JP3693920B2 - Decorative metal plate covering resin film, decorative metal plate, and method for producing decorative metal plate - Google Patents
Decorative metal plate covering resin film, decorative metal plate, and method for producing decorative metal plate Download PDFInfo
- Publication number
- JP3693920B2 JP3693920B2 JP2000583990A JP2000583990A JP3693920B2 JP 3693920 B2 JP3693920 B2 JP 3693920B2 JP 2000583990 A JP2000583990 A JP 2000583990A JP 2000583990 A JP2000583990 A JP 2000583990A JP 3693920 B2 JP3693920 B2 JP 3693920B2
- Authority
- JP
- Japan
- Prior art keywords
- metal plate
- resin film
- polybutylene terephthalate
- decorative metal
- terephthalate resin
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/06—Embossing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2451/00—Decorative or ornamental articles
Description
【０００１】
【技術分野】
本発明は、エンボス加工などを施して表面に凹凸模様を形成させたポリブチレンテレフタレート樹脂からなる化粧金属板被覆用樹脂フィルム、その樹脂フィルムを被覆した化粧金属板及び化粧金属板の製造方法に関する。
【０００２】
【背景技術】
成形加工性、意匠性、耐薬品性などに優れた熱可塑性樹脂を金属板に被覆してなる化粧金属板は、建材、家具、電器・電子機器、音響機器、事務機器等の外板あるいは内部部品をはじめ、ユニットバスなどの耐水性を必要とする用途にも広く用いられている。これらの場合、金属板に熱可塑性樹脂を被覆することは素材の金属板に防食効果を付与することが主目的であるが、同時に化粧金属板に高級感を持たせることを目的として、エンボス加工などを施して表面に凹凸模様を形成させることが従来より行われていた。このような目的に使用するエンボス加工を施す熱可塑性樹脂フィルムとしては、加工が容易であること、安価であることなどの観点から、ポリ塩化ビニル樹脂、ポリエチレンやポリプロピレンなどのポリオレフィン樹脂、熱可塑性アクリル樹脂、フッ素を含有するフッ素樹脂などからなるフィルムやポリエステル樹脂の２軸延伸フィルムなどが従来より多用されている。
しかし、ポリ塩化ビニル樹脂は経済性、エンボス加工性、成形加工性などには優れているが、成形加工を容易にするためジブチルフタレートやジオクチルフタレートなどの可塑剤を含んでおり、長期間の経時によって表面に可塑剤がブリードしたり、また燃焼時に塩化水素ガスを発生し、これに起因して環境へ悪影響を及ぼしたりするなどの問題がある。
このため、可塑剤を添加しないポリ塩化ビニル樹脂などが検討されているが、可塑剤を添加しない樹脂は硬質であり、エンボス加工が困難である。また、ポリ塩化ビニル樹脂に替わる樹脂として、ポリエチレンやポリプロピレンなどのポリオレフィン樹脂が検討されているが、これらの樹脂はエンボス加工性は良好であるが、金属板に被覆して成形加工すると、加工部が白色化して意匠性が損なわれる。このため、樹脂を軟質化させるためにゴム成分を添加する方法も考えられるが、可塑剤を添加したポリ塩化ビニル樹脂同様の軟質樹脂になってしまう。
また、熱可塑性アクリル樹脂、フッ素樹脂はそれぞれ特徴のある特性を有しているが、可塑化ポリ塩化ビニル樹脂と同水準の軟質樹脂である。近年、ラミネート材料としてポリエチレンテレフタレートを主成分とする樹脂からなる２軸延伸ポリエステルフィルムが着目されているが、エンボス加工を施した場合に深く鮮明な凹凸模様が得られにくく意匠性に乏しいこと、および、高温多湿の雰囲気中で長時間経時した場合、樹脂の結晶化の進行や加水分解により、皮膜が劣化するなどの問題を有しており、化粧金属板用の被覆樹脂フィルムへの適用は困難である。
本発明は、上記の問題を解決することを目的として、従来のポリ塩化ビニル樹脂と同等以上のエンボス加工性、成形加工性、および耐水経時性に優れた化粧金属板被覆用樹脂フィルム、その樹脂フィルムを被覆した化粧金属板及び化粧金属板の製造方法を提供することを課題とする。
【０００３】
【発明の開示】
本発明の請求項１の化粧金属板被覆用樹脂フィルムは、固有粘度（ＩＶ値）が１．０〜２．０であるポリブチレンテレフタレート樹脂からなるポリブチレンテレフタレート樹脂フィルムの表面にエンボス加工を設けたことを特徴とする。
請求項２の化粧金属板被覆用樹脂フィルムは、請求項１において、前記ポリブチレンテレフタレート樹脂フィルムのエンボス加工面と反対側の面に印刷層を有することを特徴とする。
請求項３の化粧金属板は、請求項１又は２の化粧金属板被覆用樹脂フィルムを、最表面がエンボス加工面となるようにして金属板に積層してなることを特徴とする。
請求項４化粧金属板の製造方法は、固有粘度（ＩＶ値）が１．０〜２．０であるポリブチレンテレフタレート樹脂からなるポリブチレンテレフタレート樹脂フィルムを金属板に積層した後、該樹脂の融点±１０℃の温度に加熱した金属板と共に、彫刻ロールを使用して圧着して前記ポリブチレンテレフタレート樹脂フィルム表面にエンボス加工を施すことを特徴とする。
【０００４】
