JP3486219B2 - Film adhesive and method for producing the same - Google Patents
Film adhesive and method for producing the sameInfo
- Publication number
- JP3486219B2 JP3486219B2 JP02871094A JP2871094A JP3486219B2 JP 3486219 B2 JP3486219 B2 JP 3486219B2 JP 02871094 A JP02871094 A JP 02871094A JP 2871094 A JP2871094 A JP 2871094A JP 3486219 B2 JP3486219 B2 JP 3486219B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- adhesive
- resin
- metal foil
- weight
- 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.)
- Expired - Fee Related
Links
- 239000000853 adhesive Substances 0.000 title claims description 64
- 230000001070 adhesive effect Effects 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title description 4
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 239000002985 plastic film Substances 0.000 claims description 21
- 239000003822 epoxy resin Substances 0.000 claims description 11
- 229920000647 polyepoxide Polymers 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229920006255 plastic film Polymers 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229920001225 polyester resin Polymers 0.000 claims description 7
- 239000004645 polyester resin Substances 0.000 claims description 7
- 239000012790 adhesive layer Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 229920005749 polyurethane resin Polymers 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 description 31
- 239000002131 composite material Substances 0.000 description 21
- -1 polyethylene terephthalate Polymers 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 239000011889 copper foil Substances 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 6
- 239000002313 adhesive film Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920006289 polycarbonate film Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000417 polynaphthalene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、プラスチックなどの物
品の接着に幅広く使用できるフィルム状接着剤、特に金
属箔（アルミニウム、銅、ステンレスなど）とプラスチ
ックフィルム（ポリエチレンテレフタレート、ポリナフ
タレンテレフタレートなど）との接着に好適に使用され
るフィルム状接着剤及びその製造方法に関するものであ
る。FIELD OF THE INVENTION The present invention relates to a film adhesive which can be widely used for adhering articles such as plastics, particularly metal foil (aluminum, copper, stainless steel, etc.) and plastic film (polyethylene terephthalate, polynaphthalene terephthalate, etc.). The present invention relates to a film-like adhesive that is preferably used for adhering a sheet and a method for producing the same.
【０００２】[0002]
【従来の技術】金属箔／ポリエチレンテレフタレート接
着フィルムを電波シールド用として用いる場合、リード
線との接続、その他の理由で金属箔の１部を切り取った
り、また逆にポリエチレンテレフタレートフィルムの１
部を切り取ったりする場合がある。金属箔を除去する場
合には、薬品液による溶解除去、即ちエッチングが普通
用いられているが、エッチングには時間や手間がかか
り、また廃液処理の問題もあるので、簡単に金属箔に切
目を入れて、はぎ取る方法も行われている。しかしなが
ら、金属箔をはぎ取る方法によると、金属箔が切目に
沿ってきれいに、しかも軽くはがれなけれはならない
が、一般には金属箔とフィルムとの間の接着強度が強す
ぎてきれいにはがれない場合が多い。一方、きれいには
がれる場合は、金属箔の接着強度が低すぎて製品となっ
た場合にも金属箔がはがれやすいという問題が生じる。
金属箔とフィルムとの接着に粘接着剤を用いれば、硬
化（主として加熱による）前は接着強度が低く、金属箔
のはぎ取りが容易であり、その後硬化すれば接着強度が
上昇して金属箔がはがれるような事故はなくなるもの
の、金属箔をはぎ取った直後は硬化前の粘接着剤がフィ
ルム上に露出しているので、フィルムを積み重ねるとフ
ィルム同志がくっついてしまい、作業がスムースに実行
できないという問題がある。さらに、粘接着剤を使用
すると、粘接着剤は室温で放置しておいても硬化反応が
進行するものが多く、時間が経過すると金属箔のはぎ取
りが困難となるという問題がある。2. Description of the Related Art When a metal foil / polyethylene terephthalate adhesive film is used as a radio wave shield, a part of the metal foil is cut off due to connection with a lead wire or other reasons, and conversely, a polyethylene terephthalate film is used.
The part may be cut off. When removing the metal foil, dissolution removal with a chemical solution, that is, etching is usually used, but since it takes time and labor for etching and there is a problem of waste liquid treatment, it is easy to cut the metal foil. There is also a method of putting in and stripping. However, according to the method of stripping the metal foil, the metal foil should not be peeled off cleanly and lightly along the notch, but in general, the adhesive strength between the metal foil and the film is too strong, and the metal foil is often not peeled off cleanly. On the other hand, when the metal foil is peeled off cleanly, there is a problem that the metal foil is easily peeled off even when the metal foil has a too low adhesive strength to be a product.
If a tacky adhesive is used to bond the metal foil to the film, the adhesive strength will be low before curing (mainly by heating) and the metal foil can be easily peeled off, and if it is subsequently cured, the adhesive strength will increase and the metal foil will increase. Although there is no accident of peeling, the adhesive before curing is exposed on the film immediately after peeling the metal foil, so when stacking the films, the films stick to each other and the work cannot be performed smoothly. There is a problem. Further, when the tacky-adhesive is used, the tackiness-adhesive often undergoes a curing reaction even if it is left at room temperature, and there is a problem that it becomes difficult to peel off the metal foil over time.
