WO2009116297A1 - 樹脂組成物 - Google Patents
樹脂組成物 Download PDFInfo
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- WO2009116297A1 WO2009116297A1 PCT/JP2009/001239 JP2009001239W WO2009116297A1 WO 2009116297 A1 WO2009116297 A1 WO 2009116297A1 JP 2009001239 W JP2009001239 W JP 2009001239W WO 2009116297 A1 WO2009116297 A1 WO 2009116297A1
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- resin 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
Definitions
- the present invention relates to a resin composition that can be used as a heat-resistant material, for example, a resin composition that can be used as a raw material for a plastic card that requires heat resistance.
- PET copolymerized polyester resin
- PETG is inferior in heat resistance
- PETG is inferior in heat resistance
- PETG when a plastic card is produced using PETG as a main raw material, there is a problem that dimensional change or deformation due to heat or curling occurs.
- Patent Documents 1-3 and the like disclose a technique for improving the heat resistance of a card by blending a heat resistant material such as polycarbonate resin with PETG.
- Japanese Patent No. 3045112 Japanese Patent Laid-Open No. 2001-80251 JP 2006-35740 A
- ETC cards ETC cards and reception management cards for digital broadcasts, etc.
- reception management cards for digital broadcasts, etc. that can be mounted or left in the car have appeared. Since the interior of a car in the summer becomes extremely hot, these cards are required to have excellent heat resistance.
- ETC card a specification that the dimensional change after being left at 90 ° C. for 6 hours is 0.2% or less has been determined.
- the present invention advances research on a resin composition containing a polyester-based resin such as PETG and a polycarbonate-based resin, and provides a new resin composition excellent in heat resistance based on the new knowledge obtained in this research. It is something to be done.
- the present invention provides a polycarbonate resin (A), a dicarboxylic acid component containing terephthalic acid as a main component, and 1,4-cyclohexane relative to 80 to 60 (molar ratio) of ethylene glycol as the main component.
- a resin composition comprising a polyester resin (B) obtained by polycondensation with a glycol component containing 20 to 40 (molar ratio, total 100) of dimethanol, and a metal oxide (C), wherein the strain is 0.
- a resin composition is proposed in which the glass transition temperature (also referred to as Tg) is in the range of 90 to 140 ° C.
- PC resin a polycarbonate resin
- CHDM 1,4-cyclohexanedimethanol
- PC resins and polyester resins having a CHDM ratio of more than 50 mol% are compatible with each other. It has been known that it is not compatible with a polyester resin (referred to as “PETG”) having a CHDM ratio of about 30 mol%.
- 3 is a measurement graph of dynamic viscoelasticity of the resin composition obtained in Example 2.
- 3 is a measurement graph of dynamic viscoelasticity of the resin composition obtained in Comparative Example 1.
- the present resin composition a resin composition (hereinafter referred to as “the present resin composition”) as an example of an embodiment of the present invention will be described.
- the scope of the present invention is not limited to the embodiments described below.
- This resin composition is a resin composition containing a polycarbonate resin (A), a polyester resin (B), and a metal oxide (C).
- Polycarbonate resin (A) The polycarbonate resin (A) that can constitute the resin composition is composed of carbonic acid and glycol or dihydric phenol, and is represented by the general formula: — (O—R—O—CO—) n— (R Is a divalent fatty acid or aromatic group).
- bisphenol A synthesized from phenol and acetone or bisphenol A and a dicarboxylic acid derivative such as tere (iso) phthalic acid dichloride
- examples thereof include those obtained by copolymerization or those obtained by polymerization of bisphenol A derivatives such as tetramethylene bisphenol A.
- the weight average molecular weight of the polycarbonate resin is not particularly limited. For example, those in the range of 10,000 to 100,000, particularly 20,000 to 30,000, particularly 23,000 to 28,000 are preferred.
- the melt flow rate of the polycarbonate resin is not particularly limited.
- the melt flow rate measured at 300 ° C. and 1.2 kg load is 5 to 20 based on JISK7210.
- One type of polycarbonate may be used alone, or two or more types of polycarbonate may be mixed and used.
- polyester resin (B) The polyester resin (B) that can constitute the resin composition comprises a dicarboxylic acid component containing terephthalic acid as a main component and 1,4-cyclohexanedi with respect to ethylene glycol 80 to 60 (molar ratio) as the main component.
- This is a so-called “PETG” polyester resin obtained by polycondensation with a glycol component containing 20 to 40 (molar ratio, total 100) of methanol (“CHDM”).
- the polyester resin (B) only needs to contain terephthalic acid as a main component as a dicarboxylic acid component, and may contain a dicarboxylic acid component other than terephthalic acid.
- the glycol component may contain 20 to 40 (molar ratio, total 100) of 1,4-cyclohexanedimethanol (“CHDM”) as a main component with respect to ethylene glycol 80 to 60 (molar ratio). It may well contain a small amount of other glycol components such as diethylene glycol.
- CHDM 1,4-cyclohexanedimethanol
- PCTG having a CHDM ratio exceeding 50 mol% is commercially available in addition to PETG having a CHDM ratio of 40 mol% or less. It is known that a mixed system of PCTG and PC resin is compatible with each other, but a mixed system of PCTG and PC resin is inferior in terms of solvent resistance and discoloration due to ultraviolet irradiation. PETG having a ratio of 40 mol% or less is employed.
- the CHDM ratio of PETG is 25 to 40 mol%, more preferably 30 to 34 mol%. Further, it is desirable that the cis / trans ratio of CHDM is approximately 70%.
- PETG having an intrinsic viscosity (IV value) of 0.70 or more is preferable.
- PETG having a CHDM ratio of 40 mol% or less and a PC resin are mixed is known to be an incompatible system, but may be compatible by blending a predetermined metal oxide (C). I understood that.
- the metal oxide (C) that can constitute the resin composition is preferably an oxide or composite oxide of one or more metals selected from the group consisting of copper, molybdenum, tin, and antimony.
- a composite oxide of two or more metals selected from the group consisting of copper, molybdenum, tin, and antimony is preferable.
- a composite oxide containing copper and molybdenum is preferable.
- the metal oxide (C) include a composite oxide represented by CuO.xMoO 3 .ySnO 2 .zSb 2 O 5 (wherein x, y and z are arbitrary numbers). .
- a metal composite oxide is an oxide containing two or more types of metal ions, and two or more types of oxides are combined, and each metal ion forms an ion lattice in the close-packed gap of O ions. It is a solid solution formed.
- the volume average particle diameter (D50) of the metal oxide is not particularly limited, but is preferably 0.1 ⁇ m to 10 ⁇ m, particularly preferably 0.1 ⁇ m to 3 ⁇ m.
- the volume average particle size (D50) is a particle size having a volume integrated value of 50% measured with a Microtrac particle size distribution measuring device.
- the metal composite oxide can be obtained by making a raw material metal oxide material to be composited into a homogeneous dry mixture and firing at a high temperature of 600 ° C. or higher. After firing, wet or dry pulverization, annealing, etc. are optional.
- the metal oxide (C) may have been subjected to surface treatment with various known inorganic compounds, organic compounds, and metals.
- the metal at this time include Si, Al, Zn, Co, Fe, Ni, Cr, Mn, W, Ti, Zr, Y, Hf, V, Nb, Ta, Sb, and Sn.
- the metal oxide (C) is preferably blended in an amount of 0.01 to 1% by weight, particularly 0.05 to 0.2%, based on the total amount of the polycarbonate resin (A) and the polyester resin (B). It is even more preferable to blend in mass%.
- Tg glass transition temperature
- This resin composition is a composition having a characteristic that the glass transition temperature (Tg) is single.
- the single glass transition temperature (Tg) of the resin composition means a dynamic viscoelastic temperature dispersion performed at a strain of 0.1%, a frequency of 10 Hz, and a temperature rising rate of 3 ° C./min.
- only one inflection point indicating the glass transition temperature appears when the glass transition temperature is measured using a differential scanning calorimeter at a heating rate of 10 ° C./min according to JIS K7121.
- a single glass transition temperature (or maximum value of loss tangent) of the polymer blend composition means that the resin to be mixed is in a compatible state on the nanometer order (molecular level). It can be recognized that the system is.
- the glass transition temperature (Tg) of the resin composition is represented by the temperature indicating the peak value of the main dispersion of the loss elastic modulus measured by the above-described dynamic viscoelasticity temperature dispersion measurement. It is important that Tg) is in the range of 90-140 ° C.
- the glass transition temperature of the resin composition is 90 ° C. or higher, the dimensional change when stored at 90 ° C. for a long time can be suppressed to be quite small. On the other hand, if it exceeds 140 ° C. and is too high, the press fusing temperature at the time of carding becomes too high, and the production becomes difficult.
- the glass transition temperature of the resin composition is more preferably 95 to 135 ° C., and particularly preferably 110 to 130 ° C.
- the manufacturing method of this resin composition is not specifically limited, For example, polycarbonate-type resin (A), polyester-type resin (B), metal oxide (C), and other components (as needed)
- the resin composition can be obtained by heat-melting and kneading D).
- the form of the resin composition may be an arbitrary shape such as a pellet shape or a film / sheet shape.
- the heating temperature at the time of melting by heating is preferably 230 ° C. to 280 ° C., particularly 240 ° C. to 260 ° C.
- Tg glass transition temperature
- Examples of the other component (D) include pigments, fillers, lubricants, impact modifiers, antioxidants, and the like.
- examples of fillers include talc, kaolin, calcium carbonate, alumina, glass fiber, and the like that are usually used for resins.
- lubricant examples include higher alcohols, fatty acid amides, higher fatty acids and their esters or metal salts, waxes such as montanic acid esters, alkylbenzene sulfonates, and various surfactants.
- this resin composition Since this resin composition is excellent in heat resistance, it can be used as a heat resistant material. For example, by preparing a sheet from the resin composition and laminating the sheet on various sheets or plates, the heat resistance of the various sheets or plates can be improved.
- plastic cards such as transparent oversheets and white core sheets.
- plastic cards that require heat resistance, such as a card that is used for a long time in a vehicle such as a reception management card such as an ETC card or digital broadcasting.
- a reception management card such as an ETC card or digital broadcasting.
- a three-dimensional molded product such as a container, a cap, a pipe, or a part can be molded using the resin composition.
- These molded products may have a multilayer structure, or may be a part of a part constituting the composite molded product.
- a known method such as injection molding, extrusion molding, hollow molding, rotational molding, powder molding, vacuum molding or the like can be employed.
- molded article examples include, for example, containers for foods, detergents, pharmaceuticals, cosmetics, beverage products and caps thereof, various parts such as automobile parts, electronic parts, electric parts, electric parts, mechanical parts, construction materials, etc. Can be mentioned.
- various films can be formed using the resin composition.
- a known method such as inflation processing, multilayer inflation processing, T-die film processing, vertical / horizontal simultaneous biaxial stretching method by flat film method, vertical / horizontal sequential biaxial stretching method, tube film method or the like is adopted. be able to.
- Films obtained in this way are ordinary thermoplastic resin films such as food packaging, textile packaging, miscellaneous goods packaging, medicine packaging, tapes, insulating materials, agricultural films, various sheets, various seals, labels, cards, etc. It is used in the same field as the field where is used.
- film refers to a thin flat product that is extremely small compared to its length and width and whose maximum thickness is arbitrarily limited, usually supplied in the form of a roll.
- sheet generally refers to a product that is thin by definition in JIS and generally has a thickness that is small and flat for the length and width.
- sheet since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.
- the expression “main component” includes the intention to allow other components to be contained within a range that does not interfere with the function of the main component, unless otherwise specified.
- the content ratio of the main component is not specified, but the component (when two or more components are main components, the total amount thereof) is 50% by mass or more, particularly 70% by mass or more in the composition. Of these, 90% by mass or more (including 100%) is preferable.
- X to Y (X and Y are arbitrary numbers) is described, it means “preferably greater than X” or “within the meaning of“ X or more and Y or less ”unless otherwise specified.
- preferably smaller than Y is also included.
- Example 1-5 A polycarbonate resin (A), a polyester resin (B) and a metal oxide (C) were mixed as shown in Table 1, respectively, and a set temperature of 260 ° C. was used using a 2-vent type co-directional twin-screw extruder having a diameter of 65 mm. A sheet having a thickness of 0.3 mm was obtained by a T-die extrusion method.
- Example 1 In Example 1, the compound was prepared in the same manner as in Example 1 except that the metal oxide (C) was not blended and the polycarbonate resin (A) and the polyester resin (B) were mixed as shown in Table 1. Obtained.
- the polycarbonate resin (A) used in Examples and Comparative Examples had a weight average molecular weight of approximately 21000 and a melt flow rate of 15 measured at 300 ° C. and 1.2 kg load based on JISK7210.
- the polyester resin (B) is composed of a dicarboxylic acid component containing terephthalic acid as a main component, and a glycol component composed of 66 mol% ethylene glycol, 32 mol% 1,4-cyclohexanedimethanol and 2 mol% diethylene glycol. It was PETG formed by polycondensation, and the intrinsic viscosity IV was 0.76.
- the glass transition temperature (Tg) is single, and the polycarbonate resin (A) and the polyester resin (B) It is confirmed that the glass transition temperature (Tg) can be adjusted in the range between the Tg (about 140 ° C.) of the polycarbonate resin (A) and the Tg (about 80 ° C.) of the polyester resin (B) depending on the ratio. did it. Therefore, it was found that both were in a compatible state.
- the glass transition temperature (Tg) is 2 corresponding to the Tg of each of the polycarbonate resin (A) and the polyester resin (B). It was found that both were incompatible.
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Abstract
Description
本樹脂組成物を構成し得るポリカーボネート系樹脂(A)は、炭酸とグリコール又は2価フェノールとからなり、一般式:-(O-R-O-CO-)n-で表されるもの(Rは二価の脂肪酸又は芳香族基)である。
本樹脂組成物を構成し得るポリエステル系樹脂(B)は、テレフタル酸を主成分として含むジカルボン酸成分と、主成分としてのエチレングリコール80~60(モル比率)に対して1,4-シクロヘキサンジメタノール(「CHDM」)を20~40(モル比率、合計100)含むグリコール成分とが重縮合してなるポリエステル系樹脂、所謂「PETG」である。
CHDM比率が40モル%以下のPETGとPC樹脂とを混合した系は非相溶系であることが知られているが、所定の金属酸化物(C)を配合することで相溶する場合があることが分かった。
本樹脂組成物において、ポリカーボネート系樹脂(A)、ポリエステル系樹脂(B)および金属酸化物(C)の配合比率に関しては、ポリカーボネート系樹脂(A)とポリエステル系樹脂(B)とを10:90~90:10の質量比率で配合するのが好ましく、特に30:70~70:30の比率で配合するのがより一層好ましい。
通常、PC樹脂とCHDM比率40モル%以下であるPETGとのブレンド系は相溶しないため、ガラス転移温度(以下「Tg」と言う)を測定すると、PC樹脂のTg(約150℃)とPETGのTg(約80℃)の2つが明確に現れる。この非相溶系組成物は、80℃を越える温度下に長時間放置されると軟化や変形が起こるため、この組成物からなるカードを例えば夏の車内に長時間放置すると、カードが縮んだり曲がったりすることがある。そのため、例えば車載テレビの受信管理用カードのように車内に長期間置かれることがあるカード用途には好ましくない。
本樹脂組成物の製造方法は、特に限定するものではないが、例えばポリカーボネート系樹脂(A)と、ポリエステル系樹脂(B)と、金属酸化物(C)と、必要に応じて他の成分(D)とを、加熱溶融して混練することにより本樹脂組成物を得ることができる。
本樹脂組成物は耐熱性に優れているため耐熱材料として用いることができる。例えば本樹脂組成物からシートを作製し、このシートを各種シート乃至プレートに積層することにより、当該各種シート乃至プレートの耐熱性を高めることができる。
一般的に「フィルム」とは、長さ及び幅に比べて厚さが極めて小さく、最大厚さが任意に限定されている薄い平らな製品で、通常、ロールの形で供給されるものをいい(日本工業規格JISK6900)、一般的に「シート」とは、JISにおける定義上、薄く、一般にその厚さが長さと幅のわりには小さく平らな製品をいう。しかし、シートとフィルムの境界は定かでなく、本発明において文言上両者を区別する必要がないので、本発明においては、「フィルム」と称する場合でも「シート」を含むものとし、「シート」と称する場合でも「フィルム」を含むものとする。
粘弾性スペクトロメーターDVA-200(アイティー計測制御株式会社製)を用い、歪み0.1%、周波数10Hz、昇温速度3℃/分の条件で動的粘弾性温度分散測定を行った。そして損失弾性率の主分散のピークを示す温度をガラス転移温度(Tg)とした。
ポリカーボネート系樹脂(A)、ポリエステル系樹脂(B)および金属酸化物(C)をそれぞれ表1に示すように混合し、直径65mmの2ベント式同方向二軸押出機を用い、設定温度260℃にてTダイ押出法により厚さ0.3mmのシートを得た。
実施例1において、金属酸化物(C)を配合せず、ポリカーボネート系樹脂(A)およびポリエステル系樹脂(B)を、表1に示すように混合した以外は実施例1と同様にしてコンパウンドを得た。
金属酸化物(C)を含有する実施例1~5の場合には、ガラス転移温度(Tg)は単一となっており、かつ、ポリカーボネート系樹脂(A)とポリエステル系樹脂(B)との比率によって、ポリカーボネート系樹脂(A)のTg(約140℃)とポリエステル系樹脂(B)のTg(約80℃)との間の範囲でガラス転移温度(Tg)が調整できていることが確認できた。従って両者が相溶している状態であることが分かった。
Claims (9)
- ポリカーボネート系樹脂(A)、テレフタル酸を主成分として含むジカルボン酸成分と、主成分としてのエチレングリコール80~60(モル比率)に対して1,4-シクロヘキサンジメタノールを20~40(モル比率、合計100)含むグリコール成分とが重縮合してなるポリエステル系樹脂(B)、および、金属酸化物(C)を含む樹脂組成物であって、
歪み0.1%、周波数10Hz、昇温速度3℃/分にて行われる動的粘弾性の温度分散測定により測定される損失弾性率の主分散のピークが一つ存在し、かつ該ピーク値を示す温度(Tg)が90~140℃の範囲に存在することを特徴とする樹脂組成物。 - 金属酸化物(C)は、銅、モリブデン、錫及びアンチモンからなる群から選ばれる1種以上の金属の酸化物或いは複合酸化物であることを特徴とする請求項1に記載の樹脂組成物。
- 金属酸化物(C)は、銅、モリブデン、錫及びアンチモンからなる群から選ばれる2種以上の金属の複合酸化物であることを特徴とする請求項1又は2に記載の樹脂組成物。
- 金属酸化物(C)は、銅及びモリブデンを含む複合酸化物であることを特徴とする請求項1又は2に記載の樹脂組成物。
- 金属酸化物(C)は、CuO・xMoO3・ySnO2・zSb2O5(式中x、y及びzは任意の数)で表わされる複合酸化物であることを特徴とする請求項1又は2に記載の樹脂組成物。
- 請求項1~5のいずれかに記載の樹脂組成物を用いてなる成形体。
- 請求項1~5のいずれかに記載の樹脂組成物を用いてなるシート。
- 請求項1~5のいずれかに記載の樹脂組成物を用いてなるカード用シート。
- 請求項8に記載のシートを用いてなるカード。
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CN200980110355.3A CN101977993B (zh) | 2008-03-21 | 2009-03-19 | 树脂组合物 |
MYPI2010004359A MY174405A (en) | 2008-03-21 | 2009-03-19 | Resin composition |
HK11102921.7A HK1148763A1 (en) | 2008-03-21 | 2011-03-23 | Resin composition |
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JP2008-073792 | 2008-03-21 | ||
JP2008073792A JP5390112B2 (ja) | 2008-03-21 | 2008-03-21 | 樹脂組成物 |
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KR (1) | KR101215661B1 (ja) |
CN (1) | CN101977993B (ja) |
HK (1) | HK1148763A1 (ja) |
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CN104744916B (zh) * | 2015-04-08 | 2016-06-08 | 台州市元嘉工业有限公司 | 一种纳米结晶复合氧化物改性的聚碳酸酯材料及其制备方法 |
CN106317829B (zh) * | 2016-08-26 | 2019-05-24 | 沈丽媛 | 一种pc合金材料及其制备方法和应用 |
KR102013019B1 (ko) * | 2016-12-30 | 2019-08-21 | 롯데첨단소재(주) | 열전도성 수지 조성물 및 이를 포함하는 복합체 |
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JP2004514011A (ja) * | 2000-11-07 | 2004-05-13 | ゼネラル・エレクトリック・カンパニイ | 透明ポリカーボネート−ポリエステル組成物及び方法 |
JP2005054179A (ja) * | 2003-07-23 | 2005-03-03 | Sumitomo Bakelite Co Ltd | カード用コアシート及びそれを用いた耐熱カード |
JP2005530003A (ja) * | 2002-06-13 | 2005-10-06 | ゼネラル・エレクトリック・カンパニイ | 熱可塑性組成物及びその製造方法 |
WO2007067462A1 (en) * | 2005-12-05 | 2007-06-14 | General Electric Company | Weatherable resinous composition with low heat storage and method |
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JP3159140B2 (ja) * | 1996-08-05 | 2001-04-23 | 東レ株式会社 | ポリエステル樹脂組成物 |
JP3045112B2 (ja) * | 1996-08-05 | 2000-05-29 | 東レ株式会社 | カード用多層ポリエステルシート |
JP4596788B2 (ja) * | 2004-02-12 | 2010-12-15 | 三菱樹脂株式会社 | 樹脂被覆金属板用シート及びその製造方法、並びに該シートを用いた樹脂被覆金属板 |
JP2005232435A (ja) * | 2004-01-20 | 2005-09-02 | Mitsubishi Plastics Ind Ltd | 熱収縮性フィルム |
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JP2003525335A (ja) * | 2000-02-29 | 2003-08-26 | ゼネラル・エレクトリック・カンパニイ | 特殊視覚効果を有するポリカーボネート/ポリエステル組成物 |
JP2004514011A (ja) * | 2000-11-07 | 2004-05-13 | ゼネラル・エレクトリック・カンパニイ | 透明ポリカーボネート−ポリエステル組成物及び方法 |
JP2003141495A (ja) * | 2001-11-05 | 2003-05-16 | Sumitomo Bakelite Co Ltd | カード |
JP2005530003A (ja) * | 2002-06-13 | 2005-10-06 | ゼネラル・エレクトリック・カンパニイ | 熱可塑性組成物及びその製造方法 |
JP2005054179A (ja) * | 2003-07-23 | 2005-03-03 | Sumitomo Bakelite Co Ltd | カード用コアシート及びそれを用いた耐熱カード |
WO2007067462A1 (en) * | 2005-12-05 | 2007-06-14 | General Electric Company | Weatherable resinous composition with low heat storage and method |
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CN101864161A (zh) * | 2010-06-24 | 2010-10-20 | 上海达凯塑胶有限公司 | 聚碳酸酯/改性共聚酯共混压延基材及其制备方法 |
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KR20100123772A (ko) | 2010-11-24 |
TW200946593A (en) | 2009-11-16 |
JP2009227788A (ja) | 2009-10-08 |
KR101215661B1 (ko) | 2012-12-26 |
JP5390112B2 (ja) | 2014-01-15 |
TWI444429B (zh) | 2014-07-11 |
HK1148763A1 (en) | 2011-09-16 |
CN101977993B (zh) | 2013-04-17 |
CN101977993A (zh) | 2011-02-16 |
MY174405A (en) | 2020-04-16 |
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