【発明を実施するための最良の形態】
本発明の発明者等は、樹脂フィルムの特性とエンボス加工性の関係について鋭意検討した結果、一定範囲の固有粘度を有するポリブチレンテレフタレート樹脂からなるフィルムを使用した場合に、エンボス加工によって深く鮮明な凹凸模様が得られ、この樹脂フィルムを金属板に被覆した場合、飛躍的に意匠性に優れた化粧金属板が得られることを見出した。
この結果、樹脂フィルムを金属板に積層して得られた樹脂被覆金属板を成形加工しても加工部分が白色化して意匠性が損なわれることなく、ポリ塩化ビニル樹脂と同等程度のエンボス加工性が得られ、さらに耐水経時性に優れたポリブチレンテレフタレート樹脂の優れた特性をそのまま維持することができた。以下に本発明についてその内容を説明する。
【０００５】
（使用する金属板）
本発明の化粧金属板に使用する金属板としては、鋼板、アルミニウム板、アルミニウム合金板、銅板、銅合金板など、広く金属板であれば使用可能である。銅板としては、厚さ０．１０〜１．２ｍｍの普通鋼冷延鋼板が好ましい。中でも、厚さ０．１０〜０．５０ｍｍの普通鋼の冷延鋼板が好ましい。冷延鋼板の中でも低炭素または極低炭素アルミキルド鋼板が好ましく使用されるが、Ｎｂ、Ｔｉなどを添加した非時効性鋼、３〜１８重量％のクロムを含有するクロム含有鋼板、種々の組成を有するステンレス鋼板なども使用することができる。これらの冷延鋼板の表面に表面処理を施した表面処理鋼板も使用可能である。表面処理としてはめっき、化成処理や塗装処理などがあり、めっきとしては例えば亜鉛めっき、亜鉛−アルミニウム合金めっき、亜鉛−コバルト−モリブデンめっき、錫めっき、ニッケルめっき、クロムめっき、ニッケル−りんめっき、ニッケル−亜鉛めっき、ニッケル−コバルトめっき、ニッケル−錫めっき、アルミニウムめっきなどがあり、化成処理としては例えばクロメート処理、リン酸塩処理など公知の処理でよい。塗装処理としては種々の塗料をその性質に応じて塗装し、焼き付ける方法で実施される。
【０００６】
（使用する樹脂フィルムなど）
本発明の化粧金属板被覆用の樹脂フィルムとしては、ポリブチレンテレフタレート樹脂フィルムを好適に用いることができる。エンボス加工性の観点からは延伸フィルムよりも未延伸フィルムであることが好ましい。また、ポリブチレンテレフタレート樹脂の固有粘度は１．０〜２．０の範囲であることが好ましい。固有粘度は定法を用い、樹脂をフェノール／テトラクロロエタンの１：１混合溶液に溶解させた後、３０℃の恒温浴槽中でウベローデ粘度計により、比粘度を測定し、固有粘度を求めることができる。
固有粘度が１．０未満の場合は金属板に被覆して恒温多湿の雰囲気中に長期間経時した際に十分な耐衝撃性（耐水劣化性）が得られず、一方、固有粘度が２．０を超える場合は、樹脂を加熱溶融し押出機から押し出してフィルムに製膜する際に高粘度となり過ぎて押出機のトルクが上がるため製膜困難となる。より好ましい固有粘度の範囲は、耐水劣化性および製膜性の観点から１．２〜１．５である。
【０００７】
上記のポリブチレンテレフタレート樹脂フィルムの厚さは特に限定するものではないが、２０〜３００μｍ、中でも７０〜２００μｍであることが好ましい。また上記のポリブチレンテレフタレート樹脂にポリエチレンテレフタレート樹脂、ポリカーボネート樹脂、アイオノマー樹脂などをブレンドした樹脂、またはこれらのブレンド樹脂の２種以上をブレンドした樹脂、また、ポリブチレンテレフタレートと他のポリエステル樹脂との共重合体、例えばテレフタル酸の１部をイソフタル酸やアジピン酸などに置き換えた共重合体、およびまたはブタンジオールの１部をエチレングリコールなどに置き換えた共重合体からなる樹脂からなるフィルムも使用可能である。さらに、上記の種々の樹脂からなるフィルムを２種以上積層してなる複合樹脂フィルムも使用可能である。
【０００８】
また、本発明の化粧金属板被覆用の樹脂フィルムは上記のポリブチレンテレフタレート樹脂フィルムを単層で用いてもよいが、上記のポリブチレンテレフタレート樹脂フィルムの後記するエンボス加工を施す面と反対の面に、接着層、着色層、印刷層の少なくとも１種の層を積層してなる多層樹脂フィルムとして用いてもよい。金属板との接着力を高度に要求されるものに対しては、接着層としてポリブチレンテレフタレート樹脂以外の低融点のポリエステル樹脂フィルムや、例えばポリエステル樹脂系やウレタン樹脂系などの一般的な接着剤からなる接着剤層を設けても差し支えない。また着色層として、上記のポリブチレンテレフタレート樹脂と同一のポリブチレンテレフタレート樹脂からなるフィルム、または他のポリエステル樹脂フィルムに顔料を添加した着色フィルムを積層した複合樹脂フィルムも使用可能である。
【０００９】
ポリブチレンテレフタレート樹脂フィルムは微細結晶を生成することにより、硬く平滑な表面が得られやすく、印刷性に優れている。そのため、上記のポリブチレンテレフタレート樹脂フィルムの後記するエンボス加工を施す面と反対の面に、グラビア、オフセット、スクリーン印刷などによる全面着色印刷層、または部分着色印刷層を設けた複合樹脂フィルムも使用可能である。
さらに、ポリブチレンテレフタレート樹脂フィルムの後記するエンボス加工を施す表面に、エンボス加工による凹凸を消失させない程度に潤滑性や耐摩耗性を付与するために、表面保護層を設けても差し支えない。
【００１０】
（エンボス加工方法）
上記のポリブチレンテレフタレート樹脂フィルムのエンボス加工方法としては、加熱溶融した樹脂をＴダイからエンボス加工を施したキャスティングロール上に押出して片面にエンボス目を有するフィルムに製膜する方法、フィルムを直接チルドロールの間に通す方法、フィルムを加熱してチルドロールの間に通す方法、回転スクリーンロールに通して真空で吸引する力でエンボス加工する方法、フィルムをパーフォレーター（目打ち機）に通すホットニードルプロセス、刻印ロールを使用して圧縮する方法など、いずれの方法を用いてエンボス加工してもよい。また、金属板に上記のポリブチレンテレフタレート樹脂フィルムを積層した後、樹脂の融点±１０℃の温度範囲に加熱した金属板と共に、彫刻ロールを使用して圧着してエンボス加工してもよい。