【０００３】一方、金属箔／ポリエチレンテレフタレー
ト接着フィルムからポリエチレンテレフタレートフィル
ムをはぎ取りる場合にも上記及びのような問題があ
る。尚、ポリエチレンテレフタレート（以後ＰＥＴと略
称）フィルム用接着剤としては、一般的に変性飽和ポリ
エステル樹脂が用いられ、金属箔／ＰＥＴフィルムの接
着でも良好な成績を示している。しかし、接着強度が強
すぎて金属箔のはぎ取りが困難である。接着力の弱い塩
酢ビ樹脂、ブチラール樹脂などを使用すれば、金属箔の
はぎ取りは容易であるが製品とした場合、金属箔がはが
れる故障がおこりやすい。On the other hand, when the polyethylene terephthalate film is stripped from the metal foil / polyethylene terephthalate adhesive film, there are the above problems. As a polyethylene terephthalate (hereinafter abbreviated as PET) film adhesive, a modified saturated polyester resin is generally used, and good adhesion is also exhibited in metal foil / PET film adhesion. However, the adhesive strength is so strong that it is difficult to remove the metal foil. If a vinyl chloride resin, butyral resin, or the like, which has a weak adhesive force, is used, the metal foil can be easily peeled off, but when the product is manufactured, the metal foil is easily peeled off and a failure occurs.
【０００４】本発明者らは、このような状況下におい
て、複数のフィルムを常温又は低温で加圧して一時的に
接着し、例えば不用部分を切り剥がした場合に、不用部
分が剥離しやすく、かつ剥離した部分の上に、別のフィ
ルムを重ねても両者が接着しにくく、又、高温に加熱す
ることによって硬化して優れた接着強度が得られるとい
った特性を有する接着剤組成物を開発して、すでに特許
出願している（特願平４−２３７３３６号）。しかしな
がら、この接着剤組成物は、接着成分を有機溶剤に溶解
又は分散した形態にあるため、使用しにくいといった問
題がある。Under these circumstances, the inventors of the present invention, when a plurality of films are pressed at room temperature or low temperature to be temporarily adhered to each other and, for example, the unnecessary portions are cut off, the unnecessary portions are easily peeled off, In addition, we developed an adhesive composition that has characteristics that it is difficult for both to adhere even if another film is placed on the peeled part, and that it cures when heated to high temperature to obtain excellent adhesive strength. Have already applied for a patent (Japanese Patent Application No. 4-237336). However, this adhesive composition has a problem that it is difficult to use because the adhesive component is in a form of being dissolved or dispersed in an organic solvent.
【０００５】[0005]
【発明が解決すべき課題】従って、本発明は、複数のフ
ィルムを常温又は低温で加圧して一時的に接着し、例え
ば不用部分を切り剥がした場合に、不用部分が剥離しや
すく、かつ剥離した部分の上に、別のフィルムを重ねて
も両者が接着しにくく、又、高温に加熱することによっ
て硬化して優れた接着強度が得られ、かつ使用性に優れ
たフィルム状接着剤を提供することを目的とする。本発
明は、又、該フィルム状接着剤の製造方法を提供するこ
とを目的とする。SUMMARY OF THE INVENTION Therefore, according to the present invention, when a plurality of films are pressed at room temperature or a low temperature to be temporarily adhered to each other and the unnecessary portions are cut off, the unnecessary portions are easily peeled off and peeled off. Provides a film-like adhesive that does not easily adhere to each other even if another film is placed on the formed part, and that it can be cured by heating at high temperature to obtain excellent adhesive strength and that it has excellent usability The purpose is to do. Another object of the present invention is to provide a method for producing the film adhesive.
【０００６】[0006]
【課題を解決するための手段】本発明は、接着剤組成物
を構成する成分である特定のポリエステル樹脂又はポリ
ウレタン樹脂／エポキシ樹脂／ブロックイソシアネート
潜在性エポキシ樹脂硬化剤／金属系硬化促進剤をを有機
溶剤に溶解又は分散した後、剥離フィルム上に流延さ
せ、乾燥すると、使用性に優れたフィルム状接着剤が得
られるとの知見に基づいてなされたのである。すなわ
ち、本発明は、剥離フィルム上に、（ａ）結晶性ポリエ
ステル樹脂またはポリウレタン樹脂、（ｂ）エポキシ樹
脂、（ｃ）ブロックイソシアネート潜在性エポキシ硬化
剤及び（ｄ）金属系硬化促進剤を含有してなる接着剤層
を設けたことを特徴とするフィルム状接着剤を提供す
る。本発明は、又、成分（ａ）、（ｂ）、（ｃ）及び
（ｄ）を有機溶剤に溶解又は分散した後、剥離フィルム
上に施すことを特徴とする上記フィルム状接着剤の製造
方法をも提供する。The present invention provides a specific polyester resin or polyurethane resin / epoxy resin / blocked isocyanate which is a component constituting an adhesive composition, a latent epoxy resin curing agent / metal type curing agent. This was done based on the finding that a film adhesive having excellent usability can be obtained by dissolving or dispersing the accelerator in an organic solvent, casting the solution on a release film, and drying. That is, the present invention contains (a) a crystalline polyester resin or polyurethane resin, (b) an epoxy resin, (c) a blocked isocyanate latent epoxy curing agent, and (d) a metal-based curing accelerator on a release film. There is provided a film-like adhesive characterized in that an adhesive layer is formed. The present invention also provides a method for producing the above film-like adhesive, which comprises dissolving or dispersing the components (a), (b), (c) and (d) in an organic solvent and then applying the solution on a release film. Will also be provided.
【０００７】本発明では、成分（ａ）〜（ｄ）の比率は
任意とすることができるが、成分（ａ）を３０〜９０重
量部、成分（ｂ）を５〜６０重量部、成分（ｃ）を１〜
２０重量部及び成分（ｄ）を0.０１〜５重量部含有する
のが好ましい。又、これらを有機溶剤に、所望の粘度と
なるように溶解又は分散して使用する。通常、固形分濃
度が１０〜５０重量％となるように溶媒を用いるのがよ
い。本発明の接着剤に用いられる（ａ）成分の結晶性ポ
リエステル樹脂としてはTg０℃以下で比較的結晶化速度
の大な変性ポリブチレンテレフタレート系の樹脂が好適
である。このような樹脂は、バイロンＧＭ−９００及び
バイロン３０Ｐ〔東洋紡（株）製〕などとして市販され
ている。又、（ａ）成分の変性ポリウレタン樹脂として
は、商品名 デスモコール５１０及び５００〔住友バイ
エル・ウレタン（株）製〕などの市販の樹脂を使用でき
る。
（ｂ）成分のエポキシ樹脂としては、ウレタン樹脂とビ
スフェノールＡ型エポキシとを結合させたウレタン化エ
ポキシ樹脂が好適であり、これの添加により初期接着強
度の低下が可能となる。このような樹脂は、商品名 ア
デカレジンＥＰＵ−７３及びＥＰＵ−６Ａ〔旭電化
（株）製〕などとして市販されている。又、ビフェノー
ルＦ型エポキシ樹脂（商品名 エピコート８０７、油化
シェルエポキシ（株）製）やビフェニル型エポキシ樹脂
〔エピコートＹＸ４０００ 油化シェルエポキシ
（株）〕も使用することができる。In the present invention, the ratio of the components (a) to (d) can be arbitrary, but the component (a) is 30 to 90 parts by weight, the component (b) is 5 to 60 parts by weight, and the component ( c) 1 to
It is preferable to contain 20 parts by weight and 0.01 to 5 parts by weight of the component (d). Further, these are dissolved or dispersed in an organic solvent so as to have a desired viscosity and used. Usually, it is preferable to use a solvent so that the solid content concentration is 10 to 50% by weight. As the crystalline polyester resin as the component (a) used in the adhesive of the present invention, a modified polybutylene terephthalate resin having a relatively high crystallization rate at Tg of 0 ° C. or lower is suitable. Such resins are commercially available as Byron GM-900 and Byron 30P (manufactured by Toyobo Co., Ltd.). As the modified polyurethane resin as the component (a), commercially available resins such as Desmocol 510 and 500 (produced by Sumitomo Bayer Urethane Co., Ltd.) can be used. As the epoxy resin as the component (b), a urethane-modified epoxy resin obtained by combining a urethane resin and a bisphenol A type epoxy is suitable, and the addition of this makes it possible to reduce the initial adhesive strength. Such resins are commercially available under the trade names of Adeka Resin EPU-73 and EPU-6A (manufactured by Asahi Denka Co., Ltd.). Further, it is possible to biphenol F type epoxy resin (trade name Epikote 807, Yuka Shell Epoxy Co., Ltd.) and biphenyl type epoxy resin [Epikote YX400 0 Yuka Shell Epoxy Co.] also be used.
【０００８】（ｃ）成分の潜在性エポキシ硬化剤として
は、ブロックポリイソシアネートを用いる。この潜在性
硬化剤の添加により、加熱時の接着強度が向上する。こ
のような硬化剤は、フェノールブロックポリイソシアネ
ート（商品名 デスモジュールＣＴステーブルやＡＰス
テーブル、住友バイエル・ウレタン（株）製）及びノバ
キュアＨＳ３７２１（日産化学（株）製）などとして市
販されている。
（ｄ）成分の硬化促進剤としては、ジブチル錫ジラウレ
ート、ジブチル錫ジオクテートの如き有機錫や金属石鹸
などの金属系硬化促進剤を用いる。これによると初期接
着強度の低下に卓効あり、しかも加熱後の接着強度は低
下しない。また、接着剤皮膜のブロッキング性防止にも
役立つ。このような硬化促進剤は、ニッカオクチック錫
（日本化学産業（株）製）などとして市販されている。
又、有機溶媒としては、ジオキサン、トルエン、メチル
エチルケトン、酢酸エチルやトリクロロエチレンなどを
使用することができる。以上の成分の他シリカ等フィラ
ーの添加（ブロッキング防止）、ポリエチエマルション
の添加（ブロッキング防止）、界面活性剤の添加（帯電
防止及びブロッキング防止）も場合によって有効であ
る。Block polyisocyanate is used as the latent epoxy curing agent as the component (c). The addition of this latent curing agent improves the adhesive strength during heating. Such curing agents are commercially available as Phenol Block Polyisocyanate (trade name: Desmodur CT Stable and AP Stable, manufactured by Sumitomo Bayer Urethane Co., Ltd.) and Novacure HS3721 (manufactured by Nissan Chemical Co., Ltd.). . As the curing accelerator of the component (d), a metal curing accelerator such as organic tin such as dibutyltin dilaurate or dibutyltin dioctate or metal soap is used. This is effective in reducing the initial adhesive strength, and does not lower the adhesive strength after heating. It also helps prevent blocking of the adhesive film. Such a curing accelerator is commercially available as Nikka Octic Tin (manufactured by Nippon Kagaku Sangyo Co., Ltd.) and the like.
Further, as the organic solvent, dioxane, toluene, methyl ethyl ketone, ethyl acetate, trichloroethylene, etc. can be used. In addition to the above components, addition of a filler such as silica (prevention of blocking), addition of polyethylene emulsion (prevention of blocking), and addition of surfactant (prevention of electrostatic charge and prevention of blocking) are also effective in some cases.
【０００９】本発明のフィルム状接着剤は、上記成分を
有機溶媒に溶解又は分散した後、剥離フィルム上に流延
させることによって容易に製造することができる。具体
的には、上記成分を有機溶媒に固形分濃度が３０〜５０
重量％となるように溶解又は分散した後、この液をクリ
アランス２００〜５００μｍのアプリケーターで剥離フ
ィルム上に所望の厚みに塗布し、例えば６０〜１２０℃
で乾燥して製造することができる。ここで、剥離フィル
ムとしては、剥離プラスチックフィルム、例えば、ポリ
エチレンフィルムやポリプロピレンフィルムなどのプラ
スチックフィルム自体や、各種プラスチックフィルムの
少なくとも片面（接着剤層が施される面）、好ましくは
両面に剥離剤が施されているプラスチックフィルムや紙
の少なくとも片面、好ましくは両面に剥離剤が施されて
いる紙などを用いることができる。剥離フィルムの厚み
は、任意であるが、２０〜１００μであるのが好まし
い。又、剥離フィルム上に設ける接着剤層の厚みは、任
意とすることができるが、２０〜１００μとするのが好
ましい。The film-like adhesive of the present invention can be easily produced by dissolving or dispersing the above components in an organic solvent and then casting the solution on a release film. Specifically, the solid content of the above components in an organic solvent is 30 to 50.
After being dissolved or dispersed so as to have a weight percentage, this solution is applied to a release film at a desired thickness with an applicator having a clearance of 200 to 500 μm, for example, 60 to 120 ° C.
It can be dried and manufactured. Here, as the release film, a release plastic film, for example, a plastic film itself such as a polyethylene film or a polypropylene film, or at least one surface (a surface to which an adhesive layer is applied) of various plastic films, preferably a release agent on both surfaces. It is possible to use a plastic film or paper that has been applied and a paper that has a release agent applied to at least one side, preferably both sides. Although the thickness of the release film is arbitrary, it is preferably 20 to 100 μm. The thickness of the adhesive layer provided on the release film may be arbitrary, but is preferably 20 to 100 μm.
【００１０】本発明では、上記フィルム状接着剤を用い
て種々の物品を接着することができる。例えば、金属フ
ィルムを本発明のフィルム状接着剤を重合わせた後、約
１００℃に加圧加熱して、フィルム状接着剤を金属フィ
ルムに接着させ、次いで、フィルム状接着剤から剥離フ
ィルムを剥がし、さらにその上にポリエチレンテレフタ
レート等のプラスチックフィルムを重ね、例えば５０〜
７０℃で加熱して該プラスチックフィルムを本発明のフ
ィルム状接着剤を介して金属フィルムを接着することが
できる（ラミネートフィルム（イ））。同様にして、
（ロ）プラスチックシートとプラスチックシートとを、
本発明のフィルム状接着剤を介して重合わせてなる複合
シート、及び（ハ）金属シートとプラスチックシートの
ラミネート品中のプラスチックシートと別のプラスチッ
クシートとを、上記ラミネート品に本発明のフィルム状
接着剤を介して重合わせてなる複合シートが好ましい。
ここで、金属シートとしては、アルミニウム箔、銅箔、
鉄や鋼などの箔があげられる。厚みは任意とすることが
できるが、２０〜１００μｍ程度が好ましい。又、プラ
スチックシートとしては、ポリエステル樹脂、ポリ塩化
ビニル樹脂、ナイロン樹脂製のシートがあげられる。
又、各種ＦＲＰのような積層板も使用できる。このよう
な電気絶縁性を有するプラスチックシートを用いると、
上記（イ）と（ハ）の複合シートは、電磁波遮蔽用シー
トとして好適に使用することができる。尚、プラスチッ
クシートの厚みも任意とすることができるが、５０μｍ
〜１mm程度とするのがよい。In the present invention, various articles can be adhered using the above film adhesive. For example, after the metal film is laminated with the film adhesive of the present invention, it is pressurized and heated to about 100 ° C. to adhere the film adhesive to the metal film, and then the release film is peeled from the film adhesive. , And further lay a plastic film such as polyethylene terephthalate on it, for example 50-
A metal film can be adhered to the plastic film by heating at 70 ° C. via the film adhesive of the present invention (laminate film (a)). Similarly,
(B) A plastic sheet and a plastic sheet
The composite sheet obtained by laminating the film-like adhesive of the present invention with each other, and (c) the plastic sheet in the laminated product of the metal sheet and the plastic sheet and another plastic sheet are added to the above-mentioned laminated product to obtain the film-like composition of the present invention. A composite sheet formed by laminating via an adhesive is preferable.
Here, as the metal sheet, aluminum foil, copper foil,
Foil such as iron or steel can be used. The thickness can be arbitrary, but it is preferably about 20 to 100 μm. Examples of the plastic sheet include polyester resin, polyvinyl chloride resin, and nylon resin sheets.
Also, laminated plates such as various FRPs can be used. When a plastic sheet having such electrical insulation is used,
The composite sheet of (a) and (c) above can be suitably used as an electromagnetic wave shielding sheet. The thickness of the plastic sheet may be arbitrary, but is 50 μm.
It is recommended to set it to about 1 mm.
【００１１】本発明のフィルム状接着剤を用いて接着さ
れてできた複合フィルムは、該複合フィルムを構成する
プラスチックシート又は金属箔の不用部分にナイフなど
で切り込みを入れて、剥がしとることができ、特に剥が
し取りを容易に行うことができる。又、この状態で、複
数の複合フィルムを重合わせてもこれらが接着すること
がない。本発明のフィルム状接着剤を用いて接着されて
できた複合フィルムは、さらに、例えば６０〜１２０°
Ｃに加熱して接着剤組成物を硬化させると、ＰＥＴフィ
ルムと金属箔とを完全に接着させることができる。この
ようにして製造された複合フィルムは、電波及び電磁波
シールド用として、又プリント基板用などとして幅広く
使用することができる。さらに、プラスチック成型物へ
金属箔の接着、プラスチック同士の接着にも有用であ
る。The composite film obtained by adhering the film-like adhesive of the present invention can be peeled off by making a notch in a unnecessary portion of the plastic sheet or metal foil constituting the composite film with a knife or the like. In particular, it can be easily peeled off. Further, in this state, even if a plurality of composite films are overlapped with each other, they do not adhere to each other. The composite film obtained by adhering using the film adhesive of the present invention further has, for example, 60 to 120 °.
When the adhesive composition is cured by heating to C, the PET film and the metal foil can be completely bonded. The composite film produced in this manner can be widely used as a shield for radio waves and electromagnetic waves, a printed circuit board, and the like. Further, it is also useful for adhering metal foil to plastic moldings and adhering plastics to each other.
【００１２】[0012]
【発明の効果】本発明のフィルム状接着剤は、比較的高
温で金属箔などに転写後、プラスチックフィルムなどと
比較的低温で接着し、複合フィルムを形成することがで
きる。このようにして形成された複合フィルムは、例え
ば不用部分を切り剥がした場合に、不用部分が剥離しや
すく、かつ剥離した部分の上に、別のフィルムを重ねて
も両者が接着しにくく、又、高温に加熱することによっ
て硬化して優れた接着強度が得られる。又、このフィル
ム状接着剤により接着した金属とプラスチックシートと
の複合シート及びプラスチックシートとプラスチックシ
ートとの複合シートは、不用部分を切り剥がして使用す
るのに、極めて好適である。又、短期間の加熱によって
強固な接着力が得られるので、ドライエッチング用とし
ても好適である。本発明のフィルム状接着剤は、経時安
定性が良好であり、ロール状に巻いて又は複数のフィル
ム状接着剤を積み重ねて長期間保存しておいても優れた
接着特性を発揮する。次に実施例により本発明を説明す
る。The film adhesive of the present invention can be transferred to a metal foil or the like at a relatively high temperature and then bonded to a plastic film or the like at a relatively low temperature to form a composite film. The composite film formed in this manner, for example, when the unnecessary portion is cut off, the unnecessary portion is easily peeled off, and even if another film is stacked on the peeled portion, it is difficult for both to adhere, By heating to a high temperature, it is cured to obtain excellent adhesive strength. Further, the composite sheet of metal and plastic sheet and the composite sheet of plastic sheet and plastic sheet adhered by the film-like adhesive are extremely suitable for use by cutting off unnecessary portions. Moreover, since a strong adhesive force can be obtained by heating for a short period of time, it is also suitable for dry etching. The film adhesive of the present invention has good stability over time, and exhibits excellent adhesive properties even when wound in a roll or stacked with a plurality of film adhesives and stored for a long period of time. Next, the present invention will be described with reference to examples.
