JP2002052672A - Heat-shrinkable polyester multilayered film - Google Patents
Heat-shrinkable polyester multilayered filmInfo
- Publication number
- JP2002052672A JP2002052672A JP2000242641A JP2000242641A JP2002052672A JP 2002052672 A JP2002052672 A JP 2002052672A JP 2000242641 A JP2000242641 A JP 2000242641A JP 2000242641 A JP2000242641 A JP 2000242641A JP 2002052672 A JP2002052672 A JP 2002052672A
- Authority
- JP
- Japan
- Prior art keywords
- film
- temperature
- heat
- shrinkage
- polyester
- 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.)
- Granted
Links
Landscapes
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ボトルの収縮ラベ
ル等として好適に使用できる熱収縮性ポリエステル系多
層フイルムに係り、特に収縮被覆工程において低温より
収縮を開始するとともに、フイルムのしわ、ひずみ、収
縮斑などを極めて少なく抑えた収縮仕上がりに優れた熱
収縮性ポリエステル系多層フイルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-shrinkable polyester-based multilayer film which can be suitably used as a shrinkable label for bottles and the like. The present invention relates to a heat-shrinkable polyester-based multi-layer film excellent in shrink finish in which shrinkage spots and the like are extremely suppressed.
【０００２】[0002]
【従来の技術とその課題】収縮包装や収縮結束包装、あ
るいはプラスチック容器のラベル、ガラス容器の破壊飛
散防止包装やラベル、キャップシールなどに広く利用さ
れる熱収縮性フイルムの材質としては、ポリ塩化ビニル
（以下「ＰＶＣ」と表記する）が最もよく知られ、また
使用されてきた。これはＰＶＣから作られた熱収縮性フ
イルムが、機械強度、剛性、光学特性、収縮特性等の実
用特性、およびコスト性も含めて、ユーザーの要求を比
較的広く満足するからである。ところが、ＰＶＣは熱収
縮性フイルムとしての優れた実用特性とコスト性を有し
ているものの、廃棄後焼却すると塩素を含んだガスを発
生する等の環境への影響から、近年ＰＶＣ以外の材料が
要望されるようになってきた。2. Description of the Related Art A heat-shrinkable film widely used for shrink wrapping, shrink-wrapping wrapping, plastic container labels, glass container destruction and scattering prevention packaging, labels, cap seals, etc. Vinyl (hereinafter "PVC") is best known and has been used. This is because a heat-shrinkable film made of PVC satisfies user requirements relatively widely, including practical properties such as mechanical strength, rigidity, optical properties, shrinkage properties, and cost. However, although PVC has excellent practical properties and cost properties as a heat-shrinkable film, materials other than PVC have recently been used due to environmental effects such as generation of chlorine-containing gas when incinerated after disposal. It has come to be desired.
【０００３】このようなＰＶＣ以外の材料の一つとし
て、スチレン−ブタジエンブロック共重合体（以下「Ｓ
ＢＳ」と表記することがある）を主たる材料とするポリ
スチレン系熱収縮性フイルムが提案され使用されている
が、このポリスチレン系フイルムは、加熱収縮時の収縮
斑やしわが少なく収縮仕上がり性は優れているものの、
室温における剛性が乏しく、自然収縮（常温よりやや高
い温度、例えば夏場においてフイルムが本来の使用前に
少し収縮してしまうこと）率が大きいことや、耐破断性
に劣る等の問題を有している。As one of the materials other than PVC, a styrene-butadiene block copolymer (hereinafter referred to as "S
A heat-shrinkable polystyrene film whose main material is sometimes referred to as "BS" has been proposed and used, but this polystyrene-based film has less shrinkage spots and wrinkles during heat shrinkage, and has excellent shrink finish. Although,
It has poor rigidity at room temperature, large spontaneous shrinkage (slightly higher than normal temperature, for example, the film shrinks slightly before use in summer), and has poor rupture resistance. I have.
【０００４】さらにＰＶＣ以外の材料として、ポリエス
テル系樹脂を主たる材料とした熱収縮性ポリエステル系
フイルムも提案され使用されている。この熱収縮性ポリ
エステル系フイルムは室温の剛性が高く、透明性に優
れ、自然収縮率は非常に低いものの、ＰＶＣやＳＢＳか
らなるフイルムと比較すると、加熱収縮時に収縮斑やし
わが発生し易く収縮仕上がり性に劣る傾向が見られる。
最近の熱収縮性フイルムにおけるラベリング工程では、
内容物を容器に充填した後にフイルムのシュリンクを行
うことが主流となりつつあり、この方法では内容物の温
度上昇による品質低下を回避すると共にコストダウンの
ためＰＥＴボトルの薄肉化を進めている。そのためにシ
ュリンク時の温度を下げ、ボトルの変形を防ぐ必要が出
てきている。従って、なるべく低温から収縮を開始する
と共に、低温での収縮仕上がりの優れた外観が得られる
熱収縮性ポリエステル系フイルムが切望されている。Further, as a material other than PVC, a heat-shrinkable polyester film using a polyester resin as a main material has been proposed and used. This heat-shrinkable polyester film has high rigidity at room temperature, excellent transparency, and a very low natural shrinkage ratio. However, when compared with a film made of PVC or SBS, shrinkage spots and wrinkles easily occur during heat shrinkage and shrink. There is a tendency that the finish is inferior.
In the labeling process of recent heat-shrinkable films,
Shrinking a film after filling the contents into a container is becoming the mainstream. In this method, a PET bottle is made thinner in order to avoid quality deterioration due to a rise in the temperature of the contents and to reduce costs. Therefore, it is necessary to lower the temperature at the time of shrinkage and prevent the bottle from being deformed. Therefore, a heat-shrinkable polyester film which starts shrinking at a low temperature as much as possible and which can provide an excellent appearance of a shrink finish at a low temperature is desired.