エンボス形状としては、ランダムマット、四角形、ダイヤモンド形、深絞り形、砂目（ＳＧ目と呼称）など、種々に模様を製品のニーズに応じて選択することができる。
【００１１】
（積層方法）
上記のようにしてエンボス加工を施したポリブチレンテレフタレート樹脂フィルムを、公知の熱融着法などを用いて金属板に積層する。すなわち、金属板をポリブチレンテレフタレート樹脂の融点以上の温度に加熱し、ポリブチレンテレフタレート樹脂フィルムのエンボス加工を施さない面を金属板に当接し、１対のラミネートロールで両者を挟み付け、直ちに水中に浸漬して急冷する。
金属板との接着力を高度に要求されるものに対しては、前記のように、ポリブチレンテレフタレート樹脂に接着層を設けるか、または金属板に接着層を設け、接着層を介在させて金属板とポリブチレンテレフタレート樹脂フィルムを積層させることも可能である。
【００１２】
（エンボス加工性の良否の判定）
本発明のポリブチレンテレフタレート樹脂フィルムのエンボス加工性の良否は、エンボス加工を施した樹脂フィルムの表面粗さによって判断される。本発明においては樹脂フィルムの表面を肉眼観察し、エンボス加工性の良否を下記の３段階の基準で評価した。
○：良好、△：やや不良、×：不良 なお、上記の評価基準は、ポリ塩化ビニル樹脂フィルムの表面平均粗さ（Ｒａ：μｍ）を東京精密社製ＳＵＲＦＣＯＭ表面粗さ計を用いてＪＩＳ Ｂ０６０１に準拠して測定し、表面平均粗さが４μｍである場合をエンボス加工性の合格基準とし、表面平均粗さが４μｍのポリ塩化ビニル樹脂フィルムの表面と同等以上の外観を有するものを良好（○）とし、ポリ塩化ビニル樹脂フィルムの表面と比べてやや劣るが実用上問題ない外観を有するものをやや不良（△）とし、エンボス加工が入らないものを不良（×）として、判定した。
【００１３】
（加工性の評価）
表面平均粗さＲａ＝１１μｍの凹凸が付与されたＳＧ目の彫刻ロールに一定速度で通過させエンボス加工を施した、一定の長さおよび幅を有する厚さが０．１０ｍｍのポリブチレンテレフタレート樹脂フィルムを、ポリブチレンテレフタレート樹脂の融点以上の温度に加熱された、ポリブチレンテレフタレート樹脂フィルムと同一の長さおよび幅を有する厚さ０．５０ｍｍの亜鉛めっき鋼板に当接し、両者を１対のロールで挟み付けて圧着し試験片とした。このようにして得られた試験片の衝撃加工性を、ＪＩＳ Ｋ ５４００に規定されたデュポン衝撃試験機で、衝撃部の外径０．５インチ、重さ１ｋｇ、落下高さ５０ｃｍの条件で試験した。評価は下記のように、肉眼観察により３段階で評価した。
○：樹脂フィルムに割れは認められない、
△：樹脂フィルムの一部に細かい割れが認められる、
×：樹脂フィルム全体に割れが著しい。
上記の評点において、○および△は使用上の問題はない。なお、この試験は１０枚の試験片について実施した。
【００１４】
（耐水劣化性の評価）
本発明のポリブチレンテレフタレート樹脂フィルムにエンボス加工を施した状態で恒温多湿の状態で長時間経時させた場合（例えばユニットバスの内装材として用いた場合など）を想定し、長時間水と接した場合の樹脂フィルムの耐水劣化性をデュポン衝撃試験法で評価した。
表面平均粗さＲａ＝１１μｍの凹凸が付与されたＳＧ目の彫刻ロールに一定速度で通過させエンボス加工を施した、一定の長さおよび幅を有する厚さが０．１０ｍｍのポリブチレンテレフタレート樹脂フィルムを、ポリブチレンテレフタレート樹脂の融点以上の温度に加熱された、ポリブチレンテレフタレート樹脂フィルムと同一の長さおよび幅を有する厚さ０．５０ｍｍの亜鉛めっき鋼板に当接し、両者を１対のロールで挟み付けて圧着し試験片とした。このようにして得られた試験片を６０ｍｍ×６０ｍｍの大きさに切り出し、３８±２℃の温度に保持されたイオン交換水中に１カ月間浸漬した後室温で乾燥し、デュポン衝撃試験機を用い、ＪＩＳ Ｋ ５４００に準拠した条件（衝撃部の外径０．５インチ、重さ１ｋｇ、落下高さ５０ｃｍ）で衝撃を負荷した。衝撃を負荷した後の樹脂フィルムの状態を肉眼観察し、下記の５段階で評価した。
５：樹脂フィルムに割れが認められない。
４：樹脂フィルムの一部に細かい割れが認められる。
３：樹脂フィルムのエンボス加工部全体に細かい割れが認められる。
２：樹脂フィルムのエンボス加工部全体に大きな割れが認められる。
１：樹脂フィルム全体に割れが著しい。
上記の評点において、５および４は使用上の問題はない。なお、この試験は１０枚の試験片について実施した。
【００１５】
（実施例）
以下、実施例にて本発明をさらに詳細に説明する。表１に示す固有粘度を有するポリブチレンテレフタレート樹脂を押出機を用いて０．１０ｍｍの膜厚の未延伸フィルムを作成した。これらの樹脂フィルムの製膜に際しては、樹脂フィルムを加熱溶融し、表面平均粗さＲａ＝１１μｍの凹凸が付与されたＳＧ目の彫刻を施したキャスティングロール上に加熱溶融した樹脂をＴダイから押し出し、樹脂フィルムの片面にエンボス加工を施した。１部のフィルムについては、エンボス加工を施した面と反対の面にグラビア印刷により全面着色印刷を施した。また、比較例として表１に示す固有粘度を有するポリエチレンテレフタレート樹脂を押出機を用い、上記のポリブチレンテレフタレート樹脂と同様に製膜して、片面にエンボス加工を施した０．１０ｍｍの膜厚の未延伸フィルムを作成した。このようにして得られた樹脂フィルムのエンボス加工性の良否を肉眼観察により評価した。評価結果を表２に示す。
【００１６】