【００１３】[0013]
実施例１
ポリブチレンテレフタレート系樹脂（商品名 バイロン
ＧＭ−９００、東洋紡（株）製）８０重量部、ウレタン
化エポキシ樹脂（商品名 アデカレジンＥＰＵ−７３、
旭電化（株）製）２０重量部、フェノールブロックポリ
イソシアネート（商品名 デスモジュールＣＴステーブ
ル、住友バイエル・ウレタン（株）製）１０重量部、ジ
ブチル錫ジラウレート0.１重量部をジオキサン３４０重
量部に溶解、固型分２５％の接着剤溶液を作成した。こ
の接着剤溶液を厚さ４０μm のポリプロピレンフィルム
に、アプリケーター（クリアランス３００μ）で塗布、
乾燥し、接着剤層の厚みが４０μのフィルム状接着剤を
製造した。これを厚さ３５μm の電解銅箔（三井金属鉱
業（株）３ＥＣIII ）にラミネーターを用いて１００℃
で転写後、剥離フィルムであるポリプロピレンフィルム
を剥がし、フィルム状接着剤層上に１００μ厚のポリエ
チレンテレフタレート（ＰＥＴ）を５０℃×０．２cm／
min ×１４Kg/cm3で接着した。この複合フィルムの銅箔
にカッターで切目を入れ、銅箔を部分的にはいだとこ
ろ、軽くきれいにはがす事ができ、接着剤皮膜は銅箔側
に付着し、ＰＥＴフィルム上には残らなかった。又、こ
の複合フィルムを１２０℃で１０分間加熱したところ、
接着強度が大幅に向上した。
実施例２
実施例１と同様にして製造したフィルム状接着剤をアル
ミニウム箔（厚み３０μm ）に９０℃で転写した後、Ｐ
ＥＴフィルム（１００μm ）と８０℃×０．５cm／min
×１４Kg/cm3のラミネート条件で接着した。この複合フ
ィルムのアルミニウム箔にカッターで切目を入れ、アル
ミニウム箔を部分的にはいだところ、軽くきれいにはが
す事ができ、接着剤皮膜はＰＥＴフィルム上には残らな
かった。又、この複合フィルムを１２０℃で１０分間加
熱したところ、接着強度が大幅に向上した。Example 1 80 parts by weight of polybutylene terephthalate resin (trade name: Byron GM-900, manufactured by Toyobo Co., Ltd.), urethanized epoxy resin (trade name: ADEKA RESIN EPU-73,
20 parts by weight of Asahi Denka Co., Ltd., 10 parts by weight of phenol block polyisocyanate (trade name: Desmodule CT Stable, manufactured by Sumitomo Bayer Urethane Co., Ltd.), 0.1 part by weight of dibutyltin dilaurate, 340 parts by weight of dioxane. And an adhesive solution having a solid content of 25% was prepared. This adhesive solution is applied to a polypropylene film having a thickness of 40 μm with an applicator (clearance 300 μ),
After drying, a film-like adhesive having an adhesive layer thickness of 40 μm was produced. This was applied to a 35 μm thick electrolytic copper foil (Mitsui Mining & Smelting Co., Ltd. 3ECIII) using a laminator at 100 ° C
After transfer with, peel off the polypropylene film, which is the release film, and add 100μ thick polyethylene terephthalate (PET) on the film adhesive layer at 50 ℃ × 0.2cm /
Bonding was carried out at min × 14 kg / cm 3 . When the copper foil of this composite film was cut with a cutter and the copper foil was partially peeled off, it could be peeled off lightly and cleanly, and the adhesive film adhered to the copper foil side and did not remain on the PET film. Also, when this composite film was heated at 120 ° C. for 10 minutes,
Adhesive strength is greatly improved. Example 2 A film adhesive produced in the same manner as in Example 1 was transferred to an aluminum foil (thickness 30 μm) at 90 ° C., and then P
ET film (100μm) and 80 ℃ × 0.5cm / min
Adhesion was carried out under the laminating condition of × 14 Kg / cm 3 . When the aluminum foil of this composite film was cut with a cutter and the aluminum foil was partially peeled off, it could be peeled off lightly and cleanly, and no adhesive film remained on the PET film. When this composite film was heated at 120 ° C. for 10 minutes, the adhesive strength was significantly improved.
【００１４】実施例３
実施例１と同様にして製造したフィルム状接着剤を３５
μm の電解銅箔（三井金属鉱業（株）３ＥＣIII ）にラ
ミネータを用いて転写した後、１００μm 厚のポリカー
ボネートフィルム（帝人製パンフィルム）と７５℃×
０．２cm／min ×１４Kg/cm3のラミネート条件で接着し
た。この複合フィルムの銅箔にカッターで切目を入れ、
銅箔を部分的にはいだところ、軽くきれいにはがす事が
でき、接着剤皮膜は銅箔側に付着し、ポリカーボネート
フィルムフィルム上には残らなかった。又、この複合フ
ィルムを１２０℃で１０分間加熱したところ、接着強度
が大幅に向上した。又、１２０℃×０．１ｍ／min ×１
４Kg/cm3のラミネート条件で接着したところ剥離強度は
約２８００ｇ／cmであった。
比較例１
実施例１の接着剤からジブチル錫ジラウレートを除いた
処方で４０μのフィルム状接着剤を製造し、実施例１と
同様にして銅箔／ＰＥＴフィルムラミネート品を製造し
た。この銅箔上の一部に切目を入れてはがしたがはくり
が重く、接着剤はＰＥＴフィルム側に残った。Example 3 A film adhesive prepared in the same manner as in Example 1 was used.
After transferring with a laminator to an electrolytic copper foil (3ECIII, Mitsui Mining & Smelting Co., Ltd.) with a thickness of 100 μm, a polycarbonate film with a thickness of 100 μm (Teijin bread film) and 75 ° C ×
Bonding was carried out under the lamination conditions of 0.2 cm / min × 14 kg / cm 3 . Make a cut in the copper foil of this composite film with a cutter,
When the copper foil was partially peeled off, it could be lightly and cleanly removed, and the adhesive film adhered to the copper foil side and did not remain on the polycarbonate film. When this composite film was heated at 120 ° C. for 10 minutes, the adhesive strength was significantly improved. Also, 120 ° C x 0.1 m / min x 1
When bonded under a laminating condition of 4 kg / cm 3, the peel strength was about 2800 g / cm. Comparative Example 1 A film-like adhesive having a thickness of 40 μm was produced with a formulation obtained by removing dibutyltin dilaurate from the adhesive of Example 1, and a copper foil / PET film laminate was produced in the same manner as in Example 1. A part of the copper foil was cut and peeled off, but the peeling was heavy, and the adhesive remained on the PET film side.
【００１５】実施例１〜３及び比較例における複合フィ
ルムの接着強度を表−１に示す。尚、はくり強度は、複
合フィルム（未加熱品、つまり高温で加熱していないも
の）及び１２０℃で１０分間加熱接着した複合フィルム
（加熱品）のそれぞれから幅１０mmのサンプルを切り出
し、９０°及び１８０°はくり強度（ｇ／10mm) をクロ
スヘットスピード 200nm/minで測定した（ＪＩＳ Ｃ−
６４７１準拠）。Table 1 shows the adhesive strength of the composite films in Examples 1 to 3 and Comparative Example. The peeling strength was 90 ° when a sample with a width of 10 mm was cut out from each of the composite film (unheated product, that is, not heated at high temperature) and the composite film (heated product) heat-bonded at 120 ° C. for 10 minutes. And 180 ° peel strength (g / 10 mm) were measured at a crosshead speed of 200 nm / min (JIS C-
6471).
【００１６】[0016]
【表１】 表−１ はくり角度 実施例１ ２ ３ 比較例１ 未加熱品 90° 35 80 125 530 未加熱品 180° 75 205 250 950 加熱品 90° 1270 180 620 820 加熱品 180° 1500 450 1120 1370 熱[Table 1] Table-1 Peeling angle Example 1 2 3 Comparative example 1 Unheated product 90 ° 35 80 125 530 Unheated product 180 ° 75 205 250 950 Heated product 90 ° 1270 180 620 820 Heated product 180 ° 1500 450 1120 1370 heat
フロントページの続き (56)参考文献 特開 昭62−141083（ＪＰ，Ａ) 特開 平４−199695（ＪＰ，Ａ) 特開 平４−199694（ＪＰ，Ａ) 特開 平３−43481（ＪＰ，Ａ) 特開 昭58−145725（ＪＰ，Ａ) 特開 昭58−103526（ＪＰ，Ａ) 新保正樹編，エポキシ樹脂ハンドブッ ク，日刊工業新聞社，1987年12月25日, 224−230 (58)調査した分野(Int.Cl.7，ＤＢ名) C09J 4/00 - 201/10 Continuation of the front page (56) Reference JP 62-141083 (JP, A) JP 4-199695 (JP, A) JP 4-199694 (JP, A) JP 3-43481 (JP , A) JP-A-58-145725 (JP, A) JP-A-58-103526 (JP, A) Masaki Shinbo, Epoxy Resin Handbook, Nikkan Kogyo Shimbun, December 25, 1987, 224-230 58) Fields investigated (Int.Cl. 7 , DB name) C09J 4/00-201/10
Claims (4)
ステル樹脂またはポリウレタン樹脂、（ｂ）エポキシ樹
脂、（ｃ）ブロックイソシアネート潜在性エポキシ硬化
剤及び（ｄ）金属系硬化促進剤を含有してなる接着剤層
を設けたことを特徴とするフィルム状接着剤。1. A release film containing (a) a crystalline polyester resin or polyurethane resin, (b) an epoxy resin, (c) a blocked isocyanate latent epoxy curing agent, and (d) a metal-based curing accelerator. A film-like adhesive, which comprises an adhesive layer of
（ｂ）を５〜６０重量部、成分（ｃ）を１〜２０重量部
及び成分（ｄ）を0.０１〜５重量部含有する請求項１記
載のフィルム状接着剤。2. Component (a) is 30 to 90 parts by weight, component (b) is 5 to 60 parts by weight, component (c) is 1 to 20 parts by weight, and component (d) is 0.01 to 5 parts by weight. The film adhesive according to claim 1, which contains the film adhesive.
ルム又は剥離紙である請求項１記載のフィルム状接着
剤。3. The film adhesive according to claim 1, wherein the release film is a release plastic film or release paper.
リウレタン樹脂、（ｂ）エポキシ樹脂、（ｃ）ブロック
イソシアネート潜在性エポキシ硬化剤及び（ｄ）金属系
硬化促進剤を有機溶剤に溶解又は分散した後、剥離フィ
ルム上に施すことを特徴とする請求項１記載のフィルム
状接着剤の製造方法。4. (a) Crystalline polyester resin or polyurethane resin, (b) Epoxy resin, (c) Block
An isocyanate latent epoxy curing agent and (d) a metal-based curing accelerator are dissolved or dispersed in an organic solvent and then applied on a release film to produce a film-like adhesive according to claim 1. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02871094A JP3486219B2 (en) | 1994-02-28 | 1994-02-28 | Film adhesive and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02871094A JP3486219B2 (en) | 1994-02-28 | 1994-02-28 | Film adhesive and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07238265A JPH07238265A (en) | 1995-09-12 |
| JP3486219B2 true JP3486219B2 (en) | 2004-01-13 |
Family
ID=12256019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02871094A Expired - Fee Related JP3486219B2 (en) | 1994-02-28 | 1994-02-28 | Film adhesive and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3486219B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6582824B1 (en) | 1998-10-02 | 2003-06-24 | 3M Innovative Properties Company | Sealant composition, article and method |
| JP5555034B2 (en) * | 2010-04-06 | 2014-07-23 | 株式会社Ｕａｃｊ | Metal material-metal material joining paint, metal material obtained by using the same, metal material-coated metal material for joining metal material, and metal material-metal material joining method using the same |
| CN114248042B (en) * | 2022-01-07 | 2023-04-07 | 苏州唯特偶电子材料科技有限公司 | Special soldering flux for non-crystallization photovoltaic module series welding machine |
-
1994
- 1994-02-28 JP JP02871094A patent/JP3486219B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 新保正樹編，エポキシ樹脂ハンドブック，日刊工業新聞社，１９８７年１２月２５日，２２４−２３０ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07238265A (en) | 1995-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3308672B2 (en) | Adhesive sheet | |
| US5785789A (en) | Low dielectric constant microsphere filled layers for multilayer electrical structures | |
| JPH06212130A (en) | Multilayer foamed pressure-sensitive adhesive tape and its production | |
| JP3486219B2 (en) | Film adhesive and method for producing the same | |
| JP3405576B2 (en) | Thermal release film and release method | |
| JP2832596B2 (en) | Composite sheet | |
| JP2649636B2 (en) | Adhesive composition | |
| JP3680669B2 (en) | Multilayer anisotropic conductive film laminate | |
| JP2002317156A (en) | Double-coated tape | |
| JP3487313B2 (en) | Release liner and double-sided adhesive tape or sheet | |
| US20110159307A1 (en) | Method for Gluing Two Plastic Surfaces Together | |
| JP3144777B2 (en) | Recycled wallpaper | |
| JP3352553B2 (en) | Manufacturing method of interior materials | |
| JP4919112B2 (en) | Manufacturing method of multilayer printed wiring board | |
| JPH1187920A (en) | Adhesive film for manufacturing multilayered circuit board with ivh | |
| JPH0543843A (en) | Pressure-sensitive adhesive double-sided tape and products with double-sided tape attached | |
| JP2001341239A (en) | Antistatic film, release film for adhesive tape or sheet using the antistatic film, and adhesive tape or sheet | |
| JP2784453B2 (en) | Adhesive type heat-resistant laminated sheet and method for producing the same | |
| JPH0617012A (en) | Adhesive sheet | |
| JPH03210377A (en) | Adhesive sheet | |
| JP2001098246A (en) | Curable adhesive composition | |
| JP2000037827A (en) | Release film | |
| JP2523216B2 (en) | Flexible printed wiring board | |
| JP2002161251A (en) | Adhesive film, method for producing the same, and method for adhering the same | |
| JPH1020787A (en) | Conductive transfer film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081024 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091024 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101024 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111024 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121024 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131024 Year of fee payment: 10 |
|
| LAPS | Cancellation because of no payment of annual fees |