【０００５】[0005]
【課題を解決するための手段】本発明は、上記問題点を
解決するために種々検討の結果、多層ポリエステル系フ
イルムにおいて、特定の粘弾性特性を有する多層の原シ
ートを延伸することによって単層ポリエステル系フイル
ムよりさらに良好な収縮仕上がりを有するフイルムが得
られることを見出して完成するに至ったものである。According to the present invention, as a result of various studies to solve the above-mentioned problems, a multi-layer polyester film is formed by stretching a multi-layer original sheet having a specific viscoelastic property by stretching it. The inventors have found that a film having a better shrink finish than that of a polyester film can be obtained, and have completed the present invention.
【０００６】すなわち、本発明の要旨は、中間層と表裏
層を有し、動的粘弾性測定により周波数１０Ｈｚ、昇温
速度１℃／分で測定した、貯蔵弾性率（Ｅ'）及び損失
弾性率（Ｅ"）の測定値が下記の関係を満足する多層の
ポリエステル系樹脂原シートを用い、少なくとも一軸方
向に延伸してなる熱収縮性ポリエステル系多層フイル
ム。（Ｅ"）のピークが７０℃以下に存在すると共に、
このピーク温度をＡとし、Ａ−５℃における（Ｅ'）の
値を（Ｅ'ｌ）、Ａ＋５℃における（Ｅ'）の値を（Ｅ'
ｈ）とした場合、（Ｅ'ｌ）／（Ｅ'ｈ）≦７．０、好ま
しくは（Ｅ'ｌ）／（Ｅ'ｈ）≦５．０の範囲である。That is, the gist of the present invention is to provide a storage elastic modulus (E ') and a loss elasticity which have an intermediate layer and front and back layers, and are measured by dynamic viscoelasticity at a frequency of 10 Hz and a heating rate of 1 ° C./min. A heat-shrinkable polyester-based multilayer film obtained by stretching at least uniaxially using a multilayered polyester-based resin sheet whose measured value of the rate (E ") satisfies the following relationship. The peak of (E") is 70 ° C. Exists below,
The peak temperature is defined as A, the value of (E ′) at A-5 ° C. is (E′l), and the value of (E ′) at A + 5 ° C. is (E ′).
h), the range is (E′l) / (E′h) ≦ 7.0, preferably (E′l) / (E′h) ≦ 5.0.
【０００７】さらに上記多層フイルムであって、中間層
に全層厚みの５〜４５％の表裏層を配し、中間層と表裏
層の間に全層厚みの２０％以下の接着層を配したものを
含んでいる。Further, in the above-mentioned multilayer film, a front and back layer having a thickness of 5 to 45% of the total thickness is disposed on the intermediate layer, and an adhesive layer having a thickness of not more than 20% of the total thickness is disposed between the intermediate layer and the front and back layers. Includes things.
【０００８】[0008]
【発明の実施の形態】以下本発明を詳しく説明する。本
発明フイルムでは、多層のポリエステル系樹脂原シート
の粘弾性特性を特定の範囲にする必要がある。この粘弾
性特性は上記シートを動的粘弾性測定により周波数１０
Ｈｚ、昇温速度１０℃／分で測定したものであり、貯蔵
弾性率（Ｅ'）及び損失弾性率（Ｅ"）の測定グラフの一
例を図１の概略図に示した。図１において横軸は温度、
縦軸は（Ｅ'）及び（Ｅ"）の対数値である。本発明フイ
ルムの延伸前の多層の原シートは、（Ｅ"）のピーク
（図１において△で示した極大値）が７０℃以下に存在
すると共に、このピーク温度をＡとし、Ａ−５℃におけ
る（Ｅ'）の値を（Ｅ'ｌ）、Ａ＋５℃における（Ｅ'）
の値を（Ｅ'ｈ）とした場合、（Ｅ'ｌ）／（Ｅ'ｈ）≦
７．０の範囲、好ましくは（Ｅ'ｌ）／（Ｅ'ｈ）≦５．
０の範囲である。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the film of the present invention, it is necessary that the viscoelastic properties of the multilayer polyester resin raw sheet be in a specific range. This viscoelastic property is obtained by measuring the sheet at a frequency of 10
An example of a measurement graph of the storage elastic modulus (E ′) and the loss elastic modulus (E ″) is shown in the schematic diagram of FIG. The axis is temperature,
The vertical axis is the logarithmic value of (E ') and (E "). In the multilayer original sheet before stretching of the film of the present invention, the peak of (E") (the maximum value indicated by △ in FIG. 1) is 70. , The peak temperature is A, the value of (E ') at A-5 ° C is (E'l), and (E') at A + 5 ° C.
Is (E'h), then (E'l) / (E'h) ≦
7.0, preferably (E′l) / (E′h) ≦ 5.
It is in the range of 0.
【０００９】上記のピーク温度Ａが７０℃を越えるシー
トを延伸したフイルムは収縮の開始温度が高く、低温か
ら収縮するフィルムとならないという問題がある。ま
た、（Ｅ'ｌ）／（Ｅ'ｈ）の数値が７．０を越えるフイ
ルムでは、加熱収縮後の仕上がりにおいて収縮斑やしわ
が発生し、商品価値が低下するという問題がある。この
原因としては（Ｅ'ｌ）／（Ｅ'ｈ）の数値が７．０を越
えた場合、収縮時に弾性率の急激な低下を伴ないつつ収
縮していくことにあると考えられる。（Ｅ'ｌ）の具体
的数値は６．０×１０８〜１．５×１０９Ｎ/ｍ２、
（Ｅ'ｈ）の具体的数値は８．０×１０６〜６．０×１
０８Ｎ/ｍ２の範囲が好ましい。A film obtained by stretching a sheet having a peak temperature A of more than 70 ° C. has a problem that the starting temperature of shrinkage is high and the film does not shrink from a low temperature. Further, a film having a value of (E'l) / (E'h) exceeding 7.0 has a problem in that uneven spots and wrinkles occur in the finished product after heat shrinkage, and the commercial value is reduced. It is considered that the reason for this is that when the value of (E'l) / (E'h) exceeds 7.0, shrinkage occurs with a sharp decrease in elastic modulus during shrinkage. Specific numerical values of (E′l) are 6.0 × 10 8 to 1.5 × 10 9 N / m 2 ,
The specific numerical value of (E′h) is 8.0 × 10 6 to 6.0 × 1.
0 8 range of N / m 2 are preferred.
