JP2001096702A - Decorative sheet of melamine resin - Google Patents
Decorative sheet of melamine resinInfo
- Publication number
- JP2001096702A JP2001096702A JP28263099A JP28263099A JP2001096702A JP 2001096702 A JP2001096702 A JP 2001096702A JP 28263099 A JP28263099 A JP 28263099A JP 28263099 A JP28263099 A JP 28263099A JP 2001096702 A JP2001096702 A JP 2001096702A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- melamine resin
- decorative
- impregnated
- paper
- 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)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は屈曲性の優れたメラ
ミン樹脂化粧シートに関するもので、高圧メラミン樹脂
化粧板の持つ優れた表面性能を活かしつつ、常温加工
性、現場施工性等の機能を有し、化粧シートを貼り付け
た化粧パネルのコストの低減を図ることを可能とするも
のである。具体的用途として従来高圧メラミン化粧板を
表面化粧材として使用するポストフォーム加工物、或い
は塩ビシート貼り化粧パネル、曲面形状部位の車両用内
装材等の広範囲の有効活用が期待出来る。また厚みを薄
くした場合、経時劣化した化粧表面材を取り替えず、そ
の上に上貼り加工するリニューアル材料としても有効で
あり、環境保全、産業廃棄物対策として有用な材料を提
供するものでもある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a melamine resin decorative sheet having excellent flexibility, and has functions such as room temperature workability and on-site workability while utilizing the excellent surface performance of a high-pressure melamine resin decorative sheet. In addition, it is possible to reduce the cost of the decorative panel to which the decorative sheet is attached. As a specific application, a wide range of effective utilization can be expected of a post-form processed product using a conventional high-pressure melamine decorative board as a surface decorative material, a decorative panel attached with a PVC sheet, a vehicle interior material having a curved surface portion, and the like. Further, when the thickness is reduced, it is also effective as a renewal material that is applied over the decorative surface material that has deteriorated with time without replacing the decorative surface material, and provides a material that is useful for environmental protection and industrial waste countermeasures.
【０００２】[0002]
【従来の技術】メラミン樹脂化粧板は、表面が硬く、耐
熱性や耐汚染性にも優れ、かつ意匠性でも豊富な色柄が
選択出来るとから、従来よりテーブルトップ、流し台、
会議用テーブル、デスク天板等の表面化粧材として広く
使用されている。しかし、こうした優れた表面性能を有
する反面、高い剛性を有することや雰囲気湿度変化に伴
う寸法変化が大きいことから、２次加工、パネル接着加
工等を困難にしたり、使用接着剤の制約を受ける等の欠
点を有していた。また、ポストフォーム加工物の天板表
面材としての適用も以前から行われているが、１３０〜
１７０℃の加熱加工で曲げ加工するため専用加工設備が
必要であった。これらの加工上の制約は、高圧メラミン
樹脂化粧板の需要を抑える結果となり、これに代わる塩
ビシート、ＦＲＰ成形品或いは人工大理石等に置き換え
られる状況が増えていた。2. Description of the Related Art A melamine resin decorative board has a hard surface, excellent heat resistance and stain resistance, and a variety of designs can be selected.
It is widely used as a surface decoration material for conference tables and desk tops. However, while having such excellent surface performance, it has high rigidity and large dimensional changes due to changes in atmospheric humidity, making secondary processing and panel bonding processing difficult, or being restricted by the adhesive used. Had the disadvantages of In addition, application of a post-form processed material as a top plate surface material has been performed for some time,
Special bending equipment was required to perform bending by heating at 170 ° C. These restrictions on processing have resulted in a reduction in demand for high-pressure melamine resin decorative boards, and there has been an increasing number of situations in which substitute sheets such as PVC sheets, FRP molded articles, or artificial marble are used.
【０００３】近年、産業廃棄物処理や塩ビ焼却時のダイ
オキシン問題に代表される環境保全への社会ニーズが高
まる中で、化粧材料にも新たな対応が求められる様にな
り、一方では低コスト化の要求が益々強くなっている。
そうした市場変化にあって、高圧メラミン樹脂化粧板の
持つ高耐久性が見直され期待感が出て来ている。しかし
前述した高圧メラミン樹脂化粧板固有の課題の改善は、
これまでの検討経過においても相当困難であった。[0003] In recent years, as social needs for environmental protection represented by the dioxin problem at the time of industrial waste treatment and PVC incineration have increased, new measures have also been required for cosmetic materials, and on the other hand, cost reduction has been achieved. Are increasingly demanding.
Amid such market changes, the high durability of high-pressure melamine resin decorative boards has been reviewed, and expectations have emerged. However, the improvement of the above-mentioned problems unique to the high-pressure melamine resin decorative board,
It has been quite difficult in the course of the study so far.
【０００４】産業廃棄物の対策を考える場合、大別して
２つの対策になる。１つは分別回収された各廃棄物を再
利用する方法であり、もう一つは材料あるいは加工物が
廃棄物となるまでのライフサイクルを長期化することで
ある。高圧メラミン樹脂化粧板の場合、再利用に関して
は燃料用補助材、熱硬化性成形材料用充填材等が実用化
されている。一方、材料のライフサイクルについては、
もともと高圧メラミン樹脂化粧板が高耐久性素材である
が、１５〜３０年前に使用された化粧パネル天板（例え
ば、スチールデスク、流し台カウンター、トイレブース
等）や車両内装材のリニューアルが、最近の産業廃棄物
問題と相まって重要な課題となっている。When considering measures for industrial waste, there are roughly two measures. One is a method of reusing the separated and collected waste, and the other is to lengthen the life cycle until the material or processed product becomes the waste. In the case of a high-pressure melamine resin decorative board, an auxiliary material for fuel, a filler for thermosetting molding materials, and the like have been put to practical use for reuse. On the other hand, regarding the material life cycle,
Originally, high-pressure melamine resin decorative board is a highly durable material, but renewal of decorative panel top boards (for example, steel desks, sink counters, toilet booths, etc.) and vehicle interior materials used 15 to 30 years ago have recently been developed. It is an important issue in conjunction with the industrial waste problem.
