TWI444429B - Resin composition, and molding, sheet, sheet for card and card using the same - Google Patents

Resin composition, and molding, sheet, sheet for card and card using the same Download PDF

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TWI444429B
TWI444429B TW098107625A TW98107625A TWI444429B TW I444429 B TWI444429 B TW I444429B TW 098107625 A TW098107625 A TW 098107625A TW 98107625 A TW98107625 A TW 98107625A TW I444429 B TWI444429 B TW I444429B
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resin composition
card
resin
sheet
metal oxide
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TW200946593A (en
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Yoshiki Nishikawa
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Mitsubishi Plastics Inc
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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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

樹脂組成物，使用其之成形物，片材，卡片用片材，及卡片Resin composition, using the formed article, sheet, card sheet, and card

本發明係關於可作為耐熱材料使用之樹脂組成物，例如可作為要求耐熱性之塑膠卡片的原料使用之樹脂組成物。The present invention relates to a resin composition which can be used as a heat resistant material, for example, a resin composition which can be used as a raw material of a plastic card which is required to have heat resistance.

塑膠卡片大多是將著色為白色的芯片材、與透明的覆片材積層而製作。作為此等片材原料，以往係以聚氯乙烯(PVC)為主流，惟隨著環保問題之日益受到重視，現今聚酯系樹脂漸成為主流。其中，尤以將聚對苯二甲酸乙二酯樹脂之乙二醇成分的約30莫耳%取代為1,4-環己烷二甲醇所成之共聚合聚酯樹脂(稱為「PETG」)廣泛被採用。Most of the plastic cards are made by laminating a chip material colored in white and a transparent cover sheet. As a raw material for these sheets, polyvinyl chloride (PVC) has been the mainstream in the past, but with the increasing attention to environmental issues, polyester resins are becoming mainstream. Among them, a copolymerized polyester resin obtained by substituting about 30 mol% of the ethylene glycol component of the polyethylene terephthalate resin into 1,4-cyclohexanedimethanol (referred to as "PETG") ) Widely adopted.

然而，由於PETG之耐熱性差，若以PETG作為主原料製作塑膠卡片，則會發生因熱導致尺寸改變或變形或捲曲等，是其問題。However, since the heat resistance of PETG is poor, if a plastic card is produced using PETG as a main raw material, dimensional change, deformation, curling, or the like due to heat may occur, which is a problem.

因此，於以PETG作為原料之塑膠卡片及其樹脂組成物中，設法提高卡片之耐熱性之各種技術曾有報告提出。Therefore, various techniques for improving the heat resistance of cards in plastic cards and resin compositions using PETG as raw materials have been reported.

例如，於專利文獻1～3等中，曾揭示出在PETG中摻合聚碳酸酯系樹脂等之耐熱材料，藉以提高卡片之耐熱性的技術。For example, in Patent Documents 1 to 3 and the like, a technique of blending a heat-resistant material such as a polycarbonate resin with PETG to improve the heat resistance of the card has been disclosed.

[專利文獻1]日本專利第3045112號公報[Patent Document 1] Japanese Patent No. 3045112

[專利文獻2]日本專利特開2001-80251號公報[Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-80251

[專利文獻3]日本專利特開2006-35740號公報[Patent Document 3] Japanese Patent Laid-Open Publication No. 2006-35740

最近出現如ETC卡片或數位播放等之收訊管理用卡片般的有搭載或放置於車內的可能性之卡片。由於夏季的車內溫度極高，故此等卡片須要求有優異的耐熱性。例如，於ETC卡片，規定之規格為90℃、6小時放置後的尺寸改變須為0.2%以下等，對於此等塑膠卡片的耐熱性之要求日益升高。Recently, cards such as cards for receiving management such as ETC cards or digital broadcasting have been placed or placed in the vehicle. Due to the extremely high temperature inside the car in summer, these cards are required to have excellent heat resistance. For example, in an ETC card, the specified size is 90 ° C, and the dimensional change after being placed for 6 hours must be 0.2% or less, and the heat resistance of such plastic cards is increasing.

因此，本發明乃針對含有PETG等之聚酯系樹脂與聚碳酸酯系樹脂之樹脂組成物進行研究，依據此研究所得到之發現而提供耐熱性優異的嶄新樹脂組成物。Therefore, the present invention has been studied for a resin composition containing a polyester resin such as PETG or a polycarbonate resin, and has been found to provide a novel resin composition excellent in heat resistance based on the findings obtained in this study.

鑑於此課題，本發明提出一種樹脂組成物，係含有：聚碳酸酯系樹脂(A)、聚酯系樹脂(B)(係以對苯二甲酸作為主成分而含有之二羧酸成分、與含有相對於作為主成分之乙二醇80~60(莫耳比例)為20~40(莫耳比例，合計100)的1,4-環己烷二甲醇之二醇成分進行聚縮合所得者)、及金屬氧化物(C)者；其特徵在於，存在有藉由在應變0.1%、頻率10Hz、升溫速度3℃/分鐘下進行動態黏彈性溫度分散測定所測定之損失彈性模數的主分散波峰一個，且表示該波峰值之溫度(亦稱為玻璃轉移溫度或Tg)存在於90~140℃之範圍。In view of the above, the present invention provides a resin composition comprising a polycarbonate resin (A) and a polyester resin (B) (a dicarboxylic acid component containing terephthalic acid as a main component, and A polycondensation of a diol component of 1,4-cyclohexanedimethanol having a ratio of 80 to 60 (molar ratio) of ethylene glycol as a main component of 20 to 40 (mole ratio, total 100) And a metal oxide (C); characterized in that there is a main dispersion of the loss elastic modulus measured by dynamic viscoelastic temperature dispersion measurement at a strain of 0.1%, a frequency of 10 Hz, and a temperature increase rate of 3 ° C/min. The peak is one, and the temperature at which the peak of the wave (also known as the glass transition temperature or Tg) exists in the range of 90 to 140 °C.

通常，關於聚碳酸酯系樹脂(亦稱「PC樹脂」)、以對苯二甲酸作為主成分之二羧酸成分、與由乙二醇及1,4-環己烷二甲醇(亦稱「CHDM」)所構成之二醇成分進行聚縮合所得之聚酯系樹脂的混合系，PC樹脂與CHDM比例超過50莫耳%之聚酯系樹脂(稱為「PCTG」)會相溶，而PC樹脂與CHDM比例約為30莫耳%的程度之聚酯系樹脂(稱為「PETG」)則不相溶乃周知者。然而，本發明者經積極研究之結果，得知即使於PC樹脂與PETG的混合系中，若添加特定之金屬氧化物(C)則可相溶，並發現該情況下之玻璃轉移溫度(Tg)若調整於90～140℃，可成為作為卡片用材料之特佳的樹脂組成物。Usually, a polycarbonate resin (also called "PC resin"), a dicarboxylic acid component containing terephthalic acid as a main component, and ethylene glycol and 1,4-cyclohexane dimethanol (also known as " The polyester-based resin obtained by polycondensation of the diol component composed of CHDM"), the PC resin and the polyester resin (referred to as "PCTG") having a CHDM ratio of more than 50 mol% are compatible, and PC It is well known that polyester resins (referred to as "PETG") having a resin to CHDM ratio of about 30 mol% are incompatible. However, as a result of active research, the present inventors have found that even in the mixed system of PC resin and PETG, if a specific metal oxide (C) is added, it is compatible, and the glass transition temperature (Tg) in this case is found. When it is adjusted to 90 to 140 ° C, it can be a particularly preferable resin composition as a material for cards.

以下針對作為本發明之實施形態的一例之樹脂組成物(以下稱為「本樹脂組成物」)進行說明。惟，本發明之範圍並非限定於以下所說明之實施形態。Hereinafter, a resin composition (hereinafter referred to as "the present resin composition") which is an example of the embodiment of the present invention will be described. However, the scope of the invention is not limited to the embodiments described below.

本樹脂組成物為含有聚碳酸酯系樹脂(A)、聚酯系樹脂(B)、與金屬氧化物(C)之樹脂組成物。The resin composition is a resin composition containing a polycarbonate resin (A), a polyester resin (B), and a metal oxide (C).

(聚碳酸酯系樹脂(A))(Polycarbonate resin (A))

可用以構成本樹脂組成物之聚碳酸酯系樹脂(A)，係由碳酸與二醇或2價苯酚所構成，為以通式：-(O-R-O-CO-)n -表示者(R為二價脂肪酸或芳香族基)。The polycarbonate resin (A) which can be used to constitute the resin composition is composed of carbonic acid and a diol or a divalent phenol, and is represented by the formula: -(ORO-CO-) n - (R is two Valence fatty acids or aromatic groups).

可舉出例如：使用由苯酚與丙酮所合成之雙酚A藉由界面聚合法、酯交換法、吡啶法等製造者；藉由雙酚A與二羧酸衍生物(例如，對(間)苯二甲酸二氯等)之共聚合所得者；藉由雙酚A之衍生物(例如四伸甲基雙酚A等)之聚合所得者等。For example, a bisphenol A synthesized from phenol and acetone is produced by an interfacial polymerization method, a transesterification method, a pyridine method or the like; by bisphenol A and a dicarboxylic acid derivative (for example, A copolymerization product obtained by diphenyl phthalate or the like; a polymer obtained by a derivative of bisphenol A (for example, tetramethyl bisphenol A or the like).

聚碳酸酯系樹脂之重量平均分子量並無特別限定，惟以10,000～100,000為佳，以20,000～30,000為更佳，尤以23,000～28,000的範圍者為特佳。The weight average molecular weight of the polycarbonate resin is not particularly limited, but is preferably 10,000 to 100,000, more preferably 20,000 to 30,000, particularly preferably 23,000 to 28,000.

又，聚碳酸酯系樹脂之熔融流動速率並無特別限定，較佳者為，依據JIS K7210於300℃、1.2kg荷重下測得之熔融流動速率為5～20。Further, the melt flow rate of the polycarbonate resin is not particularly limited, and it is preferably a melt flow rate of 5 to 20 as measured according to JIS K7210 at 300 ° C under a load of 1.2 kg.

又，可單獨使用1種之聚碳酸酯，亦可混合使用2種以上之聚碳酸酯。Further, one type of polycarbonate may be used alone or two or more types of polycarbonate may be used in combination.

(聚酯系樹脂(B))(Polyester resin (B))

可構成本樹脂組成物之聚酯系樹脂(B)，為以對苯二甲酸作為主成分而含有之二羧酸成分、與含有相對於作為主成分之乙二醇80～60(莫耳比例)為20～40(莫耳比例，合計100)之1,4-環己烷二甲醇(「CHDM」)的二醇成分進行聚縮合所得之聚酯系樹脂，即所謂「PETG」。The polyester resin (B) which can constitute the resin composition is a dicarboxylic acid component containing terephthalic acid as a main component, and contains 80 to 60 (mole ratio) of ethylene glycol as a main component. The polyester resin obtained by polycondensation of a diol component of 1,4-cyclohexanedimethanol ("CHDM") of 20 to 40 (mole ratio, total 100) is a so-called "PETG".

聚酯系樹脂(B)中，作為二羧酸成分，可含有對苯二甲酸作為主成分，亦可含有對苯二甲酸以外之二羧酸成分。In the polyester resin (B), terephthalic acid may be contained as a main component as a dicarboxylic acid component, and a dicarboxylic acid component other than terephthalic acid may be contained.

又，作為二醇成分，可含有相對於作為主成分之乙二醇80～60(莫耳比例)為20～40(莫耳比例，合計100)之1,4-環己烷二甲醇(「CHDM」)，亦可為含有少量二乙二醇等其他二醇成分者。Further, the diol component may contain 1,4-cyclohexanedimethanol having a ratio of 80 to 60 (mole ratio) of ethylene glycol as a main component of 20 to 40 (mole ratio, total 100) (" CHDM") may also be a small amount of other diol components such as diethylene glycol.

又，關於聚酯系樹脂(B)之CHDM比例，於CHDM比例為40莫耳%以下之PETG之外，CHDM比例超過50莫耳%之PCTG亦為商業上可取得者。PCTG與PC樹脂之混合系互相可相溶乃周知者，然而由於PCTG與PC樹脂所混合者於耐溶劑性及紫外線照射所致之變色性較差，故本發明採用CHDM比例為40莫耳%以下之PETG。Further, regarding the CHDM ratio of the polyester resin (B), in addition to PETG having a CHDM ratio of 40 mol% or less, PCTG having a CHDM ratio of more than 50 mol% is also commercially available. It is well known that the mixture of PCTG and PC resin is compatible with each other. However, since the combination of PCTG and PC resin has poor discoloration property due to solvent resistance and ultraviolet irradiation, the present invention adopts a CHDM ratio of 40 mol% or less. PETG.

較佳的PETG之CHDM比例為25～40莫耳%，尤以30～34莫耳%為更佳。又，CHDM之順式/反式比，以反式比約為70%為佳。A preferred PETG has a CHDM ratio of from 25 to 40 mol%, more preferably from 30 to 34 mol%. Further, the cis/trans ratio of CHDM is preferably about 70% in a trans ratio.

其中，尤以固有黏度(IV值)為0.70以上之PETG為佳。Among them, PETG having an intrinsic viscosity (IV value) of 0.70 or more is particularly preferable.

(金屬氧化物(C))(metal oxide (C))

CHDM比例為40莫耳%以下之PETG與PC樹脂之混合系為非相溶系乃周知者，惟吾人得知藉由調配既定的金屬氧化物(C)會有可相溶之情形。It is well known that a mixture of PETG and PC resin having a CHDM ratio of 40 mol% or less is incompatible, but it is known that it is compatible by blending a predetermined metal oxide (C).

作為可構成本樹脂組成物之金屬氧化物(C)，以選自由銅、鉬、錫及銻所構成的群中之1種以上的金屬氧化物或複合氧化物為佳。其中，以選自由銅、鉬、錫及銻所構成的群中之2種以上的金屬之複合氧化物為更佳。其中，尤以含有銅及鉬之複合氧化物又更佳。The metal oxide (C) which can constitute the resin composition is preferably one or more metal oxides or composite oxides selected from the group consisting of copper, molybdenum, tin and antimony. Among them, a composite oxide of two or more kinds of metals selected from the group consisting of copper, molybdenum, tin, and antimony is more preferable. Among them, a composite oxide containing copper and molybdenum is more preferable.

作為金屬氧化物(C)之較佳具體例，可舉出：以CuO‧xMoO3 ‧ySnO2 ‧zSb2 O5 (式中，x、y及z為任意數)表示之複合氧化物等。A preferred example of the metal oxide (C) is a composite oxide represented by CuO‧xMoO 3 ‧ySnO 2 ‧zSb 2 O 5 (wherein x, y, and z are arbitrary numbers).

又，所謂「金屬之複合氧化物」係含有2種以上的金屬離子之氧化物，2種以上的氧化物之組合，各分別之金屬離子於0離子之最緊密填充縫隙形成離子格子而成為固溶體。Further, the "composite oxide of a metal" is an oxide containing two or more kinds of metal ions, and a combination of two or more kinds of oxides, and each of the metal ions forms an ion lattice at the closest filling gap of the zero ions to form a solid Solution.

金屬氧化物之體積平均粒徑(D50)並無特別限定，以0.1μm～10μm為佳，尤以0.1μm～3μm為特佳。The volume average particle diameter (D50) of the metal oxide is not particularly limited, and is preferably 0.1 μm to 10 μm, particularly preferably 0.1 μm to 3 μm.

所謂「體積平均粒徑(D50)」係以Microtrack粒度分布測定裝置所測定之體積積分值50%之粒度。The "volume average particle diameter (D50)" is a particle size of 50% by volume integral value measured by a Microtrack particle size distribution measuring apparatus.

上述金屬之複合氧化物，可將所要複合化之原料金屬氧化物材料作成為均質乾燥混合物，於600℃以上之高溫進行燒成而得到。燒成後，進行濕式或乾式粉碎，或進一步進行退火與否等可任意決定。The composite oxide of the above metal can be obtained by calcining a raw material metal oxide material to be composited into a homogeneous dry mixture at a high temperature of 600 ° C or higher. After the firing, wet or dry pulverization, or further annealing or the like can be arbitrarily determined.

金屬氧化物(C)可為公知之各種無機化合物‧有機化合物.金屬之施行有表面處理者。此時，作為金屬，可舉出例如：Si、Al、Zn、Co、Fe、Ni、Cr、Mn、W、Ti、Zr、Y、Hf、V、Nb、Ta、Sb、Sn等。The metal oxide (C) may be any of various known inorganic compounds ‧ organic compounds. The surface treatment of the metal is carried out. In this case, examples of the metal include Si, Al, Zn, Co, Fe, Ni, Cr, Mn, W, Ti, Zr, Y, Hf, V, Nb, Ta, Sb, and Sn.

(調配比例)(mixing ratio)

本樹脂組成物中，有關聚碳酸酯系樹脂(A)、聚酯系樹脂(B)及金屬氧化物(C)之調配比例，較佳者為，使聚碳酸酯系樹脂(A)與聚酯系樹脂(B)以10:90～90:10的質量比例調配，尤以30:70～70:30的比例調配為更佳。In the resin composition, the blending ratio of the polycarbonate resin (A), the polyester resin (B), and the metal oxide (C) is preferably such that the polycarbonate resin (A) and the poly The ester resin (B) is blended in a mass ratio of 10:90 to 90:10, more preferably in a ratio of 30:70 to 70:30.

又，相對於聚碳酸酯系樹脂(A)與聚酯系樹脂(B)的合計量，金屬氧化物(C)以調配0.01～1質量%為佳，尤以0.05~0.2質量%為更佳。In addition, the metal oxide (C) is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.2% by mass, based on the total amount of the polycarbonate resin (A) and the polyester resin (B). .

(玻璃轉移溫度)(glass transition temperature)

通常，由於PC樹脂與CHDM比例40莫耳%以下的PETG之混合系不相溶，故若測定玻璃轉移溫度(以下稱為「Tg」)，會明確地出現PC樹脂的Tg(約150℃)與PETG的Tg(約80℃)兩者。由於此非相溶系組成物若於超過80℃的溫度下長時間放置會發生軟化、變形，故由此組成物所作成之卡片，例如於夏天長時間放置於車內，卡片會收縮或彎曲。因此，不適於使用在例如，車用電視之收訊管理用卡片等之須長時間放置於車內的卡片用途中。Usually, since the mixture of PC resin and CHDM is not compatible with the PETG mixture of 40 mol% or less, when the glass transition temperature (hereinafter referred to as "Tg") is measured, the Tg of the PC resin (about 150 ° C) is clearly present. Both with the Tg of PETG (about 80 ° C). Since the non-phase-soluble composition softens and deforms when left at a temperature exceeding 80 ° C for a long time, the card made of the composition, for example, is placed in the vehicle for a long time in the summer, and the card shrinks or bends. Therefore, it is not suitable for use in a card application in which a card for reception management of a car television is required to be placed in the vehicle for a long time.

然而吾人發現：若添加特定的金屬氧化物(C)，則成為相溶系，確認得Tg與tan δ的極大值成為一個。而且，此情況下，藉由將Tg與tan δ的極大值調整於既定的範圍內，可得到特別適於卡片的用途之樹脂組成物。However, it has been found that when a specific metal oxide (C) is added, it becomes a compatible system, and it is confirmed that the maximum value of Tg and tan δ becomes one. Further, in this case, by adjusting the maximum value of Tg and tan δ within a predetermined range, a resin composition which is particularly suitable for use in a card can be obtained.

本樹脂組成物為具有單一的玻璃轉移溫度(Tg)的特徵之組成物。The present resin composition is a composition having a single glass transition temperature (Tg).

本發明中所謂「本樹脂組成物的玻璃轉移溫度(Tg)為單一」者，係指存在有藉由在應變0.1%、頻率10Hz、升溫速度3℃/分鐘下進行動態黏彈性溫度分散測定(JIS K-7198A法之動態黏彈性測定)所測定之損失彈性模數的主分散波峰一個，換言之為單一之波峰。此亦可說是存在有一個損失正切(tan δ)的極大值。又，亦可說是依據JIS K 7121，於加 熱速度10℃/分鐘下用示差掃描熱量計測定玻璃轉移溫度時，只呈現出一個表示玻璃轉移溫度之轉折點。In the present invention, the "glass transition temperature (Tg) of the present resin composition is a single one" means that the dynamic viscoelastic temperature dispersion measurement is performed at a strain of 0.1%, a frequency of 10 Hz, and a temperature increase rate of 3 ° C / min ( The dynamic dispersion test of the JIS K-7198A method) is one of the main dispersion peaks of the loss elastic modulus measured, in other words, a single peak. It can also be said that there is a maximum value of loss tangent (tan δ). Also, it can be said that it is based on JIS K 7121, Yu Jia When the glass transition temperature was measured by a differential scanning calorimeter at a thermal speed of 10 ° C/min, only one turning point indicating the glass transition temperature was exhibited.

所謂聚合物摻合組成物之玻璃轉移溫度(或損失正切之極大值)為單一者，係意味著混合之樹脂於奈米層次(分子層次)為相溶之狀態，可認為係相溶系。The glass transition temperature (or the maximum value of the loss tangent) of the polymer blended composition is a single one, which means that the mixed resin is in a state of being compatible at the nano layer (molecular level), and is considered to be a phase-soluble system.

本樹脂組成物之玻璃轉移溫度(Tg)係以藉由上述動態黏彈性之溫度分散測定所測得損失彈性模數之主分散波峰值表示的溫度表示者，該溫度(Tg)於90~140℃的範圍是重要的。The glass transition temperature (Tg) of the resin composition is expressed by the temperature expressed by the peak value of the main dispersion wave of the loss elastic modulus measured by the temperature dispersion measurement of the dynamic viscoelasticity, and the temperature (Tg) is 90 to 140. The range of °C is important.

本樹脂組成物的玻璃轉移溫度若為90℃以上，於90℃下長時間保管時之尺寸變化可抑制於相當小。另一方面，若超過140℃過多，於製卡片時之熔著溫度會過高，致製造困難。When the glass transition temperature of the resin composition is 90 ° C or more, the dimensional change at the time of storage at 90 ° C for a long period of time can be suppressed to be relatively small. On the other hand, if the temperature exceeds 140 °C, the melting temperature at the time of card making is too high, which makes manufacturing difficult.

基於此種考量，本樹脂組成物的玻璃轉移溫度以95~135℃為更佳，尤以110~130℃特佳。Based on such considerations, the glass transition temperature of the resin composition is preferably from 95 to 135 ° C, particularly preferably from 110 to 130 ° C.

(製造方法)(Production method)

本樹脂組成物之製造方法並無特別限定，例如，可藉由將聚碳酸酯系樹脂(A)、聚酯系樹脂(B)、金屬氧化物(C)、與必要時之其他成分(D)加熱熔融進行混練而製得本樹脂組成物。The method for producing the resin composition is not particularly limited, and for example, a polycarbonate resin (A), a polyester resin (B), a metal oxide (C), and other components as necessary (D) may be used. The resin composition is obtained by heating and melting and kneading.

作為本樹脂組成物之形態，可為顆粒狀、膜．片狀等任意形狀。As a form of the resin composition, it may be in the form of particles or a film. Any shape such as a sheet.

又，於上述製造例中，加熱熔融時之加熱溫度以230℃~280℃為佳，尤以240℃～260℃為特佳。Further, in the above production example, the heating temperature at the time of heating and melting is preferably from 230 ° C to 280 ° C, particularly preferably from 240 ° C to 260 ° C.

本樹脂組成物之玻璃轉移溫度(Tg)之調整，可舉出調整聚碳酸酯系樹脂(A)與聚酯系樹脂(B)的混合比例之方法。The method of adjusting the glass transition temperature (Tg) of the resin composition may be a method of adjusting the mixing ratio of the polycarbonate resin (A) and the polyester resin (B).

作為其他成分(D)，可舉出例如：顏料、填料、滑劑、衝擊改良劑、氧化防止劑等。Examples of the other component (D) include a pigment, a filler, a lubricant, an impact modifier, and an oxidation inhibitor.

例如，作為填料，可舉出：滑石、高嶺土、碳酸鈣、氧化鋁、玻璃纖維等通常使用於樹脂者。For example, examples of the filler include talc, kaolin, calcium carbonate, alumina, and glass fiber which are generally used in resins.

作為滑劑，可舉出：高級醇、脂肪酸醯胺、高級脂肪酸及其酯或金屬鹽、褐煤酸酯等之蠟類、烷基苯磺酸鹽及各種界面活性劑等。Examples of the slip agent include higher alcohols, fatty acid decylamines, higher fatty acids and esters or metal salts thereof, waxes such as montanic acid esters, alkylbenzenesulfonates, various surfactants, and the like.

(用途)(use)

由於本樹脂組成物於耐熱性優異，故可作為耐熱材料使用。例如，由本樹脂組成物製作片材，藉由將此片材積層為各種片材乃至板片，可提高各個該片材乃至板片之耐熱性。Since this resin composition is excellent in heat resistance, it can be used as a heat resistant material. For example, a sheet is produced from the present resin composition, and by laminating the sheet into various sheets or sheets, the heat resistance of each of the sheets and the sheets can be improved.

又，可利用於作為各種塑膠卡片之材料(例如，透明覆片或白色芯片)的原料等。尤其適於作為要求耐熱性的塑膠卡片之原料，例如，ETC卡片與數位播放等之收訊管理用卡片等之須於車內長時間使用的卡片之原料。藉由將本樹脂組成物成形為片材狀，可製作成卡片，例如ETC卡片與數位播放等之收訊管理用卡片，尤其是其芯卡。Further, it can be used as a material for various plastic card materials (for example, a transparent cover sheet or a white chip). It is particularly suitable as a raw material for a plastic card that requires heat resistance, for example, a card for a card for management such as an ETC card and a digital broadcast, which is required to be used for a long time in the vehicle. By forming the resin composition into a sheet shape, it is possible to produce a card, for example, an ETC card and a digitally-received card for receiving management, in particular, a core card.

又，用本樹脂組成物，可成形為例如：容器、蓋、管、零件等之3維成形物。此等成形物可為多層構成者，亦可為構成複合成形物的零件之一部分。Further, the present resin composition can be molded into a three-dimensional molded article such as a container, a lid, a tube, or a part. These molded articles may be composed of a plurality of layers or may be part of a part constituting the composite molded article.

作為成形方法，可採用射出成形、擠壓成形、中空成形、旋轉成形、粉末成形、真空成形等公知的方法。As the molding method, a known method such as injection molding, extrusion molding, hollow molding, rotary molding, powder molding, or vacuum molding can be employed.

具體而言，可舉出例如：食品、洗劑、醫藥品、化妝品、飲料製品等之容器或其蓋子類、汽車零件、電子零件、電氣零件、電機零件、機械零件等之各種零件、建設資材等。Specifically, for example, containers such as foods, lotions, pharmaceuticals, cosmetics, and beverage products, or covers thereof, automobile parts, electronic parts, electrical parts, motor parts, mechanical parts, and the like, and construction materials may be mentioned. Wait.

又，亦可用本樹脂組成物形成各種薄膜。Further, various films can be formed using the resin composition.

作為成形方法，可採用充氣(inflation)加工、多層充氣加工、T模薄膜加工、平面膜(flat film)法之同時縱橫進行的雙軸延伸法或依序縱橫進行的雙軸延伸法、試管薄膜法等公知的方法。As the forming method, a biaxial stretching method in which the vertical and horizontal directions are simultaneously carried out by inflation processing, multi-layer inflation processing, T-die film processing, flat film method, or biaxial stretching method in sequence, and a test tube film can be employed. A well-known method such as law.

得到之薄膜可用於食品包裝、纖維包裝、雜貨包裝、藥品類包裝、膠帶、絕緣材料、農藥用薄膜、各種片材、各種填縫材、標籤、卡片等之與通常的熱可塑性樹脂薄膜所使用之同樣的用途。The obtained film can be used for food packaging, fiber packaging, grocery packaging, pharmaceutical packaging, tape, insulating materials, films for pesticides, various sheets, various filler materials, labels, cards, etc., and is used for usual thermoplastic resin films. The same use.

(術語之說明)(Description of terms)

通常「薄膜」係指長與寬相比之厚度極薄，最大厚度可任意限定的薄而平之製品，通常係以成捲的形態供應者(日本工業規格JIS K6900)；通常所謂「片材(sheet)」係指於JIS之定義上薄(通常，其厚度相較於長與寬為極小)而平之製品。然而，片材與薄膜之區分並無界定，於本發明中並無須在字面上對兩者加以區別，故本發明中稱為「薄膜」時亦包含「片材」，稱為「片材」時亦包含「薄膜」。Usually, "thin film" refers to a thin and flat product whose thickness is extremely thin compared to the width and can be arbitrarily limited in maximum thickness. It is usually supplied in a roll form (Japanese Industrial Standard JIS K6900); usually called "sheet" ") means a product that is thin (usually, its thickness is extremely small compared to the length and width) in the definition of JIS. However, the distinction between the sheet and the film is not defined. In the present invention, there is no need to distinguish between the two. Therefore, the term "film" in the present invention also includes "sheet", which is called "sheet". It also contains "film".

本發明中以「主成分」表現之情況，只要未特別記述，亦包含「容許在不妨礙該主成分的作用之範圍內含有其他成分」之意義。該主成分的含有比例並未特別規定，惟其成分(於主成分為2成分以上之情況為其合計量)以於組成物中宜為佔50質量%以上，以70質量%以上為更佳，尤以90質量%以上(包含100%)為特佳。In the case of the "main component" in the present invention, the meaning of "may allow other components to be contained within a range that does not interfere with the action of the main component" unless otherwise specified. The content of the main component is not particularly limited, and the component (in the case where the main component is two or more components, the total amount thereof) is preferably 50% by mass or more, and more preferably 70% by mass or more. Especially, 90% by mass or more (including 100%) is particularly preferable.

又，於本說明書中，於記述為「X~Y」(X、Y為任意數)之情況，只要未特別說明，係包含「X以上、Y以下」，亦包含「以大於X為佳」或「以小於Y為佳」之含意。In addition, in this specification, when it is described as "X~Y" (X, Y is an arbitrary number), unless otherwise specified, "X or more, Y or less" is included, and "It is preferable to be larger than X". Or the meaning of "less than Y".

[實施例][Examples]

以下揭示實施例，針對本發明更具體地進行說明，惟本發明並非限定於此等，於不脫離本發明之技術性主旨的範圍內之各種應用皆屬可能。The present invention is described in detail below with reference to the preferred embodiments of the present invention, but the invention is not limited thereto, and various applications within the scope of the technical spirit of the invention are possible.

(1)玻璃轉移溫度之測定方法(1) Method for measuring glass transition temperature

用黏彈性Spectrometer DVA-200(I.T.計測控制(股)製)，在應變0.1%、頻率10Hz、升溫速度3℃/分鐘下進行動態黏彈性溫度分散測定。再以表示損失彈性模數的主分散波峰之溫度作為玻璃轉移溫度(Tg)。Dynamic viscoelasticity temperature dispersion measurement was carried out using a viscoelastic Spectrometer DVA-200 (manufactured by I.T. Measurement Control Co., Ltd.) at a strain of 0.1%, a frequency of 10 Hz, and a temperature increase rate of 3 ° C/min. Further, the temperature of the main dispersion peak indicating the loss elastic modulus is taken as the glass transition temperature (Tg).

(實施例1~5)(Examples 1 to 5)

將聚碳酸酯系樹脂(A)、聚酯系樹脂(B)及金屬氧化物(C)分別如表1所示般混合，用直徑65mm之2排氣孔(vent)式同方向雙軸擠壓機，於設定溫度260℃藉由T模擠壓法製得厚度0.3mm之片材。The polycarbonate resin (A), the polyester resin (B), and the metal oxide (C) were mixed as shown in Table 1, and vented in the same direction by a vent type of 65 mm in diameter. A press was used to obtain a sheet having a thickness of 0.3 mm by a T-die extrusion method at a set temperature of 260 °C.

(比較例1)(Comparative Example 1)

除了於實施例1中未調配金屬氧化物(C)，將聚碳酸酯系樹脂(A)及聚酯系樹脂(B)如表1所示般混合之外，係以與實施例1相同之做法製得混合物(compound)。Except that the metal oxide (C) was not blended in Example 1, the polycarbonate resin (A) and the polyester resin (B) were mixed as shown in Table 1, and the same as in Example 1. The procedure produces a compound.

又，實施例及比較例中使用之聚碳酸酯系樹脂(A)，其重量平均分子量約為21000，依據JIS K7210於300℃、1.2kg荷重下測定之熔融流動速率為15。Further, the polycarbonate resin (A) used in the examples and the comparative examples had a weight average molecular weight of about 21,000, and had a melt flow rate of 15 in accordance with JIS K7210 at 300 ° C and a load of 1.2 kg.

又，聚酯系樹脂(B)為使以對苯二甲酸作為主成分之二羧酸成分、由乙二醇66莫耳%及1,4-環己烷二甲醇32莫耳%及二乙二醇2莫耳%所構成之二醇成分進行聚縮合所得之PETG，固有黏度IV為0.76。Further, the polyester resin (B) is a dicarboxylic acid component containing terephthalic acid as a main component, 32 mol % of ethylene glycol 66, and 32 mol% of 1,4-cyclohexane dimethanol, and 2 PETG obtained by polycondensation of a diol component composed of 2% diol of diol has an intrinsic viscosity IV of 0.76.

作為金屬氧化物(C)，係用由CuO‧xMoO3 ‧ySnO2 ‧zSb2 O5 (式中，x=2、y=1、z=1)表示之複合氧化物。此複合氧化物係使複合化之原料金屬氧化物材料作成為均質乾燥混合物，於800℃下燒成所得者。As the metal oxide (C), a composite oxide represented by CuO‧xMoO 3 ‧ySnO 2 ‧zSb 2 O 5 (wherein x=2, y=1, and z=1) is used. This composite oxide is obtained by firing a composite raw material metal oxide material into a homogeneous dry mixture at 800 °C.

(探討)(discussion)

於含有金屬氧化物(C)之實施例1~5的情況，確認得知：玻璃轉移溫度(Tg)成為單一，且藉由聚碳酸酯系樹脂(A)與聚酯系樹脂(B)之比例，玻璃轉移溫度(Tg)可調整於聚碳酸酯系樹脂(A)之Tg(約140℃)與聚酯系樹脂(B)之Tg(約80℃)間的範圍。因而，可知兩者為相溶狀態。In the case of Examples 1 to 5 containing the metal oxide (C), it was confirmed that the glass transition temperature (Tg) was single and the polycarbonate resin (A) and the polyester resin (B) were used. The ratio of the glass transition temperature (Tg) can be adjusted between the Tg (about 140 ° C) of the polycarbonate resin (A) and the Tg (about 80 ° C) of the polyester resin (B). Therefore, it can be seen that the two are in a compatible state.

另一方面，於未含有金屬氧化物(C)之比較例1的情況，玻璃轉移溫度(Tg)存在有分別相當於聚碳酸酯系樹脂(A)及聚酯系樹脂(B)的Tg之2個溫度，可知兩者為非相溶狀態。On the other hand, in the case of Comparative Example 1 which does not contain the metal oxide (C), the glass transition temperature (Tg) corresponds to the Tg of the polycarbonate resin (A) and the polyester resin (B), respectively. At two temperatures, it is known that the two are incompatible.

又，將實施例2及比較例1的場合之動態黏彈性測定數據分別示於圖1、圖2。曲線圖中，Er為貯藏彈性模數、Ei為損失彈性模數、tan δ為損失正切之數據。Further, the dynamic viscoelasticity measurement data in the case of Example 2 and Comparative Example 1 are shown in Fig. 1 and Fig. 2, respectively. In the graph, Er is the data of the storage elastic modulus, Ei is the loss elastic modulus, and tan δ is the loss tangent.

又，用與實施例1~5同樣地製作得到之樹脂組成物製作使用於卡片之芯卡，確認得知其良好地適合作為卡片材料。因而，若考量實施例1~5中得到之樹脂組成物(片材)之Tg的範圍，只要Tg為90～140℃的範圍內，可較佳地使用作為卡片材料。又，於實施例1～5之中，特別是實施例2、3、4之結果良好，針對此結果考量，得知Tg若為110～130℃的範圍內，可更佳地使用作為卡片材料。Further, the resin composition produced in the same manner as in Examples 1 to 5 was used to produce a core card for use in a card, and it was confirmed that it was favorably used as a card material. Therefore, the range of the Tg of the resin composition (sheet) obtained in Examples 1 to 5 can be preferably used as a card material as long as the Tg is in the range of 90 to 140 °C. Further, among Examples 1 to 5, in particular, the results of Examples 2, 3, and 4 were good, and it was found from the results that Tg was more preferably used as a card material in the range of 110 to 130 °C. .

於前述實施例中，作為金屬氧化物(C)係使用由CuO‧xMoO3 ‧ySnO2 ‧zSb2 O5 (式中，x=2、y=1、z=1)表示之複合氧化物，惟綜合迄今所進行之試驗結果，大致而言，即使是使用選自由銅、鉬、錫及銻所構成的群中之1種以上的金屬之氧化物或複合氧化物，亦可期待與CuO‧xMoO3 ‧ySnO2 ‧zSb2 O5 (式中，x=2、y=1、z=1)同樣的效果，其中以選自由銅、鉬、錫及銻所構成的群中之2種以上的金屬之複合氧化物為佳，其中尤以含有銅及鉬的複合氧化物可期待有較佳的效果。In the above embodiment, as the metal oxide (C), a composite oxide represented by CuO‧xMoO 3 ‧ySnO 2 ‧zSb 2 O 5 (wherein x=2, y=1, z=1) is used. However, in general, even if an oxide or a composite oxide of one or more kinds of metals selected from the group consisting of copper, molybdenum, tin, and antimony is used, it is expected to be combined with CuO‧ xMoO 3 ‧ySnO 2 ‧zSb 2 O 5 (wherein x=2, y=1, z=1), the same effect, in which two or more selected from the group consisting of copper, molybdenum, tin, and antimony A composite oxide of a metal is preferable, and a composite oxide containing copper and molybdenum is particularly expected to have a preferable effect.

圖1為實施例2中得到之樹脂組成物的動態黏彈性之測定曲線圖。Fig. 1 is a graph showing the measurement of the dynamic viscoelasticity of the resin composition obtained in Example 2.

圖2為比較例1中得到之樹脂組成物的動態黏彈性之測定曲線圖。Fig. 2 is a graph showing the measurement of dynamic viscoelasticity of the resin composition obtained in Comparative Example 1.

Claims (9)

一種樹脂組成物，其含有：聚碳酸酯系樹脂(A)；聚酯系樹脂(B)，係含有對苯二甲酸作為主成分之二羧酸成分、與含有相對於作為主成分之乙二醇80~60莫耳比例為20~40莫耳比例(合計100莫耳比例)的1,4-環己烷二甲醇之二醇成分進行聚縮合所得；及金屬氧化物(C)；其特徵在於，存在有一個藉由在應變0.1%、頻率10Hz、升溫速度3℃/分鐘下進行動態黏彈性溫度分散測定所測定之損失彈性模數的主分散波峰，且表示該波峰值之溫度Tg存在於90~140℃之範圍。 A resin composition comprising: a polycarbonate resin (A); a polyester resin (B), a dicarboxylic acid component containing terephthalic acid as a main component, and a second component as a main component a diol component having a ratio of 80 to 60 moles of 20 to 40 moles (total 100 moles) of 1,4-cyclohexanedimethanol obtained by polycondensation; and a metal oxide (C); Therefore, there is a main dispersion peak of the loss elastic modulus measured by dynamic viscoelastic temperature dispersion measurement at a strain of 0.1%, a frequency of 10 Hz, and a temperature increase rate of 3 ° C/min, and the temperature Tg of the peak is present. In the range of 90 ~ 140 ° C. 如申請專利範圍第1項之樹脂組成物，其中，金屬氧化物(C)係選自由銅、鉬、錫及銻所構成的群中之1種以上的金屬之氧化物或複合氧化物。 The resin composition of the first aspect of the invention, wherein the metal oxide (C) is an oxide or a composite oxide of one or more selected from the group consisting of copper, molybdenum, tin and antimony. 如申請專利範圍第1項之樹脂組成物，其中，金屬氧化物(C)係選自由銅、鉬、錫及銻所構成的群中之2種以上的金屬之複合氧化物。 The resin composition of the first aspect of the invention, wherein the metal oxide (C) is a composite oxide of two or more kinds of metals selected from the group consisting of copper, molybdenum, tin and antimony. 如申請專利範圍第1項之樹脂組成物，其中，金屬氧化物(C)係含有銅及鉬之複合氧化物。 The resin composition of claim 1, wherein the metal oxide (C) contains a composite oxide of copper and molybdenum. 如申請專利範圍第1項之樹脂組成物，其中，金屬氧化物(C)係以CuO．xMoO3 ．ySnO2 ．zSb2 O5 表示之複合氧化物；式中，x、y及z為任意數。The resin composition of claim 1, wherein the metal oxide (C) is CuO. xMoO 3 . ySnO 2 . a composite oxide represented by zSb 2 O 5 ; wherein x, y and z are arbitrary numbers. 一種成形物，其係使用申請專利範圍第1至5項中任一 項之樹脂組成物所作成。 A molded article which is used in any one of claims 1 to 5 The resin composition of the item is made. 一種片材，其係使用申請專利範圍第1至5項中任一項之樹脂組成物所作成。 A sheet which is produced by using the resin composition of any one of claims 1 to 5. 一種卡片用片材，其係使用申請專利範圍第1至5項中任一項之樹脂組成物所作成。 A sheet for a card, which is produced by using the resin composition of any one of claims 1 to 5. 一種卡片，其係使用申請專利範圍第8項之片材所作成。A card made using the sheet of claim 8 of the patent application.
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