【００１０】上記の粘弾性特性は多層の原シート全体で
の規定であるが、中間層及び表裏層の各々の樹脂を用い
た単層原シートの貯蔵弾性率をそれぞれ（Ｅ'ｃ）、
（Ｅ'ｓ）及び、対応する損失弾性率を（Ｅ"ｃ）、
（Ｅ"ｓ）とした場合、これらの測定値が下記関係を満
足するポリエステル系樹脂を積層することにより、上記
の粘弾性特性を容易に得ることができる。単層原シート
の粘弾性特性は上記原シート全体と同一の条件で測定し
たものであり、貯蔵弾性率（Ｅ'）及び損失弾性率
（Ｅ"）の測定グラフの一例を図２の概略図に示した。
図２において横軸は温度、縦軸は（Ｅ'）及び（Ｅ"）の
対数値である。The above viscoelastic properties are defined for the entire multilayer original sheet. The storage elastic moduli of the single-layer original sheet using the resins of the intermediate layer and the front and back layers are respectively (E'c),
(E's) and the corresponding loss modulus are (E "c),
In the case of (E "s), the above viscoelastic properties can be easily obtained by laminating a polyester resin whose measured values satisfy the following relationship. FIG. 2 shows an example of a measurement graph of the storage elastic modulus (E ′) and the loss elastic modulus (E ″) measured under the same conditions as the entire original sheet.
In FIG. 2, the horizontal axis represents temperature, and the vertical axis represents logarithmic values of (E ′) and (E ″).
【００１１】中間層（Ｅ"ｃ）のピーク温度をＡｃと
し、表裏層（Ｅ"ｓ）のピーク温度をＡｓとするとその
温度差Ａｃ−Ａｓが２０℃以下である。 中間層：（Ｅ"ｃ）のピーク温度をＡｃとし、Ａｃ−５
℃における（Ｅ'ｃ）の値を（Ｅ'ｃｌ）、Ａｃ＋５℃に
おける（Ｅ'ｃ）の値を（Ｅ'ｃｈ）とした場合、（Ｅ'
ｃｌ）／（Ｅ'ｃｈ）≦８．０ （Ｅ'ｃｌ）の具体的数値は６．０×１０８〜１．８×
１０９Ｎ/ｍ２、（Ｅ'ｃｈ）の具体的数値は７．０×１
０６〜６．０×１０８Ｎ/ｍ２の範囲が好ましい。 表裏層：（Ｅ"ｓ）のピーク温度をＡｓとし、Ａｓ−５
℃における（Ｅ'ｓ）の値を（Ｅ'ｓｌ）、Ａｓ＋５℃に
おける（Ｅ'ｓ）の値を（Ｅ'ｓｈ）とした場合、（Ｅ'
ｓｌ）／（Ｅ'ｓｈ）≦１０．０ （Ｅ'ｓｌ）の具体的数値は６．０×１０８〜１．８×
１０９Ｎ/ｍ２、（Ｅ'ｓｈ）の具体的数値は７．０×１
０６〜６．０×１０８Ｎ/ｍ２の範囲が好ましい。Assuming that the peak temperature of the intermediate layer (E "c) is Ac and the peak temperature of the front and back layers (E" s) is As, the temperature difference Ac-As is 20 ° C. or less. Intermediate layer: The peak temperature of (E "c) is Ac, and Ac-5
When the value of (E'c) at ° C is (E'cl) and the value of (E'c) at Ac + 5 ° C is (E'ch), (E'ch)
cl) / (E′ch) ≦ 8.0 Specific values of (E′cl) are 6.0 × 10 8 to 1.8 ×
The specific numerical value of 10 9 N / m 2 and (E′ch) is 7.0 × 1
0 6 to 6.0 range × 10 8 N / m 2 are preferred. Front and back layers: The peak temperature of (E "s) is As, and As-5
When the value of (E's) at ° C is (E'sl) and the value of (E's) at As + 5 ° C is (E'sh), (E '
sl) / (E'sh) ≦ 10.0 The specific numerical value of (E'sl) is 6.0 × 10 8 to 1.8 ×
The specific numerical value of 10 9 N / m 2 and (E'sh) is 7.0 × 1
0 6 to 6.0 range × 10 8 N / m 2 are preferred.
【００１２】本発明の熱収縮性ポリエステル系フイルム
においては、上記の収縮特性を発現すると共に材料特性
も工夫したほうが良い。本来ポリエステル系樹脂は結晶
性樹脂であり、フイルムを延伸することによって配向結
晶化してしまう。収縮フィルムは通常、印刷及び溶剤を
用いた製袋工程が伴う。そこで、印刷適性及び溶剤シー
ル性を向上させるために構成材料自体の結晶性を下げる
ことが必要となる。しかし、構成材料の樹脂を完全に非
晶性としてしまうと、熱収縮性フイルムとして十分に要
求特性を満足させることが困難となる。従って、適度な
結晶性を付与させることが重要である。非晶性のポリエ
ステル系フイルムでは、その粘弾性特性に応じて急激な
収縮カーブの立ち上がりと、非常に高い収縮応力を有し
ている。一方、適度な結晶性を付与させることによっ
て、高温時での収縮率が低減されるために、結果的に収
縮カーブ曲線が緩やかになり収縮仕上がり性を向上させ
ることが期待できる。さらに、結晶性を付与させること
によって延伸後のフイルムの厚み精度に影響を及ぼす。
延伸加工条件によっても厚み精度を向上させる方法はい
くつかあるが、最も厚み精度に影響するのは構成材料の
樹脂の結晶性である。In the heat-shrinkable polyester film of the present invention, it is better to exhibit the above-mentioned shrinkage property and to devise material properties. Originally, a polyester resin is a crystalline resin, and is oriented and crystallized by stretching a film. Shrink films usually involve a printing and bag making process using a solvent. Therefore, it is necessary to lower the crystallinity of the constituent material itself in order to improve printability and solvent sealability. However, if the resin of the constituent material is made completely amorphous, it becomes difficult to sufficiently satisfy the required characteristics as a heat-shrinkable film. Therefore, it is important to impart appropriate crystallinity. An amorphous polyester film has a sharp rise of a shrinkage curve and a very high shrinkage stress according to its viscoelastic properties. On the other hand, by imparting appropriate crystallinity, the shrinkage rate at high temperature is reduced, and as a result, it is expected that the shrinkage curve curve becomes gradual and the shrink finish is improved. Further, by imparting crystallinity, the thickness accuracy of the stretched film is affected.