次いで上記のエンボス加工を施した樹脂フィルムを下記の要領で金属板に積層した。厚さ０．５０ｍｍの低炭素アルミキルド冷延鋼板に０．００２ｍｍの厚さに亜鉛をめっきした。この亜鉛めっき鋼板を２４０℃に加熱し、その片面にポリブチレンテレフタレート樹脂フィルムのエンボス加工を施さない面を当接し、１対のラミネートロールで両者を挟み付けて圧着した後、直ちに水中に浸漬し急冷した。片面に印刷を施したフィルムの場合は、印刷を施した面上にウレタン樹脂系の接着剤を塗布し乾燥させた後、接着剤塗布面を加熱した亜鉛めっき鋼板に当接し、上記と同様にして積層した。このようにして、ポリブチレンテレフタレート樹脂フィルム被覆亜鉛めっき鋼板を得た。また前記と同一の亜鉛めっき鋼板を２８０℃に加熱し、その片面にポリエチレンテレフタレート樹脂フィルムのエンボス加工を施さない面を当接し、１対のラミネートロールで両者を挟み付けて圧着した後、直ちに水中に浸漬し急冷した。このようにして、ポリエチレンテレフタレート樹脂フィルム被覆亜鉛めっき鋼板を得た。
上記のようにして得られたポリブチレンテレフタレート樹脂フィルム被覆亜鉛めっき鋼板およびポリエチレンテレフタレート樹脂フィルム被覆亜鉛めっき鋼板についてＪＩＳ Ｋ ５４００に準拠した条件でデュポン衝撃試験機を用い、樹脂フィルムの加工性を評価した。評価結果を表２に示す。
また、それぞれの樹脂フィルム被覆亜鉛めっき鋼板から６０ｍｍ×６０ｍｍの大きさの試験片を切り出し、３８±２℃の温度に保持されたイオン交換水中に１ヶ月間浸漬した後室温で乾燥した後、ＪＩＳ Ｋ ５４００に準拠した条件でデュポン衝撃試験機を用い、樹脂フィルムの加工性を評価した。本発明の実施例と比較例の樹脂フィルムを下記の表１に示す。その評価結果を下記の表２に示す。
【００１７】
【表１】
【表２】
表２に評価結果を示したが、固有粘度１．０以上のポリブチレンテレフタレート樹脂からなるフィルムを被覆した亜鉛めっき鋼板は、ポリエチレンテレフタレート樹脂からなるフィルムを被覆した亜鉛めっき鋼板に比べて、エンボス性、加工性、および耐水劣化性において同等以上の特性を示す。また、印刷を施したフィルムを被覆した亜鉛めっき鋼板は、印刷層の美麗な色調に加え、エンボス加工を施した透明なフィルムの厚みによる立体感が得られ、意匠性に優れている。
【００２０】
【産業上の利用可能性】
本発明は、ポリブチレンテレフタレート樹脂の固有粘度（ＩＶ値）が１．０〜２．０であり、少なくとも片面の表面がエンボス加工され、またエンボス加工面と反対側の面に印刷層を有する化粧金属板被覆用樹脂フィルム、およびそのポリブチレンテレフタレート樹脂フィルムを被覆した化粧金属板であり、本発明のポリブチレンテレフタレート樹脂フィルムを被覆した化粧金属板は、成形加工しても加工部分が白色化して意匠性が損なわれることなく、ポリ塩化ビニル樹脂と同等程度のエンボス加工性が得られ、さらに耐水経時性に優れたポリブチレンテレフタレート樹脂の優れた特性をそのまま維持することができ樹脂フイルムの加工性および耐水劣化性に優れており、ユニットバスなどの耐水性を必要とする建材などに適用可能である。[0001]
【Technical field】
The present invention relates to a decorative metal plate covering resin film made of a polybutylene terephthalate resin having an uneven surface formed by embossing and the like, a decorative metal plate coated with the resin film, and a method of manufacturing the decorative metal plate .
[0002]
[Background]
A decorative metal plate made by coating a metal plate with a thermoplastic resin excellent in molding processability, designability, chemical resistance, etc. is the outer plate or interior of building materials, furniture, electrical / electronic equipment, acoustic equipment, office equipment, etc. It is widely used for applications that require water resistance such as parts and unit baths. In these cases, the main purpose of coating the metal plate with a thermoplastic resin is to provide an anticorrosive effect to the metal plate of the material, but at the same time, embossing for the purpose of giving the decorative metal plate a sense of quality. It has been conventionally performed to form an uneven pattern on the surface by applying the above. The thermoplastic resin film to be embossed for such purposes is polyvinyl chloride resin, polyolefin resin such as polyethylene or polypropylene, thermoplastic acrylic from the viewpoint of easy processing and low cost. Conventionally, a film made of a resin, a fluorine resin containing fluorine, a biaxially stretched film of a polyester resin, and the like have been widely used.
However, polyvinyl chloride resin is excellent in economic efficiency, embossability, moldability, etc., but contains plasticizers such as dibutyl phthalate and dioctyl phthalate to facilitate the molding process. As a result, the plasticizer bleeds on the surface, and hydrogen chloride gas is generated during combustion, resulting in adverse effects on the environment.
For this reason, polyvinyl chloride resin and the like to which a plasticizer is not added have been studied. However, a resin to which no plasticizer is added is hard and difficult to emboss. In addition, polyolefin resins such as polyethylene and polypropylene have been investigated as a substitute for polyvinyl chloride resin, but these resins have good embossing properties, but if they are coated on a metal plate and processed, Becomes white and the design is impaired. For this reason, a method of adding a rubber component to soften the resin can be considered, but it becomes a soft resin similar to a polyvinyl chloride resin to which a plasticizer is added.
Thermoplastic acrylic resins and fluororesins have characteristic properties, but are soft resins at the same level as plasticized polyvinyl chloride resins. In recent years, biaxially stretched polyester films made of a resin mainly composed of polyethylene terephthalate have attracted attention as a laminate material. However, when embossing is performed, it is difficult to obtain a deep and clear uneven pattern, and the design is poor. If the film is aged for a long time in a high-temperature and high-humidity atmosphere, the film will deteriorate due to the progress of crystallization of the resin or hydrolysis, making it difficult to apply to the coated resin film for decorative metal plates. It is.
For the purpose of solving the above-mentioned problems, the present invention provides a resin film for coating a decorative metal plate, which has excellent embossability, molding processability, and water aging resistance equivalent to or higher than those of conventional polyvinyl chloride resins, and the resin. It is an object of the present invention to provide a decorative metal plate coated with a film and a method for producing the decorative metal plate .
[0003]
DISCLOSURE OF THE INVENTION
The resin film for coating a decorative metal sheet according to claim 1 of the present invention is provided with an embossing on the surface of a polybutylene terephthalate resin film made of a polybutylene terephthalate resin having an intrinsic viscosity (IV value) of 1.0 to 2.0. It is characterized by that.
A resin film for covering a decorative metal plate according to a second aspect is characterized in that, in the first aspect, the polybutylene terephthalate resin film has a printed layer on a surface opposite to the embossed surface.
A decorative metal plate of claim 3 is characterized in that the decorative metal plate-covering resin film of claim 1 or 2 is laminated on a metal plate so that the outermost surface is an embossed surface.
According to a fourth aspect of the present invention, there is provided a method for producing a decorative metal plate, comprising: laminating a polybutylene terephthalate resin film made of a polybutylene terephthalate resin having an intrinsic viscosity (IV value) of 1.0 to 2.0 on a metal plate; The polybutylene terephthalate resin film surface is embossed by pressure bonding with a metal plate heated to a temperature of ± 10 ° C. using an engraving roll.
[0004]
BEST MODE FOR CARRYING OUT THE INVENTION
The inventors of the present invention have intensively studied the relationship between the characteristics of the resin film and the embossability, and as a result, when using a film made of polybutylene terephthalate resin having a certain range of intrinsic viscosity, the film is deeply sharpened by embossing. It was found that when a concavo-convex pattern was obtained and this resin film was coated on a metal plate, a decorative metal plate with dramatically improved design was obtained.
As a result, even if the resin-coated metal plate obtained by laminating the resin film on the metal plate is molded, the processed part is whitened and the design is not impaired, and the embossability is equivalent to that of polyvinyl chloride resin. In addition, the excellent characteristics of the polybutylene terephthalate resin excellent in water aging resistance could be maintained as it was. The contents of the present invention will be described below.
[0005]
(Metal plate used)
As a metal plate used for the decorative metal plate of the present invention, any metal plate such as a steel plate, an aluminum plate, an aluminum alloy plate, a copper plate, or a copper alloy plate can be used. As the copper plate, a plain steel cold-rolled steel plate having a thickness of 0.10 to 1.2 mm is preferable. Among these, a cold-rolled steel plate of ordinary steel having a thickness of 0.10 to 0.50 mm is preferable. Among cold-rolled steel sheets, low-carbon or ultra-low-carbon aluminum killed steel sheets are preferably used, but non-aging steels containing Nb, Ti, etc., chromium-containing steel sheets containing 3 to 18% by weight of chromium, and various compositions. A stainless steel plate or the like can also be used. A surface-treated steel sheet having a surface treated on the surface of these cold-rolled steel sheets can also be used. Surface treatment includes plating, chemical conversion treatment, and coating treatment. Examples of plating include zinc plating, zinc-aluminum alloy plating, zinc-cobalt-molybdenum plating, tin plating, nickel plating, chromium plating, nickel-phosphorus plating, and nickel. -There are zinc plating, nickel-cobalt plating, nickel-tin plating, aluminum plating, and the like, and the chemical conversion treatment may be a known treatment such as chromate treatment, phosphate treatment. The coating process is carried out by a method in which various paints are applied and baked according to their properties.
[0006]
(Used resin film, etc.)
As the resin film for covering a decorative metal plate of the present invention, a polybutylene terephthalate resin film can be suitably used. From the viewpoint of embossability, an unstretched film is preferable to a stretched film. The intrinsic viscosity of the polybutylene terephthalate resin is preferably in the range of 1.0 to 2.0. Intrinsic viscosity can be determined by using a conventional method, and after dissolving the resin in a 1: 1 mixed solution of phenol / tetrachloroethane, the specific viscosity can be determined by measuring the specific viscosity with a Ubbelohde viscometer in a constant temperature bath at 30 ° C. .