【０００５】化粧パネルやその加工物では、一部の部材
の機能が失われる（例えば、表面材の外観意匠性、美観
が損なわれる）と、パネルや加工物全体を廃棄すること
が多く実施されて来たため、その他の部材自体はライフ
があるにもかかわらず、廃棄されるため必要以上に廃棄
物が多くなる結果を生じている。[0005] In the decorative panel and its processed product, if the function of some members is lost (for example, the appearance design and appearance of the surface material are impaired), the entire panel and the processed product are often discarded. As a result, the other members themselves have a life, but are discarded, resulting in more waste than necessary.
【０００６】[0006]
【発明が解決しようとする課題】本発明者は、上記した
ように、高圧メラミン樹脂化粧板の高耐久性に対する期
待感から新たな需要に対応する上で、素材の持つ２次加
工性の改善という課題を解決し、今日の市場ニーズに合
った機能を付加するかについて鋭意検討を加えた結果、
寸法変化が小さく、２次加工性の優れたメラミン樹脂化
粧シートを完成させたものである。SUMMARY OF THE INVENTION As described above, the inventor of the present invention has improved the secondary workability of a material in order to meet new demand from the expectation of high durability of a high-pressure melamine resin decorative board. After a thorough study on whether to add features that meet today's market needs,
A melamine resin decorative sheet with small dimensional change and excellent secondary workability is completed.
【０００７】本来、高圧メラミン樹脂化粧板は、表面に
メラミン樹脂化粧層を持ち、厚みの大部分はその下のフ
ェノール樹脂コア層で形成されている。これは、熱硬化
後のメラミン樹脂が硬く、透明性に優れ、耐汚染性や耐
薬品性にも優れる反面、脆くまた吸脱湿にて寸法変化が
大きいという欠点を有するため、表面に必要な機能だけ
をメラミン樹脂層に残し、メラミン樹脂の欠点をフェノ
ール樹脂層で補完する構成になっている。本発明におい
ては、表面性能はメラミン樹脂層により引き出し、メラ
ミン樹脂の欠点は従来とは異なる方策により解決したも
のである。[0007] Originally, a high-pressure melamine resin decorative board has a melamine resin decorative layer on the surface, and most of the thickness is formed by a phenol resin core layer thereunder. This is because the melamine resin after heat curing is hard, excellent in transparency, excellent in stain resistance and chemical resistance, but has the disadvantage that it is brittle and has a large dimensional change due to moisture absorption and desorption, so it is necessary for the surface. Only the function is left in the melamine resin layer, and the disadvantage of the melamine resin is complemented by the phenol resin layer. In the present invention, the surface performance is derived by the melamine resin layer, and the disadvantage of the melamine resin is solved by a different method from the conventional one.
【０００８】[0008]
【課題を解決するための手段】本発明は、（Ａ）メラミ
ン樹脂含浸紙からなる表面層と、（Ｂ）最下層又は中間
層として少なくとも１枚の金属箔及び／又は熱可塑性樹
脂シートとが配されてなるメラミン樹脂化粧シートであ
る。メラミン樹脂化粧シートとしての表面性能は、メラ
ミン樹脂含浸紙からなる表面層により優れたものとなっ
ている。一方、最下層又は中間層に金属箔又は熱可塑性
樹脂シートを少なくとも１層挿入することにより、化粧
シート表面から裏面への吸湿透過性を低減し、このこと
により化粧シートの寸法安定性を大きく向上させること
ができたものである。According to the present invention, (A) a surface layer comprising melamine resin-impregnated paper and (B) at least one metal foil and / or thermoplastic resin sheet as a lowermost layer or an intermediate layer are provided. It is a melamine resin decorative sheet arranged. The surface performance as a melamine resin decorative sheet is more excellent due to the surface layer made of melamine resin impregnated paper. On the other hand, by inserting at least one layer of a metal foil or a thermoplastic resin sheet into the lowermost layer or the intermediate layer, the moisture absorption permeability from the front surface to the back surface of the decorative sheet is reduced, thereby greatly improving the dimensional stability of the decorative sheet. It was something that could be done.
【０００９】本発明の化粧シートは、厚みを薄くした場
合、経時劣化した化粧表面材を取り替えず、その上に上
貼り加工するリニューアル材料としても有効である。こ
のような使用のためには、化粧シートの厚みを０．５ｍ
ｍ以下、更には０．３ｍｍとすることが好ましい。但し
０．１５ｍｍ以下とすることは困難である。０．５ｍｍ
を越えるとリニューアルされた化粧パネルの厚みがリニ
ューアル前に比べて厚くなりすぎて好ましくない。さら
に、好ましくは、メラミン樹脂化粧層に使用するメラミ
ン樹脂は水性熱可塑性樹脂を混合して可塑化を行い、脆
さの改善と柔軟性の付与及び寸法変化率の大幅な軽減を
実現することができた。かかるメラミン樹脂において、
メラミン樹脂と水性熱可塑性樹脂との配合割合は、メラ
ミン樹脂１００重量部に対して水性熱可塑性樹脂５〜６
０重量部が好ましい。５重量部未満では、水性熱可塑性
樹脂による上記の効果が小さく、６０重量部より多い
と、可撓性が大き過ぎて、メラミン樹脂の有する表面硬
度や耐熱性が低下するようになる。When the decorative sheet of the present invention is reduced in thickness, it is also effective as a renewal material that is overlaid on a decorative surface material that has deteriorated with time without being replaced. For such use, the thickness of the decorative sheet should be 0.5 m
m or less, more preferably 0.3 mm. However, it is difficult to make it 0.15 mm or less. 0.5mm
If the thickness exceeds the limit, the thickness of the renewed decorative panel becomes too thick as compared to before the renewal, which is not preferable. Further, preferably, the melamine resin used in the melamine resin decorative layer is mixed with an aqueous thermoplastic resin to perform plasticization, thereby realizing improvement in brittleness, imparting flexibility, and greatly reducing a dimensional change rate. did it. In such a melamine resin,
The mixing ratio of the melamine resin and the aqueous thermoplastic resin is such that the aqueous thermoplastic resin is 5 to 6 parts per 100 parts by weight of the melamine resin.
0 parts by weight is preferred. If the amount is less than 5 parts by weight, the above-mentioned effect of the aqueous thermoplastic resin is small. If the amount is more than 60 parts by weight, the flexibility is too large, and the surface hardness and heat resistance of the melamine resin are reduced.
【００１０】なお、前記金属箔又は熱可塑性樹脂シート
とメラミン樹脂含浸層との接着は、次の２つの方法によ
り行うことができる。即ち、ひとつは、金属箔又は熱可
塑性樹脂シートの片面に予め接着剤を塗布して接着剤層
を設ける方法であり、他は、フェノール樹脂又はエポキ
シ樹脂の含浸紙を挿入する方法である。前者の方法は、
化粧シートを薄厚化することができ、接着剤層に使用す
る樹脂の成形時の収縮が小さく化粧シートのカールや剛
直化を防止でき、後者の方法では、化粧シートのカール
や剛直化を最小限に抑えるとともに強固な層間接着強
度、高耐熱性を付与することが出来る。何れの方法を選
択するかは、適用用途により決定される。The bonding between the metal foil or the thermoplastic resin sheet and the melamine resin impregnated layer can be performed by the following two methods. That is, one is a method of applying an adhesive in advance on one side of a metal foil or a thermoplastic resin sheet to provide an adhesive layer, and the other is a method of inserting a phenol resin or epoxy resin impregnated paper. The former method is
The decorative sheet can be made thinner, and the resin used for the adhesive layer has a small shrinkage during molding, which prevents curling and stiffening of the decorative sheet.The latter method minimizes curling and stiffening of the decorative sheet. And a high interlayer adhesive strength and high heat resistance can be imparted. Which method is selected depends on the application.
【００１１】また、最下層に金属箔又は熱可塑性樹脂シ
ートを配置させるのは、寸法安定性のためであるが、雰
囲気中の吸・脱湿変化だけでなく、化粧シートを基板に
貼り付けるパネル化工程における吸湿等による膨潤を極
力なくし、かつ適用接着剤の種類を広げることをも可能
にする。また、金属箔を使用すれば、良好な熱放散性か
ら耐熱性が改善され、接着剤との組合せにより、金属箔
と接着剤層間で剥がし易くなるため、将来のリサイクル
性の付与も可能となる。The reason why the metal foil or the thermoplastic resin sheet is disposed in the lowermost layer is for dimensional stability. In addition to the change in absorption and dehumidification in the atmosphere, the panel for attaching the decorative sheet to the substrate is not limited. In addition, it is possible to minimize swelling due to moisture absorption or the like in the forming process, and to widen the types of adhesives to be applied. In addition, if a metal foil is used, heat resistance is improved from good heat dissipation, and in combination with an adhesive, it becomes easy to peel off between the metal foil and the adhesive layer, so that future recyclability can be imparted. .
【００１２】また、本発明の化粧シートは、厚みを０．
５ｍｍ以下と薄くし、メラミン樹脂として熱可塑性樹脂
配合メラミン樹脂を使用し、且つ中間層又は最下層に厚
み０．２ｍｍ以下の金属箔又は厚み０．３ｍｍ以下の熱
可塑性樹脂シートを使用することにより、常温での曲げ
加工が極めて容易となり、化粧面を外側又は内側にして
曲げた場合、曲げ半径１５ｍｍ以下を実現することがで
きた。Further, the decorative sheet of the present invention has a thickness of 0.1.
By thinning to 5 mm or less, using a melamine resin blended with a thermoplastic resin as the melamine resin, and using a metal foil having a thickness of 0.2 mm or less or a thermoplastic resin sheet having a thickness of 0.3 mm or less in the intermediate layer or the lowermost layer. Bending at room temperature became extremely easy, and a bending radius of 15 mm or less could be realized when the decorative surface was bent outside or inside.
【００１３】以下、本発明の化粧シートについて、図面
により説明する。図１は、オーバーレイ１、メラミン樹
脂含浸化粧紙２及び接着剤層４が塗布されたアルミ箔３
からなるメラミン樹脂化粧シートであり、図２は、オー
バーレイがなく、メラミン樹脂含浸化粧紙２、フェノー
ル樹脂含浸紙５及び金属箔６からなるメラミン樹脂化粧
シートである。図１において、オーバーレイ１は、メラ
ミン樹脂含浸紙からなり、メラミン樹脂化粧シートとし
ての表面性能を形成する。その直下にメラミン樹脂含浸
化粧紙２を配置しているので、この層１は透明度を必要
とすることから、厚さ２０〜４０μｍとすることが好ま
しい。含浸させるメラミン樹脂は、通常の一般的高圧メ
ラミン樹脂化粧板用のメラミン樹脂ワニスが適用され
る。化粧シートの柔軟性や耐クラック性を考えた場合、
メラミン樹脂にはポストフォームタイプの化粧板に使用
する可撓性メラミン樹脂がより好適である。Hereinafter, the decorative sheet of the present invention will be described with reference to the drawings. FIG. 1 shows an overlay 1, a melamine resin impregnated decorative paper 2, and an aluminum foil 3 coated with an adhesive layer 4.
FIG. 2 is a melamine resin decorative sheet having no overlay and comprising a melamine resin impregnated decorative paper 2, a phenol resin impregnated paper 5, and a metal foil 6. In FIG. 1, the overlay 1 is made of melamine resin-impregnated paper and forms the surface performance as a melamine resin decorative sheet. Since the decorative paper 2 impregnated with the melamine resin is disposed immediately below the layer, the layer 1 needs to have transparency, so that the thickness is preferably 20 to 40 μm. As the melamine resin to be impregnated, a general melamine resin varnish for a general high-pressure melamine resin decorative board is applied. Considering the flexibility and crack resistance of the decorative sheet,
As the melamine resin, a flexible melamine resin used for a post-form type decorative board is more preferable.
【００１４】次に、メラミン樹脂含浸化粧紙２は、本発
明における重要な構成であり、使用されるメラミン樹脂
は以下の理由により改質することが本発明の特徴の一つ
である。その目的のひとつはメラミン樹脂の欠点である
脆さと寸法収縮の軽減であり、他の目的は、図１のよう
に、化粧紙２と金属箔及び／又は熱可塑性樹脂シート３
との間にフェノール樹脂又はエポキシ樹脂含浸紙を挿入
せず、金属箔及び／又は熱可塑性樹脂シートの片面に塗
布した接着剤層にて接着する場合において、良好な層間
接着強度を良好にすることである。これらの点から、メ
ラミン樹脂の改質に使用する素材の必要特性としては、
次の４点が挙げられる。Next, the melamine resin impregnated decorative paper 2 is an important component of the present invention, and one of the features of the present invention is that the melamine resin used is modified for the following reasons. One of the purposes is to reduce brittleness and dimensional shrinkage, which are the drawbacks of melamine resin, and the other is to use decorative paper 2 and metal foil and / or thermoplastic resin sheet 3 as shown in FIG.
When the adhesive layer is applied to one side of the metal foil and / or thermoplastic resin sheet without inserting a phenol resin or epoxy resin impregnated paper between them, good interlayer adhesive strength is to be obtained. It is. From these points, the necessary properties of the material used to modify the melamine resin include:
There are the following four points.
【００１５】１つは、接着剤と親和性があり、成形後に
一定の層間強度を発現出来ること、２つめは、メラミン
樹脂と相溶性があり、成形後の化粧シートが吸水処理、
熱処理下にて層間強度を維持出来ること、３つ目は、吸
湿・脱湿処理による寸法変化が小さいこと、４つ目は、
材料コストが安価なことである。これらの必要特性を考
慮すれば、適用される樹脂は基本的に水溶性タイプが好
ましく、また成形時に生じるメラミン樹脂からの縮合水
による加水分解等の影響を受け難いことが望まれる。One is that it has an affinity with the adhesive and can exhibit a certain interlayer strength after molding. The second is that it is compatible with melamine resin and the decorative sheet after molding has a water absorbing treatment.
The third is that the interlayer strength can be maintained under heat treatment. The third is that the dimensional change due to moisture absorption / dehumidification is small.
Material cost is low. In consideration of these required properties, the resin to be applied is basically preferably a water-soluble resin, and it is desired that the resin is hardly affected by hydrolysis of melamine resin generated during molding by condensed water.
【００１６】本発明において、水性熱可塑性樹脂とは、
水に溶解又は水で分散可能な樹脂をいい、例えば、水性
アクリル樹脂、水性ウレタン樹脂、酢酸ビニール樹脂、
ポリビニールアルコール等があるが、上記の必要特性か
ら、水性アクリル樹脂が好ましいことが確認された。In the present invention, the aqueous thermoplastic resin is
Refers to a resin that can be dissolved or dispersed in water, for example, an aqueous acrylic resin, an aqueous urethane resin, a vinyl acetate resin,
Although there is polyvinyl alcohol and the like, it was confirmed that an aqueous acrylic resin was preferable from the above-mentioned necessary characteristics.
【００１７】水性アクリル樹脂は、エマルジョンタイプ
と非エマルジョンタイプに分けられるが、エマルジョン
タイプがやや良好である。その理由として、エマルジョ
ンタイプの場合、粒子化しているため粒径の制約から、
紙基材の内部へ浸透せず、基材表面上に残る効果があ
る。これは、接着剤層を使って接着する方法において
は、金属箔や熱可塑性樹脂シートの片面に塗工された接
着剤が加圧成形の際に紙基材中へ浸透して層間強度形成
能を低下させたり、接着剤の種類によっては、浸透した
接着剤が上層の化粧層の変色や層間強度の低下をもたら
す現象を防止するためのバリアとしての作用を付与する
ためである。また、図２の場合のごとく、フェノール樹
脂含浸紙又はエポキシ樹脂含浸紙を挿入する方法におい
ても、加圧成形中に直上にある化粧メラミン樹脂含浸化
粧紙への移行による変色、シミ出し等を軽減し、耐光性
安定化に寄与する。また、非エマルジョンタイプでは接
着剤の化粧紙への浸透性を考慮し、接着剤塗布量を数１
０％程度ないし２倍程度多くする必要がある。塗布量が
少ない場合は、この層での層間接着強度が低下すること
がある。The aqueous acrylic resin is classified into an emulsion type and a non-emulsion type, and the emulsion type is slightly better. The reason is that in the case of the emulsion type, since it is made into particles, the particle size is limited,
This has the effect of not penetrating into the paper base material and remaining on the base material surface. This is because, in the method of bonding using an adhesive layer, the adhesive applied to one side of a metal foil or thermoplastic resin sheet penetrates into the paper base material during pressure molding and forms an interlayer strength. This is because, depending on the type of the adhesive, the permeated adhesive acts as a barrier for preventing the upper decorative layer from discoloring or lowering the interlayer strength. Also, as in the case of FIG. 2, the method of inserting a phenol resin-impregnated paper or an epoxy resin-impregnated paper also reduces discoloration, spotting, etc. due to transfer to the decorative melamine resin-impregnated decorative paper immediately above during pressure molding. And contributes to stabilization of light resistance. In the case of the non-emulsion type, the amount of the adhesive applied is set to several tens in consideration of the permeability of the adhesive into decorative paper.
It needs to be increased by about 0% to about 2 times. If the coating amount is small, the interlayer adhesion strength of this layer may decrease.
【００１８】メラミン樹脂含浸化粧紙２の樹脂量は、外
観状態をみて決められるが、およそ４０〜６０重量％
（乾燥後の含浸紙総重量中の樹脂固形分比率）でよい。
また揮発分比率は、通常の高圧メラミン樹脂化粧板に使
用される化粧紙用メラミン樹脂含浸紙よりも低水準に調
整することが望まれる。メラミン樹脂単独では、低揮発
分化すると含浸紙が柔軟性をなくしその取扱いに支障を
きたすが、本発明に使用する変性メラミン樹脂含浸紙で
は、変性樹脂による柔軟性付与の効果で可能であり、か
つ縮合水の影響を軽減する上でも低揮発分化することが
好ましく、通常のメラミン樹脂含浸化粧紙が６〜８重量
％であるのに対して、４．５〜６．５重量％（乾燥後の
含浸紙総重量中の揮発分比率）に調整するのが適当であ
る。The resin content of the melamine resin-impregnated decorative paper 2 is determined depending on the external appearance, but is about 40 to 60% by weight.
(The ratio of the resin solid content to the total weight of the impregnated paper after drying) may be used.
Further, it is desired that the volatile content ratio be adjusted to a lower level than that of a melamine resin-impregnated paper for decorative paper used for a normal high-pressure melamine resin decorative board. Melamine resin alone, the impregnated paper loses flexibility when low volatilization differentiates and hinders its handling, but the modified melamine resin impregnated paper used in the present invention is possible due to the effect of imparting flexibility by the modified resin, and In order to reduce the influence of the condensed water, it is preferable that low volatile differentiation is performed. In contrast to ordinary melamine resin impregnated decorative paper which is 6 to 8% by weight, 4.5 to 6.5% by weight (after drying) It is appropriate to adjust the ratio to the volatile content in the total weight of the impregnated paper).