Although there are several methods for improving the thickness accuracy depending on the stretching conditions, the crystallinity of the constituent material resin most affects the thickness accuracy.
【００１３】延伸加工の初期の段階において、加熱され
るフイルムを部分的に見た場合、不均一な温度分布を示
すことがある。この場合、より高い温度の個所から延伸
が開始される。使用する樹脂が非晶性樹脂の場合では、
延伸され薄くなった個所がより延伸され、フイルム全体
が不均一な延伸となる。一方、結晶性がある場合、初期
に延伸された部分は薄くなるとともに配向結晶化により
延伸応力が大きくなるので、非延伸部分が延伸されやす
くなり、その結果フイルム全体で均一延伸されることに
よって厚み精度が向上するのである。When the film to be heated is partially viewed at an early stage of the stretching process, the film may show an uneven temperature distribution. In this case, stretching starts at a higher temperature. When the resin used is an amorphous resin,
The stretched and thinned portions are further stretched, and the entire film becomes unevenly stretched. On the other hand, when there is crystallinity, the initially stretched portion becomes thinner and the stretching stress increases due to the orientation crystallization, so that the non-stretched portion is easily stretched, and as a result, the film is uniformly stretched over the entire film, thereby increasing the thickness. Accuracy improves.
【００１４】本発明フイルムの素材となるポリエステル
樹脂は、ジカルボン酸成分としてテレフタル酸、ジオー
ル成分としてエチレングリコールを主成分とするエチレ
ンテレフタレート系共重合ポリエステルが好適に用いら
れる。共重合成分としては、ジカルボン酸としてイソフ
タル酸、アジピン酸、セバシン酸等、ジオール成分とし
てネオペンチルグリコール、ジエチレングリコール、
１，４−シクロヘキサンジメタノール、１，４−ブタン
ジオールなどを用いた共重合ポリエステルが工業的に容
易に入手でき、かつ収縮性も良好で好ましい。本発明に
おいて用いる共重合ポリエステルにおいては、ジカルボ
ン酸成分１００モル％およびジオール成分１００モル％
の合計量２００モル％中、共重合成分が合計２０モル％
以上、より好ましくは３０モル％以上とするのがよい。
共重合成分が合計２０モル％未満の共重合ポリエステル
はフイルムにした際の結晶化度が高くなり、収縮仕上が
り、溶剤シール性が劣るので好ましくない。As the polyester resin used as a material of the film of the present invention, an ethylene terephthalate copolymer polyester containing terephthalic acid as a dicarboxylic acid component and ethylene glycol as a diol component as a main component is preferably used. As the copolymerization component, isophthalic acid, adipic acid, sebacic acid and the like as dicarboxylic acids, neopentyl glycol, diethylene glycol as diol components,
Copolymerized polyesters using 1,4-cyclohexanedimethanol, 1,4-butanediol, and the like can be easily obtained industrially and have good shrinkage, which is preferable. In the copolyester used in the present invention, 100 mol% of a dicarboxylic acid component and 100 mol% of a diol component
Of the total amount of 200 mol% of the copolymer component is 20 mol%
It is more preferably at least 30 mol%.
Copolymerized polyesters having a total copolymerization component of less than 20 mol% are not preferred because the crystallinity when formed into a film is high, the shrinkage finish is poor, and the solvent sealing property is inferior.
【００１５】本発明フイルムにおいて、上述した粘弾性
特性を付与させるためには、ポリエーテルを共重合した
ポリブチレンテレフタレートをブレンドすることが好ま
しい。ポリブチレンテレフタレート自体でもＴｇは非常
に低く、配合することによってＴｇを下げる効果は十分
に期待できるが、ポリブチレンテレフタレートの添加量
のみで、より低温収縮性を付与させる場合、上記に示し
た通り、結晶性が上昇しすぎてしまい、溶剤シール性、
インキ密着性が低下し易い。従って、結晶性樹脂は表裏
層よりも中間層への添加が好ましい。特に、ポリエーテ
ルのなかでもポリテトラメチレングリコールが、重合面
や品質面から最も良好である。なお、上記ポリエーテル
をポリブチレンテレフタレート中に共重合することによ
り粘弾性特性を満足させるだけではなくＴｇを下げる効
果も期待できることから最も良好な組成の1つである。
ポリブチレンテレフタレート中のポリテトラメチレング
リコール含有量はジオール成分中０．３〜１０モル％が
好ましく、より好ましくは０．５〜３モル％である。ポ
リテトラメチレングリコールユニットが０．３モル％未
満ではポリブチレンテレフタレート単体の場合と同様に
物性が変化しない。一方、１０モル％を越える場合、他
の混合樹脂との相溶性が悪くなり透明性の低下をもたら
し易い。In order to impart the above-mentioned viscoelastic properties to the film of the present invention, it is preferable to blend polybutylene terephthalate obtained by copolymerizing polyether. Polybutylene terephthalate itself has a very low Tg, and the effect of lowering Tg by blending can be expected to be sufficient. Crystallinity will rise too much, solvent sealing properties,
Ink adhesion tends to decrease. Therefore, the crystalline resin is preferably added to the intermediate layer rather than the front and back layers. In particular, among polyethers, polytetramethylene glycol is the best in terms of polymerization and quality. It is one of the best compositions because copolymerization of the above polyether in polybutylene terephthalate not only satisfies the viscoelastic properties but also can expect an effect of lowering Tg.
The content of polytetramethylene glycol in the polybutylene terephthalate is preferably from 0.3 to 10 mol%, more preferably from 0.5 to 3 mol%, in the diol component. If the polytetramethylene glycol unit is less than 0.3 mol%, the physical properties do not change as in the case of polybutylene terephthalate alone. On the other hand, if it exceeds 10 mol%, the compatibility with other mixed resins is deteriorated and the transparency tends to be lowered.
【００１６】なお、本発明フイルムの極限粘度は０．５
以上、好ましくは０．６以上がよい。フイルムの極限粘
度が０．５未満であると耐破断性が低下し易い。また本
発明のフイルムでは、フイルムの易滑性を向上させるた
め、表裏層に有機滑材、無機滑材などの微粒子を含有さ
せてもよく、静防剤等を練り込み方法やコーティング方
法によって付与させることも可能である。本発明に使用
される原料は各成分をもつポリエステル樹脂を混合した
状態で使用されるにとどまらず、重合段階において上記
内容と同等のポリエステルを作成し、使用することもで
きる。The intrinsic viscosity of the film of the present invention is 0.5
Above, preferably 0.6 or more. If the intrinsic viscosity of the film is less than 0.5, the rupture resistance tends to decrease. Further, in the film of the present invention, in order to improve the lubricity of the film, fine particles such as an organic lubricant and an inorganic lubricant may be contained in the front and back layers, and an antistatic agent or the like is applied by a kneading method or a coating method. It is also possible to make it. The raw materials used in the present invention are used not only in a state where a polyester resin having each component is mixed, but also in the polymerization stage, a polyester equivalent to the above can be prepared and used.
【００１７】つぎに本発明フイルムの製造法を具体的に
説明するが、下記製造法には限定されない。重縮合反応
によって得られた共重合ポリエステル等を混合し、２０
０〜３２０℃の温度で溶融押出する。押出に際しては、
Ｔダイ法、チューブラ法等の通常の製膜方法により行う
ことが出来る。Ｔダイ法を用いた場合、多層の原シート
を共押出した後、表面温度１５〜８０℃のキャスティン
グドラム上で急冷して、厚さ３０〜３００μｍの未延伸
フイルムを形成する。得られた未延伸フイルムを、加熱
縦延伸ロールを用いて、ロール温度６０〜１２０℃にて
１．０〜２．０倍、好ましくは１．０〜１．５倍延伸す
る、縦延伸後、テンターを用いて延伸温度６０〜１２０
℃にて１．７〜７．０倍延伸し、６０〜１００℃の温度
で熱処理して巻き取る。Next, the method for producing the film of the present invention will be described specifically, but is not limited to the following method. The copolymerized polyester obtained by the polycondensation reaction is mixed, and 20
Melt extrude at a temperature of 0-320 ° C. For extrusion,
It can be performed by a usual film forming method such as a T-die method and a tubular method. When the T-die method is used, a multi-layer raw sheet is co-extruded, and then rapidly cooled on a casting drum having a surface temperature of 15 to 80 ° C. to form an unstretched film having a thickness of 30 to 300 μm. The obtained unstretched film is stretched 1.0 to 2.0 times, preferably 1.0 to 1.5 times at a roll temperature of 60 to 120 ° C. using a heated longitudinal stretching roll. Stretching temperature of 60 to 120 using a tenter
The film is stretched 1.7 to 7.0 times at ℃, heat-treated at a temperature of 60 to 100 ℃ and wound up.
【００１８】ここで、前記フイルムの諸特性のうち、収
縮特性は主に延伸倍率と延伸温度に依存するので、主収
縮方向の収縮率を上げるという面からは高倍率、低温延
伸が好ましい。一方収縮応力も延伸温度の主に依存し、
高倍率、低温延伸ほど収縮能力が大きくなり、また延伸
後の熱処理（アニーリング、特に弛緩熱処理）の影響も
ある。収縮率の温度依存性をよりなだらかに設定するた
めには、やや高温での延伸を行いつつ延伸倍率を調整す
るのが一つの方法であり、延伸後のフイルムの平坦性改
良や収縮率調整のために熱処理を行う場合にはポリエス
テルの結晶化を促進しない低温で行うことである。それ
により、加熱収縮時初期のフイルムの挙動に大きく影響
する収縮応力を低く抑えなだらかな収縮特性を示すフイ
ルムを得ることが可能になる。具体的な温度条件は使用
するポリエステルの種類に応じて適宜設定することがで
きる。Here, among the various characteristics of the film, the shrinkage characteristics mainly depend on the stretching ratio and the stretching temperature. Therefore, from the viewpoint of increasing the shrinkage ratio in the main shrinking direction, high-magnification and low-temperature stretching are preferred. On the other hand, the shrinkage stress also depends mainly on the stretching temperature,
The higher the draw ratio and the lower the temperature, the greater the shrinkage ability, and there is also the effect of heat treatment (annealing, especially relaxation heat treatment) after stretching. In order to set the temperature dependence of the shrinkage rate more smoothly, one method is to adjust the draw ratio while stretching at a relatively high temperature, and to improve the flatness of the film after stretching and adjust the shrinkage rate. Therefore, when heat treatment is performed, the heat treatment is performed at a low temperature that does not promote crystallization of the polyester. As a result, it is possible to obtain a film exhibiting a gradual shrinkage characteristic while suppressing the shrinkage stress, which greatly affects the behavior of the film at the time of heat shrinkage, at a low level. Specific temperature conditions can be appropriately set according to the type of polyester used.
【００１９】また、本発明のポリエステル系多層フイル
ムにおいては、ポリエステル系多層フイルムに比べ紫外
線吸収成分を含む樹脂や着色した樹脂を中間層に使用す
ることにより少量の添加剤で紫外線防止効果を得ること
ができる。また、ポリエステル系多層フイルムの表裏層
と中間層の間に接着層を配することにより層間の接着強
度を低下させることなく表裏層や中間層への機能成分を
添加しやすくなるとともに、触感をより柔らかくするこ
とができる。これは、加熱収縮後ポリエステル系フイル
ムが硬いことによりラベルをペットボトルから剥がす際
つかみ難いなどの問題に効果がある。接着層としては通
常の無水カルボン酸等により酸変成した接着性ポリオレ
フィン樹脂等を使用することができる。このような接着
層を設ける場合、中間層に全層厚みの５〜４５％の表裏
層を配し、中間層と表裏層の間に全層厚みの２０％以下
の接着層を配することが好ましい。Further, in the polyester-based multilayer film of the present invention, compared to the polyester-based multilayer film, a resin containing an ultraviolet absorbing component or a colored resin is used for the intermediate layer to obtain an ultraviolet ray preventing effect with a small amount of additives. Can be. In addition, by disposing an adhesive layer between the front and back layers and the intermediate layer of the polyester-based multilayer film, it becomes easy to add the functional component to the front and back layers and the intermediate layer without lowering the adhesive strength between the layers, and to improve the tactile sensation. Can be softened. This is effective in the problem that the polyester film is hard after the heat shrinkage, so that it is difficult to grasp the label when peeling the label from the PET bottle. As the adhesive layer, an adhesive polyolefin resin or the like which has been acid-modified with ordinary carboxylic anhydride or the like can be used. When such an adhesive layer is provided, it is possible to arrange the front and back layers of 5 to 45% of the total thickness in the intermediate layer, and to arrange the adhesion layer of 20% or less of the total thickness between the intermediate layer and the front and back layers. preferable.
