KR100810105B1 - Thermoplastic resin composition having extremely low transmittance - Google Patents
Thermoplastic resin composition having extremely low transmittance Download PDFInfo
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- KR100810105B1 KR100810105B1 KR1020060136261A KR20060136261A KR100810105B1 KR 100810105 B1 KR100810105 B1 KR 100810105B1 KR 1020060136261 A KR1020060136261 A KR 1020060136261A KR 20060136261 A KR20060136261 A KR 20060136261A KR 100810105 B1 KR100810105 B1 KR 100810105B1
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/78—Stabilisers against oxidation, heat, light or ozone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/84—Flame-proofing or flame-retarding additives
Abstract
Description
발명의 분야Field of invention
본 발명은 열가소성 수지 조성물에 관한 것이다. 보다 구체적으로 본 발명은 열가소성 수지와 판상의 무기물을 블랜딩하여 제조된 광투과율이 극히 낮은 열가소성 수지 조성물에 관한 것이다.The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition having an extremely low light transmittance prepared by blending a thermoplastic resin and a plate-like inorganic material.
발명의 배경Background of the Invention
일반적으로 열가소성 수지는 전기·전자, 자동차 분야에서 경량화와 생산비 절감을 목적으로 다양한 분야에 사용되고 있다. 최근, 전기·전자 제품의 박막화 경향에 따라 하우징(housing) 재료로 사용되는 열가소성 수지 성형물도 박막화되고 있다. In general, thermoplastic resins are used in various fields for the purpose of weight reduction and production cost reduction in electric, electronic and automotive fields. In recent years, the thermoplastic resin molding used as a housing material has also become thinner according to the tendency of thinning electrical and electronic products.
열가소성 수지로 성형된 하우징이 박막화되면서, 전기·전자제품 내부에서 발생하는 불빛이 하우징 외부로 새어 나오는 문제가 발생하고 있다. 이를 해결하기 위해 카본 블랙(carbon black)을 열가소성 수지와 혼합하거나, 과량의 산화티탄을 혼합하는 등의 방법이 사용되고 있다. 그러나, 이 방법들은 하우징(housing)의 색깔이 검정색 계열로 한정되거나, 충격에 취약해지는 문제가 있다.As the housing molded of the thermoplastic resin becomes thinner, there is a problem that light generated inside the electrical and electronic products leaks out of the housing. In order to solve this problem, a method of mixing carbon black with a thermoplastic resin, or mixing excess titanium oxide is used. However, these methods have a problem that the color of the housing (housing) is limited to the black series or is vulnerable to impact.
또한, 하우징 성형품의 외부에 두꺼운 도장을 하는 방법도 있으나, 이는 공정비용이 상당히 증가할 뿐만 아니라, 성형품의 내충격성이 저하되는 문제가 있다.In addition, there is also a method of applying a thick coating on the outside of the housing molded article, which not only significantly increases the process cost, but also has a problem that the impact resistance of the molded article is lowered.
이에 본 발명자들은 종래의 단점을 극복하고자 연구한 결과, 열가소성 수지에 판상의 무기물을 혼합하는 경우, 내충격성과 고백색도를 가지면서, 광투과율을 현저히 저하시킬 수 있다는 사실을 발견하였으며, 이 결과를 바탕으로 내충격성과 고백색도를 가지면서, 광투과율이 현저히 낮은 열가소성 수지 조성물을 개발하기에 이른 것이다.Accordingly, the present inventors have studied to overcome the disadvantages of the prior art, and found that when mixing a plate-like inorganic material with a thermoplastic resin, the light transmittance can be significantly reduced while having impact resistance and high whiteness. In order to develop a thermoplastic resin composition having impact resistance and high whiteness and a significantly low light transmittance.
본 발명의 목적은 광투과율이 극히 낮은 열가소성 수지 조성물을 제공하기 위한 것이다.An object of the present invention is to provide a thermoplastic resin composition having an extremely low light transmittance.
본 발명의 다른 목적은 광투과율이 낮으면서도 내충격성이 동시에 우수한열가소성 수지 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a thermoplastic resin composition having low light transmittance and excellent impact resistance at the same time.
본 발명의 또 다른 목적은 고백색도를 갖는 열가소성 수지 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a thermoplastic resin composition having a high whiteness.
본 발명의 상기 및 기타의 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
발명의 요약Summary of the Invention
본 발명에 따른 광투과율이 극히 낮은 열가소성 수지 조성물은 (A) 열가소성 수지 90∼99.9 중량부, 및 (B) 직경 1∼100 ㎛이고 길이/두께 비율이 10 이상인 판상의 무기물 0.1∼10 중량부로 이루어지는 것을 특징으로 한다.The thermoplastic resin composition having an extremely low light transmittance according to the present invention comprises (A) 90 to 99.9 parts by weight of a thermoplastic resin, and (B) 0.1 to 10 parts by weight of a plate-shaped inorganic material having a diameter of 1 to 100 µm and a length / thickness ratio of 10 or more. It is characterized by.
본 발명에서 상기 판상의 무기물(B)은 (b1) 마이카, 탈크, 카오린, 월라스토나이트, 휘스크 및 클레이로 이루어진 군으로부터 선택된 최소한 하나 이상의 기재에 (b2) 산화티탄, 황화아연, 산화아연, 수산화알루미늄, 칼슘카보네이트 및 황산바륨으로 이루어진 군으로부터 선택된 최소한 하나 이상의 코팅 물질을 코팅한 것이 바람직하다.In the present invention, the plate-like inorganic material (B) is (b 1 ) at least one substrate selected from the group consisting of mica, talc, kaolin, wollastonite, whisk and clay (b 2 ) titanium oxide, zinc sulfide, zinc oxide Preferably, at least one coating material selected from the group consisting of aluminum hydroxide, calcium carbonate and barium sulfate is coated.
상기 판상의 무기물을 이루는 기재(b1)와 코팅 물질(b2)의 중량비는 1∼10 인 것이 바람직하다.The weight ratio of the base material (b 1 ) and the coating material (b 2 ) constituting the plate-shaped inorganic material is preferably 1 to 10.
이하 본 발명의 내용을 하기에 상세히 설명한다.Hereinafter, the content of the present invention will be described in detail.
발명의 구체예에 대한 상세한 설명Detailed Description of the Invention
(A) 열가소성 수지(A) thermoplastic resin
본 발명에 따른 열가소성 수지 조성물에 사용되는 열가소성 수지(A)는 상업적으로 이용 가능한 열가소성 수지를 사용하며, 특별히 한정되지는 않는다. 예를 들어, 폴리카보네이트, 폴리에스테르, 펠리페닐렌에테르, 폴리에틸렌, 폴리프로필렌, 아크릴로니트릴-부타디엔-스티렌(ABS) 등 멜트(melt) 가공으로 성형할 수 있는 모든 열가소성 수지가 포함된다.The thermoplastic resin (A) used in the thermoplastic resin composition according to the present invention uses a commercially available thermoplastic resin, and is not particularly limited. For example, all thermoplastic resins which can be molded by melt processing, such as polycarbonate, polyester, phenylphenylene ether, polyethylene, polypropylene, acrylonitrile-butadiene-styrene (ABS), are included.
본 발명에서 상기 열가소성 수지(A)의 함량은 90∼99.9 중량부이다.In the present invention, the content of the thermoplastic resin (A) is 90 to 99.9 parts by weight.
(B) 판상의 무기물(B) plate minerals
본 발명에서 사용하는 판상의 무기물(B)은, 직경이 1∼100 ㎛이고, 길이/두께 비율이 10이상인 판상의 무기물이다. 본 발명에서 판상의 무기물(B)의 직경이 1㎛ 이하이면 광투과율이 높아지고, 100㎛ 이상이면 성형품의 내충격성이 저하된다. 길이/두께 비율이 10 미만인 경우, 광투과율이 높아질 수 있다. 상기 판상의 무기물의 길이/두께 비율은 10∼1000 사이인 것이 바람직하다.The plate-shaped inorganic material (B) used by this invention is a plate-shaped inorganic material whose diameter is 1-100 micrometers, and length / thickness ratio is 10 or more. In the present invention, if the diameter of the plate-shaped inorganic material (B) is 1 µm or less, the light transmittance is high, and if it is 100 µm or more, the impact resistance of the molded article is lowered. If the length / thickness ratio is less than 10, the light transmittance may be high. It is preferable that the length / thickness ratio of the said plate-shaped inorganic material is between 10-1000.
상기 판상의 무기물은 사각형, 원형, 타원형 등의 형상을 갖는 얇은 판형의 물질이며, 본 명세서에서 "직경"이란 상기 형상의 내부를 이루는 가장 긴 길이의 직선을 의미한다. 예를 들어, 원형일 경우 직경은 지름을 말하고, 타원형인 경우 장경을, 사각형일 경우 대각선 중의 긴 것을 의미한다.The plate-shaped inorganic material is a thin plate-like material having a shape of a rectangle, a circle, an oval, and the like, and the term "diameter" refers to the longest straight line that forms the inside of the shape. For example, in the case of a circle, the diameter means a diameter, in the case of an ellipse, the long diameter, and in the case of a rectangle, the length of a diagonal line.
본 발명에서 상기 판상의 무기물은 (b1) 마이카, 탈크, 카오린, 월라스토나이트, 휘스크, 클레이 등으로부터 선택된 1종 이상의 기재에 (b2) 산화티탄, 황화아 연, 산화아연, 수산화알루미늄, 칼슘카보네이트, 황산바륨 등으로부터 선택된 1종 이상의 코팅 물질을 코팅하여 얻어진다. 코팅 방법은 촉매를 이용한 방법이나 증착에 의한 방법 등 공지된 코팅 방법을 적용할 수 있다. 이 때의 (b1)/(b2)의 중량비는 1∼10 이다. (b1)/(b2)의 중량비가 1 이하이거나 10 이상이면, 기재나 코팅물질의 양이 너무 적으므로 경우 각 물질의 굴절율 차이에 의해 광투과율을 낮추는 효과가 저하되어, 결국 광투과율이 높아질 수 있다.In the present invention, the plate-like inorganic material is (b 1 ) at least one substrate selected from mica, talc, kaolin, wollastonite, whisk, clay and the like (b 2 ) titanium oxide, zinc sulfide, zinc oxide, aluminum hydroxide, It is obtained by coating at least one coating material selected from calcium carbonate, barium sulfate and the like. As a coating method, well-known coating methods, such as a method using a catalyst and a method by vapor deposition, can be applied. The weight ratio of (b 1 ) / (b 2 ) at this time is 1-10. If the weight ratio of (b 1 ) / (b 2 ) is 1 or less or 10 or more, since the amount of the substrate or coating material is too small, the effect of lowering the light transmittance due to the difference in refractive index of each material is lowered. Can be high.
본 발명의 열가소성 수지 제조방법에 있어서 각각의 용도에 따라 충격보강제, 난연제, 활제, 항균제, 이형제, 핵제, 가소제, 열안정제, 산화방지제, 광안정제, 상용화제, 안료, 염료 및 무기물 첨가제가 더 부가될 수 있다.In the thermoplastic resin manufacturing method of the present invention, an impact modifier, a flame retardant, a lubricant, an antibacterial agent, a mold release agent, a nucleating agent, a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a compatibilizer, a pigment, a dye, and an inorganic additive are further added. Can be.
또한, 상술한 열가소성 수지 조성물을 제조하고, 이러한 수지 조성물을 압출기 내에서 용융 압출하는 등의 통상적인 방법을 통해, 열가소성 수지 또는 이로부터 제조되는 플라스틱 성형품을 제조할 수 있다. 따라서, 이러한 성형품은 각종 전기ㅇ전자 제품 또는 자동차 부품에서 사용될 수 있다.In addition, a thermoplastic resin or a plastic molded article produced therefrom can be produced by a conventional method such as preparing the above-mentioned thermoplastic resin composition and melt extruding such resin composition in an extruder. Thus, such shaped articles can be used in various electrical and electronic products or automotive parts.
본 발명은 하기의 실시예에 의하여 보다 구체화될 것이며, 하기 실시예는 본 발명의 구체적인 예시에 불과하며 본 발명의 보호범위를 한정하거나 제한하고자 하는 것은 아니다.The present invention will be further illustrated by the following examples, which are merely illustrative of the present invention and are not intended to limit or limit the scope of the present invention.
실시예 Example
본 발명의 실시예 및 비교실시예에서 사용된 (A) 열가소성 수지, (B) 판상의 무기물의 사양은 다음과 같다.Specifications of the (A) thermoplastic resin and (B) plate-shaped inorganic material used in Examples and Comparative Examples of the present invention are as follows.
(A) 열가소성 수지(A) thermoplastic resin
중량평균 분자량이 25,000 g/mol인 비스페놀-A 형 선형 폴리카보네이트(A1)와 I.V 1.0 인 폴리에스테르수지 폴리부틸렌테레프탈레이트(A2)를 사용하였다.Bisphenol-A linear polycarbonate (A1) having a weight average molecular weight of 25,000 g / mol and a polyester resin polybutylene terephthalate (A2) having I.V 1.0 were used.
(B) 판상의 무기물(B) plate minerals
(B1) 직경이 평균 15 ㎛이고 직경/두께비가 100이며, 기재(b1)가 마이카, 30%의 코팅물질(b2)이 산화티탄인 판상의 무기물(B1)을 사용하였다.(B1) A plate-shaped inorganic material (B1) having an average diameter of 15 μm, a diameter / thickness ratio of 100, a base material (b 1 ) of mica, and 30% of a coating material (b 2 ) of titanium oxide was used.
(B2) 직경이 평균 2 ㎛이고 직경/두께비가 100이며, 기재(b1)가 카오린, 30%의 코팅물질(b2)이 수산화알루미늄인 판상의 무기물을 사용하였다.(B2) A plate-shaped inorganic material having an average diameter of 2 μm, a diameter / thickness ratio of 100, a base material (b 1 ) of kaolin, and 30% of a coating material (b 2 ) of aluminum hydroxide was used.
(B3) 직경이 평균 500 ㎛이고 직경/두께비가 100이며, 기재(b1)가 마이카, 30%의 코팅물질(b2)이 산화티탄인 판상의 무기물을 사용하였다.(B3) A plate-shaped inorganic material having an average diameter of 500 μm, a diameter / thickness ratio of 100, a base material (b 1 ) as a mica, and 30% of a coating material (b 2 ) as titanium oxide was used.
(C) 산화티탄(C) titanium oxide
비교실시예에서 판상의 무기물을 대체하기 위하여 사용하였으며, 직경/두께 비가 1인 구형인 산화티탄을 사용하였다.In Comparative Example, it was used to replace the plate-shaped inorganic material, spherical titanium oxide having a diameter / thickness ratio of 1 was used.
실시예Example 1∼3 1 to 3
위의 각 성분을 하기 표 1에 나타낸 조성비에 따라 혼합하여 φ=45 mm인 이축 압출기를 사용하여 펠렛으로 제조하였다. 제조된 펠렛은 100 ℃에서 3 시간 이상 건조 후 10 oz 사출기에서 성형온도 260∼330 ℃, 금형온도 60∼100 ℃ 조건으로 사출하였다.Each of the above components were mixed according to the composition ratio shown in Table 1 below to prepare pellets using a twin screw extruder having a diameter of 45 mm. The prepared pellets were dried at 100 ° C. for at least 3 hours, and then injected into a 10 oz injection machine under molding conditions of 260 to 330 ° C. and mold temperatures of 60 to 100 ° C.
비교실시예Comparative Example 1∼5 1 to 5
비교실시예 1∼5는 표 1에 기재된 바와 같이 각 구성성분의 조성을 달리한 것을 제외하고는 상기 실시예 1∼3과 동일한 방법으로 시편을 제조하였다. Comparative Examples 1 to 5 were prepared in the same manner as in Examples 1 to 3 except that the composition of each component was changed as described in Table 1.
상기 실시예 및 비교실시예에 따라 제조된 각각의 시편에 대하여 다음과 같은 방법으로 물성을 평가하였으며, 그 결과를 표 2에 나타내었다.The physical properties of each specimen prepared according to the Examples and Comparative Examples were evaluated in the following manner, and the results are shown in Table 2.
(1) 백색도 : 6 inch × 6 inch의 평면사각 시편을 사출한 후, 측정장비(Gretag MacBeth Color-Eye 7000A)로 L값을 측정하였다. L값이 클수록 백색도가 우수한 것이다.(1) Whiteness: After injecting a 6 inch × 6 inch flat square specimen, the L value was measured by a measuring device (Gretag MacBeth Color-Eye 7000A). The larger the L value, the better the whiteness.
(2) 투명도 : 두께 0.5 ㎜의 평면 시편을 사출한 후, 측정장비(Gretag MacBeth Color-Eye 7000A)로 빛 투과율을 측정하였다. 투명도(transmittance)가 낮을수록 빛 투과율이 낮다.(2) Transparency: After injecting a flat specimen having a thickness of 0.5 mm, the light transmittance was measured by a measuring device (Gretag MacBeth Color-Eye 7000A). The lower the transparency, the lower the light transmittance.
(3) 내충격성 : ASTM D256 (1/4", 23℃)에 의해 측정하였으며 단위는 kgf·cm/cm이다.(3) Impact resistance: measured by ASTM D256 (1/4 ", 23 ℃), the unit is kgf · cm / cm.
상기 표 2에서 NB는 "No Break"를 의미함.In Table 2, NB means "No Break."
상기 표 2의 결과로부터, 판상의 무기물이 일정 비율로 사용된 실시예 1∼3 의 경우, 직경이 평균 500 ㎛인 판상의 무기물을 사용하거나 직경/두께비가 1인 산화티탄을 사용한 비교실시예 1∼5 에 비해 백색도를 유지하면서, 우수한 내충격성과 낮은 광투과율을 가짐을 확인할 수 있다.From the results of Table 2, in Examples 1 to 3 in which the plate-shaped inorganic material was used at a constant ratio, Comparative Example 1 using a plate-shaped inorganic material having an average diameter of 500 µm or using a titanium oxide having a diameter / thickness ratio of 1 was used. It can be confirmed that it has excellent impact resistance and low light transmittance while maintaining whiteness as compared with -5.
본 발명은 백색도와 광투과율이 우수하면서도 내충격성이 저하되지 않는 열가소성 수지 조성물을 제공하는 발명의 효과를 갖는다.This invention has the effect of providing the thermoplastic resin composition which is excellent in whiteness and light transmittance, but whose impact resistance does not fall.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 이용될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.
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| KR101105202B1 (en) | 2009-07-30 | 2012-01-13 | 웅진케미칼 주식회사 | Polymer composition for dye-based polarized film, polarized film using the same and method for preparing the same |
| CN103833308A (en) * | 2012-11-26 | 2014-06-04 | 李学富 | Alcohol-substituted gel and preparation method thereof |
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| US5478878A (en) | 1992-04-14 | 1995-12-26 | Sumitomo Chemical Company, Limited | Thermoplastic composition |
| JP2006052292A (en) | 2004-08-11 | 2006-02-23 | Mitsubishi Plastics Ind Ltd | Resin composition and film containing platy filler |
| JP2006225440A (en) | 2005-02-15 | 2006-08-31 | Toyobo Co Ltd | Polyester resin composition for light-reflecting molded article |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5478878A (en) | 1992-04-14 | 1995-12-26 | Sumitomo Chemical Company, Limited | Thermoplastic composition |
| JP2006052292A (en) | 2004-08-11 | 2006-02-23 | Mitsubishi Plastics Ind Ltd | Resin composition and film containing platy filler |
| JP2006225440A (en) | 2005-02-15 | 2006-08-31 | Toyobo Co Ltd | Polyester resin composition for light-reflecting molded article |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101105202B1 (en) | 2009-07-30 | 2012-01-13 | 웅진케미칼 주식회사 | Polymer composition for dye-based polarized film, polarized film using the same and method for preparing the same |
| CN103833308A (en) * | 2012-11-26 | 2014-06-04 | 李学富 | Alcohol-substituted gel and preparation method thereof |
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