【００１９】次に金属箔及び／又は熱可塑性樹脂シート
３については、これまで述べた通り、吸湿透過性の小さ
いものが好適であり、フェノール樹脂含浸紙又はエポキ
シ樹脂含浸紙を介さずにメラミン樹脂含浸紙と接着する
場合は、片面に接着剤４が塗布される。金属箔又は熱可
塑性樹脂シート３の厚みは、０．０１〜０．３０ｍｍの
範囲が適当であるが、金属箔使用の場合は、材質、重
量、価格等を考えると０．０２〜０．２０ｍｍが好まし
く、熱可塑性樹脂シートの場合は、一般的には０．０８
〜０．３０ｍｍが好ましい。また、金属箔を使用する場
合、図２に示すごとく、重量及び価格の低減を図るため
厚みの薄い金属箔６をフェノール樹脂含浸紙５（あるい
はエポキシ樹脂含浸紙）を介して接着成形する方法も有
効である。この場合、熱硬化性樹脂の硬化収縮は、含浸
紙が金属箔間に挟まれた状態で成形されるため、前記し
たメラミン樹脂含浸層と金属箔間の接着成形する場合に
比較して殆ど影響しない。使用する金属箔としては、ア
ルミ箔、銅箔、ステンレス箔が考えられるが、汎用性と
経時安定性、価格、成形後の加工性等から、アルミ箔が
好ましい。Next, as described above, the metal foil and / or the thermoplastic resin sheet 3 are preferably those having a low moisture absorption and permeability, and the melamine resin sheet is not passed through the phenol resin impregnated paper or the epoxy resin impregnated paper. When bonding with the impregnated paper, the adhesive 4 is applied to one side. The thickness of the metal foil or the thermoplastic resin sheet 3 is suitably in the range of 0.01 to 0.30 mm, but in the case of using a metal foil, the material, weight, price, etc. are considered to be 0.02 to 0.20 mm. Is preferable, and in the case of a thermoplastic resin sheet, generally 0.08
~ 0.30 mm is preferred. When a metal foil is used, as shown in FIG. 2, a method of bonding a thin metal foil 6 through a phenol resin impregnated paper 5 (or an epoxy resin impregnated paper) to reduce the weight and the price is also available. It is valid. In this case, the curing shrinkage of the thermosetting resin is hardly affected as compared with the case where the melamine resin-impregnated layer and the metal foil are bonded and molded, because the impregnated paper is molded in a state sandwiched between the metal foils. do not do. As the metal foil to be used, aluminum foil, copper foil, and stainless steel foil can be considered, but aluminum foil is preferable in terms of versatility, stability over time, cost, workability after molding, and the like.
【００２０】図２において、フェノール樹脂含浸紙５
は、通常、フェノールに対するホルムアルデヒドのモル
比１．０〜２．０にて反応した脱水濃縮型レゾール型フ
ェノール樹脂を薄葉紙に含浸乾燥して得られる。フェノ
ール樹脂含浸紙は、厚み２０〜４０μｍが好ましく、樹
脂量は通常５０〜６０重量％程度である。また、揮発分
は通常のフェノール樹脂含浸紙（揮発分５〜７重量％）
より小さく、３．５〜５．０重量％程度とすることによ
り、フェノール樹脂による化粧層の変色等の欠陥をなく
することができる。このフェノール樹脂含浸紙の代わり
にエポキシ樹脂含浸紙を使用することもできる。使用さ
れるエポキシ樹脂は、特に限定されず、ビスフェノ−ル
型、ノボラック型等であるが、可撓性のあるものが好ま
しい。適当な硬化剤、硬化促進剤とともに溶剤に溶解し
たワニスの形で薄葉紙に含浸される。エポキシ樹脂含浸
紙の厚み、樹脂含有率はフェノール樹脂含浸紙の場合と
同様である。In FIG. 2, phenol resin impregnated paper 5
Is usually obtained by impregnating tissue paper with a dehydration-concentrated resol-type phenolic resin reacted at a molar ratio of formaldehyde to phenol of 1.0 to 2.0, followed by drying. The phenolic resin-impregnated paper preferably has a thickness of 20 to 40 μm, and the amount of the resin is usually about 50 to 60% by weight. The volatile content is normal phenolic resin impregnated paper (volatile content 5-7% by weight)
By making it smaller and about 3.5 to 5.0% by weight, defects such as discoloration of the decorative layer due to the phenol resin can be eliminated. Epoxy resin-impregnated paper can be used instead of the phenol resin-impregnated paper. The epoxy resin to be used is not particularly limited, and may be a bisphenol type, a novolak type, or the like, but is preferably a flexible one. The tissue paper is impregnated in the form of a varnish dissolved in a solvent together with a suitable curing agent and a curing accelerator. The thickness and the resin content of the epoxy resin-impregnated paper are the same as those of the phenol resin-impregnated paper.
【００２１】次に、金属箔又は熱可塑性樹脂シートに塗
布する接着剤４について述べる。接着剤樹脂としては、
エチレン−酢酸ビニル樹脂、水性アクリル樹脂、エポキ
シ樹脂、ロジン変性フェノール樹脂、ロジン変性アルキ
ッド樹脂等があるが、エチレン−酢酸ビニル樹脂、エポ
キシ樹脂が塗布処理での作業性及び化粧シートの実用特
性から好適である。また塗布量は、固形分量で３０ｇ／
ｍ2 以下で、望ましくは５〜２０ｇ／ｍ2の範囲が好ま
しい。３０ｇ／ｍ2 を越えても大きな問題はないが、揮
発分の乾燥処理、材料のコストアップ等から経済的でな
く、また、５ｇ／ｍ2 未満では、塗布量が不足し、層間
接着強度が不安定となる。Next, the adhesive 4 applied to the metal foil or the thermoplastic resin sheet will be described. As an adhesive resin,
Ethylene-vinyl acetate resin, water-based acrylic resin, epoxy resin, rosin-modified phenolic resin, rosin-modified alkyd resin, etc., but ethylene-vinyl acetate resin and epoxy resin are suitable from the viewpoint of workability in coating treatment and practical properties of decorative sheet It is. The coating amount is 30 g / solid content.
m 2 or less, preferably in the range of 5 to 20 g / m 2 . If it exceeds 30 g / m 2 , there is no major problem. However, it is not economical due to drying of volatile components and increase in cost of the material. If it is less than 5 g / m 2 , the coating amount is insufficient and the interlayer adhesive strength is low. Becomes unstable.
【００２２】成形方法については、高圧メラミン樹脂化
粧板の汎用技術の適用で可能であるが、一般の高圧メラ
ミン樹脂化粧板よりは、比較的高温で成形する方が望ま
しい。通常の高圧メラミン樹脂化粧板の場合、製品最高
温度は、１２５〜１４３℃程度に調整されるが、本発明
のメラミン樹脂化粧シートでは、水性熱可塑性樹脂の配
合により樹脂の流れが低下し、メラミン樹脂の硬化が遅
くなるので、１３８〜１５２℃の成形温度に調整するこ
とが好ましい。この場合、揮発分の少ないフェノール樹
脂含浸紙を使用するとフェノール樹脂による化粧層の変
色等の危険はなく、この温度で加圧成形しても、良好な
外観と十分な常温加工性を有する。As for the molding method, it is possible to apply a general-purpose technique of a high-pressure melamine resin decorative board, but it is more preferable to mold at a relatively high temperature than a general high-pressure melamine resin decorative board. In the case of a normal high-pressure melamine resin decorative board, the maximum product temperature is adjusted to about 125 to 143 ° C. However, in the melamine resin decorative sheet of the present invention, the flow of the resin decreases due to the mixing of the aqueous thermoplastic resin, Since the curing of the resin becomes slow, it is preferable to adjust the molding temperature to 138 to 152 ° C. In this case, if a phenolic resin-impregnated paper with a low volatile content is used, there is no danger of the decorative layer being discolored by the phenolic resin, and even if it is pressed at this temperature, it has a good appearance and sufficient room-temperature processability.
【００２３】[0023]
【実施例】以下、本発明について実施例にて具体的に説
明する。ここで、「％」は「重量％」を示す。EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples. Here, “%” indicates “% by weight”.
【００２４】実施例１ オーバーレイとして、米坪４０ｇ／ｍ2 の晒し薄葉紙か
らなる基材に、メラミンに対するホルムアルデヒドのモ
ル比１．８、数平均分子量２４０、粘度４５ｃｐｓ／２
０℃の水溶性メラミン樹脂を水により粘度２４ｃｐｓ／
３０℃に調整し、触媒、内部離型剤を添加して得た含浸
用メラミン樹脂ワニスを含浸し、加熱乾燥して、樹脂量
６０％、揮発分７％のオーバーレイ紙１を得た。次に、
前記モル比１．６、数平均分子量２３０、粘度４０ｃｐ
ｓ／２０℃のポストフォーム用水溶性メラミン樹脂に固
形分４５％、粘度３５ｃｐｓ／２０℃の水性アクリル樹
脂エマルジョンを重量比で１００：３５の比率で混合
し、水により粘度２０ｃｐｓ／２５℃に調整した後、触
媒を添加し含浸用メラミン樹脂ワニスを得た。このワニ
スを、通常の高圧メラミン樹脂化粧板用化粧紙（単色抄
き込み紙：米坪１３０ｇ／ｍ2 ）に含浸し、加熱乾燥し
て、樹脂量４５％、揮発分５％のメラミン樹脂含浸化粧
紙２を得た。一方、厚さ４０μｍのアルミ箔に、エチレ
ン−酢酸ビニル樹脂を接着剤とし、乾燥後の固形分が１
２ｇ／ｍ2 になる様にバーコーターにて塗布し加熱乾燥
して接着剤層４を有するアルミ箔３を得た。EXAMPLE 1 As an overlay, a base material composed of bleached thin paper having a rice weighing of 40 g / m 2 was used, and the molar ratio of formaldehyde to melamine was 1.8, the number average molecular weight was 240, and the viscosity was 45 cps / 2.
A water-soluble melamine resin at 0 ° C. is treated with water at a viscosity of 24 cps /
It was adjusted to 30 ° C., impregnated with a melamine resin varnish for impregnation obtained by adding a catalyst and an internal release agent, and dried by heating to obtain overlay paper 1 having a resin amount of 60% and a volatile content of 7%. next,
The molar ratio of 1.6, the number average molecular weight of 230, and the viscosity of 40 cp
An aqueous acrylic resin emulsion having a solid content of 45% and a viscosity of 35 cps / 20 ° C. was mixed at a weight ratio of 100: 35 with a water-soluble melamine resin for post foam at s / 20 ° C., and the viscosity was adjusted to 20 cps / 25 ° C. with water. Thereafter, a catalyst was added to obtain a melamine resin varnish for impregnation. This varnish is impregnated into a normal decorative paper for a high-pressure melamine resin decorative board (monocolor paper: 130 g / m 2 of rice tsubo), dried by heating, and impregnated with a melamine resin having a resin amount of 45% and a volatile content of 5%. Decorative paper 2 was obtained. On the other hand, an ethylene-vinyl acetate resin was used as an adhesive on an aluminum foil having a thickness of 40 μm, and the solid content after drying was 1%.
The resultant was applied with a bar coater to 2 g / m 2 and dried by heating to obtain an aluminum foil 3 having an adhesive layer 4.
【００２５】これらのオーバーレイ紙１、メラミン樹脂
含浸化粧紙２、接着剤層４を有するアルミ箔３を順次重
ね合わせ、通常の高圧メラミン樹脂化粧板の加圧成形と
同様にして、ステンレス鏡面板とオーバーレイ紙１が接
触する様に、かつ、鏡面板間に、当該化粧シート素材セ
ットを背中合わせに２組ずつ組み込んだ。プレスは、圧
力１００ｋｇ／ｃｍ2 に保持したままで加熱・冷却し
た。熱盤温度を１６０℃とし、製品最高温度が１４３〜
１４８℃の範囲に入る様に加熱した後、４０℃まで冷却
し、厚さ０．２８ｍｍのメラミン樹脂化粧シート（図
１）を得た。The overlay paper 1, the melamine resin impregnated decorative paper 2, and the aluminum foil 3 having the adhesive layer 4 are sequentially superimposed on each other. Two sets of the decorative sheet material set were assembled back-to-back so that the overlay paper 1 was in contact and between the mirror plates. The press was heated and cooled while maintaining the pressure at 100 kg / cm 2 . The hot platen temperature is 160 ° C and the maximum product temperature is 143 ~
After heating so as to fall within the range of 148 ° C., it was cooled to 40 ° C. to obtain a melamine resin decorative sheet (FIG. 1) having a thickness of 0.28 mm.
【００２６】実施例２ 実施例１にて用いた化粧紙（単色抄き込み紙：米坪１３
０ｇ／ｍ2 ）を基材とし、実施例１と同じく、粘度２０
ｃｐｓ／２５℃に調整した水性アクリル樹脂エマルジョ
ン配合メラミン樹脂に、触媒、内部離型剤及び充填フィ
ラー等を添加して得た含浸用メラミン樹脂ワニスを前記
基材に含浸し、加熱乾燥して、樹脂量５０％、揮発分６
％のメラミン樹脂含浸化粧紙２を得た。続いて、米坪３
７ｇ／ｍ 2 の薄葉紙からなる基材に、フェノールに対す
るホルムアルデヒドのモル比１．３にて反応した脱水濃
縮型レゾール型フェノール樹脂を含浸し、加熱乾燥し
て、樹脂量５８％、揮発分５％のフェノール樹脂含浸薄
葉紙５を得た。金属箔は、実施例１と同様に、厚さ２５
μｍのアルミ箔６を使用したが、接着剤塗布処理は行わ
なかった。メラミン樹脂含浸化粧紙２、フェノール樹脂
含浸薄葉紙５、アルミ箔６を順次重ね合わせ、実施例１
と同様にして成形し、厚さ０．２８ｍｍのメラミン樹脂
化粧シート（図２）を得た。製品最高温度は１４５℃で
あった。Example 2 Decorative paper used in Example 1 (monochromatic paper: rice tsubo 13)
0 g / mTwo) As the base material and having a viscosity of 20 as in Example 1.
Waterborne acrylic resin emuljo adjusted to cps / 25 ° C
Catalyst, internal release agent and filler
Melamine resin varnish for impregnation obtained by adding
Impregnated into base material, dried by heating, resin content 50%, volatile content 6
% Melamine resin-impregnated decorative paper 2 was obtained. Next, Yonetsubo 3
7g / m TwoTo phenol on a base made of thin paper
Concentrated by reaction at a molar ratio of formaldehyde of 1.3
Impregnated with a compacted resol type phenol resin, heat dried
Phenolic resin impregnated with 58% resin content and 5% volatile matter
Leaf paper 5 was obtained. The metal foil has a thickness of 25 as in the first embodiment.
μm aluminum foil 6 was used, but the adhesive was applied.
Did not. Melamine resin impregnated decorative paper 2, phenolic resin
Example 1 An impregnated thin paper 5 and an aluminum foil 6 were superimposed one after another.
Molded in the same manner as above, melamine resin 0.28mm thick
A decorative sheet (FIG. 2) was obtained. The maximum product temperature is 145 ° C
there were.
【００２７】実施例３ 上記実施例２の構成にさらに実施例２で使用したフェノ
ール樹脂含浸薄葉紙７及びアルミ箔８を追加で組み込ん
だものを１セットとし、実施例１と同様の方法にて製品
最高温度１４５℃で成形し、厚さ０．３８ｍｍのメラミ
ン樹脂化粧シート（図３）を得た。Example 3 A product obtained by additionally incorporating the phenolic resin-impregnated thin paper 7 and the aluminum foil 8 used in Example 2 in addition to the structure of Example 2 above was used as one set, and the product was manufactured in the same manner as in Example 1. Molding was performed at a maximum temperature of 145 ° C. to obtain a melamine resin decorative sheet (FIG. 3) having a thickness of 0.38 mm.
【００２８】比較例１ 上記実施例２の構成で、メラミン樹脂含浸化粧紙２で使
用したメラミン樹脂ワニスの代わりに、通常のポストフ
ォームタイプ高圧メラミン化粧板製造で使用するメラミ
ン樹脂ワニスを使用して得た、樹脂量５３％、揮発分７
％のメラミン樹脂含浸化粧紙９を使用した以外は、実施
例２と同様にして製品最高温度１４３℃で成形し、厚さ
０．２８ｍｍのメラミン樹脂化粧シート（図４）を得
た。Comparative Example 1 In the structure of Example 2, the melamine resin varnish used in the production of a normal high pressure melamine decorative board was used instead of the melamine resin varnish used in the melamine resin impregnated decorative paper 2. Obtained resin amount 53%, volatile matter 7
% Melamine resin impregnated decorative paper 9 was used, and molded at the maximum product temperature of 143 ° C. in the same manner as in Example 2 to obtain a melamine resin decorative sheet having a thickness of 0.28 mm (FIG. 4).
【００２９】比較例２ 通常の高圧メラミン樹脂化粧板製造法により厚さ０．７
０ｍｍのポストフォームタイプ化粧板を得た。製品最高
温度は１３５℃であった。COMPARATIVE EXAMPLE 2 A thickness of 0.7 was obtained by an ordinary method for producing a high-pressure melamine resin decorative board.
A 0 mm post foam type decorative board was obtained. The maximum product temperature was 135 ° C.
【００３０】実施例及び比較例にて得られた各メラミン
樹脂化粧シートについて特性を測定した。その結果を表
１に示す。The characteristics of each melamine resin decorative sheet obtained in Examples and Comparative Examples were measured. Table 1 shows the results.
【００３１】[0031]
【表１】 [Table 1]
【００３２】（測定方法） １．寸法変化率：ＪＩＳＫ６９０２により行った。 ２．常温屈曲性：ＪＩＳＫ６９０２の屈曲性試験装置に
よる。 ３．加熱成形性：ＪＩＳＫ６９０２のポストフォーム曲
げ試験装置による。 ４．表面鉛筆硬度：ＪＩＳＫ５４０１の塗膜鉛筆引っ掻
き試験による。(Measurement method) Dimensional change rate: Performed according to JIS K6902. 2. Room temperature flexibility: Measured by a bending tester according to JIS K6902. 3. Heat formability: According to JIS K6902 post-form bending tester. 4. Surface pencil hardness: According to JIS K5401 coating film pencil scratch test.
【００３３】[0033]
【発明の効果】以上の説明から明らかなように、本発明
のメラミン樹脂化粧シートは、従来の高圧メラミン樹脂
化粧板の優れた表面性能を保持しながら、常温加工性と
寸法安定性という課題を大きく改善することができ、従
って、加工施工費の削減による低コスト化も達成され
る。更には、厚みを薄くすることにより、常温での曲げ
加工が容易となり、化粧パネルに上貼りするリニューア
ル需要等にも適用でき、化粧板用途の拡大を可能にし
た。また金属箔又は熱可塑性樹脂シート部分の接着力を
適正に制御することにより今後のリサイクル対応の面で
も有効な手段を提供できるものと期待される。As is apparent from the above description, the melamine resin decorative sheet of the present invention has the problems of room temperature workability and dimensional stability while maintaining the excellent surface performance of the conventional high-pressure melamine resin decorative plate. It is possible to greatly improve, and accordingly, cost reduction is achieved by reduction of processing and construction costs. Furthermore, by reducing the thickness, bending at room temperature becomes easy, and it can be applied to the renewal demand for pasting on a decorative panel, and the use of decorative boards can be expanded. Further, it is expected that by appropriately controlling the adhesive force of the metal foil or the thermoplastic resin sheet portion, an effective means can be provided in terms of recycling in the future.
【図１】 実施例１にて得られた化粧板の構成を示す断
面図。FIG. 1 is a cross-sectional view showing a configuration of a decorative board obtained in Example 1.
【図２】 実施例２にて得られた化粧板の構成を示す断
面図。FIG. 2 is a cross-sectional view illustrating a configuration of a decorative board obtained in Example 2.
【図３】 実施例３にて得られた化粧板の構成を示す断
面図。FIG. 3 is a cross-sectional view illustrating a configuration of a decorative board obtained in Example 3.
【図４】 比較例１にて得られた化粧板の構成を示す断
面図。FIG. 4 is a cross-sectional view showing a configuration of a decorative board obtained in Comparative Example 1.
１ オーバーレイ（メラミン樹脂含浸薄葉紙） ２ メラミン樹脂含浸化粧紙 ３ 金属箔又は熱可塑性樹脂シート（アルミ箔） ４ 接着剤層 ５ フェノール樹脂含浸薄葉紙 ６ 金属箔又は熱可塑性樹脂シート（アルミ箔） ７ フェノール樹脂含浸薄葉紙 ８ アルミ箔 ９ メラミン樹脂含浸化粧紙 Reference Signs List 1 overlay (melamine resin impregnated thin paper) 2 melamine resin impregnated decorative paper 3 metal foil or thermoplastic resin sheet (aluminum foil) 4 adhesive layer 5 phenol resin impregnated thin paper 6 metal foil or thermoplastic resin sheet (aluminum foil) 7 phenol resin Impregnated thin paper 8 Aluminum foil 9 Melamine resin impregnated decorative paper
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F100 AB01B AB01C AB10 AB33 AB33B AB33C AK01A AK01B AK01C AK33D AK36A AK53D AK68G BA03 BA04 BA07 BA10A BA10C BA13 CB00 DG10A DG10D DH01A DH01D EJ20 EJ42 EJ82A EJ82D GB08 GB33 GB81 JA20 JB09A JB16B JB16C JK02 JL03 YY00 YY00A ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AB01B AB01C AB10 AB33 AB33B AB33C AK01A AK01B AK01C AK33D AK36A AK53D AK68G BA03 BA04 BA07 BA10A BA10C BA13 CB00 DG10A DG10D DH01A EJ20B EJ01B33 YY00 YY00A
Claims (6)
層と、（Ｂ）最下層又は中間層として少なくとも１枚の
金属箔及び／又は熱可塑性樹脂シートとが配されてなる
メラミン樹脂化粧シート。1. A melamine resin decorative sheet comprising (A) a surface layer made of melamine resin impregnated paper and (B) at least one metal foil and / or thermoplastic resin sheet as a lowermost layer or an intermediate layer. .
ある請求項１記載のメラミン樹脂化粧シート。2. The melamine resin decorative sheet according to claim 1, wherein the decorative sheet has a thickness of 0.5 mm or less.
が、メラミン樹脂と水性熱可塑性樹脂との混合樹脂であ
り、水性熱可塑性樹脂の混合割合が、固形分でメラミン
樹脂に対し５〜６０重量％である請求項１又は２記載の
メラミン樹脂化粧シート。3. The resin impregnated in the melamine resin-impregnated paper is a mixed resin of a melamine resin and an aqueous thermoplastic resin, and the mixing ratio of the aqueous thermoplastic resin is 5 to 60 wt. % Of the melamine resin decorative sheet according to claim 1.
熱可塑性樹脂シートとが、金属箔及び／又は熱可塑性樹
脂シートの片面に塗布された接着剤層を介して一体成形
されている請求項１，２又は３記載のメラミン樹脂化粧
シート。4. The melamine resin-impregnated paper and a metal foil and / or a thermoplastic resin sheet are integrally formed via an adhesive layer applied to one surface of the metal foil and / or the thermoplastic resin sheet. 4. The melamine resin decorative sheet according to 1, 2, or 3.
熱可塑性樹脂シートとが、フェノール樹脂含浸紙又はエ
ポキシ樹脂含浸紙を介して一体成形されている請求項
１，２又は３記載のメラミン樹脂化粧シート。5. The melamine resin according to claim 1, wherein the melamine resin-impregnated paper and the metal foil and / or the thermoplastic resin sheet are integrally formed via a phenol resin-impregnated paper or an epoxy resin-impregnated paper. Makeup sheet.
内側にして曲げた場合、曲げ半径１５ｍｍ以下である請
求項１，２，３，４又は５記載のメラミン樹脂化粧シー
ト。6. The melamine resin decorative sheet according to claim 1, wherein the bendability at room temperature is 15 mm or less when the decorative surface is bent outside or inside.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28263099A JP3789694B2 (en) | 1999-10-04 | 1999-10-04 | Melamine resin decorative sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28263099A JP3789694B2 (en) | 1999-10-04 | 1999-10-04 | Melamine resin decorative sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001096702A true JP2001096702A (en) | 2001-04-10 |
| JP3789694B2 JP3789694B2 (en) | 2006-06-28 |
Family
ID=17655029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28263099A Expired - Fee Related JP3789694B2 (en) | 1999-10-04 | 1999-10-04 | Melamine resin decorative sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3789694B2 (en) |
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