【００２０】さらに、前記延伸工程中、延伸前または延
伸後に、フイルムの片面または両面にコロナ放電処理な
どの表面活性化処理を施してフイルムの印刷層に対する
接着性を向上させることも可能である。また上記延伸工
程中、延伸前または延伸後に、フイルムの接着性、帯電
防止性、滑り性、遮光性などを向上させることも可能で
ある。Further, during or before the stretching step, one or both sides of the film may be subjected to a surface activation treatment such as a corona discharge treatment to improve the adhesiveness of the film to the printed layer. In addition, during the stretching step, before or after the stretching, it is possible to improve the adhesiveness, antistatic property, slipperiness, light-shielding property and the like of the film.
【００２１】[0021]
【実施例】以下、実施例について説明するが、本発明は
これに限定されるものではない。表１に示した酸成分と
ジオール成分からなるポリエステル系樹脂組成物を用
い、口金温度２７０℃でマルチＴダイにより溶融押出し
して未延伸の多層の原シートを得た。得られた原シート
を、テンターにより横方向に１軸延伸し、次いで熱処理
を行って厚さ５０μｍのフイルムを得た。各フイルムの
特性の評価結果を表２に示した。なお、表２に示した粘
弾性特性は上記未延伸の多層の原シートを用い、岩本製
作所（株）製粘弾性スペクトロメーターＶＥＳ−Ｆ３を
用い、周波数１０Ｈｚ、昇温速度１℃／分で、貯蔵弾性
率（Ｅ'）及び損失弾性率（Ｅ"）をサンプルの引き落と
し方向で測定し計算した数値である。なお、フイルムの
特性の評価方法は以下の通りである。The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. The polyester resin composition comprising the acid component and the diol component shown in Table 1 was melt-extruded with a multi-T die at a die temperature of 270 ° C. to obtain an unstretched multilayer original sheet. The obtained original sheet was uniaxially stretched in the transverse direction by a tenter, and then heat-treated to obtain a film having a thickness of 50 µm. Table 2 shows the evaluation results of the characteristics of each film. The viscoelastic properties shown in Table 2 were measured using the above unstretched multilayer original sheet, using a viscoelastic spectrometer VES-F3 manufactured by Iwamoto Seisakusho Co., Ltd. at a frequency of 10 Hz and a heating rate of 1 ° C./min. It is a numerical value calculated by measuring the storage elastic modulus (E ') and the loss elastic modulus (E ") in the pull-down direction of the sample.The evaluation method of the film properties is as follows.
【００２２】１）低温ラベリング性 格子目を入れたフイルムを円筒状にしてペットボトルに
かぶせ、蒸気シュリンクトンネルを通過させてボトルに
装着し、収縮外観を評価した。蒸気シュリンクの温度は
６５℃〜７０℃、にて実施した。ラベルの格子目の歪み
がなく密着性も優れ非常に美しい仕上がりのものを
（◎）、通常の仕上りのものを（○）、ゆがみ、しわな
どが僅かにあるが実用上支障がないものを（△）、完全
な収縮不足もしくは仕上がり性が完全に実用レベルに達
しないものを（×）とした。1) Low-Temperature Labeling A film having grids was formed in a cylindrical shape, covered with a plastic bottle, passed through a steam shrink tunnel, and mounted on the bottle, and the shrink appearance was evaluated. The steam shrink was performed at a temperature of 65 ° C to 70 ° C. Labels with a very beautiful finish (◎) with excellent adhesion and no lattice distortion of the label, (○) with normal finish, and those with slight distortion and wrinkles but no practical problems ( Δ), those with insufficient shrinkage or whose finishability did not completely reach the practical level were designated as (x).
【００２３】２）一般ラベリング性 蒸気シュリンクの温度を８０℃〜８５℃にて実施した以
外は上記１）と同一内容にて収縮外観を評価した。2) General Labeling Property The same shrinkage appearance as in 1) above was evaluated except that the steam shrink was carried out at a temperature of 80 ° C. to 85 ° C.
【００２４】[0024]
【表１】 [Table 1]
【００２５】TPA：テレフタル酸 IPA：イソフタル酸 EG：エチレングリコール CHDM:1,4-シクロヘキサンジ
メタノール BD:1,4-ブタンジオール PTMG:ポリテトラメチレングリ
コール DEG:ジエチレングリコール 実施例４では層間に接着層（酸変成ポリエチレン樹脂：
５μ）を介在させた。TPA: terephthalic acid IPA: isophthalic acid EG: ethylene glycol CHDM: 1,4-cyclohexane dimethanol BD: 1,4-butanediol PTMG: polytetramethylene glycol DEG: diethylene glycol In Example 4, an adhesive layer ( Acid-modified polyethylene resin:
5μ).
【００２６】[0026]
【表２】 [Table 2]
【００２７】表２から本発明の粘弾性特性であるピーク
温度範囲とＥ'式の範囲を満足する実施例１〜５は実施
例６〜７より低温および一般ラベリング性のいずれも優
れていることが分かる。これに対して比較例１〜３のフ
イルムは、ピーク温度範囲及び／又はＥ'式の範囲を逸
脱しており低温及び／又は一般ラベリング性に劣ること
が分かる。From Table 2, it can be seen that Examples 1 to 5 satisfying the peak temperature range and the range of E ', which are the viscoelastic characteristics of the present invention, are superior to Examples 6 to 7 in both low temperature and general labeling properties. I understand. On the other hand, it can be seen that the films of Comparative Examples 1 to 3 deviate from the peak temperature range and / or the range of the E ′ formula, and are inferior in low temperature and / or general labeling property.