When the intrinsic viscosity is less than 1.0, sufficient impact resistance (water deterioration resistance) cannot be obtained when it is coated on a metal plate and aged for a long time in a constant temperature and high humidity atmosphere. When it exceeds 0, when the resin is heated and melted and extruded from the extruder to form a film, the viscosity becomes too high and the torque of the extruder increases, making it difficult to form a film. A more preferable range of the intrinsic viscosity is 1.2 to 1.5 from the viewpoint of water resistance and film forming property.
[0007]
The thickness of the polybutylene terephthalate resin film is not particularly limited, but is preferably 20 to 300 μm, and more preferably 70 to 200 μm. Also, a resin obtained by blending the above polybutylene terephthalate resin with polyethylene terephthalate resin, polycarbonate resin, ionomer resin, or the like, or a resin obtained by blending two or more of these blend resins, or a co-polymer of polybutylene terephthalate and other polyester resins. It is also possible to use a film made of a resin made of a polymer, for example, a copolymer in which one part of terephthalic acid is replaced with isophthalic acid or adipic acid, or a copolymer in which one part of butanediol is replaced with ethylene glycol or the like. is there. Furthermore, a composite resin film obtained by laminating two or more kinds of films made of the various resins described above can also be used.
[0008]
The resin film for covering a decorative metal plate of the present invention may use the polybutylene terephthalate resin film as a single layer, but the surface opposite to the surface to be embossed as described later of the polybutylene terephthalate resin film. Further, it may be used as a multilayer resin film formed by laminating at least one layer of an adhesive layer, a colored layer, and a printed layer. For those that require a high degree of adhesive strength with metal plates, low-melting polyester resin films other than polybutylene terephthalate resin as adhesive layers, and general adhesives such as polyester resin and urethane resin An adhesive layer made of may be provided. As the colored layer, a film made of the same polybutylene terephthalate resin as the above polybutylene terephthalate resin, or a composite resin film obtained by laminating a colored film obtained by adding a pigment to another polyester resin film can also be used.
[0009]
The polybutylene terephthalate resin film is easy to obtain a hard and smooth surface by producing fine crystals, and is excellent in printability. Therefore, it is also possible to use a composite resin film provided with a full-colored printing layer by gravure, offset, screen printing, or partially colored printing layer on the surface opposite to the embossed surface described later, which is described later on the polybutylene terephthalate resin film. It is.
Furthermore, a surface protective layer may be provided on the surface of the polybutylene terephthalate resin film to be embossed, which will be described later, in order to impart lubricity and wear resistance to the extent that the unevenness caused by the embossing is not lost.
[0010]
(Embossing method)
As the embossing method of the polybutylene terephthalate resin film described above, a method in which a heat-melted resin is extruded from a T-die onto an embossed casting roll to form a film having embossed eyes on one side, and the film is directly chilled. A method of passing between rolls, a method of heating a film and passing it between chilled rolls, a method of embossing with a vacuum suction through a rotating screen roll, a hot needle that passes a film through a perforator You may emboss using any method, such as a process, the method of compressing using a stamping roll. Further, after laminating the above polybutylene terephthalate resin film on a metal plate, it may be embossed by pressure bonding using an engraving roll together with the metal plate heated to a temperature range of the melting point of the resin ± 10 ° C.
As the embossed shape, various patterns such as a random mat, a square shape, a diamond shape, a deep drawing shape, and a grain pattern (referred to as SG pattern) can be selected according to the needs of the product.
[0011]
(Lamination method)
The polybutylene terephthalate resin film embossed as described above is laminated on a metal plate using a known heat fusion method or the like. That is, the metal plate is heated to a temperature equal to or higher than the melting point of the polybutylene terephthalate resin, the non-embossed surface of the polybutylene terephthalate resin film is brought into contact with the metal plate, and both are sandwiched by a pair of laminate rolls, and immediately immersed in water. Immerse in and quench.
For those that require a high degree of adhesion to the metal plate, as described above, an adhesive layer is provided on the polybutylene terephthalate resin, or an adhesive layer is provided on the metal plate, and the metal is interposed between the metal plates. It is also possible to laminate a plate and a polybutylene terephthalate resin film.
[0012]
(Determining the quality of embossability)
The quality of the embossability of the polybutylene terephthalate resin film of the present invention is judged by the surface roughness of the embossed resin film. In the present invention, the surface of the resin film was observed with the naked eye, and the quality of the embossability was evaluated according to the following three criteria.
○: Good, Δ: Slightly poor, ×: Poor The above evaluation criteria are based on the surface average roughness (Ra: μm) of the polyvinyl chloride resin film using a SURFCOM surface roughness meter manufactured by Tokyo Seimitsu Co., Ltd. JIS B0601 The surface average roughness is 4 μm and the embossability is accepted as a pass standard, and the surface average roughness is 4 μm or better with the same or better appearance than the surface of the polyvinyl chloride resin film ( (Circle)), and the thing which is a little inferior compared with the surface of a polyvinyl chloride resin film, but has the appearance which does not have a problem practically was made into a some defect ((triangle | delta)), and the thing which does not enter embossing was judged as a defect (x).
[0013]
(Processability evaluation)
A polybutylene terephthalate resin film having a constant length and width and having a thickness of 0.10 mm, which is passed through an SG-shaped engraving roll having irregularities with an average surface roughness Ra = 11 μm and embossed. Is brought into contact with a 0.50 mm thick galvanized steel sheet having the same length and width as the polybutylene terephthalate resin film heated to a temperature equal to or higher than the melting point of the polybutylene terephthalate resin. The test piece was sandwiched and pressure-bonded. The test piece thus obtained was tested for impact workability using a DuPont impact tester specified in JIS K 5400 under conditions of an outer diameter of the impact part of 0.5 inch, a weight of 1 kg, and a drop height of 50 cm. did. The evaluation was made in three stages by visual observation as described below.
○: No cracks are observed in the resin film,
Δ: A fine crack is observed in a part of the resin film.
X: The crack is remarkable in the whole resin film.
In the above scores, ○ and Δ are not problematic in use. In addition, this test was implemented about ten test pieces.
[0014]
(Evaluation of water resistance)
When the polybutylene terephthalate resin film of the present invention is embossed and kept for a long time in a constant temperature and humidity state (for example, when used as an interior material of a unit bath), it is in contact with water for a long time. The water resistance of the resin film was evaluated by the DuPont impact test method.
A polybutylene terephthalate resin film having a constant length and width and having a thickness of 0.10 mm, which is passed through an SG-shaped engraving roll having irregularities with an average surface roughness Ra = 11 μm and embossed. Is brought into contact with a 0.50 mm thick galvanized steel sheet having the same length and width as the polybutylene terephthalate resin film heated to a temperature equal to or higher than the melting point of the polybutylene terephthalate resin. The test piece was sandwiched and pressure-bonded. The test piece thus obtained was cut into a size of 60 mm × 60 mm, immersed in deionized water maintained at a temperature of 38 ± 2 ° C. for 1 month, dried at room temperature, and then using a DuPont impact tester. The impact was applied under the conditions according to JIS K 5400 (the outer diameter of the impact part was 0.5 inch, the weight was 1 kg, and the drop height was 50 cm). The state of the resin film after the impact was loaded was observed with the naked eye and evaluated in the following five stages.
5: No crack is observed in the resin film.
4: A fine crack is recognized in a part of resin film.
3: A fine crack is recognized in the whole embossing part of a resin film.
2: A big crack is recognized by the whole embossing part of a resin film.
1: The crack is remarkable in the whole resin film.
In the above ratings, 5 and 4 have no problems in use. In addition, this test was implemented about ten test pieces.
[0015]
(Example)
Hereinafter, the present invention will be described in more detail with reference to examples. Using a polybutylene terephthalate resin having the intrinsic viscosity shown in Table 1, an unstretched film having a thickness of 0.10 mm was prepared using an extruder. In the production of these resin films, the resin film is heated and melted, and the heat-melted resin is extruded from a T-die onto a casting roll engraved with SG eyes provided with irregularities having a surface average roughness Ra = 11 μm. The embossing was given to the single side | surface of the resin film. For one part of the film, the entire surface was colored by gravure printing on the surface opposite to the embossed surface. In addition, as a comparative example, a polyethylene terephthalate resin having the intrinsic viscosity shown in Table 1 was formed using an extruder in the same manner as the above polybutylene terephthalate resin, and was embossed on one side and having a thickness of 0.10 mm. An unstretched film was created. The quality of the embossability of the resin film thus obtained was evaluated by visual observation. The evaluation results are shown in Table 2.
[0016]
Subsequently, the resin film which gave said embossing was laminated | stacked on the metal plate in the following way. Zinc was plated to a thickness of 0.002 mm on a low carbon aluminum killed cold-rolled steel sheet having a thickness of 0.50 mm. This galvanized steel sheet is heated to 240 ° C., and the surface of the polybutylene terephthalate resin film that is not embossed is brought into contact with one side of the galvanized steel sheet. It was cooled rapidly. In the case of a film printed on one side, after applying urethane resin adhesive on the printed surface and drying it, the adhesive coated surface is brought into contact with the heated galvanized steel sheet and the same as above. And laminated. Thus, a polybutylene terephthalate resin film-coated galvanized steel sheet was obtained. Also, the same galvanized steel sheet as above is heated to 280 ° C., the surface of the polyethylene terephthalate resin film that is not embossed is brought into contact with one surface, the two are sandwiched between a pair of laminating rolls, and immediately bonded under water. It was immersed in and rapidly cooled. In this way, a polyethylene terephthalate resin film-coated galvanized steel sheet was obtained.
The polybutylene terephthalate resin film-coated galvanized steel sheet and the polyethylene terephthalate resin film-coated galvanized steel sheet obtained as described above were evaluated for the processability of the resin film using a DuPont impact tester under the conditions in accordance with JIS K 5400. . The evaluation results are shown in Table 2.
Further, a test piece having a size of 60 mm × 60 mm was cut out from each resin film-coated galvanized steel sheet, immersed in ion-exchanged water maintained at a temperature of 38 ± 2 ° C. for 1 month, dried at room temperature, and then JIS. The processability of the resin film was evaluated using a DuPont impact tester under conditions based on K5400. The resin films of Examples and Comparative Examples of the present invention are shown in Table 1 below. The evaluation results are shown in Table 2 below.
[0017]
[Table 1]
[Table 2]
Although the evaluation results are shown in Table 2, the galvanized steel sheet coated with a film made of polybutylene terephthalate resin having an intrinsic viscosity of 1.0 or more is more embossed than the galvanized steel sheet coated with a film made of polyethylene terephthalate resin. It exhibits the same or better characteristics in processability and water resistance. In addition, the galvanized steel sheet coated with the printed film has excellent design properties because a beautiful color tone of the printed layer and a three-dimensional effect due to the thickness of the embossed transparent film are obtained.
[0020]
[Industrial applicability]
In the present invention, the intrinsic viscosity (IV value) of polybutylene terephthalate resin is 1.0 to 2.0, at least one surface is embossed, and a cosmetic layer having a printed layer on the surface opposite to the embossed surface A metal plate-covering resin film and a decorative metal plate coated with the polybutylene terephthalate resin film, and the decorative metal plate coated with the polybutylene terephthalate resin film of the present invention has a whitened processed portion even after molding. The embossing processability equivalent to that of polyvinyl chloride resin can be obtained without impairing the design, and the excellent properties of polybutylene terephthalate resin with excellent water aging resistance can be maintained as it is. It has excellent water resistance and can be applied to building materials that require water resistance such as unit baths.
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33433798 | 1998-11-25 | ||
| PCT/JP1999/006581 WO2000031167A1 (en) | 1998-11-25 | 1999-11-25 | Covering resin film for decorative metal plate and decorative metal plate having the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP3693920B2 true JP3693920B2 (en) | 2005-09-14 |
Family
ID=18276239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000583990A Expired - Fee Related JP3693920B2 (en) | 1998-11-25 | 1999-11-25 | Decorative metal plate covering resin film, decorative metal plate, and method for producing decorative metal plate |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3693920B2 (en) |
| AU (1) | AU1409600A (en) |
| TW (1) | TW495526B (en) |
| WO (1) | WO2000031167A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5929198B2 (en) * | 2012-01-05 | 2016-06-01 | 東レ株式会社 | Polybutylene terephthalate film |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5914948A (en) * | 1982-07-16 | 1984-01-25 | 帝人株式会社 | Filmy laminate |
| JPS5914947A (en) * | 1982-07-16 | 1984-01-25 | 帝人株式会社 | Filmy laminate |
| JPS62251135A (en) * | 1986-04-25 | 1987-10-31 | 東レ株式会社 | Vibration-damping metal laminated board |
| JPH07112519A (en) * | 1993-10-19 | 1995-05-02 | Goyo Paper Working Co Ltd | Shape sheet for unsaturated polyester decorative plywood |
| JPH09194604A (en) * | 1996-01-24 | 1997-07-29 | Unitika Ltd | Film for metal laminate |
| JPH09300564A (en) * | 1996-05-10 | 1997-11-25 | Daicel Chem Ind Ltd | Laminated film with embossing workability and manufacture thereof |
| JP3262031B2 (en) * | 1996-08-06 | 2002-03-04 | 東洋製罐株式会社 | Laminate and container using the same |
| JP3247053B2 (en) * | 1996-10-09 | 2002-01-15 | ユニチカ株式会社 | Polyester film for metal plate lamination and method for producing the same |
| JP3366205B2 (en) * | 1997-01-06 | 2003-01-14 | ユニチカ株式会社 | Polyester film for lamination of metal plate for can body and method for producing laminated metal plate for can body using the film |
| JPH10338756A (en) * | 1997-06-09 | 1998-12-22 | Teijin Ltd | White polyester film for laminating and processing to metal plate |
-
1999
- 1999-11-24 TW TW088120564A patent/TW495526B/en not_active IP Right Cessation
- 1999-11-25 AU AU14096/00A patent/AU1409600A/en not_active Abandoned
- 1999-11-25 JP JP2000583990A patent/JP3693920B2/en not_active Expired - Fee Related
- 1999-11-25 WO PCT/JP1999/006581 patent/WO2000031167A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000031167A1 (en) | 2000-06-02 |
| TW495526B (en) | 2002-07-21 |
| AU1409600A (en) | 2000-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3969625B2 (en) | Manufacturing method of resin film for decorative plate lamination | |
| US4313996A (en) | Formable metal-plastic-metal structural laminates | |
| EP0134958B1 (en) | Formable metal-plastic-metal structural laminates | |
| KR100884177B1 (en) | Laminated resin sheet, embossed sheet and covered substrate | |
| JP3693920B2 (en) | Decorative metal plate covering resin film, decorative metal plate, and method for producing decorative metal plate | |
| JP4727843B2 (en) | Decorative film, laminated metal plate obtained by laminating the film, and method for producing them | |
| JP4681875B2 (en) | Steel sheet decorative film | |
| JP2022130444A (en) | Exterior material for power storage device, manufacturing method thereof, and power storage device | |
| JP4763231B2 (en) | Decorative film for steel sheet and laminated decorative sheet for steel sheet | |
| JP2008221559A (en) | Laminated polyester film for covering metal sheet | |
| JP4564171B2 (en) | Decorative metal plate and unit bath using the decorative metal plate | |
| JP3722697B2 (en) | Manufacturing method of decorative metal plate with excellent embossability | |
| JP4059966B2 (en) | White film for metal lamination | |
| KR20030093295A (en) | Polyester-based resin sheet-like material and resin-covered metal plate using the resin sheet-like material | |
| JP3958936B2 (en) | Unit bath decorative board and unit bath | |
| JP7160224B1 (en) | Exterior material for power storage device, manufacturing method thereof, and power storage device | |
| JPS58183249A (en) | Coated metallic plate | |
| WO2023195472A1 (en) | Exterior material for power storage device, manufacturing method therefor, and power storage device | |
| JP4141641B2 (en) | Embossing processing method and manufacturing method of decorative metal plate | |
| JP2011202024A (en) | Resin film, decorative metal plate coated with the resin film and building material for ship interior finishing to use the decorative metal plate | |
| JP2005212241A (en) | Laminated polyester film for covering metal sheet | |
| JPH11245359A (en) | White film for metal laminate | |
| WO2000026283A1 (en) | Resin film excellent in embossing capability, embossing method for the resin film, decorative metal sheet coated with the resin film | |
| JP2002079608A (en) | Film laminated steel panel and method for manufacturing the same | |
| JPH04146128A (en) | Resin laminate having curved face |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050225 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050426 |
|
| 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: 20050621 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20050622 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 3693920 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: 20090701 Year of fee payment: 4 |
|
| 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: 20090701 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100701 Year of fee payment: 5 |
|
| 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: 20110701 Year of fee payment: 6 |
|
| 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: 20120701 Year of fee payment: 7 |
|
| 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: 20130701 Year of fee payment: 8 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |