JP2006297853A - Film for use in molding - Google Patents
Film for use in molding Download PDFInfo
- Publication number
- JP2006297853A JP2006297853A JP2005126188A JP2005126188A JP2006297853A JP 2006297853 A JP2006297853 A JP 2006297853A JP 2005126188 A JP2005126188 A JP 2005126188A JP 2005126188 A JP2005126188 A JP 2005126188A JP 2006297853 A JP2006297853 A JP 2006297853A
- Authority
- JP
- Japan
- Prior art keywords
- film
- layer
- polyester
- molding
- vapor deposition
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 238000000465 moulding Methods 0.000 title claims abstract description 34
- 238000007740 vapor deposition Methods 0.000 claims abstract description 42
- 229910052738 indium Inorganic materials 0.000 claims abstract description 17
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920006267 polyester film Polymers 0.000 claims abstract description 11
- 229920000728 polyester Polymers 0.000 claims description 84
- 238000002844 melting Methods 0.000 claims description 24
- 230000008018 melting Effects 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 abstract description 27
- 239000002184 metal Substances 0.000 abstract description 27
- 239000010410 layer Substances 0.000 description 132
- 238000000034 method Methods 0.000 description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 16
- 229920000139 polyethylene terephthalate Polymers 0.000 description 15
- 239000005020 polyethylene terephthalate Substances 0.000 description 15
- 238000011282 treatment Methods 0.000 description 15
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 230000009477 glass transition Effects 0.000 description 12
- 239000002932 luster Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000010419 fine particle Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000002356 single layer Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- -1 polyethylene terephthalate Polymers 0.000 description 9
- 238000007493 shaping process Methods 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- 229920001634 Copolyester Polymers 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
Description
本発明は成形用フィルムに関し、詳しくは成形部品の表面に用いたときに金属様の外観を呈する成形用フィルムに関する。 The present invention relates to a molding film, and more particularly to a molding film that exhibits a metal-like appearance when used on the surface of a molded part.
近年、家具や屋内装飾品、電化製品、自動車部品等に用いられる樹脂製部品において、金属光沢のある外観を得る目的で、成形部品にめっき処理やスプレー塗装等の塗装処理を施しているが、いずれも有機溶剤を使用しており、廃液処理の問題などを考慮すると今日の環境問題に対して非常に好ましくないという問題がある。また、これらの処理は、部品を成形加工した後に施される為、バッチ処理となり、生産性が低く好ましくない。 In recent years, resin parts used for furniture, interior decorations, electrical appliances, automobile parts, etc., have been subjected to coating treatment such as plating treatment and spray painting on molded parts for the purpose of obtaining a metallic glossy appearance. All of them use an organic solvent, and there is a problem that it is very unfavorable for today's environmental problems when considering the problem of waste liquid treatment. In addition, since these treatments are performed after the parts are molded, they are batch treatments, which are not preferable because of low productivity.
これらの問題を解決するべく、金属光沢のある外観を有する成形品を得るために、1)アルミ蒸着を施したフィルムと成形シートをラミネートすることで得られた積層シートを成形加工して成形品を得る技術や、2)アルミ蒸着を施したフィルム（もしくはこれと成形シートをラミネートして得られた積層シート）を成形金型に挿入した状態で射出成形し、フィルムもしくは積層シートを成形品の表層として一体化させる技術、3)離型層を介してその上にアルミ蒸着を行ったフィルムを成形金型に挿入した状態で射出成形し、アルミ蒸着層のみを成形部品に転写する技術などが用いられている。 In order to solve these problems, in order to obtain a molded product having a metallic glossy appearance, 1) a molded sheet is formed by laminating a laminated sheet obtained by laminating a film on which aluminum has been deposited and a molded sheet. 2) Injection molding with a film (or a laminated sheet obtained by laminating this and a molded sheet) subjected to aluminum vapor deposition inserted into a molding die, and the film or laminated sheet 3) Technology to integrate as a surface layer, 3) Technology to perform injection molding with a film on which aluminum is vapor-deposited via a release layer inserted into a molding die, and transfer only the aluminum vapor-deposited layer to a molded part It is used.
しかしながら、これらの技術においてはアルミ蒸着を施した後に成形加工を行うために、アルミ蒸着層が延伸され、アルミ蒸着層にひび割れが生じるため、金属光沢が劣ってしまう。また、基材となるフィルムの成形加工性が低い場合には、成形加工工程、射出成形工程においてフィルムに与えられた変形によりフィルムが切断してしまう、フィルムが十分に変形しきらずに部品として不十分となってしまう。 However, in these techniques, since the aluminum vapor deposition layer is stretched and cracked in the aluminum vapor deposition layer in order to perform molding after aluminum vapor deposition, the metallic luster is inferior. In addition, when the film formability of the base film is low, the film is cut by deformation given to the film in the molding process and the injection molding process. It will be enough.
本発明は、上述の問題点を改善することを目的とする。すなわち、本発明の課題は成形加工後においても優れた金属光沢を有するとともに、成形加工時のフィルムの成形加工性に優れる成形用フィルムを提供することにある。 The present invention aims to improve the above-mentioned problems. That is, the subject of this invention is providing the film for shaping | molding which has the outstanding metallic luster after a shaping | molding process, and is excellent in the shaping | molding processability of the film at the time of a shaping | molding process.
すなわち本発明は、１００℃における破断伸度２００〜５５０％かつ１００℃における破断応力１Ｍ〜１３０ＭＰａのポリエステルフィルムと、このうえに設けられたインジウム蒸着層とからなる、成型用フィルムである。 That is, the present invention is a molding film comprising a polyester film having a breaking elongation of 200 to 550% at 100 ° C. and a breaking stress of 1 M to 130 MPa at 100 ° C., and an indium vapor deposition layer provided thereon.
本発明によれば、成形加工後においても優れた金属光沢を有するとともに、成形加工時のフィルムの成形加工性に優れる成形用フィルムを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, while having the outstanding metallic luster after a shaping | molding process, the film for shaping | molding which is excellent in the shaping property of the film at the time of a shaping | molding process can be provided.
以下、本発明を詳細に説明する。
［基材フィルム］
本発明においては、ポリエステルフィルムを基材フィルムとして用い、このうえにインジウム蒸着層を設ける。このポリエステルフィルムとして、１００℃における破断伸度が２００〜５５０％であり、かつ１００℃における破断応力が１Ｍ〜１３０ＭＰａであるポリエステルフィルムを用いる。１００℃における破断伸度と破断応力が上記を満たさないと成型加工の際にフィルムが伸びきらず金型の形状まで変形することができず、フィルムが切断してしまうなどの問題が生じる。この特性を有するポリエステルフィルムとして、以下に説明する積層フィルムを用いることが好ましい。
Hereinafter, the present invention will be described in detail.
[Base film]
In the present invention, a polyester film is used as a base film, and an indium vapor deposition layer is provided thereon. As this polyester film, a polyester film having a breaking elongation at 100 ° C. of 200 to 550% and a breaking stress at 100 ° C. of 1 M to 130 MPa is used. If the breaking elongation and breaking stress at 100 ° C. do not satisfy the above, the film cannot be fully stretched during the molding process and cannot be deformed to the shape of the mold, resulting in problems such as the film being cut. As a polyester film having this characteristic, a laminated film described below is preferably used.
すなわち本発明においては、基材フィルムとして、融点Ｔｍ（Ａ）℃を示すポリエステルから成るポリエステル層Ａと、融点Ｔｍ（Ｂ）℃を示すポリエステルから成るポリエステル層ＢがＡ／Ｂ／Ａの順序で配置された積層フィルムであり、Ｔｍ（Ａ）＞Ｔｍ（Ｂ）であり、ポリエステル層Ａは延伸配向構造を有し、ポリエステル層Ｂは非配向構造を有する積層フィルムを用いるとよい。 That is, in the present invention, as the base film, a polyester layer A made of polyester having a melting point Tm (A) ° C. and a polyester layer B made of polyester showing a melting point Tm (B) ° C. are in the order of A / B / A. It is a laminated film that is disposed, Tm (A)> Tm (B), the polyester layer A has a stretched orientation structure, and the polyester layer B may have a non-oriented structure.
この積層フィルムのポリエステル層Ａを構成するポリエステルとしては、成膜後の１軸または２軸の延伸処理により配向結晶構造を形成し得るポリエステルを用いる。ポリエステル層Ａのポリエステルの融点は、好ましくは２０５〜２７０℃、ポリエステル層Ｂのポリエステルの融点は、好ましくは１９０〜２５０℃である。ここで融点は、ポリエステルを一度溶融した後、急冷、固化したサンプルを、示差熱熱量計で２０℃／分の速度で昇温したときの溶融吸熱ピーク温度である。フィルム、加工製品の寸法安定性、耐変形性、耐カール性を良好に維持する観点から、ポリエステル層Ａのポリエステルのガラス転移温度は好ましくは６０℃以上、さらに好ましくは７０℃以上である。このポリエステルとして、例えば共重合ポリエチレンテレフタレート、共重合ポリエチレンナフタレンジカルボキシレート、好ましくはイソフタル酸およびテトラメチレングリコールを共重合成分として含む共重合ポリエチレンテレフタレートを用いるとよい。イソフタル酸の共重合量およびテトラメチレングリコールの共重合量は、融点およびがラス転移温度が上記の範囲となるように調整すればよいが、例えばイソフタル酸を全ジカルボン酸成分あたり５〜１０モル％、テトラメチレングリコールを全ジオール成分あたり３０〜６０モル％用いるとよい。 As the polyester constituting the polyester layer A of the laminated film, a polyester capable of forming an oriented crystal structure by uniaxial or biaxial stretching treatment after film formation is used. The melting point of the polyester of the polyester layer A is preferably 205 to 270 ° C., and the melting point of the polyester of the polyester layer B is preferably 190 to 250 ° C. Here, the melting point is the melting endothermic peak temperature when the polyester is once melted, rapidly cooled and solidified, and then heated at a rate of 20 ° C./min with a differential calorimeter. From the viewpoint of maintaining good dimensional stability, deformation resistance and curl resistance of the film and processed product, the glass transition temperature of the polyester of the polyester layer A is preferably 60 ° C. or higher, more preferably 70 ° C. or higher. As this polyester, for example, copolymerized polyethylene terephthalate, copolymerized polyethylene naphthalene dicarboxylate, preferably copolymerized polyethylene terephthalate containing isophthalic acid and tetramethylene glycol as copolymerized components may be used. The copolymerization amount of isophthalic acid and the copolymerization amount of tetramethylene glycol may be adjusted so that the melting point and the lath transition temperature are within the above ranges. For example, isophthalic acid is 5 to 10 mol% per total dicarboxylic acid component. Tetramethylene glycol is preferably used in an amount of 30 to 60 mol% per diol component.
ポリエステル層Ｂを構成するポリエステルとしては、ポリエステル層Ａを構成するポリエステルの融点よりも低い融点を有するポリエステルを用いる。この融点の差は、好ましくは１５℃以上、さらに好ましくは２０℃以上、特に好ましくは３０℃以上あるとよい。フィルム、加工製品の寸法安定性、耐変形性、耐カール性を良好に維持する観点から、ポリエステル層Ｂのポリエステルのガラス転移温度は好ましくは５０℃以上、さらに好ましくは７０℃以上である。 As the polyester constituting the polyester layer B, a polyester having a melting point lower than that of the polyester constituting the polyester layer A is used. The difference in melting point is preferably 15 ° C. or higher, more preferably 20 ° C. or higher, and particularly preferably 30 ° C. or higher. From the viewpoint of maintaining good dimensional stability, deformation resistance and curl resistance of the film and processed product, the glass transition temperature of the polyester of the polyester layer B is preferably 50 ° C. or higher, more preferably 70 ° C. or higher.
ポリエステル層Ｂのポリエステルとしては、例えば以下のポリエステルを用いることができる。すなわち、1)テレフタル酸およびナフタレンジカルボン酸を主とするジカルボン酸成分とエチレングリコールを主とするジオール成分からなるコポリエステル、2)テレフタル酸およびイソフタル酸を主とするジカルボン酸成分とエチレングリコールを主とするジオール成分からなるコポリエステル、3)テレフタル酸およびナフタレンジカルボン酸およびイソフタル酸を主とするジカルボン酸成分とエチレングリコールを主とするジオール成分からなるコポリエステル、4)テレフタル酸、２，６−ナフタレンジカルボン酸およびイソフタル酸を主とするジカルボン酸成分とエチレングリコールを主とするジオール成分からなるコポリエステルである。特に4)のコポリエステルのなかでもテレフタル酸９０〜６０モル％、ナフタレンジカルボン酸５〜２０モル％およびイソフタル酸５〜２０モル％からなるジカルボン酸成分と、エチレングリコールを主たる成分とするジオール成分からなる共重合ポリエステルが好ましい。ここで主たる成分とは、全ジカルボン酸成分または全ジオール成分あたり９０モル％以上の成分をいう。 As polyester of the polyester layer B, the following polyester can be used, for example. That is, 1) a copolyester composed of a dicarboxylic acid component mainly composed of terephthalic acid and naphthalenedicarboxylic acid and a diol component mainly composed of ethylene glycol, and 2) a dicarboxylic acid component mainly composed of terephthalic acid and isophthalic acid and ethylene glycol. A copolyester composed of a diol component, 3) a copolyester composed of a dicarboxylic acid component mainly composed of terephthalic acid, naphthalene dicarboxylic acid and isophthalic acid, and a diol component mainly composed of ethylene glycol, 4) terephthalic acid, 2,6- It is a copolyester comprising a dicarboxylic acid component mainly composed of naphthalenedicarboxylic acid and isophthalic acid and a diol component mainly composed of ethylene glycol. In particular, among the copolyesters of 4), from a dicarboxylic acid component consisting of 90 to 60 mol% terephthalic acid, 5 to 20 mol% naphthalene dicarboxylic acid and 5 to 20 mol% isophthalic acid, and a diol component mainly composed of ethylene glycol. A copolyester is preferred. Here, the main component means a component of 90 mol% or more per total dicarboxylic acid component or total diol component.
夏期における車中での保管等の高温雰囲気に製品等が曝される用途では、いずれも８０℃以上のガラス転移温度を有することが好ましい。また、フィルムの厚み斑を良好にするために、ポリエステル層Ａのガラス転移点とポリエステル層Ｂのガラス転移点の差は、好ましくは２０℃以下、さらに好ましくは１０℃以下、特に好ましくは５℃以下である。ここで、ガラス転移温度は、ポリエステルを一度溶融して後、急冷、固化したサンプルを、示差熱熱量計で２０℃／分の速度で昇温したときの構造変化（比熱変化）温度をいう。 In applications where products and the like are exposed to a high temperature atmosphere such as storage in a car in summer, it is preferable that all have a glass transition temperature of 80 ° C. or higher. Moreover, in order to make the thickness unevenness of a film favorable, the difference of the glass transition point of the polyester layer A and the glass transition point of the polyester layer B becomes like this. Preferably it is 20 degrees C or less, More preferably, it is 10 degrees C or less, Most preferably, it is 5 degrees C It is as follows. Here, the glass transition temperature is a structural change (specific heat change) temperature when a sample obtained by melting a polyester once, then rapidly cooling and solidifying is heated at a rate of 20 ° C./min with a differential calorimeter.
［積層フィルムの層構成］
基材フィルムとして積層フィルムを用いる場合、積層フィルムは、好ましくはＡ／Ｂ／Ａの３層の積層構造を有する。ポリエステル層Ｂを非配向構造にするには、積層フィルムを熱処理すればよい。この熱処理はポリエステル層Ｂの両面にポリエステル層Ａを積層した状態で、ポリエステル層Ａのポリエステルの融点より低くかつポリエステル層Ｂのポリエステルの融点より高い温度で行なう。これにより、ポリエステル層Ｂのポリエステルは一時溶融状態になるため、ポリエステル層Ｂのポリマー配向構造は、熱処理前に１軸または２軸の延伸配向構造であったとしても、熱処理後には実質的に無配向な構造になる。この熱処理は、好ましくは、共押出製膜法における延伸処理後の熱固定処理時の温度を、ポリエステル層Ａのポリエステルの融点より低くかつポリエステル層Ｂのポリエステルの融点より高い温度に設定することで有効に行うことができる。
[Layer structure of laminated film]
When a laminated film is used as the base film, the laminated film preferably has a three-layer laminated structure of A / B / A. In order to make the polyester layer B non-oriented, the laminated film may be heat-treated. This heat treatment is performed at a temperature lower than the melting point of the polyester of the polyester layer A and higher than the melting point of the polyester of the polyester layer B, with the polyester layer A laminated on both sides of the polyester layer B. Thereby, since the polyester of the polyester layer B is in a temporarily melted state, even if the polymer orientation structure of the polyester layer B is a uniaxial or biaxial stretch orientation structure before the heat treatment, the polyester layer B is substantially free after the heat treatment. It becomes an oriented structure. This heat treatment is preferably performed by setting the temperature during the heat setting treatment after the stretching treatment in the coextrusion film forming method to a temperature lower than the melting point of the polyester of the polyester layer A and higher than the melting point of the polyester of the polyester layer B. It can be done effectively.
この積層フィルムの層構成は、例えばＡ／Ｂ／Ａ（なお、／は層の構成を示す）タイプの３層構成、Ａ／Ｂ／Ａ／Ｂ／Ａタイプの５層構成、さらにこれらの順序による７層、９層、２ｎ＋１（ｎは自然数）構成等マルチ多層構成を採用することができる。 The layer structure of this laminated film is, for example, a three-layer structure of A / B / A (/ indicates a layer structure) type, a five-layer structure of A / B / A / B / A type, and the order of these. A multi-layer configuration such as a 7-layer, 9-layer, and 2n + 1 (n is a natural number) configuration can be employed.
また、必要に応じて、ポリエステル層Ａが２層以上の場合、１以上の層を違うポリマーで構成することができる。ポリエステル層Ｂが２層以上の場合も同様である。例えば、ポリエステル層Ａが２種のポリマー（Ａ１、Ａ２）、ポリエステル層Ｂが２種のポリマー（Ｂ１、Ｂ２）からなるとき、Ａ１／Ｂ１／Ａ２タイプの３層構成、Ａ１／Ｂ１／Ａ２／Ｂ２／Ａ１タイプの５層構成を挙げることができる。これら層構成のうち、３層、５層が好ましく、特に３層が好ましい。なお、積層フィルムは１軸以上の延伸配向構造を有するポリエステル層Ａを最表層とする構成をとる。実質的に非配向構造であるポリエステル層Ｂを最表層とする構成をとると、フィルム製造の際に工程内の各種ロール等にフィルムが粘着しやすく不適である。 Further, if necessary, when the polyester layer A is two or more layers, one or more layers can be composed of different polymers. The same applies when the polyester layer B has two or more layers. For example, when the polyester layer A is composed of two types of polymers (A1, A2) and the polyester layer B is composed of two types of polymers (B1, B2), a three-layer configuration of A1 / B1 / A2 type, A1 / B1 / A2 / A B2 / A1 type five-layer structure can be given. Of these layer configurations, 3 layers and 5 layers are preferable, and 3 layers are particularly preferable. In addition, a laminated | multilayer film takes the structure which makes the polyester layer A which has the extending | stretching orientation structure of one axis or more the outermost layer. If the polyester layer B having a substantially non-oriented structure is used as the outermost layer, the film tends to stick to various rolls in the process and is unsuitable.
なお、フィルムの最表面の片面、もしくは両面に、滑性向上、接着性向上、制電性向上、離型性向上といった表面改質のために、コーティング処理、コロナ放電処理などの表面処理をしてもよい。コーティング処理等表面処理の方法としては、例えばポリエステル系塗布剤、ウレタン系塗布剤、アクリル系塗布剤を単独もしくは混合して、フィルム製造におけるプロセス内で塗布する方法、一旦ロール等のフィルム製品にした後に別のプロセスにて塗布する方法を挙げることができる。 In addition, surface treatment such as coating treatment and corona discharge treatment is applied to one or both surfaces of the film for surface modification such as improvement of lubricity, adhesion, antistatic, and release. May be. As a surface treatment method such as coating treatment, for example, a polyester coating agent, a urethane coating agent, and an acrylic coating agent are used alone or mixed, and applied in the process of film production, and once made into a film product such as a roll. The method of apply | coating by another process later can be mentioned.
［厚み］
基材フィルム厚み（積層フィルムの場合、全ての層の厚みの和）は、好ましくは１０〜５００μｍ、さらに好ましくは１５〜３００μｍ、特に好ましくは２０〜２００μｍである。フィルム厚みが１０μｍ未満であるとフィルムの腰が弱くフィルムが破断しやすくなり好ましくない。フィルム厚みが５００μｍを超えるとフィルムの腰が強すぎ取り扱い性に劣るとともに形加工性がおとり好ましくない。
[Thickness]
The substrate film thickness (in the case of a laminated film, the sum of the thicknesses of all layers) is preferably 10 to 500 μm, more preferably 15 to 300 μm, and particularly preferably 20 to 200 μm. A film thickness of less than 10 μm is not preferred because the film is weak and easily ruptured. When the film thickness exceeds 500 μm, the film is too strong and the handling property is inferior, and the formability is not preferred.
基材フィルムのポリエステルフィルムの厚み斑は、好ましくは１０％以下、さらに好ましくは５％以下、特に好ましくは３％以下である。厚み斑が１０％を超えるとインジウム蒸着時において蒸着膜厚みに斑が生じ、金属光沢の濃淡が生じ外観が悪化するなどの問題が生じて好ましくない。 The thickness unevenness of the polyester film of the base film is preferably 10% or less, more preferably 5% or less, and particularly preferably 3% or less. If the thickness unevenness exceeds 10%, unevenness occurs in the thickness of the deposited film during indium vapor deposition, resulting in problems such as the appearance of metallic luster and deterioration in appearance.
基材フィルムとして積層フィルムを用いる場合、積層フィルムの、１軸以上の延伸配向構造を有するポリエステル層Ａの総厚み（ａ）と、実質的に非配向構造であるポリエステル層Ｂの総厚み（ｂ）の比（ａ／ｂ）は、例えば０．０１〜１、好ましくは０．０３〜０．６７、さらに好ましくは０．０５〜０．４３である。この厚み比は、例えば層構成がＡ１（厚み：ａ１）／Ｂ（厚み：ｂ）／Ａ２（厚み：ａ２）の３層からなる場合、層Ａと層Ｂの総厚み比（ａ／ｂ）、すなわち（ａ１＋ａ２）／（ｂ）が０．０１〜１であることを意味し、また層構成がＡ１（厚み：ａ１）／Ｂ１（厚み：ｂ１）／Ａ２（厚み：ａ２）／Ｂ２（厚み：ｂ２）／Ａ３（厚み：ａ３）の５層からなる場合、層Ａと層Ｂの総厚み比（ａ／ｂ）、すなわち（ａ１＋ａ２＋ａ３）／（ｂ１＋ｂ２）が０．０１〜１であることを意味する。この総厚み比（Ａ／Ｂ）が０．０１に満たないと、ポリエステル層Ａの存在割合が少ないため、フィルム製造時の厚み制御が難しいなど問題を生じ、また、フィルムの寸法安定性が不充分である。一方、総厚み比が１を超えると、実質的に非晶構造であるポリエステル層Ｂの存在割合が少ない為、フィルムの加工性が不充分となってしまう。 When a laminated film is used as the base film, the total thickness (a) of the polyester layer A having a uniaxial stretched and oriented structure of the laminated film and the total thickness (b) of the polyester layer B having a substantially non-oriented structure. ) Ratio (a / b) is, for example, 0.01 to 1, preferably 0.03 to 0.67, and more preferably 0.05 to 0.43. For example, when the layer structure is composed of three layers of A1 (thickness: a1) / B (thickness: b) / A2 (thickness: a2), the total thickness ratio of layer A and layer B (a / b) That is, (a1 + a2) / (b) means 0.01 to 1, and the layer structure is A1 (thickness: a1) / B1 (thickness: b1) / A2 (thickness: a2) / B2 (thickness). : B2) / A3 (thickness: a3), the total thickness ratio (a / b) of layer A and layer B, that is, (a1 + a2 + a3) / (b1 + b2) is 0.01 to 1. means. If the total thickness ratio (A / B) is less than 0.01, the polyester layer A is present in a small proportion, which causes problems such as difficulty in controlling the thickness during film production, and poor dimensional stability of the film. It is enough. On the other hand, when the total thickness ratio exceeds 1, since the ratio of the polyester layer B having a substantially amorphous structure is small, the processability of the film becomes insufficient.
［添加剤］
基材フィルムは、ポリエステル層Ａおよびポリエステル層Ｂのいずれか一方または両方に、ポリオレフィン系樹脂を０．１〜３０重量％含有することが好ましい。ポリオレフィン樹脂としては、例えばポリエチレン、ポリプロピレン、ポリ４−メチルペンテンを例示することができる。
[Additive]
The base film preferably contains 0.1 to 30% by weight of a polyolefin resin in one or both of the polyester layer A and the polyester layer B. Examples of the polyolefin resin include polyethylene, polypropylene, and poly-4-methylpentene.
基材フィルムは、適度な滑り性が得られ優れたフィルムの取り扱い性を得るために、好ましくは微粒子を含有する。微粒子として、例えばシリカ、アルミナ、酸化チタン、炭酸カルシウム、カオリンといった無機微粒子；シリコーン、ポリスチレン架橋体、アクリル系架橋体といった有機微粒子；触媒残渣の析出による微粒子を例示することができる。微粒子の平均粒子径は、例えば２．５μｍ以下である。この微粒子のうち、特に平均粒子径が１．０〜２．０μｍの微粒子と平均粒子径が０．０５〜０．５μｍの微粒子の２種類の粒子を併用すると、透明性を維持しながら効率的に滑性、すなわち巻取り性や取り扱い性を向上させることができて好ましい。基材フィルムが多層フィルムである場合には、最外層のみに微粒子を含有させることで、非常に高い透明性を得ることができる。 The base film preferably contains fine particles in order to obtain appropriate slipperiness and excellent film handling. Examples of the fine particles include inorganic fine particles such as silica, alumina, titanium oxide, calcium carbonate and kaolin; organic fine particles such as silicone, polystyrene cross-linked product and acrylic cross-linked product; and fine particles resulting from precipitation of catalyst residues. The average particle diameter of the fine particles is, for example, 2.5 μm or less. Among these fine particles, in particular, when two types of particles, a fine particle having an average particle diameter of 1.0 to 2.0 μm and a fine particle having an average particle diameter of 0.05 to 0.5 μm, are used in combination, it is efficient while maintaining transparency. In particular, the slipperiness, that is, the winding property and the handleability can be improved. When the base film is a multilayer film, very high transparency can be obtained by containing fine particles only in the outermost layer.
［表面処理］
基材フィルムは、金属蒸着層との接着性を向上させる目的、印刷用インクとの接着性を向上させる目的、その他表面加工層との接着性を向上させる目的、これらの層との離型性を発現する目的、滑り性を付与する目的等において、片面もしくは両面にコーティング処理を施してもよい。透明性を維持しながら滑り性を付与する目的においては、コーティングにより滑り性を付与する事が好ましい。これによりフィルム内部の滑剤含有量をより少なくすることができる。また、同様の目的において、コロナ処理、プラズマ処理、オゾン処理等の表面処理を施してもよい。
[surface treatment]
The purpose of the base film is to improve the adhesion to the metal vapor deposition layer, to improve the adhesion to the printing ink, to improve the adhesion to the other surface treatment layer, and to release from these layers. A coating treatment may be applied to one side or both sides for the purpose of developing the property and the purpose of imparting slipperiness. For the purpose of imparting slipperiness while maintaining transparency, it is preferable to impart slipperiness by coating. Thereby, the lubricant content inside the film can be further reduced. Further, for the same purpose, surface treatment such as corona treatment, plasma treatment, ozone treatment may be performed.
基材フィルムのヘーズは、１０％以下であることが好ましい。ヘーズが１０％より大きいと、金属蒸着を施しても十分な金属光沢が得られず、良好な外観を得ることができない。ヘーズは、滑剤の種類、添加量によって調整することができる。 The haze of the base film is preferably 10% or less. If the haze is greater than 10%, sufficient metal luster cannot be obtained even if metal deposition is performed, and a good appearance cannot be obtained. The haze can be adjusted by the type and amount of lubricant.
［基材フィルムの製造方法］
基材フィルムに単層フィルムを用いる場合、基材フィルムは、当業界に蓄積されたフィルムの製造方法に従って製造することができる。
[Process for producing base film]
When using a single layer film for a base film, a base film can be manufactured according to the manufacturing method of the film accumulate | stored in this industry.
基材フィルムに積層フィルムを用いる場合、基材フィルムは、共押出製膜法で製造することが好ましい。その具体例を、例えば上記３層フィルム（Ａ／Ｂ／Ａ）の場合について説明すると、先ず、ポリエステル層Ａ用に調製したポリエステルのチップを乾燥、溶融する。これと並行して、ポリエステル層Ｂ用に調製したポリエステルのチップを乾燥、溶融する。続いて、これら溶融ポリマーをダイ内部で３層に積層し、例えばフィードブロックを設置したダイ内部で３層に積層したのち、冷却ドラム上にキャスティングして未延伸多層フィルムにし、続いて、該多層フィルムを縦軸及び／又は横軸に１軸以上の方向に延伸して１軸以上の延伸配向構造を有する多層延伸フィルムを得る。なお、５層以上の場合も、同様にすることができる。延伸処理はポリエステル層Ａが所望の配向構造を形成する条件で行い、例えば層Ａを構成するポリエステルのＴｇ（ガラス転移温度）−１０℃からＴｇ＋５０℃の温度（Ｔｃ）で、縦方向に２．５倍以上、好ましくは３〜６倍延伸し、更に好ましくは３〜４倍延伸し、次いでＴｇ＋１０からＴｇ＋５０℃の温度で、横方向に２．５倍以上、好ましくは３〜６倍延伸、更に好ましくは３〜４倍するのが、フィルムの厚み斑を良好にする点において好ましい。 When using a laminated film for the base film, the base film is preferably produced by a coextrusion film forming method. A specific example thereof will be described, for example, in the case of the three-layer film (A / B / A). First, a polyester chip prepared for the polyester layer A is dried and melted. In parallel with this, the polyester chip prepared for the polyester layer B is dried and melted. Subsequently, these molten polymers are laminated in three layers inside the die. For example, the molten polymer is laminated in three layers inside the die provided with a feed block, and then cast on a cooling drum to form an unstretched multilayer film. The film is stretched in the direction of one axis or more on the vertical axis and / or the horizontal axis to obtain a multilayer stretched film having a stretch orientation structure of one axis or more. The same applies to the case of five or more layers. The stretching treatment is performed under the condition that the polyester layer A forms a desired orientation structure, for example, at a temperature (Tc) of Tg (glass transition temperature) -10 ° C. to Tg + 50 ° C. of the polyester constituting the layer A in the longitudinal direction. Stretched 5 times or more, preferably 3 to 6 times, more preferably 3 to 4 times, then stretched at a temperature of Tg + 10 to Tg + 50 ° C., 2.5 times or more in the transverse direction, preferably 3 to 6 times. It is preferably 3 to 4 times from the viewpoint of improving the uneven thickness of the film.
以上の様にして得られる多層延伸フィルムに、さらに熱処理を実施する。この熱処理温度は、ポリエステル層Ｂの融点より高い温度であることが肝要であり、この熱処理によりポリエステル層Ｂが溶融して、１軸以上の延伸処理で形成された延伸配向構造が、実質的に無配向構造に変化する。熱処理温度は、ポリエステル層Ｂの融点より５℃以上高い温度で、かつポリエステル層Ａの融点より１０℃以上低い温度が好ましい。なお、この熱処理によって、ポリエステル層Ａには、例えば熱固定処理の効果をもたらす。この熱処理方法は特に限定されないが、例えば、フィルム製造時において延伸後直ちに工程内で熱処理する方法、フィルム製造完了後フィルムをロール状に巻き取った後熱処理する方法などが挙げられるが前者が特に好ましい。 The multilayer stretched film obtained as described above is further subjected to heat treatment. It is important that the heat treatment temperature is higher than the melting point of the polyester layer B. The polyester layer B is melted by this heat treatment, and the stretched orientation structure formed by the uniaxial or more stretch treatment is substantially It changes to a non-oriented structure. The heat treatment temperature is preferably 5 ° C. or more higher than the melting point of the polyester layer B and 10 ° C. or more lower than the melting point of the polyester layer A. By this heat treatment, the polyester layer A has, for example, an effect of heat setting treatment. The heat treatment method is not particularly limited, and examples thereof include a method of heat treatment in the process immediately after stretching in film production, a method of heat treatment after winding the film into a roll after completion of film production, and the former is particularly preferred. .
［インジウム蒸着層］
本発明の成形用フィルムは、基材フィルムのうえにインジウム蒸着層を備える。これにより金属光沢を有する外観とすることができる。インジウム蒸着層は、基材フィルムの片面に設けてもよく、両面に設けてもよい。
[Indium vapor deposition layer]
The film for molding of the present invention includes an indium vapor deposition layer on a base film. Thereby, it can be set as the external appearance which has metallic luster. An indium vapor deposition layer may be provided in the single side | surface of a base film, and may be provided in both surfaces.
インジウム蒸着層は、インジウムを蒸着した層であり、金属光沢を呈する。インジウム蒸着層の厚みは、好ましくは１００Å〜１５００Å、特に好ましくは３００〜８００Åである。１００Å未満であるとフィルムを通して向こう側が透けて見えてしまうなど金属調の外観として不十分となってしまい好ましくない。これは、成形加工後に特に顕著となる。１５００Åを超えるとインジウム蒸着する工程において蒸着時間を長くする必要があり基材フィルムが蒸着の熱により変形してしまう、生産性が低下してしまうなどの問題が生じ、好ましくない。 An indium vapor deposition layer is a layer which vapor-deposited indium, and exhibits metallic luster. The thickness of the indium vapor deposition layer is preferably 100 to 1500 mm, particularly preferably 300 to 800 mm. If it is less than 100 mm, the other side will be seen through the film, and the metallic appearance will be insufficient, which is not preferable. This is particularly noticeable after molding. If it exceeds 1500 mm, it is necessary to lengthen the vapor deposition time in the indium vapor deposition step, which causes problems such as deformation of the base film due to the heat of vapor deposition and reduced productivity.
蒸着法としては、真空蒸着法やイオンプレーティング法、スパッタリング法を例示することができる。インジウム蒸着層は、基材フィルムの全面に設けてもよく、一部に設けてもよい。基材フィルムが剥離層を有する場合は、剥離層の全面み設けてもよく一部に設けてもよい。なお、基材フィルムとインジウム蒸着層の接着性を向上させる目的で、両者間にアンカー層を介在せしめてもよい。 Examples of the vapor deposition method include a vacuum vapor deposition method, an ion plating method, and a sputtering method. An indium vapor deposition layer may be provided in the whole surface of a base film, and may be provided in a part. When the base film has a release layer, it may be provided only on the entire surface of the release layer or on a part thereof. For the purpose of improving the adhesion between the base film and the indium vapor-deposited layer, an anchor layer may be interposed between them.
以下、実施例を挙げて、本発明をさらに具体的に説明する。
なお、実施例および比較例において用いた特性の測定方法ならびに評価方法は、次のとおりである。
Hereinafter, the present invention will be described more specifically with reference to examples.
In addition, the measuring method and evaluation method of the characteristic used in the Example and the comparative example are as follows.
（１）ガラス転移温度・融点
サンプル約１０ｍｇを測定用のアルミニウム製パンに封入して示差熱量計（ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製、商品名「ＤＳＣ２９２０ Ｍｏｄｕｌａｔｅｄ」）に装着し、２５℃から２０℃／分の速度で３００℃まで昇温させ、３００℃で３分間保持した後取り出し、直ちに氷の上に移して急冷した。このパンを再度示差熱量計に装着し、２５℃から２０℃／分の速度で昇温させてガラス転移温度Ｔｇ（単位：℃）と融点Ｔｍ（単位：℃）を測定した。
(1) Glass transition temperature / melting point About 10 mg of a sample is sealed in an aluminum pan for measurement and attached to a differential calorimeter (trade name “DSC2920 Modulated” manufactured by TA Instruments), and 25 ° C. to 20 ° C./min. The temperature was raised to 300 ° C. at a speed, held at 300 ° C. for 3 minutes, then taken out, immediately transferred onto ice and rapidly cooled. The pan was again attached to the differential calorimeter, and the glass transition temperature Tg (unit: ° C) and melting point Tm (unit: ° C) were measured by increasing the temperature from 25 ° C to 20 ° C / min.
（２）固有粘度
固有粘度（［η］ｄｌ／ｇ）は、３５℃のｏ−クロロフェノール溶液で測定した。
(2) Intrinsic viscosity Intrinsic viscosity ([η] dl / g) was measured with an o-chlorophenol solution at 35 ° C.
（３）ヘーズ
ＪＩＳ Ｋ７１０５に準じて、ヘーズ測定機（日本電色工業（株）製、商品名「ＮＤＨ−２０００」）を使用して全光線透過率Ｔｔ（％）と散乱光透過率Ｔｄ（％）とを測定し、以下の式からヘーズ（％）を算出した。
ヘーズ（％）＝（Ｔｄ／Ｔｔ）×１００
(3) Haze In accordance with JIS K7105, total light transmittance Tt (%) and scattered light transmittance Td (trade name “NDH-2000” manufactured by Nippon Denshoku Industries Co., Ltd.) are used. %) And haze (%) was calculated from the following equation.
Haze (%) = (Td / Tt) × 100
（４）成形性評価−１
破断伸度と破断応力は、測定装置としてチャック部を加熱チャンバーで覆った引張試験機（東洋ボールドウィン社製、商品名「テンシロン」）を用いて測定した。成形用フィルムから、縦方向（ＭＤ）と横方向（ＴＤ）について、それぞれ長手方向１００ｍｍ×幅方向１０ｍｍのサンプルを採取し、間隔を５０ｍｍにセットしたチャックに挟んで固定した。その際、引張試験機のチャック部分に設置されている加熱チャンバーにより、サンプルの存在する雰囲気下は１００℃に保たれる。１００ｍｍ／分の速度で引張り、試験機に装着されたロードセルで荷重を測定した。荷伸曲線の破断時の荷重を読取り、引張前のサンプル断面積で割って破断応力（ＭＰａ）を計算した。また、破断伸度は、初期のチャック間隔（Ｌ０）と破断時のチャック間隔（Ｌ１）から、下記式を用いて算出し、破断伸度（％）とした。
破断伸度（％）＝（Ｌ１−Ｌ０）／Ｌ０×１００
(4) Formability evaluation-1
The breaking elongation and breaking stress were measured by using a tensile tester (manufactured by Toyo Baldwin, trade name “Tensilon”) having a chuck portion covered with a heating chamber as a measuring device. Samples of 100 mm in the longitudinal direction and 10 mm in the width direction were taken from the forming film in the longitudinal direction (MD) and the transverse direction (TD), respectively, and fixed by being sandwiched between chucks set at an interval of 50 mm. At that time, the atmosphere in which the sample exists is kept at 100 ° C. by a heating chamber installed in the chuck portion of the tensile tester. Pulling was performed at a speed of 100 mm / min, and the load was measured with a load cell attached to the testing machine. The load at the time of breaking of the unloading curve was read, and the breaking stress (MPa) was calculated by dividing by the sample cross-sectional area before tension. Further, the breaking elongation was calculated from the initial chuck interval (L 0 ) and the chuck interval at the time of breaking (L 1 ) using the following formula, and was defined as the breaking elongation (%).
Elongation at break (%) = (L 1 −L 0 ) / L 0 × 100
（５）成形性評価−２
成形用フィルムをオス／メス型を持つプレス成形機を用いて１３０℃にてプレス成形し、直径５ｍｍ、深さ３ｍｍの円筒形に成形した。成形された円筒形部分の形状を観測し、以下の基準に従い評価した。
◎：円筒形の形状は金型通りであり、フィルムにしわの発生もない。
○：円筒形の形状は金型通りであるが、フィルムに若干のしわの発生がある。
×：フィルムにしわの発生があり、また形状も金型通りでないものがある。もしくは、フィルムが切断してしまう。
(5) Formability evaluation-2
The molding film was press-molded at 130 ° C. using a male / female press molding machine, and formed into a cylindrical shape having a diameter of 5 mm and a depth of 3 mm. The shape of the formed cylindrical portion was observed and evaluated according to the following criteria.
(Double-circle): The shape of a cylindrical shape is as a metal mold | die, and a wrinkle does not generate | occur | produce on a film.
◯: The cylindrical shape is the same as the mold, but some wrinkles are generated on the film.
X: Wrinkles are generated on the film, and the shape is not exactly the same as the mold. Or, the film is cut.
（６）金属蒸着層評価
金属蒸着を施したフィルムについて、成形加工後の金属蒸着層を以下の手法で観測・評価した。測定装置としてチャック部を加熱チャンバーで覆った引張試験機（東洋ボールドウィン社製、商品名「テンシロン」）を用いて、金属蒸着を施したポリエステルフィルムから縦方向（ＭＤ）に長手方向１００ｍｍ×幅方向１０ｍｍのサンプルを採取し、間隔を５０ｍｍにセットしたチャックに挟んで固定した。その際、引張試験機のチャック部分に設置されている加熱チャンバーにより、サンプルの存在する雰囲気下は１００℃に保たった。１００ｍｍ／分の速度で引張り、チャック間隔が７５ｍｍ（フィルムの伸張が５０％）となった時点で伸張を停止してサンプルを取り出した。得られた伸張後のサンプルの金属蒸着層について、顕微鏡によりひび割れを観測し、以下の基準に従い評価した。
◎：金属蒸着層にひび割れが観測されない。
○：金属蒸着層に微小なひび割れが観測されるが、フィルムは金属光沢を保っている。
×：金属蒸着層にひび割れが多数観測され、フィルムの金属光沢が劣っている。
(6) Metal vapor deposition layer evaluation About the film which gave metal vapor deposition, the metal vapor deposition layer after a shaping | molding process was observed and evaluated with the following methods. Using a tensile testing machine (trade name “Tensilon” manufactured by Toyo Baldwin Co., Ltd.) with the chuck part covered with a heating chamber as a measuring device, the lengthwise direction is 100 mm × width direction from the polyester film subjected to metal deposition. A sample of 10 mm was taken and fixed by being sandwiched between chucks set at an interval of 50 mm. At that time, the atmosphere in which the sample existed was kept at 100 ° C. by a heating chamber installed in the chuck portion of the tensile tester. Pulling was performed at a speed of 100 mm / min, and when the chuck interval reached 75 mm (film stretching was 50%), stretching was stopped and a sample was taken out. About the metal vapor deposition layer of the obtained sample after the expansion | extension, the crack was observed with the microscope and it evaluated according to the following references | standards.
(Double-circle): A crack is not observed in a metal vapor deposition layer.
○: Although micro cracks are observed in the metal deposition layer, the film has a metallic luster.
X: Many cracks were observed in the metal vapor deposition layer, and the metallic luster of the film was inferior.
（７）ポリエステルペレットの作成
出発原料としてテレフタル酸ジメチルとエチレングリコールを用い、かつ酢酸マンガン、リン酸、３酸化アンチモンを触媒として用いて、常法によりエステル交換反応、重縮合反応を実施し、得られたポリマーを反応釜から吐出、冷却して、ポリエチレンテレフタレートのペレット（以下、ＰＥＴと呼称）を得た。得られたＰＥＴのガラス転移温度は８０℃、融点は２５５℃、固有粘度は０．６５であった。
(7) Preparation of polyester pellets Using dimethyl terephthalate and ethylene glycol as starting materials, and using manganese acetate, phosphoric acid and antimony trioxide as a catalyst, transesterification and polycondensation reactions were carried out in the usual manner. The polymer obtained was discharged from a reaction kettle and cooled to obtain polyethylene terephthalate pellets (hereinafter referred to as PET). The obtained PET had a glass transition temperature of 80 ° C., a melting point of 255 ° C., and an intrinsic viscosity of 0.65.
出発原料としてテレフタル酸ジメチル８８モル％（全酸成分に対し）およびイソフタル酸ジメチル１２モル％（全酸成分に対し）とエチレングリコールを用いる以外は、上記ＰＥＴと同様に、エステル交換反応、重縮合反応を実施し、得られたポリマーを反応釜から吐出、冷却して、共重合ポリエチレンテレフタレートのペレット（以下、ＩＡ−ＣＯ−ＰＥＴと呼称）を得た。得られたＩＡ−ＣＯ−ＰＥＴのガラス転移温度は６５℃、融点は２２３℃、固有粘度は０．６９であった。 Transesterification reaction and polycondensation in the same manner as PET except that 88 mol% dimethyl terephthalate (based on the total acid component) and 12 mol% dimethyl isophthalate (based on the total acid component) and ethylene glycol are used as starting materials. The reaction was carried out, and the resulting polymer was discharged from a reaction kettle and cooled to obtain copolymer polyethylene terephthalate pellets (hereinafter referred to as IA-CO-PET). The obtained IA-CO-PET had a glass transition temperature of 65 ° C., a melting point of 223 ° C., and an intrinsic viscosity of 0.69.
出発原料としてテレフタル酸ジメチル８８モル％（全酸成分に対し）および２，６−ナフタレンジカルボン酸ジメチル１２モル％（全酸成分に対し）とエチレングリコールを用いる以外は、上記ＰＥＴと同様に、エステル交換反応、重縮合反応を実施し、得られたポリマーを反応釜から吐出、冷却して、共重合ポリエチレンテレフタレートのペレット（以下、ＮＤＣ−ＣＯ−ＰＥＴと呼称）を得た。得られたＮＤＣ−ＣＯ−ＰＥＴのガラス転移温度は８２℃、融点は２２３℃、固有粘度は０．６９であった。 Esters are similar to PET except that 88 mol% dimethyl terephthalate (based on total acid components) and 12 mol% dimethyl 2,6-naphthalenedicarboxylate (based on total acid components) and ethylene glycol are used as starting materials. The exchange reaction and the polycondensation reaction were carried out, and the resulting polymer was discharged from the reaction kettle and cooled to obtain copolymerized polyethylene terephthalate pellets (hereinafter referred to as NDC-CO-PET). The obtained NDC-CO-PET had a glass transition temperature of 82 ° C, a melting point of 223 ° C, and an intrinsic viscosity of 0.69.
ポリブチレンテレフタレート（以下、ＰＢＴと呼称）ペレットとしては、ウィンテックポリマー（株）製デュラネックス５００ＦＰを使用した。 As a polybutylene terephthalate (hereinafter referred to as PBT) pellet, Duranex 500FP manufactured by Wintech Polymer Co., Ltd. was used.
［実施例１］
上記で得られたＩＡ−ＣＯ−ＰＥＴおよびＰＢＴのペレットを（ＩＡ−ＣＯ−ＰＥＴ）／（ＰＢＴ）＝５５／４５重量％となるように混合した混合物を乾燥し、単軸スクリュー押出し機で溶融した後、ダイより溶融押出しして冷却ドラム上にキャスティングし、未延伸フィルムを得た。続いて、該フィルムを縦方向に１００℃で３．０倍、横方向に１００℃で３．２倍に逐次２軸延伸した後、１９５℃で熱固定し、２５μｍ厚みの単層フィルムを得た。得られた単層フィルムの構成を表１に、特性を表２に示す。尚、フィルムは滑剤として平均粒子径１．７μｍの凝集シリカを８０ｐｐｍ、平均粒子径０．１μｍの真球状シリカを１５０ｐｐｍ含有している。
[Example 1]
The mixture obtained by mixing the pellets of IA-CO-PET and PBT obtained above so as to be (IA-CO-PET) / (PBT) = 55/45 wt% was dried and melted with a single screw extruder. Then, it was melt-extruded from a die and cast on a cooling drum to obtain an unstretched film. Subsequently, the film was successively biaxially stretched 3.0 times at 100 ° C. in the longitudinal direction and 3.2 times at 100 ° C. in the transverse direction, and then heat-set at 195 ° C. to obtain a single-layer film having a thickness of 25 μm. It was. The structure of the obtained single layer film is shown in Table 1, and the characteristics are shown in Table 2. The film contains 80 ppm of agglomerated silica having an average particle diameter of 1.7 μm and 150 ppm of true spherical silica having an average particle diameter of 0.1 μm as a lubricant.
［実施例２］
２軸延伸後のフィルム厚みを５０μｍとする以外は、実施例１と同様に単層フィルムを得た。得られた単層フィルムの構成を表１に、特性を表２に示す。
[Example 2]
A monolayer film was obtained in the same manner as in Example 1 except that the film thickness after biaxial stretching was 50 μm. The structure of the obtained single layer film is shown in Table 1, and the characteristics are shown in Table 2.
［実施例３］
上記で得られたＰＥＴとＩＡ−ＣＯ−ＰＥＴを、（ＰＥＴ）／（ＩＡ−ＣＯ−ＰＥＴ）＝５８／４２重量％となるように混合した混合物（フィルムとした後にポリエステル層Ａとなる）、およびＩＡ−ＣＯ−ＰＥＴとＮＤＣ−ＣＯ−ＰＥＴを（ＩＡ−ＣＯ−ＰＥＴ）／（ＮＤＣ−ＣＯ−ＰＥＴ）＝５０／５０重量％となるように混合した混合物（フィルムとした後にポリエステル層Ｂとなる）を別々に乾燥、単軸スクリュー押出し機で溶融した後、ダイ内部で（ＰＥＴとＩＡ−ＣＯ−ＰＥＴの混合物）｜（ＩＡ−ＣＯ−ＰＥＴとＮＤＣ−ＣＯ−ＰＥＴ混合物）｜（ＰＥＴとＩＡ−ＣＯ−ＰＥＴの混合物）の３層に溶融ポリマーを積層し、この状態で冷却ドラム上にキャスティングし、未延伸多層フィルムを得た。続いて、該多層フィルムを縦方向に１１０℃で３．０倍、横方向に１２０℃で３．２倍に逐次２軸延伸した後、２３５℃で熱固定し、３層フィルムを得た。この３層フィルムの厚み構成は、ＰＥＴとＩＡ−ＣＯ−ＰＥＴからなる両面の表層（ポリエステル層Ａ）が各２．５μｍ、ＩＡ−ＣＯ−ＰＥＴとＮＤＣ−ＣＯ−ＰＥＴからな内層（ポリエステル層Ｂ）が４５μｍの合計５０μｍであった。得られた３層フィルムの構成を表１に、特性を表２に示す。尚、フィルムは滑剤としてポリエステル層Ａに平均粒子径１．２μｍの真球状シリコーンを１００ｐｐｍ、平均粒子径０．１μｍの真球状シリカを６００ｐｐｍ含有している。
[Example 3]
A mixture obtained by mixing the PET obtained above and IA-CO-PET so as to be (PET) / (IA-CO-PET) = 58/42 wt% (becomes a polyester layer A after forming a film), And a mixture of IA-CO-PET and NDC-CO-PET so that (IA-CO-PET) / (NDC-CO-PET) = 50/50 wt% Are separately dried, melted in a single screw extruder, and then inside the die (mixture of PET and IA-CO-PET) | (IA-CO-PET and NDC-CO-PET mixture) | The molten polymer was laminated on three layers of a mixture of IA-CO-PET), and cast on a cooling drum in this state to obtain an unstretched multilayer film. Subsequently, the multilayer film was successively biaxially stretched 3.0 times at 110 ° C. in the longitudinal direction and 3.2 times at 120 ° C. in the transverse direction, and then heat-set at 235 ° C. to obtain a three-layer film. The thickness of this three-layer film is as follows: the surface layer (polyester layer A) made of PET and IA-CO-PET is 2.5 μm each, and the inner layer (polyester layer B) is made of IA-CO-PET and NDC-CO-PET. ) Was a total of 50 μm of 45 μm. The structure of the obtained three-layer film is shown in Table 1, and the characteristics are shown in Table 2. The film contains 100 ppm of true spherical silicone having an average particle diameter of 1.2 μm and 600 ppm of true spherical silica having an average particle diameter of 0.1 μm in the polyester layer A as a lubricant.
［実施例４］
３層フィルムの厚み構成を、ＰＥＴとＩＡ−ＣＯ−ＰＥＴからなる両面の表層（ポリエステル層Ａ）が各５μｍ、ＩＡ−ＣＯ−ＰＥＴとＮＤＣ−ＣＯ−ＰＥＴからな内層（ポリエステル層Ｂ）が９０μｍの合計１００μｍとする以外は実施例３と同様に３層フィルムを得た。得られた３層フィルムの構成を表１に、特性を表２に示す。
[Example 4]
The thickness of the three-layer film is 5 μm for each surface layer (polyester layer A) made of PET and IA-CO-PET, and 90 μm for the inner layer (polyester layer B) made of IA-CO-PET and NDC-CO-PET. A three-layer film was obtained in the same manner as in Example 3 except that the total thickness was 100 μm. The structure of the obtained three-layer film is shown in Table 1, and the characteristics are shown in Table 2.
［実施例５］
ポリエステル層Ｂを形成する樹脂として、上記で得られたＩＡ−ＣＯ−ＰＥＴを単独で用いる以外は実施例３と同様の方法でフィルム厚み５０μｍの３層フィルムを得た。得られた３層フィルムの構成を表１に、特性を表２に示す。
[Example 5]
A three-layer film having a film thickness of 50 μm was obtained in the same manner as in Example 3 except that IA-CO-PET obtained above was used alone as the resin for forming the polyester layer B. The structure of the obtained three-layer film is shown in Table 1, and the characteristics are shown in Table 2.
［実施例６］
ポリエステル層Ｂを形成する樹脂として、上記で得られたＮＤＣ−ＣＯ−ＰＥＴを単独で用いる以外は実施例３と同様の方法でフィルム厚み５０μｍの３層フィルムを得た。得られた３層フィルムの構成を表１に、特性を表２に示す。実施例１〜６で得られたフィルムについて、ヘーズ、成形性評価−１、成形性評価−２の各々の評価を実施した後にインジウムをフィルムの片面に蒸着し、金属蒸着フィルムを得た。次いで、この金属蒸着フィルムについて金属蒸着層評価を実施した。実施例１〜６で得られたフィルムの厚み斑は、何れも１０％以下であり、金属蒸着後の外観は良好であった。実施例１〜６で得られたフィルムは、１００℃雰囲気下における破断伸度と破断強度が適切な範囲であり、成形用途に用いられるフィルムとして好適であった。また、実施例１〜６の金属蒸着フィルムは、金属蒸着層評価において良好な結果を示した。つまり、実施例１〜６に示すフィルムを用いることにより、良好な金属光沢を有する成形部品を作成することができた。
[Example 6]
A three-layer film having a film thickness of 50 μm was obtained in the same manner as in Example 3 except that NDC-CO-PET obtained above was used alone as the resin for forming the polyester layer B. The structure of the obtained three-layer film is shown in Table 1, and the characteristics are shown in Table 2. About the film obtained in Examples 1-6, after performing each evaluation of haze, a moldability evaluation-1, and a moldability evaluation-2, indium was vapor-deposited on the single side | surface of the film, and the metal vapor deposition film was obtained. Subsequently, metal vapor deposition layer evaluation was implemented about this metal vapor deposition film. The thickness spots of the films obtained in Examples 1 to 6 were all 10% or less, and the appearance after metal deposition was good. The films obtained in Examples 1 to 6 were suitable for use in molding applications because the breaking elongation and breaking strength in an atmosphere at 100 ° C. were in appropriate ranges. Moreover, the metal vapor deposition film of Examples 1-6 showed the favorable result in metal vapor deposition layer evaluation. That is, by using the films shown in Examples 1 to 6, it was possible to produce a molded part having a good metallic luster.
［比較例１］
上記で得られたＰＥＴのペレットを乾燥し、単軸スクリュー押出し機で溶融した後、ダイより溶融押出しして冷却ドラム上にキャスティングし、未延伸フィルムを得た。続いて、該フィルムを縦方向に１００℃で３．３倍、横方向に１１０℃で３．５倍に逐次２軸延伸した後、２３５℃で熱固定し、フィルム厚み２５μｍの単層フィルムを得た。得られた単層フィルムの構成を表１に、特性を表２に示す。尚、フィルムは滑剤として平均粒子径０．７μｍのカオリンを８００ｐｐｍ含有している。
[Comparative Example 1]
The PET pellets obtained above were dried, melted with a single screw extruder, melt extruded from a die, and cast on a cooling drum to obtain an unstretched film. Subsequently, the film was successively biaxially stretched 3.3 times at 100 ° C. in the longitudinal direction and 3.5 times at 110 ° C. in the transverse direction, and then heat-set at 235 ° C. to form a single layer film having a film thickness of 25 μm. Obtained. The structure of the obtained single layer film is shown in Table 1, and the characteristics are shown in Table 2. The film contains 800 ppm of kaolin having an average particle size of 0.7 μm as a lubricant.
［比較例２］
上記で得られたＩＡ−ＣＯ−ＰＥＴのペレットを乾燥し、単軸スクリュー押出し機で溶融した後、ダイより溶融押出しして冷却ドラム上にキャスティングし、未延伸フィルムを得た。続いて、該フィルムを縦方向に９０℃で３．２倍、横方向に１００℃で３．４倍に逐次２軸延伸した後、１８５℃で熱固定し、フィルム厚み２５μｍの単層フィルムを得た。得られた単層フィルムの構成を表１に、特性を表２に示す。尚、フィルムは滑剤として平均粒子径１．５μｍの真球状シリカを１０００ｐｐｍ含有している。比較例１〜２で得られたフィルムについて、ヘーズ、成形性評価−１、成形性評価−２の各々の評価を実施した後にインジウムをフィルムの片面に蒸着し、金属蒸着フィルムを得た。次いで、この金属蒸着フィルムについて金属蒸着層評価を実施した。比較例１〜２で得られた２軸延伸フィルムは、１００℃雰囲気下における破断伸度と破断強度が不適切であるために、成形用途に用いられるフィルムとしては不適切であった。
[Comparative Example 2]
The IA-CO-PET pellets obtained above were dried, melted with a single screw extruder, melt extruded from a die, and cast on a cooling drum to obtain an unstretched film. Subsequently, the film was successively biaxially stretched 3.2 times at 90 ° C. in the longitudinal direction and 3.4 times at 100 ° C. in the transverse direction, and then heat-set at 185 ° C. to form a single layer film having a film thickness of 25 μm. Obtained. The structure of the obtained single layer film is shown in Table 1, and the characteristics are shown in Table 2. The film contains 1000 ppm of true spherical silica having an average particle size of 1.5 μm as a lubricant. About the film obtained by Comparative Examples 1-2, after implementing each evaluation of haze, a moldability evaluation-1, and a moldability evaluation-2, indium was vapor-deposited on the single side | surface of the film, and the metal vapor deposition film was obtained. Subsequently, metal vapor deposition layer evaluation was implemented about this metal vapor deposition film. The biaxially stretched films obtained in Comparative Examples 1 and 2 were inappropriate as films used for molding applications because the elongation at break and strength at break at 100 ° C. were inappropriate.
［比較例３］
実施例１と同様の方法でフィルム厚み２５μｍの単層フィルムを得た。比較例３で得られたフィルムについて、ヘーズ、成形性評価−１、成形性評価−２の各々の評価を実施した後にアルミニウム金属をフィルムの片面に蒸着し、金属蒸着フィルムを得た。次いで、この金属蒸着フィルムについて金属蒸着層評価を実施した。
[Comparative Example 3]
A single layer film having a film thickness of 25 μm was obtained in the same manner as in Example 1. About the film obtained by the comparative example 3, after implementing each evaluation of haze, a moldability evaluation-1, and a moldability evaluation-2, aluminum metal was vapor-deposited on the single side | surface of the film, and the metal vapor deposition film was obtained. Subsequently, metal vapor deposition layer evaluation was implemented about this metal vapor deposition film.
［比較例４］
実施例３と同様の方法でフィルム厚み５０μｍの３層フィルムを得た。比較例４で得られたフィルムについて、ヘーズ、成形性評価−１、成形性評価−２の各々の評価を実施した後にアルミニウム金属をフィルムの片面に蒸着し、金属蒸着フィルムを得た。次いで、この金属蒸着フィルムについて金属蒸着層評価を実施した。比較例３〜４で得られたフィルムは、１００℃雰囲気下における破断伸度と破断強度は適切な範囲であったが、その金属蒸着フィルムは、金属蒸着層評価において多数のひび割れが観測された。
[Comparative Example 4]
A three-layer film having a film thickness of 50 μm was obtained in the same manner as in Example 3. The film obtained in Comparative Example 4 was subjected to the evaluations of haze, moldability evaluation-1, and moldability evaluation-2, and then aluminum metal was deposited on one side of the film to obtain a metal deposited film. Subsequently, metal vapor deposition layer evaluation was implemented about this metal vapor deposition film. In the films obtained in Comparative Examples 3 to 4, the elongation at break and the strength at break at 100 ° C. were in an appropriate range, but the metal vapor-deposited film was observed to have many cracks in the evaluation of the metal vapor-deposited layer. .
本発明の成形用フィルムは成型加工性に優れたフィルムであるので、フィルムを用いて成形加工を施す用途に特に好適である。インジウム蒸着層により金属光沢を有し、且つ成形加工後にも金属光沢が維持されるため、金属調の外観を有する成形部品を作成する用途に特に好適である。このような部品は、特に電子機器や自動車部品に好ましく用いることができ、特に特に携帯電話用の成形部品として好適に使用することができる。 Since the film for molding of the present invention is a film excellent in molding processability, it is particularly suitable for applications in which molding processing is performed using the film. Since the indium vapor deposition layer has a metallic luster and the metallic luster is maintained even after the molding process, it is particularly suitable for use in forming a molded part having a metallic appearance. Such a part can be preferably used particularly for an electronic device or an automobile part, and can be particularly preferably used as a molded part for a mobile phone.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005126188A JP2006297853A (en) | 2005-04-25 | 2005-04-25 | Film for use in molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005126188A JP2006297853A (en) | 2005-04-25 | 2005-04-25 | Film for use in molding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2006297853A true JP2006297853A (en) | 2006-11-02 |
Family
ID=37466504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005126188A Pending JP2006297853A (en) | 2005-04-25 | 2005-04-25 | Film for use in molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2006297853A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008162220A (en) * | 2006-12-31 | 2008-07-17 | Mitsubishi Plastics Ind Ltd | Polyester film for molding simultaneous transfer |
| JP2008162221A (en) * | 2006-12-31 | 2008-07-17 | Mitsubishi Plastics Ind Ltd | Polyester film for molding simultaneous transfer |
| WO2008117842A1 (en) * | 2007-03-28 | 2008-10-02 | Toray Industries, Inc. | Biaxially oriented polyester film for molded member, molding laminate including the same, and process for producing the same |
| JP2009029073A (en) * | 2007-07-30 | 2009-02-12 | Teijin Dupont Films Japan Ltd | Biaxially oriented laminated polyester film for molding and simultaneous decoration |
| JP2009226615A (en) * | 2008-03-19 | 2009-10-08 | Teijin Chem Ltd | Manufacturing method of resin molding having surface functional layer and its molding |
| JP2010229371A (en) * | 2009-03-30 | 2010-10-14 | Toray Ind Inc | Polyester film for molded member and method for molding |
| JP2011173242A (en) * | 2010-01-27 | 2011-09-08 | Mitsubishi Plastics Inc | Polyester film for laminated decorative materials |
| WO2020046087A1 (en) * | 2018-08-31 | 2020-03-05 | 주식회사 엘지화학 | Method for producing decorative member film |
| KR20200025925A (en) * | 2018-08-31 | 2020-03-10 | 주식회사 엘지화학 | Manufacturing method for decoration element film |
| CN111868296A (en) * | 2018-08-31 | 2020-10-30 | 株式会社Lg化学 | Method for manufacturing decorative element and decorative element |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11208196A (en) * | 1998-01-28 | 1999-08-03 | Oike Ind Co Ltd | Metal thin film transfer foil for simultaneous forming |
| JP2000094575A (en) * | 1998-09-18 | 2000-04-04 | Oike Ind Co Ltd | Metal thin film laminate for molding |
| WO2003070460A1 (en) * | 2002-02-21 | 2003-08-28 | Teijin Limited | Multilayered polyester film and process for producing the same |
-
2005
- 2005-04-25 JP JP2005126188A patent/JP2006297853A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11208196A (en) * | 1998-01-28 | 1999-08-03 | Oike Ind Co Ltd | Metal thin film transfer foil for simultaneous forming |
| JP2000094575A (en) * | 1998-09-18 | 2000-04-04 | Oike Ind Co Ltd | Metal thin film laminate for molding |
| WO2003070460A1 (en) * | 2002-02-21 | 2003-08-28 | Teijin Limited | Multilayered polyester film and process for producing the same |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008162221A (en) * | 2006-12-31 | 2008-07-17 | Mitsubishi Plastics Ind Ltd | Polyester film for molding simultaneous transfer |
| JP2008162220A (en) * | 2006-12-31 | 2008-07-17 | Mitsubishi Plastics Ind Ltd | Polyester film for molding simultaneous transfer |
| JP5428337B2 (en) * | 2007-03-28 | 2014-02-26 | 東レ株式会社 | Biaxially oriented polyester film for molded members, molded laminate using the same, and method for producing the same |
| WO2008117842A1 (en) * | 2007-03-28 | 2008-10-02 | Toray Industries, Inc. | Biaxially oriented polyester film for molded member, molding laminate including the same, and process for producing the same |
| JP2009029073A (en) * | 2007-07-30 | 2009-02-12 | Teijin Dupont Films Japan Ltd | Biaxially oriented laminated polyester film for molding and simultaneous decoration |
| JP2009226615A (en) * | 2008-03-19 | 2009-10-08 | Teijin Chem Ltd | Manufacturing method of resin molding having surface functional layer and its molding |
| JP2010229371A (en) * | 2009-03-30 | 2010-10-14 | Toray Ind Inc | Polyester film for molded member and method for molding |
| JP2011173242A (en) * | 2010-01-27 | 2011-09-08 | Mitsubishi Plastics Inc | Polyester film for laminated decorative materials |
| WO2020046087A1 (en) * | 2018-08-31 | 2020-03-05 | 주식회사 엘지화학 | Method for producing decorative member film |
| KR20200025925A (en) * | 2018-08-31 | 2020-03-10 | 주식회사 엘지화학 | Manufacturing method for decoration element film |
| CN111868296A (en) * | 2018-08-31 | 2020-10-30 | 株式会社Lg化学 | Method for manufacturing decorative element and decorative element |
| JP2021528565A (en) * | 2018-08-31 | 2021-10-21 | エルジー・ケム・リミテッド | Manufacturing method of film for decorative members |
| KR102474038B1 (en) | 2018-08-31 | 2022-12-02 | 주식회사 엘지화학 | Manufacturing method for decoration element film |
| JP7207833B2 (en) | 2018-08-31 | 2023-01-18 | エルジー・ケム・リミテッド | Method for manufacturing film for decorative member |
| US11634821B2 (en) | 2018-08-31 | 2023-04-25 | Lg Chem, Ltd. | Method for manufacturing film for decoration element |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4839012B2 (en) | Polyester film for in-mold molding | |
| JP4968064B2 (en) | Biaxially oriented polyester film and metallic laminate film | |
| JP5309564B2 (en) | Biaxially oriented polyester film for molded parts | |
| JP2006297853A (en) | Film for use in molding | |
| KR100721323B1 (en) | Biaxially stretched polyester film for forming | |
| JP4655365B2 (en) | Biaxially stretched polyester film for molding | |
| JPWO2007094382A1 (en) | Polyester film for molded parts | |
| JPWO2008117842A1 (en) | Biaxially oriented polyester film for molded members, molded laminate using the same, and method for producing the same | |
| JP5674227B2 (en) | Polyester film for in-mold transfer | |
| JP2007203571A (en) | Polyester film for simultaneous molding and decoration | |
| JP4955480B2 (en) | Biaxially stretched laminated polyester film for simultaneous decoration | |
| JP2010065065A (en) | Polyester film for molding | |
| JP4583699B2 (en) | Polyester film, polyester film for molding, and molded member using the same | |
| JP2009220479A (en) | Biaxially oriented polyester film for molding member and laminate for molding | |
| JP2002187963A (en) | Biaxially oriented polyester film | |
| JP4826200B2 (en) | Biaxially oriented polyester film for molded parts | |
| JP4923558B2 (en) | Biaxially oriented polyester film for molded parts | |
| JP2012140498A (en) | Biaxially oriented polyester film for concurrent deep drawing and transfer | |
| JP4361419B2 (en) | Multilayer film | |
| JP6779755B2 (en) | Colored biaxially stretched polyester film for metal plate laminating molding processing | |
| JP2004009599A (en) | Laminated polyester film for metal laminate | |
| JP5225828B2 (en) | Polyester film for in-mold transfer foil | |
| JP5331272B2 (en) | Polyester film for in-mold transfer foil | |
| JP2001200073A (en) | Polyester film for lamination | |
| JP4779250B2 (en) | Biaxially stretched polyester film for processing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080125 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100427 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100428 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20100831 |