【００２８】[0028]
【発明の効果】本発明によれば、低温のシュリンカーで
も十分対応し、収縮時のフイルムのしわ、ひずみ、収縮
斑などの極めて少ない、収縮特性の優れたフイルムが得
られる。According to the present invention, it is possible to obtain a film which can sufficiently cope with a low-temperature shrinker, has very little wrinkles, strains and shrinkage during shrinkage, and has excellent shrinkage characteristics.
【図１】多層フイルム原シートの測定グラフの一例を示
す概略図である。FIG. 1 is a schematic view showing an example of a measurement graph of an original multilayer film sheet.
【図２】表裏層、中間層における各層のフイルム原シー
トの測定グラフの一例を示す概略図である。FIG. 2 is a schematic view showing an example of a measurement graph of a film original sheet of each of the front and back layers and the intermediate layer.
Ａ … ピーク温度 （Ｅ'ｌ）… Ａ−５℃における（Ｅ'）の値 （Ｅ'ｈ）… Ａ＋５℃における（Ｅ'）の値 A: peak temperature (E′l): value of (E ′) at A-5 ° C. (E′h): value of (E ′) at A + 5 ° C.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ２９Ｌ 9:00 Ｂ２９Ｌ 9:00 Ｆターム(参考） 4F100 AK41A AK41B AK41C BA01 BA03 BA06 BA10A BA10C BA16 CB00 EJ37 JA03 JA20A JA20C JK07 YY00A YY00C 4F210 AA24 AE01 AG01 AG03 RA03 RC02 RG02 RG04 RG09 RG43──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B29L 9:00 B29L 9:00 F term (Reference) 4F100 AK41A AK41B AK41C BA01 BA03 BA06 BA10A BA10C BA16 CB00 EJ37 JA03 JA20A JA20C JK07 YY00A YY00C 4F210 AA24 AE01 AG01 AG03 RA03 RC02 RG02 RG04 RG09 RG43
Claims (3)
により周波数１０Ｈｚ、昇温速度１℃／分で測定した、
貯蔵弾性率（Ｅ'）及び損失弾性率（Ｅ"）の測定値が下
記の関係を満足する多層のポリエステル系樹脂原シート
を用い、少なくとも一軸方向に延伸してなる熱収縮性ポ
リエステル系多層フイルム。（Ｅ"）のピークが７０℃
以下に存在すると共に、このピーク温度をＡとし、Ａ−
５℃における（Ｅ'）の値を（Ｅ'ｌ）、Ａ＋５℃におけ
る（Ｅ'）の値を（Ｅ'ｈ）とした場合、（Ｅ'ｌ）／
（Ｅ'ｈ）≦７．０Claims: 1. An intermediate layer and a front and back layer having a frequency of 10 Hz and a temperature rising rate of 1 ° C./min by dynamic viscoelasticity measurement.
A heat-shrinkable polyester-based multilayer film formed by stretching at least uniaxially using a multilayered polyester resin raw sheet whose measured values of storage elastic modulus (E ′) and loss elastic modulus (E ″) satisfy the following relationship: (E ″) peak at 70 ° C.
And the peak temperature is A, and A-
When the value of (E ′) at 5 ° C. is (E′l) and the value of (E ′) at A + 5 ° C. is (E′h), (E′l) /
(E′h) ≦ 7.0
とを特徴とする請求項１記載の熱収縮性ポリエステル系
多層フイルム。2. The heat-shrinkable polyester multilayer film according to claim 1, wherein (E′l) / (E′h) ≦ 5.0.
を配し、中間層と表裏層の間に全層厚みの２０％以下の
接着層を配することを特徴とする請求項１乃至２記載の
熱収縮性ポリエステル系多層フイルム。3. An intermediate layer having a front and back layer having a thickness of 5 to 45% of the total thickness, and an adhesive layer having a thickness of 20% or less of the total thickness between the intermediate layer and the front and back layers. Item 3. The heat-shrinkable polyester-based multilayer film according to Item 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000242641A JP3960741B2 (en) | 2000-08-10 | 2000-08-10 | Heat-shrinkable polyester multilayer film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000242641A JP3960741B2 (en) | 2000-08-10 | 2000-08-10 | Heat-shrinkable polyester multilayer film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002052672A true JP2002052672A (en) | 2002-02-19 |
| JP3960741B2 JP3960741B2 (en) | 2007-08-15 |
Family
ID=18733639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000242641A Expired - Fee Related JP3960741B2 (en) | 2000-08-10 | 2000-08-10 | Heat-shrinkable polyester multilayer film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3960741B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004018205A1 (en) * | 2002-08-23 | 2004-03-04 | Teijin Dupont Films Japan Limited | Heat-shrinkable multilayered polyester film for packaging |
| WO2005095106A1 (en) * | 2004-03-31 | 2005-10-13 | Mitsubishi Plastics, Inc. | Heat-shrinkable layered polyolefin film, heat-shrinkable label, and container with the label attached thereto |
| JP2005288729A (en) * | 2004-03-31 | 2005-10-20 | Mitsubishi Plastics Ind Ltd | Heat shrinkable polyolefin laminated film |
| WO2006051920A1 (en) * | 2004-11-11 | 2006-05-18 | Mitsubishi Plastics, Inc. | Heat-shrinkable laminated film, and molded articles, heat-shrinkable labels and containers, made by using the film |
| JP2013056509A (en) * | 2011-09-09 | 2013-03-28 | Unitika Ltd | Linearly-tearable biaxially-oriented polyester film that reduces oligomer foreign matter to be deposited thereon |
| US20130095371A1 (en) * | 2011-10-14 | 2013-04-18 | Avery Dennison Corporation | Shrink Film for Label |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04193526A (en) * | 1990-11-27 | 1992-07-13 | Sekisui Chem Co Ltd | Heat-shrinkable polyester film |
| JPH04278348A (en) * | 1991-03-07 | 1992-10-02 | Sekisui Chem Co Ltd | Heat-shrinkable polyester laminated film |
| JPH0827260A (en) * | 1994-07-14 | 1996-01-30 | Mitsubishi Rayon Co Ltd | Heat-shrinkable polyester film |
| JPH10244644A (en) * | 1997-03-06 | 1998-09-14 | Mitsubishi Plastics Ind Ltd | Heat-shrinkable polyester laminated film |
-
2000
- 2000-08-10 JP JP2000242641A patent/JP3960741B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04193526A (en) * | 1990-11-27 | 1992-07-13 | Sekisui Chem Co Ltd | Heat-shrinkable polyester film |
| JPH04278348A (en) * | 1991-03-07 | 1992-10-02 | Sekisui Chem Co Ltd | Heat-shrinkable polyester laminated film |
| JPH0827260A (en) * | 1994-07-14 | 1996-01-30 | Mitsubishi Rayon Co Ltd | Heat-shrinkable polyester film |
