중합체 혼합물(A) 50~80 중량%에 또 다른 단량체 혼합물(B) 20~50 중량%를 첨가하여 유화중합방법에 의한 그라프트 중합을 수행하여 본 발명의 열가소성수지를 제조한다. 그라프트 중합시 고무질 중합체 혼합물(A)이 50 중량% 미만 사용될 경우에는 고무중합에 의한 고충격강도의 수지를 얻을 수 없고, 80 중량%를 초과하면 분체로써 그라프트 공중합체를 회수하는데 어려움이 있다.The thermoplastic resin of the present invention is prepared by adding 20-50 wt% of another monomer mixture (B) to 50-80 wt% of the rubbery polymer mixture (A) as described above to perform graft polymerization by an emulsion polymerization method. When the rubbery polymer mixture (A) is used in the graft polymerization of less than 50% by weight, it is difficult to obtain a resin of high impact strength by rubber polymerization, and when it exceeds 80% by weight, it is difficult to recover the graft copolymer as a powder. .

이때, 단량체 혼합물(B)은 스티렌, α-메틸스티렌 및 비닐톨루엔 중에서 선택된 1종 또는 2종 이상의 방향족 비닐화합물 60~80 중량%와, 아크릴로니트릴, 메타크릴로니트릴 등의 비닐시안화 화합물과 아크릴산, 메틸아크릴산, 에틸아크릴산, 프로필아크릴산, n-부틸 아크릴산, i-부틸아크릴산 및 이들의 메타아크릴산과 같은 아크릴계 화합물 중에서 선택된 1종 또는 2종 이상의 화합물 20~40 중량%로 이루어져 있다. 단량체 혼합물(B)의 조성에 있어서, 방향족 비닐화합물의 함량이 60 중량% 미만이면 비닐시안화 화합물의 함량이 증가하여 백색도가 낮아지고, 80 중량%를 초과하면 백색도는 향상되나 물성이 저하되는 문제가 있다.At this time, the monomer mixture (B) is 60 to 80% by weight of one or two or more aromatic vinyl compounds selected from styrene, α-methylstyrene and vinyltoluene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile and acrylic acid And 20 to 40% by weight of one or two or more compounds selected from acrylic compounds such as methyl acrylic acid, ethyl acrylic acid, propyl acrylic acid, n-butyl acrylic acid, i-butyl acrylic acid, and methacrylic acid thereof. In the composition of the monomer mixture (B), when the content of the aromatic vinyl compound is less than 60% by weight, the content of the vinyl cyanide compound is increased to lower the whiteness, and when it exceeds 80% by weight, the whiteness is improved but the physical properties are deteriorated. have.

또한, 본 발명에서는 최종 성형품의 외관 특성 즉, 고백색도와 고광택도의 유지를 위하여 상기 단량체 혼합물에 페놀계 산화안정제, 아민계 산화안정제, 황계 산화안정제 및 인계 산화안정제 중에서 선택된 1종 이상의 산화안정제를 고무질 중합체 혼합물(A)와 단량체 혼합물(B)의 총사용량(이하, (A)와 (B)의 총사용량이라 함)에 대하여 0.01~2.0 중량부 첨가하였다. 이때 산화안정제의 사용량이 (A)와 (B)의 총사용량 100 중량부에 대하여 0.01 중량부 미만이면 황변방지 효과를 나타낼 수 없고, 2.0 중량부를 초과하면 비용이 상승하고 온줄무늬(silver streak)가 나타나는 현상이 발생한다.In addition, in the present invention, in order to maintain the appearance characteristics of the final molded article, that is, high whiteness and high gloss, at least one oxidizing stabilizer selected from phenolic oxidizing agent, amine oxidizing stabilizer, sulfur type oxidizing stabilizer and phosphorus oxidizing stabilizer is added to the monomer mixture. 0.01 to 2.0 parts by weight of the rubber polymer mixture (A) and the monomer mixture (B) were added based on the total amount of use (hereinafter, referred to as the total amount of use of (A) and (B)). At this time, if the amount of the oxidizing stabilizer is less than 0.01 parts by weight based on 100 parts by weight of the total amount of (A) and (B), the yellowing prevention effect cannot be exhibited. When it exceeds 2.0 parts by weight, the cost increases and the silver streak What happens?

또한, 본 발명에 따른 그라프트 유화중합시 사용되는 유화제는 지방산 알칼리금속염, 지방산 황산에스테르염 및 불균화로진산 알칼리금속염 중에서 선택된 통상의 비닐단량체의 유화중합에 이용되는 유화제이며, 이들의 사용에 있어서 특별한 제한은 없으며 다만 (A)와 (B)의 총사용량 100중량부에 대하여 0.1~2.0 중량부 사용함이 바람직하다.In addition, the emulsifier used in the graft emulsion polymerization according to the present invention is an emulsifier used for the emulsion polymerization of a conventional vinyl monomer selected from fatty acid alkali metal salts, fatty acid sulfate ester salts and disproportionated rosin acid alkali metal salts, There is no limitation, but it is preferable to use 0.1 to 2.0 parts by weight based on 100 parts by weight of the total used amount of (A) and (B).

중합개시제로는 수용성이나 지용성 중합개시제 등 어느 것이나 제한없이 사용가능하며, 수용성 중합개시제로는 과황산칼륨, 과황산암모늄 등이 사용될 수 있고, 지용성 개시제로는 큐멘하이드로퍼옥시드, t-부틸퍼옥시드 또는 벤조일퍼옥시드 등이 사용될 수 있으며, 이 밖에도 유기 하이드로퍼옥시드-철염 등의 산화-환원개시제도 사용가능하다. 중합개시제는 (A)와 (B)의 총사용량 100 중량부에 대하여 0.01~0.5 중량부 사용함이 바람직하다.As the polymerization initiator, any water soluble or fat soluble polymerization initiator can be used without limitation, and as the water soluble polymerization initiator, potassium persulfate, ammonium persulfate, etc. can be used, and cumene hydroperoxide, t-butylperoxol as a fat soluble initiator. Seed or benzoyl peroxide and the like can be used, and in addition, an oxidation-reduction initiator such as organic hydroperoxide-iron salt can also be used. The polymerization initiator is preferably used in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of the total used amount of (A) and (B).

중합조절제로는 메르캅탄류, 테르펜류, 할로겐화물 등을 사용하며, 그 사용량은 (A)와 (B)의 총사용량 100 중량부에 대하여 0.01~1.0 주량부 사용함이 바람직하다.As the polymerization regulator, mercaptans, terpenes, halides, and the like are used, and the amount of use thereof is preferably 0.01 to 1.0 parts by weight based on 100 parts by weight of the total amount of (A) and (B).

본 발명에 따른 그라프트 유화중합 과정을 좀더 구체적으로 설명하면 다음과 같다.Referring to the graft emulsion polymerization process according to the present invention in more detail as follows.

별도의 용기에 단량체 혼합물(B), 산화안정제, 중합조절제 및 열안정제를 투입하고 40~60℃의 온도에서 혼합 교반하여 용액을 만든다. 그리고 또 다른 상온의 중합조에 고무질 중합체 혼합물(A)와 이온교환수를 투입하고 0.1~0.5시간 교반한 다음, 40~60℃로 승온하고 여기에 상기에서 별도로 제조한 용액중 1~90 중량%와 중합개시제 전량을 1차 사입한다. 그리고 중합조의 온도를 60~80℃로 승온하고 여기에 상기에서 제조한 용액 잔량과 유화제 전량을 3~6시간동안 연속적으로 2차 사입한다.The monomer mixture (B), the oxidation stabilizer, the polymerization regulator and the thermal stabilizer are added to a separate container and mixed and stirred at a temperature of 40 to 60 ° C. to make a solution. Then, the rubbery polymer mixture (A) and ion-exchanged water were added to another room temperature polymerization tank and stirred for 0.1 to 0.5 hours, and then heated to 40 to 60 ° C, and 1 to 90% by weight of the solution prepared separately above. Firstly, the total amount of polymerization initiator is injected. Then, the temperature of the polymerization tank is raised to 60 to 80 ° C., and the solution remaining amount and the total amount of the emulsifier prepared above are continuously injected into the reactor for 3 to 6 hours.

상기와 같은 본 발명의 그라프트 유화중합방법에서는 고무질 중합체 혼합물(A) 전량을 이온교환수지 전량과 함께 먼저 교반시킴으로써 중합계의 안정성을 높히고자 하였고, 또한 단량체 혼합물(B)을 한꺼번에 사입하지 않고 분할하여 사입함으로써 중합계의 안정성과 동시에 그라프트 효율을 높히고자 하였다.In the graft emulsion polymerization method of the present invention as described above, the entirety of the rubbery polymer mixture (A) was first stirred together with the total amount of the ion exchange resin to improve the stability of the polymerization system, and also the monomer mixture (B) was not injected at once and divided. In order to increase the graft efficiency and stability of the polymerization system.

또한, 본 발명의 그라프트 유화중합방법에서 사용되는 첨가제 예를 들면 중합조절제, 열안정제 및 중합개시제는 일시적으로 한꺼번에 첨가해도 좋고, 수회 분할 첨가해도 좋으며 또한 연속 첨가해도 무방하다.In addition, additives used in the graft emulsion polymerization method of the present invention, such as a polymerization regulator, a thermal stabilizer and a polymerization initiator, may be added at once, may be added in several portions, or may be added continuously.

상기와 같은 중합방법에 의해 제조된 본 발명의 열가소성수지는 단독으로 사용될 수 있으나, 보다 더 고광택성과 백색도를 필요로 할 경우 시판되고 있는 아크릴로니트릴-스티렌(AS 수지), HALS(hindered amine sulfate)게, 하이드로퀴논 또느 벤조트리아졸 등의 광안정제 및 폴리에틸렌 왁스 또는 에틸렌 비스 스테아미드 등의 활제 등을 본 발명의 수지 조성물 중에 0.01~2.0 중량% 함유시켜도 좋다.The thermoplastic resin of the present invention prepared by the polymerization method as described above may be used alone, but commercially available acrylonitrile-styrene (AS resin) and HALS (hindered amine sulfate) when higher glossiness and whiteness are required. Light stabilizers such as crab, hydroquinone or benzotriazole and lubricants such as polyethylene wax or ethylene bis steamide may be contained in the resin composition of the present invention in an amount of 0.01 to 2.0% by weight.

상기와 같은 제조방법에 의해 제조된 본 발명의 열가소성수지는 종래의 괴상 중합법에 의해 제조된 열가소성수지가 갖고 있는 낮은 충격강도와 낮은 광택도의 문제점을 해결할 수 있고, 또한 소입경 고무를 입자 비대화시켜 만든 대입경 고무질 중합체와 소입경 고무질 중합체를 일정 비율로 혼합 사용함으로써 고무질 중합체의 중합시간을 단축하고 이로써 물리적 특성과 광택도를 개선시켰다. 그리고, 산화안정제를 단량체 혼합물에 첨가하여 중합도중 고분자의 변색을 방지함으로써 고백색도와 고광택도를 갖는 최종 성형품의 제조가 가능하였다.The thermoplastic resin of the present invention prepared by the above manufacturing method can solve the problems of low impact strength and low glossiness of the thermoplastic resin prepared by the conventional bulk polymerization method, and also increase the particle size of the small size rubber. By using a mixture of a large-diameter rubber polymer and a small-size rubber polymer in a proportion to reduce the polymerization time of the rubber polymer, thereby improving the physical properties and gloss. In addition, by adding an oxidative stabilizer to the monomer mixture to prevent discoloration of the polymer during polymerization, it was possible to prepare a final molded article having high whiteness and high gloss.

이하, 본 발명을 실시예에 의거하여 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited by the Examples.

[제조예 1][Production Example 1]

교반장치, 가열장치 및 원료첨가배관을 갖추고 있는 용량 35ℓ의 중합조에 상기 물질을 사입하고 65℃에서 교반 반응시켰다. 중합반응시킨지 2시간이 지나면 고급 지방산나트륨 0.5 중량%을 중합계에 첨가하여 12시간 반응을 계속시킨 후 냉각시켜 반응을 종료시켰다. 전환율을 98% 이상, 중합체의 평균입경은 0.1㎛, 겔 함량은 70%, 팽윤지수는 15이었다. 여기서 얻은 라텍스를 라텍스 1이라 표기한다.The material was introduced into a polymerization tank having a capacity of 35 L equipped with a stirring device, a heating device, and a raw material addition pipe, and stirred at 65 ° C. After 2 hours of polymerization, 0.5% by weight of higher fatty acid sodium was added to the polymerization system, the reaction was continued for 12 hours, and then cooled to terminate the reaction. The conversion was 98% or more, the average particle diameter of the polymer was 0.1 µm, the gel content was 70%, and the swelling index was 15. The latex obtained here is called latex 1.

[제조예 2][Production Example 2]

[대입경 고무질 중합체의 제조][Preparation of large particle rubbery polymer]

50℃에서 상기 제조예 1과 동일한 방법에 의해 제조된 소입경 고무질 중합체 100 중량부에 10% 염화나트륨 수용액 24 중량부를 15분간에 걸쳐 첨가하였다. 이때 첨가된 염화나트륨 수용액이 라텍스내에 균일하게 분산되도록 완만하게 교반하였다. 염화나트륨을 전량 첨가 후 5~10ns 경과하면 라텍스계는 점도가 높게 되어 크리밍이 발생하였다. 라텍스 온도를 65℃로 승온하면서 5~10분 정도 교반하면 처음과 같이 점도가 낮은 균일한 라텍스계로 환원되며 이때 고무질 중합체의 라텍스의 평균입경은 0.35㎛이었다. 비대화시킨 라텍스 중의 고형분은 36.8%, 겔 함량은 72%, 그리고 팽윤지수는 22이었다. 여기서 얻은 라텍스를 라텍스2라 표기한다.24 parts by weight of an aqueous 10% sodium chloride solution was added over 15 minutes to 100 parts by weight of the small particle rubbery polymer prepared by the same method as in Preparation Example 1 at 50 ° C. At this time, the aqueous sodium chloride solution was gently stirred so as to be uniformly dispersed in the latex. After 5-10 ns of the total amount of sodium chloride was added, the latex system had a high viscosity and creaming occurred. When the temperature of the latex was raised to 65 ° C. and stirred for about 5 to 10 minutes, the result was reduced to a uniform latex system having a low viscosity as described above. At this time, the average particle diameter of the latex of the rubbery polymer was 0.35 μm. The solid content in the enlarged latex was 36.8%, the gel content was 72%, and the swelling index was 22. The latex obtained here is called latex 2.

[제조예 3][Manufacture example 3]

교반장치, 가열장치 및 원료 첨가배관을 갖추고 있는 35ℓ의 중합조에 상기 물질을 사입하여 60℃에서 반응을 시작하였다. 중합반응도중 3시간, 8시간에 각각 0.5 중량부의 고급 지방산 나트륨의 10 중량% 수용액을 중합계에 첨가한 후 중합온도를 70℃로 승온하여 35시간 반응을 게속시킨 후 냉각시켜 반응을 종료시켰다. 전환율은 98% 이상, 라텍스의 고형분은 52%, 중합체의 평균입경은 0.3㎛, 겔 함량은 87%, 그리고 팽윤지수는 25이었다. 여기서 얻은 라텍스를 라텍스 3이라 표기한다.The material was introduced into a 35 L polymerization tank equipped with a stirring device, a heating device and a raw material addition pipe, and the reaction was started at 60 ° C. The reaction was terminated by adding a 10 wt% aqueous solution of 0.5 parts by weight of higher fatty acid sodium to the polymerization system at 3 hours and 8 hours during the polymerization, and then increasing the polymerization temperature to 70 ° C. to continue the reaction for 35 hours. The conversion was 98% or more, the solid content of the latex was 52%, the average particle diameter of the polymer was 0.3 µm, the gel content was 87%, and the swelling index was 25. The latex obtained here is referred to as latex 3.

[제조예 4][Production Example 4]

교반장치, 가열장치 및 원료 첨가배관을 갖추고 있는 35ℓ의 중합조에 상기 물질을 사입하여 60℃에서 반응을 시작하고, 반응도중 1시간, 5시간, 10시간, 15시간째에서 다음의 물질을 나누어 첨가하였다.Insert the material into a 35 L polymerization tank equipped with a stirring device, a heating device, and a raw material addition pipe and start the reaction at 60 ° C. The following materials are added separately at 1 hour, 5 hours, 10 hours, and 15 hours during the reaction. It was.

6시간 반응을 시킨 후 70℃로 승온하여 10시간 게속 중합을 실시한 다음 반응을 종료시켰다. 중합체의 평균입경은 0.6㎛, 겔 함량은 70%, 그리고 팽윤지수는 20이었다. 여기서 얻은 라텍스를 라텍스 4라 표기한다.After the reaction was carried out for 6 hours, the temperature was raised to 70 ° C, continuous polymerization was performed for 10 hours, and the reaction was terminated. The average particle diameter of the polymer was 0.6 mu m, the gel content was 70%, and the swelling index was 20. The latex obtained here is called latex 4.

[제조예 5]Production Example 5

[겔함량이 낮은 소입경 고무질중합체의 제조][Preparation of small particle size rubbery polymer with low gel content]

상기 제조예 1과 동일한 방법에 의해 실시하되, 다만 도데실메르캅탄 0.2 중량부 대신에 0.4 중량부를 사요하였고, 중합온도는 5℃이었다. 그 결과 얻어진 고무줄 중합체의 입자크기는 0.08㎛, 겔 함량은 52.8, 그리고 팽윤지수는 42이었다. 여기서 얻은 라텍스를 라텍스 5라 표기한다.The same method as in Preparation Example 1 was carried out, except that 0.4 parts by weight of 0.2 parts by weight of dodecyl mercaptan was used, and the polymerization temperature was 5 ° C. The resultant rubber polymer had a particle size of 0.08 µm, a gel content of 52.8, and a swelling index of 42. The latex obtained here is called latex 5.

[실시예 1]Example 1

상기 제조예 1에서 얻은 소입경의 고무줄 중합체(라텍스 1) 50 중량%와 제조예 2에서 얻은 대입경의 고무질 중합체(라텍스 2) 20 중량%를 혼합하였으며, 고무질 중합체 혼합물의 평균입경은 0.4㎛, 겔 함량은 75%, 그리고 팽윤지수는 20이었다.50% by weight of the rubber polymer (latex 1) of the small particle size obtained in Preparation Example 1 and 20% by weight of the rubbery polymer (latex 2) of the large particle size obtained in Preparation Example 2 were mixed, and the average particle diameter of the rubbery polymer mixture was 0.4 µm. The content was 75% and the swelling index was 20.

30ℓ의 중합조에 상기 고무질 중합체 혼합물과 이온교환수를 사입하고 30분간 교반시킨 다음, 중합조의 온도를 서서히 50℃까지 올렸다. 별도의 50℃의 용기에서 스티렌, 아크릴로니트릴, 3급 메르캅탄 및 산화안정제를 혼합교반시켜 용액을 제조하였으며, 용액 전량중 5 중량%와 개시제 전량을 상기 중합조에 사입하였다.The rubbery polymer mixture and ion-exchanged water were introduced into a 30 L polymerization tank and stirred for 30 minutes, and then the temperature of the polymerization tank was gradually raised to 50 ° C. In a separate 50 ° C. container, styrene, acrylonitrile, tertiary mercaptan, and an oxidative stabilizer were mixed and stirred to prepare a solution, and 5 wt% of the total solution and the total amount of the initiator were injected into the polymerization tank.

중합온도를 73℃로 승온시키고, 1시간동안 교반한 후 상기 용액 잔량과 유화제 스티렌 잔량을 4시간 동안 연속첨가하였다. 그 결과 중합율 98.9%로 열가소성수지를 얻었다.The polymerization temperature was raised to 73 ° C., stirred for 1 hour, and the remaining solution and emulsifier styrene were continuously added for 4 hours. As a result, a thermoplastic resin was obtained with a polymerization rate of 98.9%.

[실시예 2~7]EXAMPLES 2-7

상기 실시예 1과 동일한 방법에 의해 열가소성수지를 제조하되 다만, 다음 표1에 나타낸 바와 같이 고무질중합체 혼합물의 비율, 단량체 혼합물의 비율 그리고 산화안정제의 종류와 사용량을 달리하였다.The thermoplastic resin was prepared in the same manner as in Example 1, except that the ratio of the rubbery polymer mixture, the ratio of the monomer mixture, and the type and amount of the oxidizing stabilizer were different.

[비교예 1]Comparative Example 1

상기 실시예 1과 동일한 방법에 의해 열가소성수지를 제조하되 다만, 고무질 중합체로서 상기 제조예 3에서 얻은 라텍스 3만을 70중량% 사용하였다.A thermoplastic resin was prepared in the same manner as in Example 1, except that only 70 wt% of the latex 3 obtained in Preparation Example 3 was used as a rubbery polymer.

[비교예 2]Comparative Example 2

상기 실시예 1과 동일한 방법에 의해 열가소성수지를 제조하되 다만, 고무질 중합체로서 상기 제조예 4에서 얻은 라텍스 4만을 70 중량% 사용하였다.A thermoplastic resin was prepared in the same manner as in Example 1, except that only 70 wt% of the latex 4 obtained in Preparation Example 4 was used as a rubbery polymer.

[비교예 3]Comparative Example 3

상기 실시예 1과 동일한 방법에 의해 열가소성수지를 제조하되 다만, 상기 제조예 5에서 얻은 라텍스 5만을 70 중량% 사용하였다.A thermoplastic resin was prepared in the same manner as in Example 1, except that only 70 wt% of the latex 5 obtained in Preparation Example 5 was used.

[비교예 4][Comparative Example 4]

상기 제조예 1에서 얻은 소입경의 고무질 중합체(라텍스 1)20 중량%와 대입경이 고무질 중합체(라텍스 2) 10 중량%를 혼합하였으며, 고무질중합체 혼합물의 평균입경은 0.35㎛, 겔 함량은 78%, 그리고 팽윤지수는 18이었다.20% by weight of the rubbery polymer (latex 1) of the small particle size obtained in Preparation Example 1 and 10% by weight of the large-diameter rubbery polymer (latex 2) were mixed, and the average particle diameter of the rubbery polymer mixture was 0.35 µm, and the gel content was 78%, The swelling index was 18.

30ℓ의 중합조에 상기 고무질 중합체 혼합물과 이온교환수를 사입하고 30분간 교반시킨 다음, 중합조의 온도를 서서히 50℃까지 올렸다. 별도의 50℃의 용기에서 스티렌, 아크릴로니트릴, 3급 메르캅탄 및 산화안정제를 혼합교반시켜 용액을 제조하였으며, 용액 전량중 5 중량%와 개시제 전량을 상기 중합조에 사입하였다.The rubbery polymer mixture and ion-exchanged water were introduced into a 30 L polymerization tank and stirred for 30 minutes, and then the temperature of the polymerization tank was gradually raised to 50 ° C. In a separate 50 ° C. container, styrene, acrylonitrile, tertiary mercaptan, and an oxidative stabilizer were mixed and stirred to prepare a solution, and 5 wt% of the total solution and the total amount of the initiator were injected into the polymerization tank.

중합온도를 73℃로 승온시키고, 1시간동안 교반시킨 후 상기 용액 잔량과 유화제 스티렌 잔량을 4시간동안 연속첨가하였다. 그 결과 중합율 97.6%로 열가소성수지를 얻었다.The polymerization temperature was raised to 73 ° C., stirred for 1 hour, and the remaining solution and emulsifier styrene were continuously added for 4 hours. As a result, a thermoplastic resin was obtained with a polymerization rate of 97.6%.

[비교예 5][Comparative Example 5]

30ℓ의 중합조에 상기 제조예 1에서 얻은 소입경의 고무질 중합체(라텍스 1)과 이온교환수를 사입하고 30분간 교반시킨 다음, 중합조의 온도를 서서히 50℃까지 올렸다.Into a 30-liter polymerization tank, the rubbery polymer (latex 1) of the small particle size obtained in Preparation Example 1 and ion-exchanged water were inserted and stirred for 30 minutes, and then the temperature of the polymerization tank was gradually raised to 50 ° C.

별도의 50℃의 용기에서 스티렌, 아크릴로니트릴, 3급 메르캅탄 및 산화안정제를 혼합교반시켜 용액을 제조하였으며, 용액 전량중 5 중량%와 개시제 전량을 상기 중합종 사입하였다.In a separate 50 ° C. container, styrene, acrylonitrile, tertiary mercaptan, and an oxidative stabilizer were mixed and stirred to prepare a solution, and 5 wt% of the total solution and the total amount of the initiator were injected into the polymerization species.

중합온도를 73℃로 승온시키고, 1시간동안 교반한 후 상기 요액 잔량과 유화제 스티렌 잔량을 4시간동안 연속첨가하였다. 그 결과 중합율 99.0%로 열가소성수지를 얻었다.The polymerization temperature was raised to 73 ° C., stirred for 1 hour, and the remaining amount of the urine solution and the remaining amount of the emulsifier styrene were continuously added for 4 hours. As a result, a thermoplastic resin was obtained at a polymerization rate of 99.0%.

[실험예 1]Experimental Example 1

[열변색 시험][Thermal Discoloration Test]

상기 실시예 1~7, 비교예 1~5에서 제조한 열가소성수지 100 중량부에 응고제인 전해질 황산마그네슘 5.0 중량부를 첨가한 후 응고, 수세, 건조하여 각각의 수지분말을 얻었다. 각각의 수지분말(5g)을 알루미늄호일로 포장하여 170℃의 오븐내에서 3시간 체류후 변색정도를 상대비교하였다. 그 결과는 다음 표1에 나타내었다.5.0 parts by weight of electrolytic magnesium sulfate as a coagulant was added to 100 parts by weight of the thermoplastic resins prepared in Examples 1 to 7 and Comparative Examples 1 to 5, and then solidified, washed with water and dried to obtain respective resin powders. Each resin powder (5 g) was packaged in aluminum foil, and compared with each other for 3 hours in a 170 ° C. oven for discoloration. The results are shown in Table 1 below.

[충격강도, 인장강도 측정][Measurement of impact strength and tensile strength]

상기에서 얻은 각각의 수지 분말 60 중량%에 시판되고 있는 AS 수지(미원유화제 SAN 300 Grade) 40 중량%를 혼합하고 이들 함량 100 중량부에 활제로서 에틸렌 비스스테아릴아미드 1.0 중량부를 첨가 혼합시킨 후 40Φ 압출기를 사용하여 220℃에서 페렛트화시켰다.40 wt% of a commercially available AS resin (SAN 300 Grade) was mixed with 60 wt% of each resin powder obtained above, and then mixed with 100 wt% of this content and 1.0 wt part of ethylene bisstearylamide as a lubricant. Pelletization at 220 ° C. using an extruder.

ASTM의 시험편을 5온스 성형기로 성형하여 ASTM 시험조건에서 측정한 충격강도 및 인장강도는 다음 표1에 나타내었다.The impact strength and tensile strength measured under ASTM test conditions by molding ASTM test pieces with a 5 ounce molding machine are shown in Table 1 below.

[백색도, 황변도, 광택도 측정][Whiteness, Yellowness, Glossiness Measurement]

상기 각각의 페렛을 칼라칩 시편(크기 10㎝×5㎝×0.32㎝(두께))을 성형하여 ccm(color computor matching, 제조회사 미국 AGS사, 모델명 ; ACS 2018 SYSTEM)를 이용하여 백색도, 황변도 및 광택도를 측정하였다. 그 결과는 다음 표1에 나타내었다.Each ferret was molded into color chip specimens (size 10 cm × 5 cm × 0.32 cm (thickness)) to obtain whiteness and yellowness using ccm (color computor matching, manufacturer AGS, model name; ACS 2018 SYSTEM). And glossiness was measured. The results are shown in Table 1 below.

상기 표1의 결과에 의하여 본 발명에 따른 실시예 1~7은 열변색 시험결과가 양호하였으며 충격강도 등의 물리적 특성이 우수하면서 광택도, 백색도 등이 우수한데 반하여, 비교예 1~5는 열변색이 떨어지면서 백색도 및 광택도가 저하되며 비교예 4의 경우 열변색은 양호하나 물성 등이 낮다.According to the results of Table 1, Examples 1 to 7 according to the present invention had good thermal discoloration test results, and excellent physical properties such as impact strength, and excellent gloss and whiteness, whereas Comparative Examples 1 to 5 were heat. As the discoloration falls, the whiteness and gloss are lowered. In Comparative Example 4, the thermal discoloration is good but the physical properties are low.

[실험예 2]Experimental Example 2

상기 실시예 1에서 제조한 열가소성수지와 비교예 1에서 제조한 열가소성수지 각각 100중량부에 백색도 발현을 위해 첨가되는 백색안료(TiO2)의 첨가량을 변화시키면서 백색도를 측정하였으며, 그 결과는 다음 표2에 나타내었다.The whiteness was measured while varying the amount of the white pigment (TiO 2) added to express the whiteness in 100 parts by weight of the thermoplastic resin prepared in Example 1 and the thermoplastic resin prepared in Comparative Example 1, and the results are shown in Table 2 below. Shown in

상기 표 2의 백색도에 의하면, 본 발명에 의해 제조된 열가소성수지(실시예 1)는 백색안료 1.5 중량부를 사용했을 때 백색도 70을 나타내는데 반하여, 비교예 1은 실시예 1의 2배 이상의 양인 3.2 중량부를 사용하여야 만이 백색도 70을 나타낼 수 있다.According to the whiteness of Table 2, the thermoplastic resin prepared in accordance with the present invention (Example 1) exhibits a whiteness of 70 when 1.5 parts by weight of white pigment is used, whereas Comparative Example 1 is 3.2 times the amount of 2 or more times of Example 1. Only with parts can the whiteness show 70.

따라서, 본 발명에 따른 열가소성수지는 백색안료를 소량 첨가하여도 충분한 백색도를 발현할 수 있다.Therefore, the thermoplastic resin according to the present invention can express sufficient whiteness even when a small amount of white pigment is added.

Claims (6)

입자경이 다른 고무질중합체와 비닐계 및 아크릴계 단량체 혼합물이 중합되어 이루어진 열가소성수지에 있어서, 중량 평균입경이 0.05~0.20㎛인 소입경 고무질 중합체 50~80 중량%(고형분 환산)와 중량 평균입경이 0.4~1.0㎛인 대입경 고무질 중합체 20~50 중량%(고형분 환산)로 이루어진 부타디엔계 고무질 중합체 혼합물(A) 50~80 중량%를 본체로 하고, 여기에 비닐 방향족 화합물 단량체 60~80 중량% 및 비닐시안화 화합물과 아크릴계 화합물 중에서 선택된 1종 또는 2종 이상의 단량체 20~40 중량%로 이루어진 단량체(B) 20~50 중량%가 40~60℃에서 1차, 60~80℃에서 2차로 그라프트 유화중합된 것을 특징으로 하는 열가소성 수지.In a thermoplastic resin obtained by polymerizing a rubbery polymer having a different particle diameter and a mixture of vinyl and acrylic monomers, 50 to 80% by weight (in terms of solids) of a small particle rubbery polymer having a weight average particle diameter of 0.05 to 0.20 µm and a weight average particle diameter of 0.4 to 50 to 80% by weight of a butadiene-based rubbery polymer mixture (A) composed of 20 to 50% by weight (in terms of solid content) of a large particle rubbery polymer having a particle size of 1.0 µm is used as the main body, and 60 to 80% by weight of a vinyl aromatic compound monomer and vinyl cyanide. 20-50% by weight of the monomer (B) consisting of 20-40% by weight of one or two or more monomers selected from the compound and the acryl-based compound is first graft emulsion-polymerized at 40-60 ° C and secondly at 60-80 ° C. Thermoplastic resin, characterized in that. 입자경이 다른 고무질중합체 혼합물과 비닐계 및 아크릴계의 단량체 혼합물을 그라프트 중합반응시켜 열가소성수지를 제조하는 방법에 있어서, 중량 평균입경이 0.05~0.20㎛인 소입경 고무질중합체 50~80 중량%(고형분 환산)와 중량 평균 입경이 0.4~1.0㎛인 대입경 고무질 중합체 20~50 중량%(고형분 환산)로 이루어진 고무질 중합체 혼합물(A) 50~80 중량%와 비닐 방향족 화합물 단량체 60~80 중량% 및 비닐시안화 화합물과 아크릴계 화합물 중에서 선택된 1종 또는 2종 이상의 단량체 20~40 중량%로 이루어진 단량체(B) 20~50 중량%를 그라프트 유합중합시키되, 상기 고무질중합체(A)를 본체로 하고 여기에 단량체를 그라프트 중합반응시킬 때 40~60℃에서 단량체 전량중의 1~90 중량%를 1차 사입하고 중합반응 온도를 60~80℃로 승온하며, 나머지 단량체 잔량을 2차 사입시켜서 됨을 특징으로 하는 열가소성수지의 제조방법.In a method for producing a thermoplastic resin by graft polymerization of a mixture of rubber polymers having different particle diameters with a monomer mixture of vinyl and acrylic resins, 50 to 80% by weight of a small particle rubber polymer having a weight average particle diameter of 0.05 to 0.20 µm (in terms of solid content). ) And 50 to 80% by weight of a rubbery polymer mixture (A) consisting of 20 to 50% by weight (in terms of solids) of a large-size rubbery polymer having a weight average particle diameter of 0.4 to 1.0 µm, 60 to 80% by weight of a vinyl aromatic compound monomer, and vinyl cyanide. 20 to 50% by weight of a monomer (B) consisting of 20 to 40% by weight of one or two or more monomers selected from a compound and an acryl-based compound is graft-polymerized, wherein the rubbery polymer (A) is used as the main body. In the graft polymerization reaction, 1 to 90% by weight of the total amount of the monomers are firstly injected at 40 to 60 ° C, the polymerization temperature is raised to 60 to 80 ° C, and the remaining monomers are secondly injected. Process for producing a thermoplastic resin as claimed. 제2항에 있어서, 상기 단량체 1차 사입시 산화안정제를 고무질 중합체와 단량체의 총사용량 100 중량부에 대하여 0.01~2.0 중량부 투입하는 것을 특징으로 하는 열가소성수지의 제조방법.The method of claim 2, wherein the oxidizing stabilizer is added in an amount of 0.01 to 2.0 parts by weight based on 100 parts by weight of the total amount of the rubbery polymer and the monomer. 제3항에 있어서, 상기 산화안정제로는 페놀계 산화안정제, 아민계 산화안정제, 황계 산화안정제 및 인계 산화안정제 중에서 선택된 것을 사용하는 것을 특징으로 하는 열가소성수지의 제조방법.The method of claim 3, wherein the oxidative stabilizer is selected from a phenolic oxidative stabilizer, an amine oxidative stabilizer, a sulfur type oxidative stabilizer, and a phosphorus oxidative stabilizer. 제2항에 있어서, 상기 고무질 중합체로는 중량 평균입경이 0.05~0.20㎛인 소입경 고무질 중합체 50~80 중량%(고형분 환산)와 중량 평균입경이 0.4~1.0㎛인 대입경 고무질 중합체 20~50 중량%(고형분 환산)로 이루어진 고무질 중합체 혼합물을 사용하는 것을 특징으로 하는 열가소성수지의 제조방법.The rubbery polymer according to claim 2, wherein the rubbery polymer is 50 to 80% by weight (in terms of solid content) of a small particle rubbery polymer having a weight average particle diameter of 0.05 to 0.20 µm and a large particle rubbery polymer of 20 to 50 having a weight average particle diameter of 0.4 to 1.0 µm. A method for producing a thermoplastic resin, characterized by using a rubbery polymer mixture composed of weight% (solid content conversion). 제5항에 있어서, 상기 대입경 고무질 중합체로는 소입경 고무질 중합체를 고분자 응집제, 산 또는 산염에 의해 비대화시킨 것을 사용하는 것을 특징으로 하는 열가소성수지의 제조방법.The method for producing a thermoplastic resin according to claim 5, wherein the large-diameter rubbery polymer is obtained by enlarging a small-size rubbery polymer with a polymer flocculant, an acid, or an acid salt.
KR1019950041089A 1995-11-13 1995-11-13 Thermoplastic resins and preparation thereof KR100199090B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019950041089A KR100199090B1 (en) 1995-11-13 1995-11-13 Thermoplastic resins and preparation thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1019950041089A KR100199090B1 (en) 1995-11-13 1995-11-13 Thermoplastic resins and preparation thereof

Publications (2)

Publication Number Publication Date
KR970027131A KR970027131A (en) 1997-06-24
KR100199090B1 true KR100199090B1 (en) 1999-06-15

Family

ID=19433949

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1019950041089A KR100199090B1 (en) 1995-11-13 1995-11-13 Thermoplastic resins and preparation thereof

Country Status (1)

Country Link
KR (1) KR100199090B1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022059903A1 (en) * 2020-09-18 2022-03-24 (주) 엘지화학 Method for preparing graft copolymer and method for preparing thermoplastic resin composition comprising graft copolymer
US11932709B2 (en) 2018-12-20 2024-03-19 Lg Chem, Ltd. Diene-based rubber latex, method for preparing thereof and graft copolymer with core-shell structure comprising the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11932709B2 (en) 2018-12-20 2024-03-19 Lg Chem, Ltd. Diene-based rubber latex, method for preparing thereof and graft copolymer with core-shell structure comprising the same
WO2022059903A1 (en) * 2020-09-18 2022-03-24 (주) 엘지화학 Method for preparing graft copolymer and method for preparing thermoplastic resin composition comprising graft copolymer

Also Published As

Publication number Publication date
KR970027131A (en) 1997-06-24

Similar Documents

Publication Publication Date Title
EP2404941B1 (en) Method of manufacturing rubbery polymer and rubber reinforced thermoplastic resin composition using the same
JP6594426B2 (en) Process for producing large-diameter diene rubber latex and acrylonitrile-butadiene-styrene graft copolymer containing the same
CN105008406A (en) Transparent ABS resin and transparent ABS resin composition
KR102068650B1 (en) Graft copolymer, method for preparing the graft copolymer, thermoplastic resin composition and molding product
JPS6347745B2 (en)
KR100574324B1 (en) Method for preparing thermoplastic resin with good impact resistance and natural color property
TW202128800A (en) Alkyl acrylate compound-vinyl cyanide compound-aromatic vinyl compound graft copolymer, method of preparing the same, and thermoplastic resin composition including the same
JPS6243450B2 (en)
KR100199090B1 (en) Thermoplastic resins and preparation thereof
KR100564816B1 (en) Method of Preparing ABS Resin Composition with Good Heat Resistance, Transparence and Natural Color
KR100419230B1 (en) Manufacturing method of thermoplastic resin with excellent whiteness and impact resistance
KR100455101B1 (en) Method of Preparing SAN-Grafted Copolymer Resin with Excellent Appearance and Whiteness
KR100507412B1 (en) Thermoplastic Resin Composition With Good Transparency and Impact Strength and Wet-proof Property and Method for Preparing the Same
KR950010124B1 (en) Manufacture method of excellent heat-stability thermoplastic resin
KR100453875B1 (en) Method of Preparing the New Grafted Copolymer Having High Rubber Contents and High Performance
KR0161504B1 (en) Thermoplastic resin compositions
KR101182066B1 (en) Thermoplastic Transparent Resin for Transparent Extrusion Films, Thermoplastic Transparent Resin Composition for Transparent Extrusion Films comprising the Thermoplastic Transparent Resin, And Transparent Extrusion Films Prepared from thereof
US3662026A (en) Process for preparing graft copolymers containing n,n-di(beta-hydroxyethyl) glycine salts
KR100429062B1 (en) Thermoplastic Resin Composition With Good Transparent and Impact Strength and Method for Preparing the Same
KR100402281B1 (en) Thermoplastic Resin Composition with Good Impact Strength, Gloss and Weather Durability and Method of Preparing the Same
KR100507336B1 (en) Method of Preparing Thermoplastic Resin Composition with Good Heat Resistance and Good Transparence
KR100463301B1 (en) Thermoplastic Resin Composition with Good Transparent, Impact Strength and Wet-Proof Property
KR950011451B1 (en) Process for producing thermoplastic resins having a good impact resistance
KR100369378B1 (en) Process for preparing thermoplastic resin composition having excellent impact resistance and tensile property
KR950010123B1 (en) Manufacture method of thermo plastic resin having excellent impact resistance and eldngation character

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20130108

Year of fee payment: 15

FPAY Annual fee payment

Payment date: 20140304

Year of fee payment: 16

LAPS Lapse due to unpaid annual fee