| JPH10244644A (en) * | 1997-03-06 | 1998-09-14 | Mitsubishi Plastics Ind Ltd | Heat-shrinkable polyester laminated film |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004018205A1 (en) * | 2002-08-23 | 2004-03-04 | Teijin Dupont Films Japan Limited | Heat-shrinkable multilayered polyester film for packaging |
| WO2005095106A1 (en) * | 2004-03-31 | 2005-10-13 | Mitsubishi Plastics, Inc. | Heat-shrinkable layered polyolefin film, heat-shrinkable label, and container with the label attached thereto |
| JP2005288729A (en) * | 2004-03-31 | 2005-10-20 | Mitsubishi Plastics Ind Ltd | Heat shrinkable polyolefin laminated film |
| US7727620B2 (en) | 2004-03-31 | 2010-06-01 | Mitsubishi Plastics, Inc. | Heat-shrinkable layered polyolefin film, heat-shrinkable label, and container with the label attached thereto |
| WO2006051920A1 (en) * | 2004-11-11 | 2006-05-18 | Mitsubishi Plastics, Inc. | Heat-shrinkable laminated film, and molded articles, heat-shrinkable labels and containers, made by using the film |
| JP2006159905A (en) * | 2004-11-11 | 2006-06-22 | Mitsubishi Plastics Ind Ltd | Heat shrinkable laminated film, molded product using it, heat shrinkable label and container |
| JP4678637B2 (en) * | 2004-11-11 | 2011-04-27 | 三菱樹脂株式会社 | Heat-shrinkable laminated film, molded product using the film, heat-shrinkable label, and container |
| TWI393637B (en) * | 2004-11-11 | 2013-04-21 | Mitsubishi Plastics Inc | Heat-shrinkable laminated film, and formed articles heat-shrinkable labels and containers using the film |
| JP2013056509A (en) * | 2011-09-09 | 2013-03-28 | Unitika Ltd | Linearly-tearable biaxially-oriented polyester film that reduces oligomer foreign matter to be deposited thereon |
| US20130095371A1 (en) * | 2011-10-14 | 2013-04-18 | Avery Dennison Corporation | Shrink Film for Label |
| JP2014534911A (en) * | 2011-10-14 | 2014-12-25 | エーブリー デニソン コーポレイションＡｖｅｒｙ Ｄｅｎｎｉｓｏｎ Ｃｏｒｐｏｒａｔｉｏｎ | Shrink film for labels |
| US10525678B2 (en) | 2011-10-14 | 2020-01-07 | Avery Dennison Corporation | Shrink film for label |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3960741B2 (en) | 2007-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7254730B2 (en) | Copolyester raw materials for amorphous films, heat-shrinkable polyester films, heat-shrinkable labels, and packages | |
| US8673414B2 (en) | Heat-shrinkable polyester film, process for production thereof, and package | |
| KR950008560B1 (en) | Shrinkable polyester film | |
| JP4782002B2 (en) | Method for producing shrink polymer film comprising propanediol copolymer polyester resin | |
| US8722161B2 (en) | Heat shrinkable polyester film, method for producing same, and packaged body | |
| KR102463003B1 (en) | Heat-shrinkable polyester film and packaging material | |
| JP6717407B2 (en) | Heat-shrinkable polyester-based tubular label roll and method for producing the same | |
| JP7151855B2 (en) | METHOD FOR MANUFACTURING HEAT-SHRINKABLE POLYESTER-BASED LABEL | |
| JP3939470B2 (en) | Heat-shrinkable polyester film | |
| JP3960741B2 (en) | Heat-shrinkable polyester multilayer film | |
| JP4802371B2 (en) | Method for producing heat-shrinkable polyester film | |
| WO2020026972A1 (en) | Copolyester raw material for amorphous film, heat-shrinkable polyester-based film, heat-shrinkable label, and package | |
| JPH05254015A (en) | Polyester-based shrink film | |
| JP3271774B2 (en) | Polyester shrink film | |
| JP2001181416A (en) | Heat-shrinkable polyester film | |
| JP2022084685A (en) | Heat-shrinkable film, heat-shrinkable label, and package | |
| JP6721071B2 (en) | Heat-shrinkable polyester film and package | |
| JP2004051888A (en) | Heat shrinkable polyester film | |
| JP2009102529A (en) | Heat-shrinkable polyester-based film | |
| JP6641999B2 (en) | Polyester film with excellent folding retention, low shrinkage and concealment | |
| JP4250383B2 (en) | Heat-shrinkable polyester film | |
| JP2611752B2 (en) | Polyester resin film or sheet containing fine voids and method for producing the same | |
| JP3971261B2 (en) | Heat-shrinkable polyester film | |
| WO2022181436A1 (en) | Heat-shrinkable polyester film | |
| WO2021230207A1 (en) | Copolyester raw material for films, heat-shrinkable polyester films, heat-shrinkable labels, and packages |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040524 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060207 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060314 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060515 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20070306 |
|
| R155 | Notification before disposition of declining of application |
Free format text: JAPANESE INTERMEDIATE CODE: R155 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070515 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 3960741 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110525 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110525 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120525 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120525 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130525 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130525 Year of fee payment: 6 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |