JP3468970B2 - Printed metal plate with excellent light resistance - Google Patents

Printed metal plate with excellent light resistance

Info

Publication number
JP3468970B2
JP3468970B2 JP04055696A JP4055696A JP3468970B2 JP 3468970 B2 JP3468970 B2 JP 3468970B2 JP 04055696 A JP04055696 A JP 04055696A JP 4055696 A JP4055696 A JP 4055696A JP 3468970 B2 JP3468970 B2 JP 3468970B2
Authority
JP
Japan
Prior art keywords
weight
transparent
coating film
metal plate
manufactured
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
Application number
JP04055696A
Other languages
Japanese (ja)
Other versions
JPH09206678A (en
Inventor
正樹 佐藤
和彦 高橋
博光 福本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Nisshin Co Ltd
Original Assignee
Nisshin Steel Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nisshin Steel Co Ltd filed Critical Nisshin Steel Co Ltd
Priority to JP04055696A priority Critical patent/JP3468970B2/en
Publication of JPH09206678A publication Critical patent/JPH09206678A/en
Application granted granted Critical
Publication of JP3468970B2 publication Critical patent/JP3468970B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Laminated Bodies (AREA)

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、フルカラー広告看板,
装飾用内装材,電化製品や什器の外板等として使用さ
れ、各種の印刷模様が付けられる小ロット多品種用途に
適した印刷塗装金属板に関する。
The present invention relates to a full-color advertising billboard,
The present invention relates to a printed coated metal plate suitable for use in a variety of small lots, which is used as an interior material for decoration, an outer panel of appliances and furniture, and has various printed patterns.

【0002】[0002]

【従来の技術】昇華性染料を使用して印刷塗装金属板を
製造する場合、オフセット,シルク,グラビア,転写等
の印刷法で昇華性染料を塗装金属板のトップクリヤー層
に印刷し、次いで加熱処理を施すことにより昇華性染料
をクリヤー塗膜中に浸透させている。たとえば、特開昭
51−24313号公報では、転写シートを硬化性合成
樹脂の塗布層に接触させて加熱している。特開昭54−
104907号公報では、塗装金属板上に昇華性染料を
用いた転写印刷で印刷層を形成した後、表面に更にトッ
プ塗膜を形成し、次いで加熱処理を施して塗膜の内側か
ら昇華性染料を浸透させることにより、模様を形成して
いる。また、特開平7−31931号公報では、鋼板表
面にプライマー塗膜及び有色トップ塗膜を形成したプリ
ペイント鋼板の塗膜に熱昇華性インクを浸透させてい
る。
2. Description of the Related Art When a printed coated metal plate is produced using a sublimable dye, the sublimable dye is printed on the top clear layer of the coated metal plate by a printing method such as offset, silk, gravure or transfer, and then heated. The treatment causes the sublimable dye to penetrate into the clear coating film. For example, in Japanese Patent Application Laid-Open No. 51-24313, a transfer sheet is heated by bringing it into contact with a coating layer of a curable synthetic resin. JP 54-
In Japanese Patent No. 104907, after a printing layer is formed on a coated metal plate by transfer printing using a sublimable dye, a top coating film is further formed on the surface, and then heat treatment is applied to the sublimation dye from the inside of the coating film. A pattern is formed by infiltrating. Further, in Japanese Patent Application Laid-Open No. 7-31931, a thermal sublimation ink is permeated into the coating film of a prepainted steel plate having a primer coating film and a colored top coating film formed on the steel plate surface.

【0003】[0003]

【発明が解決しようとする課題】昇華性染料を使用した
従来の印刷法では、何れもトップ塗膜中に昇華性染料を
浸透させて模様を形成している。昇華性染料は、通常、
極性の小さな分散染料又は油溶性染料であり、可塑剤,
有機薬品等で変質し易い。また、紫外線等の光によって
染料が分解され、変色又は褪色し易い。そのため、長期
間にわたって戸外に曝される使用環境では、安定した色
彩,模様等を維持することが難しい。光による変色や褪
色を防止するためには、紫外線吸収剤を塗料に配合する
ことが有効である。紫外線吸収剤は、一般的に塗料の不
揮発分に対して0.5〜3重量%の範囲で添加される。
因みに、ベンゾトリアゾール系紫外線吸収剤を塗料の不
揮発分に対して2.5重量%添加すると、厚み6μmの
透明塗膜中を透過する340nmの光は0.0001%
以下になる。しかし、このような条件下では、昇華性染
料で形成した模様の耐光性が不十分なため、内装用途に
特定しても適用が難しい。
In all of the conventional printing methods using a sublimable dye, the sublimable dye is permeated into the top coating film to form a pattern. Sublimable dyes are usually
Disperse dye or oil-soluble dye with small polarity, plasticizer,
It is easily deteriorated by organic chemicals. Further, the dye is decomposed by light such as ultraviolet rays, and discoloration or fading easily occurs. Therefore, it is difficult to maintain a stable color, pattern, etc. in a usage environment in which it is exposed outdoors for a long period of time. In order to prevent discoloration or fading due to light, it is effective to add an ultraviolet absorber to the paint. The ultraviolet absorber is generally added in the range of 0.5 to 3% by weight with respect to the nonvolatile content of the coating material.
By the way, if 2.5% by weight of the benzotriazole-based ultraviolet absorber is added to the non-volatile content of the paint, the light of 340 nm transmitted through the transparent coating film with a thickness of 6 μm is 0.0001%.
It becomes the following. However, under such conditions, the light resistance of the pattern formed by the sublimable dye is insufficient, and therefore it is difficult to apply even when specified for interior applications.

【0004】ところが、印刷に使用されるプレコート鋼
板の塗膜焼付け条件は、最高到達板温が200〜240
℃,保持時間1〜2分で、昇華性染料を塗膜中に浸透さ
せる転写条件が160〜190℃,1〜4分である。す
なわち、最終的に印刷塗装金属板を製造するまでに、紫
外線吸収剤は少なくとも2回、高温条件下に曝される。
このとき、一般に使用されているベンゾフェノン系又は
ベンゾトリアゾール系の紫外線吸収剤では、耐熱性,耐
昇華性に劣るため、塗膜中に含まれる紫外線吸収剤が昇
華によって減量する。紫外線吸収剤の減量は、昇華性染
料の変色や褪色に悪影響を及ぼすばかりでなく、紫外線
吸収剤の昇華に起因して塗膜表面が柚肌状態になって黄
変する現象が生じる。塗装する金属板が厚くなるほど塗
膜の焼付け条件,転写条件共に厳しくなることから、黄
変現象が顕著に現れる。
However, the conditions for baking the coating film of the pre-coated steel sheet used for printing are such that the maximum reached sheet temperature is 200 to 240.
The transfer conditions for permeating the sublimable dye into the coating film at 160 ° C. for 1 to 2 minutes are 160 to 190 ° C. for 1 to 4 minutes. That is, the ultraviolet absorber is exposed to high temperature conditions at least twice before finally producing the printed coated metal sheet.
At this time, generally used benzophenone-based or benzotriazole-based ultraviolet absorbers are inferior in heat resistance and sublimation resistance, and thus the amount of the ultraviolet absorber contained in the coating film is reduced by sublimation. The reduction of the amount of the ultraviolet absorber not only adversely affects the discoloration and fading of the sublimable dye, but also the phenomenon that the surface of the coating film becomes dull and turns yellow due to the sublimation of the ultraviolet absorber. The thicker the metal plate to be coated, the more severe the conditions for baking and transferring the coating film become, and the yellowing phenomenon appears remarkably.

【0005】100℃前後の低温で十分に昇華する染料
を選択するとき、転写時の昇華による紫外線吸収剤の減
少を大幅に低減することができる。しかし、低温で昇華
する染料は、分子量が小さく、耐光性,耐熱性が十分で
ない。逆に、耐光性,耐熱性の良好な昇華性染料は、高
温で昇温する。この点、耐光性を向上させる上からは、
理想的には昇華性染料をほぼその温度で昇華する染料に
特定し、可能な限り高温で昇華する昇華性染料を使用し
て昇華転写することが要求される。しかし、昇華性染料
の耐光性を向上させるとき、高い昇華温度が必要とさ
れ、塗膜中の紫外線吸収剤が昇華によって減少する。耐
昇華性,耐熱性に優れた紫外線吸収剤としては、芳香族
置換基等を導入した分子量が比較的大きなものが知られ
ている。この種の紫外線吸収剤を使用しても、通常の添
加量0.5〜3重量%では塗膜中に浸透した昇華性染料
の耐光性を屋内用途に使用可能なレベル、具体的にはサ
ンシャインカーボンアークウエザメータ63℃,240
時間,ΔE≦7まで向上させることができなかった。本
発明は、このような問題を解消すべく案出されたもので
あり、耐熱性,耐光性に優れた特定の紫外線吸収剤を従
来よりも多量に添加することにより、昇華性染料の変色
や褪色を防止し、長期間にわたって美麗な印刷模様を維
持することができる印刷塗装金属板を提供することを目
的とする。
When a dye that sublimes sufficiently at a low temperature of about 100 ° C. is selected, the reduction of the ultraviolet absorber due to sublimation during transfer can be greatly reduced. However, dyes that sublime at low temperatures have a small molecular weight and are insufficient in light resistance and heat resistance. On the contrary, a sublimable dye having good light resistance and heat resistance is heated at a high temperature. In this respect, from the viewpoint of improving light resistance,
Ideally, the sublimable dye should be specified as a dye that sublimes at approximately that temperature, and sublimation transfer using a sublimable dye that sublimes at a temperature as high as possible is required. However, when improving the light resistance of a sublimable dye, a high sublimation temperature is required, and the ultraviolet absorber in the coating film is reduced by the sublimation. Ultraviolet absorbers having excellent sublimation resistance and heat resistance are known to have a relatively large molecular weight introduced with an aromatic substituent or the like. Even if this kind of UV absorber is used, with the usual addition amount of 0.5 to 3% by weight, the light resistance of the sublimable dye that has penetrated into the coating film is at a level usable for indoor use, specifically, sunshine. Carbon arc weather meter 63 ℃, 240
The time could not be improved to ΔE ≦ 7. The present invention has been devised in order to solve such problems, heat resistance, by adding a large amount of a specific ultraviolet absorber excellent in light resistance than conventional, discoloration of the sublimable dye or An object of the present invention is to provide a printed and coated metal plate that can prevent fading and maintain a beautiful printed pattern for a long period of time.

【0006】[0006]

【課題を解決するための手段】本発明の印刷塗装金属板
は、その目的を達成するため、空気雰囲気中、昇温速度
5℃/分の加熱条件下、300℃で重量減少が10重量
%以下である熱安定性及び溶解性の良好なトリアジン系
の紫外線吸収剤、又は空気雰囲気中、昇温速度5℃/分
の加熱条件下、300℃で重量減少が10重量%以下で
あるベンゾトリアゾール系紫外線吸収剤を、塗料不揮発
分に対して6〜18重量%の割合で含有させた透明又は
半透明樹脂のトップ塗膜層が形成されており、該トップ
塗膜層に昇華性染料を浸透させたことを特徴とする。上
記トリアジン系紫外線吸収剤とベンゾトリアゾール系紫
外線吸収剤を複合して塗料不揮発分に対して6〜18重
量%の割合で含有させることができる。また、溶解性
は、キシレン,n−ブタノール,酢酸エチル等の溶媒1
00gに対して25g以上溶解するものが好ましい。
In order to achieve the object, the printed coated metal sheet of the present invention has a weight loss of 10% by weight at 300 ° C. under a heating condition of 5 ° C./min in an air atmosphere. The following is a triazine-based UV absorber having good thermal stability and solubility, or benzotriazole having a weight loss of 10% by weight or less at 300 ° C. under a heating condition of 5 ° C./min in an air atmosphere. A top coating layer of a transparent or semitransparent resin containing a UV absorber of 6 to 18% by weight with respect to the nonvolatile content of the coating is formed, and a sublimable dye is permeated into the top coating layer. It is characterized by having done. The triazine-based UV absorber and the benzotriazole-based UV absorber may be combined and contained in a proportion of 6 to 18% by weight with respect to the nonvolatile content of the coating material. In addition, the solubility is in solvent 1 such as xylene, n-butanol, ethyl acetate, etc.
It is preferable that 25 g or more dissolve in 00 g.

【0007】[0007]

【実施の形態】本発明に従った印刷塗装金属板は、図1
に示すようにめっき鋼板,ステンレス鋼板,アルミ板等
の下地金属板1の表面に透明又は半透明の樹脂層4を形
成している。下地金属板1としては、最外層に透明又は
半透明樹脂層4がある限り、白色ベースコート層2を設
けた塗装金属板(a),更にプライマー層3を形成した
塗装金属板(b),ベースコート層2やプライマー層3
がなく透明又は半透明樹脂層4だけがある塗装金属板
(c)等が使用される。下地金属板1やプライマー層3
の色調を隠すベースコート層2を設ける場合、白色に限
らず、他の色調をもったベースコート層を形成すること
ができる。ベースコート層2は、10〜20μmの塗膜
厚みをもつことが好ましい。膜厚が10μmに満たない
ベースコート層2では、下地金属板1やプライマー層3
の色調が十分に隠蔽されない。逆に20μmを超える厚
膜のベースコート層2では、焼付時に塗膜中に残留した
溶剤が急激に気化し、「わき」と呼ばれるピンホール状
の塗膜欠陥を発生させる虞れがある。
BEST MODE FOR CARRYING OUT THE INVENTION A printed coated metal plate according to the present invention is shown in FIG.
As shown in FIG. 3, a transparent or semi-transparent resin layer 4 is formed on the surface of a base metal plate 1 such as a plated steel plate, a stainless steel plate, and an aluminum plate. As the base metal plate 1, as long as the outermost layer has a transparent or semitransparent resin layer 4, a coated metal plate (a) provided with a white base coat layer 2, a coated metal plate (b) provided with a primer layer 3 and a base coat. Layer 2 and primer layer 3
A coated metal plate (c) or the like having no transparent or translucent resin layer 4 is used. Base metal plate 1 and primer layer 3
When the base coat layer 2 for hiding the color tone of is provided, the base coat layer having another color tone can be formed as well as the white color. The base coat layer 2 preferably has a coating film thickness of 10 to 20 μm. In the base coat layer 2 whose film thickness is less than 10 μm, the base metal plate 1 and the primer layer 3
The color tone of is not sufficiently hidden. On the contrary, in the thick base coat layer 2 having a thickness of more than 20 μm, the solvent remaining in the coating film is rapidly vaporized during baking, which may cause a pinhole-shaped coating film defect called “side”.

【0008】透明又は半透明樹脂層4には、転写シート
から移行してくる昇華性染料を受容して良く染まる染色
性樹脂である限り、その材質に制約を受けない。たとえ
ば、ポリビニルアルコール,ポリビニルブチラール,ポ
リビニルアセタール,ポリ酢酸ビニル,ポリ塩化ビニ
ル,ポリビニルピロリドン,ポリスチレン等のビニル系
樹脂,ポリメチル(メタ)アクリレート,ポリブチル
(メタ)アクリレート,ポリアクリルアミド,ポリアク
リロニトリル等のアクリレート系樹脂,ポリエステル樹
脂,ポリカーボネート樹脂,ポリスルホン樹脂,シリコ
ーンポリエステル樹脂,エポキシ樹脂等や、これらの共
重合体又は混合物等がある。なかでも、ポリエステル樹
脂は、昇華性染料に良く染まり、且つ得られる画像の保
存安定性にも良好であることから、染色性樹脂の少なく
とも一成分として含ませることが好ましい。
The transparent or semi-transparent resin layer 4 is not restricted in its material as long as it is a dyeable resin which can dye a sublimable dye transferred from a transfer sheet and dyes well. For example, polyvinyl-based resins such as polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyvinyl acetate, polyvinyl chloride, polyvinylpyrrolidone and polystyrene, acrylate-based resins such as polymethyl (meth) acrylate, polybutyl (meth) acrylate, polyacrylamide and polyacrylonitrile. Resins, polyester resins, polycarbonate resins, polysulfone resins, silicone polyester resins, epoxy resins, etc., and copolymers or mixtures of these. Among them, the polyester resin is preferable to be contained as at least one component of the dyeable resin, because it dyes well with the sublimable dye and also has good storage stability of the obtained image.

【0009】昇華性染料で予め模様を付けた転写シート
を下地金属板1に接触させて加熱すると、昇華した染料
が透明又は半透明樹脂4の中に浸透し、厚み方向に染着
した模様が形成される。転写シートは、グラビア印刷,
オフセット印刷,スクリーン印刷等によって作製され
る。また、小ロット印刷用には、製版工程を必要としな
いコンピュータグラフィックを用いた電子写真法,静電
記録法,インクジェット法,感熱転写法等を採用するこ
ともできる。昇華性染料は、加熱された際に昇華,揮発
等の減少によって透明又は半透明樹脂層4に転移しうる
染料であり、たとえばキノフタロン誘導体,アントラキ
ノン誘導体,アゾ系色素等の分散染料が好適に用いられ
る。また、従来から昇華熱転写,昇華転写捺染等に使用
されている染料は、特に制約なく使用することができ
る。
When a transfer sheet which is pre-patterned with a sublimable dye is brought into contact with the base metal plate 1 and heated, the sublimated dye penetrates into the transparent or translucent resin 4 and a pattern dyed in the thickness direction is formed. It is formed. Transfer sheet is gravure printing,
It is produced by offset printing, screen printing, etc. Further, for small lot printing, an electrophotographic method using a computer graphic which does not require a plate making process, an electrostatic recording method, an ink jet method, a thermal transfer method and the like can be adopted. The sublimable dye is a dye that can be transferred to the transparent or semitransparent resin layer 4 by being reduced in sublimation, volatilization, etc. when heated, and for example, disperse dyes such as quinophthalone derivative, anthraquinone derivative, and azo dye are preferably used. To be Further, dyes conventionally used for sublimation thermal transfer, sublimation transfer printing and the like can be used without particular limitation.

【0010】この種のイエロー系昇華染料としては、K
ayacet Yellow AG,Kayacet
Yellow TDN(日本化薬株式会社製),RTY
52,Dianix Yellow 5R−E, D
ianix YellowF3G−E, Dianix
Brilliant Yellow 5G−E(三菱
化学株式会社製),ブラストYellow 8040,
DY108(有本化学株式会社製),Sumikaro
n Yellow EFG,Sumikaron Ye
llow E−4GL(住友化学株式会社製),FOR
ON Brilliant Yellow SGGLP
I(Sand社製),PSイエローGG(三井東圧染料
株式会社製)等がある。
As this type of yellow sublimation dye, K
ayacet Yellow AG, Kayacet
Yellow TDN (Nippon Kayaku Co., Ltd.), RTY
52, Dianix Yellow 5R-E, D
ianix YellowF3G-E, Dianix
Brilliant Yellow 5G-E (manufactured by Mitsubishi Chemical Corporation), Blast Yellow 8040,
DY108 (manufactured by Arimoto Chemical Co., Ltd.), Sumikaro
n Yellow EFG, Sumikaron Ye
low E-4GL (Sumitomo Chemical Co., Ltd.), FOR
ON Brilliant Yellow SGGLP
I (manufactured by Sand), PS Yellow GG (manufactured by Mitsui Toatsu Dye Co., Ltd.) and the like.

【0011】マゼンタ系の昇華性染料としては、Kay
acet Red 026,Kayacet Red
130,Kayacet Red B(日本化薬株式会
社製),Oil Red DR−99,Oil Red
DK−99(有本化学株式会社製),Diacell
iton Pink B(三菱化学株式会社製),Su
mikaron Red E−FBL(住友化学株式会
社製),LatylRed B(Du Pont社
製),Sudan Red 7B(BASF社製),R
esolin Red FB,Ceres Red 7
B(Bayer社製)等がある。
As the magenta sublimation dye, Kay
acet Red 026, Kayacet Red
130, Kayacet Red B (manufactured by Nippon Kayaku Co., Ltd.), Oil Red DR-99, Oil Red.
DK-99 (manufactured by Arimoto Chemical Co., Ltd.), Diacell
iton Pink B (manufactured by Mitsubishi Chemical Corporation), Su
mikaron Red E-FBL (manufactured by Sumitomo Chemical Co., Ltd.), Layl Red B (manufactured by Du Pont), Sudan Red 7B (manufactured by BASF), R
esolin Red FB, Ceres Red 7
B (manufactured by Bayer) and the like.

【0012】シアン系の昇華染料には、Kayalon
Fast Blue FG,Kayalon Blu
e FR,Kayacet Blue 136,Kay
acet Blue 906(日本化薬株式会社製),
Oil Blue 63(有本化学株式会社製),HS
B9,RTB31(三菱化学株式会社製),Dispe
rse Blue #1(住友化学株式会社製),MS
Blue 50(三井東圧染料株式会社製),Cer
es Blue GN(Bayer社製),Duano
l Brilliant Blue 2G(ICI社
製)等がある。各色用の昇華性染料は、単独で使用して
も2種以上を併用して使用しても良い。黒色は、イエロ
ー,マゼンタ,シアン系の昇華性染料を適宜配合するこ
とにより得られる。イエロー,マゼンタ,シアン以外の
色調をもつ昇華性染料としては、昇華温度(液状状態か
ら揮発する場合も含む)が60℃以上の染料が好まし
い。昇華性染料を選択する際には、昇華温度の高い染料
の方が比較的分子量が大きく、優れた耐光性及び耐熱性
を示すことから好ましい。
For cyan dyes, Kayalon is used.
Fast Blue FG, Kayalon Blu
e FR, Kayacet Blue 136, Kay
acet Blue 906 (manufactured by Nippon Kayaku Co., Ltd.),
Oil Blue 63 (manufactured by Arimoto Chemical Co., Ltd.), HS
B9, RTB31 (manufactured by Mitsubishi Chemical Corporation), Dispe
rse Blue # 1 (Sumitomo Chemical Co., Ltd.), MS
Blue 50 (manufactured by Mitsui Toatsu Dye Co., Ltd.), Cer
es Blue GN (manufactured by Bayer), Duano
1 Brilliant Blue 2G (manufactured by ICI) and the like. The sublimable dyes for each color may be used alone or in combination of two or more. The black color is obtained by appropriately blending yellow, magenta and cyan sublimation dyes. As the sublimable dye having a color tone other than yellow, magenta, and cyan, a dye having a sublimation temperature (including a case of volatilizing from a liquid state) of 60 ° C. or higher is preferable. When selecting a sublimation dye, a dye having a high sublimation temperature is preferable because it has a relatively large molecular weight and exhibits excellent light resistance and heat resistance.

【0013】下地金属板1と接触した状態で転写シート
が加熱されると、転写シートに含まれている昇華性染料
が昇華し、図1に示すように透明又は半透明樹脂層4を
厚み方向に浸透する。そのため、厚み方向にほぼ均一に
染着された透明又は半透明樹脂層4で立体的な印刷模様
が発現される。得られた印刷模様は、透明又は半透明樹
脂層4の表層のみに昇華性染料が濃化したものでないた
め、擦れ等によって印刷薄れが生じることなく、また熱
転写で意匠を付与した後の転写印刷層を透明樹脂によっ
て保護する後工程も省略される。しかも、厚み方向にほ
ぼ均一に染着された透明又は半透明樹脂層4で印刷模様
が発現されるため、深み感,立体感,光沢度及び鮮映度
に優れた印刷模様が得られる。このようにして、必要な
模様を必要な時に簡便に付与できるため、各種模様付け
が要求される意匠鋼板の小ロット生産が容易になる。し
かも、所定の模様を付けた意匠鋼板として在庫する必要
がなくなり、ニーズに応じた模様付けが可能になる。ま
た、透明又は半透明樹脂層4と下地金属板1との間に染
料層が単独で存在していないので、従来のラミネート鋼
板にみられた層間剥離が生じない。
When the transfer sheet is heated while it is in contact with the underlying metal plate 1, the sublimable dye contained in the transfer sheet sublimes and the transparent or semitransparent resin layer 4 is formed in the thickness direction as shown in FIG. Penetrate into. Therefore, a three-dimensional printed pattern is developed by the transparent or semitransparent resin layer 4 dyed almost uniformly in the thickness direction. Since the obtained printed pattern does not have the sublimable dye concentrated only on the surface layer of the transparent or translucent resin layer 4, print thinning does not occur due to rubbing and the like, and transfer printing after applying a design by thermal transfer The subsequent step of protecting the layer with a transparent resin is also omitted. Moreover, since the printed pattern is developed by the transparent or semi-transparent resin layer 4 dyed almost uniformly in the thickness direction, a printed pattern excellent in depth feeling, three-dimensional effect, glossiness and sharpness can be obtained. In this way, the required pattern can be easily applied when needed, so that the small-lot production of the designed steel sheet that requires various patterns is facilitated. Moreover, it is not necessary to stock as a design steel sheet having a predetermined pattern, and it is possible to perform patterning according to needs. Further, since the dye layer alone does not exist between the transparent or semi-transparent resin layer 4 and the base metal plate 1, the delamination as seen in the conventional laminated steel sheet does not occur.

【0014】透明又は半透明樹脂層4には、転写時の1
50〜200℃の加熱で著しく軟化することのない熱硬
化型の樹脂を使用することが好ましい。このような樹脂
の使用により、熱転写で模様を付けた後に塗装金属板の
表面光沢が低下することがほとんどなくなる。透明又は
半透明樹脂層4の塗膜中には、太陽光線や紫外線の透過
による昇華性染料の褪色や透明又は半透明樹脂層4の光
沢低下を防止するため、透明又は半透明樹脂塗膜中に紫
外線吸収剤を添加している。紫外線吸収剤としては、ベ
ンゾトリアゾール系又はトリアジン系が使用される。好
ましくは、トリアジン系単独或いはトリアジン系とベン
ゾトリアゾール系とを複合して添加する。紫外線吸収剤
の配合量は、塗料不揮発分に対して6〜18重量%の範
囲に定められる。また、ヒンダートアミン系光安定剤を
0〜3.0重量%の割合で配合することが好ましい。
The transparent or semi-transparent resin layer 4 has a 1
It is preferable to use a thermosetting resin that does not significantly soften when heated at 50 to 200 ° C. By using such a resin, the surface gloss of the coated metal plate is hardly reduced after the pattern is formed by thermal transfer. In the coating film of the transparent or semitransparent resin layer 4, in order to prevent fading of the sublimable dye due to transmission of sunlight or ultraviolet rays and deterioration of the gloss of the transparent or semitransparent resin layer 4, UV absorber is added to. A benzotriazole-based or triazine-based UV absorber is used. Preferably, the triazine type is added alone or the triazine type and the benzotriazole type are added in combination. The blending amount of the ultraviolet absorber is determined within the range of 6 to 18% by weight with respect to the nonvolatile content of the coating material. Further, it is preferable to add a hindered amine light stabilizer in a proportion of 0 to 3.0% by weight.

【0015】トリアジン系は、熱安定性の高いベンゾト
リアゾール系とほぼ同等の熱安定性を示し、且つベンゾ
トリアゾール系に比較して有機溶剤に対する溶解性が高
い。一般に熱安定性の高いベンゾトリアゾールは、溶解
性が低いため6重量%以上の添加が難しく、たとえ添加
できたとしても塗料を保存している間に紫外線吸収剤が
析出する可能性が高い。これに対し、トリアジン系は、
熱安定性が高いにも拘らず溶解性が高いため、6重量%
以上の添加が容易であり、塗料の貯蔵安定性に優れてい
る。また、塗膜を屋外に暴露すると、塗膜中の紫外線吸
収剤が徐々に抜け出る傾向を示すが、トリアジン系とベ
ンゾトリアゾール系とを比較するとトリアジン系がより
安定で塗膜から抜けにくい特性を呈する。透明又は半透
明樹脂層4に含ませる紫外線吸収剤としては、耐熱性,
耐昇華性及び溶解性に優れていることが要求される。耐
熱性は、空気雰囲気中,昇温速度5℃/分の加熱条件下
において300℃で重量減少が10重量%以下であるこ
とが好ましい。
The triazine-based material exhibits almost the same thermal stability as the benzotriazole-based material having high thermal stability, and has a higher solubility in an organic solvent than the benzotriazole-based material. In general, benzotriazole, which has high thermal stability, has a low solubility, so that it is difficult to add 6 wt% or more, and even if it can be added, the ultraviolet absorber is likely to be deposited during the storage of the paint. In contrast, the triazine type
6% by weight due to high solubility despite high thermal stability
The above additions are easy and the storage stability of the paint is excellent. Also, when the coating film is exposed to the outdoors, the ultraviolet absorber in the coating film tends to gradually escape, but when comparing the triazine type and the benzotriazole type, the triazine type shows more stable and hard to escape from the coating film. . As the ultraviolet absorber contained in the transparent or semitransparent resin layer 4, heat resistance,
It is required to have excellent sublimation resistance and solubility. Regarding the heat resistance, it is preferable that the weight loss is not more than 10% by weight at 300 ° C. under a heating condition of 5 ° C./min in an air atmosphere.

【0016】ベンゾトリアゾール系の紫外線吸収剤に
は、オクチル−3−[3−t−ブチル−5−(2H−ベ
ンゾトリアゾ−ル−2−イル)]−4−ヒドロキシフェ
ニル]プロピネート(チバガイギー社製 TINUVI
N 384),2−[2−ヒドロキシ−3,5−ビス
(α,α’ジメチルベンジル)フェニル]−2H−ベン
ゾトリアゾール(チバガイギー社製 TINUVIN
900),メチル−3−[3−t−ブチル−5−(2H
−ベンゾトリアゾール−2−イル)]−4−ヒドロキシ
フェニル]プロピネート−ポリエチレングリコール(分
子量約300)との縮合物(チバガイギー社製 TIN
UVIN 1130),2−[2’−ヒドロキシ−3’
−(3”,4”,5”,6”−テトラヒドロフタルイミ
ドメチル)−5’−メチルフェニル]−ベンゾトリアゾ
ール(共同薬品株式会社製 Viosorb 590)
等が挙げられる。
The benzotriazole-based ultraviolet absorber includes octyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl)]-4-hydroxyphenyl] propinate (TINUVI manufactured by Ciba-Geigy).
N 384), 2- [2-hydroxy-3,5-bis (α, α 'dimethylbenzyl) phenyl] -2H-benzotriazole (manufactured by Ciba-Geigy TINUVIN)
900), methyl-3- [3-t-butyl-5- (2H
-Benzotriazol-2-yl)]-4-hydroxyphenyl] propinate-polyethylene glycol (molecular weight about 300) condensate (TIN manufactured by Ciba-Geigy)
UVIN 1130), 2- [2'-hydroxy-3 '
-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] -benzotriazole (Kyoyaku Co., Ltd. Biosorb 590)
Etc.

【0017】トリアジン系紫外線吸収剤には、たとえば
2−[4−[(2−ヒドロキシ−3−ジデシルオキシプ
ロピル)−オキシ]−2−ヒドロキシフェニル]−4,
6−ビス(2,4−ジメチルフェニル)−1,3,5−
トリアジンと2−[4−[(2−ヒドロキシ−3−トリ
デシルオキシプロピル)−オキシ]−2−ヒドロキシフ
ェニル]−4,6−ビス(2,4−ジメチルフェニル)
−1,3,5−トリアジンの混合物(チバガイギー社製
TINUVIN400)がある。これら紫外線吸収剤
は、単独でも、2種以上を混合しても使用することがで
きる。紫外線吸収剤の配合量は、塗料の不揮発分100
重量部に対して6〜18重量部に調整することが好まし
い。6重量%に満たない配合量では、透明又は半透明樹
脂層4に浸透した昇華性染料の耐光性が不十分となる。
逆に、18重量%を超える配合量では、塗膜の耐汚染
性,加工性,塗膜外観等が劣化する。また、紫外線吸収
剤によるトップ塗膜の着色も観察される。屋内用途とし
て必要な耐光性は、シアン色,マゼンタ色,イエロー色
の中で最も耐光性の低いシアン色でサンシャインカーボ
ンアークウエザメータ(63℃),240時間,ΔE≦
7が要求される。この条件を満足させるためには、紫外
線吸収剤を6重量%以上添加することが必要である。塗
膜を屋外に暴露すると紫外線吸収剤が徐々に抜け出る傾
向を示すが、6重量%以上添加することにより屋外で2
〜3年以上,屋内用途では十分な耐光性を保持できる。
したがって、塗膜中に6重量%以上の紫外線吸収剤を添
加することは、透明又は半透明樹脂層4の光沢低下及び
ベースコート層2の変色を防止するという通常のクリヤ
ー塗装に対する要求特性を満足するだけでなく、透明又
は半透明樹脂層4に浸透した昇華性染料の耐光安定性を
屋内用途で十分な程度まで向上させることになる。
Examples of the triazine-based UV absorber include 2- [4-[(2-hydroxy-3-didecyloxypropyl) -oxy] -2-hydroxyphenyl] -4,
6-bis (2,4-dimethylphenyl) -1,3,5-
Triazine and 2- [4-[(2-hydroxy-3-tridecyloxypropyl) -oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)
There is a mixture of -1,3,5-triazine (TINUVIN 400 manufactured by Ciba Geigy). These ultraviolet absorbers can be used alone or in combination of two or more. The amount of UV absorber blended is 100% of the nonvolatile content of the paint.
It is preferably adjusted to 6 to 18 parts by weight with respect to parts by weight. If the amount is less than 6% by weight, the light resistance of the sublimable dye that has penetrated into the transparent or semitransparent resin layer 4 will be insufficient.
On the contrary, if the blending amount exceeds 18% by weight, the stain resistance, workability, appearance of the coating film and the like deteriorate. Further, coloring of the top coating film by the ultraviolet absorber is also observed. The light resistance required for indoor use is the lowest light resistance cyan color among cyan color, magenta color, and yellow color. Sunshine carbon arc weather meter (63 ° C), 240 hours, ΔE ≦
7 is required. In order to satisfy this condition, it is necessary to add an ultraviolet absorber in an amount of 6% by weight or more. When the coating film is exposed to the outdoors, the UV absorber tends to come out gradually.
For more than 3 years, it can maintain sufficient light resistance for indoor use.
Therefore, the addition of 6% by weight or more of the ultraviolet absorber to the coating film satisfies the required characteristics for ordinary clear coating of preventing the gloss reduction of the transparent or translucent resin layer 4 and the discoloration of the base coat layer 2. Not only that, the light resistance stability of the sublimable dye that has penetrated into the transparent or semi-transparent resin layer 4 is improved to a sufficient degree for indoor use.

【0018】紫外線吸収剤は、塗料の溶剤として一般に
使用されているキシレン,n−ブタノール,酢酸エチル
等の有機溶媒に対する溶解度の高いものが好ましい。特
に、本発明では多量の紫外線吸収剤を配合させることか
ら、析出による貯蔵安定性の低下及び塗膜物性の低下を
防止するために、キシレン,n−ブタノール,酢酸エチ
ル等の溶媒100gに対して25g以上溶解するものが
好ましい。有機溶媒に対する溶解度の低い紫外線吸収剤
では、塗料の不揮発分に対して6重量%以上の割合で配
合することが困難であり、添加後も析出し易く、塗料の
貯蔵安定性が低下する傾向を示す。透明又は半透明樹脂
層4の耐光性を更に向上させるため、必要に応じてヒン
ダートアミン系の光安定剤を塗料不揮発分に対して0〜
3重量%の割合で配合させることが好ましい。ヒンダー
トアミン系の光安定剤には、次のものが挙げられる。
The ultraviolet absorber is preferably one having a high solubility in an organic solvent such as xylene, n-butanol, ethyl acetate or the like which is generally used as a solvent for paints. In particular, in the present invention, a large amount of an ultraviolet absorber is blended, and in order to prevent deterioration of storage stability and physical properties of a coating film due to precipitation, it is necessary to add 100 g of a solvent such as xylene, n-butanol, ethyl acetate, etc. It is preferable to dissolve 25 g or more. It is difficult to mix 6% by weight or more of the ultraviolet absorber having a low solubility in an organic solvent with respect to the non-volatile content of the coating, and it tends to precipitate even after the addition and the storage stability of the coating tends to decrease. Show. In order to further improve the light resistance of the transparent or semi-transparent resin layer 4, a hindered amine-based light stabilizer may be added in an amount of 0 to the nonvolatile content of the coating as necessary.
It is preferable to add 3% by weight. The hindered amine-based light stabilizers include the following.

【0019】ビス(2,2,6,6−テトラメチル−4
−ピペリジル)セバケート(三共株式会社製 SANO
L LS770),ビス(1,2,2,6,6−ペンタ
メチル−4−ピペリジル)セバケート(三共株式会社製
SANOL LS765),1−{2−[3−(3,
5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピ
オニルオキシ]エチル}−4−[3−(3,5−ジ−t
−ブチル−4−ヒドロキシフェニル)プロピオニルオキ
シ]−2,2,6,6−テトラメチルピペリジン(三共
株式会社製 SANOL LS2626),4−ベンゾ
イルオキシ−2,2,6,6−テトラメチルピペリジン
(三共株式会社製 SANOL LS744),8−ア
セチル−3−ドデシル−7,7,9,9−テトラメチル
−1,3,8−トリアザスピロ[4,5]デカン−2,
4−ジオン(三共株式会社製 SANOL LS44
0),2−(3,5−ジ−t−ヒドロキシベンジル)−
2−n−ブチルマロン酸ビス(1,2,2,6,6−ペ
ンタメチル−4−ピペリジル)(チバガイギー社製 T
INUVIN 144),コハク酸ビス(2,2,6,
6−テトラメチル−4−ピペリジル)エステル(チバガ
イギー社製 TINUVIN 780FF),コハク酸
ジメチルと1−(2−ヒドロキシエチル)−4−ヒドロ
キシ−2,2,6,6−テトラメチルピペリジンの重縮
合物(チバガイギー社製 TINUVIN 622L
D),ポリ{[6−(1,1,3,3−テトラメチルブ
チル)アミノ−1,3,5−トリアジン−2,4−ジイ
ル][(2,2,6,6−テトラメチル−4−ピペリジ
ル)イミノ]ヘキサメチレン[(2,2,6,6−テト
ラメチル−4−ピペリジル)イミノ]}(チバガイギー
社製CHIMASSORB 944LD),N,N’−
ビス(3−アミノプロピル)エチレンジアミンと2,4
−ビス[N−ブチル−N−(1,2,2,6,6−ペン
タメチル−4−ピペリジル)アミノ]−6−クロロ−
1,3,5−トリアジンの重縮合物(チバガイギー社製
CHIMASSORB 119FL),ビス(1,
2,2,6,6−ペンタメチル−4−ピペリジル)セバ
ケート(チバガイギー社製 TINUVIN 29
2),ビス(1−オクタオキシ−2,2,6,6−テト
ラメチル−4−ピペリジル)セバケート(チバガイギー
社製 TINUVIN 123),HA−70G(三共
株式会社製),アデカスタブ LA−52,アデカスタ
ブ LA−57,アデカスタブ LA−62,アデカス
タブ LA−63,アデカスタブ LA−67,アデカ
スタブ LA−68,アデカスタブ LA−82,アデ
カスタブ LA−87(旭電化工業株式会社製)
Bis (2,2,6,6-tetramethyl-4
-Piperidyl) Sebacate (Sankyo SANO
L LS770), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (SANOL LS765 manufactured by Sankyo Co., Ltd.), 1- {2- [3- (3,3.
5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl} -4- [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine (SANYO LS2626 manufactured by Sankyo Co., Ltd.), 4-benzoyloxy-2,2,6,6-tetramethylpiperidine (Sankyo) SANOL LS744), 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,
4-Zion (SANYO LS44 manufactured by Sankyo Co., Ltd.)
0), 2- (3,5-di-t-hydroxybenzyl)-
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2-n-butylmalonate (Ciba Geigy T
INUVIN 144), bis succinate (2, 2, 6,
6-Tetramethyl-4-piperidyl) ester (TINUVIN 780FF manufactured by Ciba-Geigy), a polycondensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine. (TINUVIN 622L manufactured by Ciba Geigy)
D), poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl- 4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]} (CHIMASORB 944LD manufactured by Ciba-Geigy), N, N'-
Bis (3-aminopropyl) ethylenediamine and 2,4
-Bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-
Polycondensate of 1,3,5-triazine (CHIMASORB 119FL manufactured by Ciba Geigy), bis (1,
2,2,6,6-Pentamethyl-4-piperidyl) sebacate (TINUVIN 29 manufactured by Ciba Geigy)
2), bis (1-octaoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (TINUVIN 123 manufactured by Ciba-Geigy), HA-70G (manufactured by Sankyo Co., Ltd.), ADK STAB LA-52, ADK STAB LA -57, ADEKA STAB LA-62, ADEKA STAB LA-63, ADEKA STAB LA-67, ADEKA STAB LA-68, ADEKA STAB LA-82, ADEKA STAB LA-87 (manufactured by Asahi Denka Kogyo Co., Ltd.)

【0020】これらの光安定剤は、単独でも或いは2種
以上を混合しても使用できる。安定剤の配合量を3.0
重量%より多量にしても、塗膜中に浸透した昇華性染料
の耐光性を向上させる効果が飽和し、増量に見合った改
善がみられず、逆に塗装外観が劣化する傾向を示す。光
安定剤は、好ましくは0.5〜1.5重量%の範囲で配
合される。透明又は半透明樹脂層4としての透明樹脂塗
膜は、ベースコート層2を介して(図1a)、ベースコ
ート層2及びプライマー層3を介して(図1b)、或い
は下地金属板1に直接(図1c)形成することができ
る。何れの場合も、下地金属板1やベースコート層2の
色調が地模様となり、染着樹脂層5を通して現れる。そ
のため、下地素材の風合いを活かした独特の深み感をも
った意匠性金属板が製造される。
These light stabilizers can be used alone or in admixture of two or more. Stabilizer content of 3.0
Even if the amount is more than 10% by weight, the effect of improving the light resistance of the sublimable dye that has penetrated into the coating film is saturated, the improvement commensurate with the increase in amount is not observed, and on the contrary, the coating appearance tends to deteriorate. The light stabilizer is preferably added in the range of 0.5 to 1.5% by weight. The transparent resin coating film as the transparent or semi-transparent resin layer 4 is provided through the base coat layer 2 (FIG. 1a), the base coat layer 2 and the primer layer 3 (FIG. 1b), or directly on the base metal plate 1 (see FIG. 1c) can be formed. In any case, the color tone of the base metal plate 1 and the base coat layer 2 becomes a ground pattern and appears through the dyeing resin layer 5. Therefore, a designable metal plate with a unique depth feeling that makes use of the texture of the base material is manufactured.

【0021】[0021]

【実施例】【Example】

実施例1(本発明例1〜9,比較例1〜6)下地金属板として使用する塗装鋼板の製造 板厚0.5mmのZnめっき鋼板に塗装前処理を施し、
白色ポリエステル系樹脂塗料(関西ペイント株式会社製
AT−1001プライマー)を乾燥塗膜厚みで18μ
mになるように塗装した後、板温220℃で1分間焼き
付けることにより白色ベースコート樹脂塗膜を形成し
た。次いで、トリアジン系紫外線吸収剤(チバガイギー
社製 TINUVIN 400)を塗料不揮発分に対し
2〜20重量%及びヒンダートアミン系光安定剤(チバ
ガイギー社製 TINUVIN 123)を0〜7.0
重量%を含むポリエステル系クリヤー樹脂塗料(関西ペ
イント株式会社製 AT−1005プライマー)を乾燥
膜厚で15μmとなるように塗装した後、板温210℃
で1分間焼き付けることにより、透明樹脂塗膜を形成し
た。なお、トリアジン系紫外線吸収剤は、熱重量分析の
結果、空気雰囲気中,昇温速度5℃/分の加熱条件下、
300℃で重量減少が3.5重量%であった。
Example 1 (Invention Examples 1 to 9 and Comparative Examples 1 to 6) Production of Painted Steel Sheet Used as Base Metal Sheet A Zn-plated steel sheet having a thickness of 0.5 mm was subjected to coating pretreatment,
White polyester resin paint (AT-1001 primer manufactured by Kansai Paint Co., Ltd.) is 18μ in dry film thickness.
After coating so as to have a thickness of m, a white base coat resin coating film was formed by baking at a plate temperature of 220 ° C. for 1 minute. Next, a triazine-based UV absorber (TINUVIN 400 manufactured by Ciba-Geigy) is used in an amount of 2 to 20% by weight based on the nonvolatile content of the paint, and a hindered amine-based light stabilizer (TINUVIN 123 manufactured by Ciba-Geigy) is used in an amount of 0 to 7.0.
A polyester clear resin paint (AT-1005 primer manufactured by Kansai Paint Co., Ltd.) containing 10 wt% was applied so that the dry film thickness was 15 μm, and then the plate temperature was 210 ° C.
A transparent resin coating film was formed by baking for 1 minute. In addition, as a result of thermogravimetric analysis, the triazine-based ultraviolet absorber was found to have a heating rate of 5 ° C./min in an air atmosphere,
At 300 ° C., the weight loss was 3.5% by weight.

【0022】昇華性染料を使用した模様の転写 シアン色の昇華性染料(三菱化学株式会社製 RTB3
1 C.I.Disperse Blue 26)から
作製した昇華性染料トナー(新日鐵化学株式会社製 昇
華捺染用トナー)を用い、静電記録方式の画像プリント
システム(Exis社製 Juna)で静電記録紙にシ
アン色のベタ模様を出力した。得られた静電記録紙を塗
装鋼板の塗装面に重合せ、温度165℃及び圧力0.5
kg/cm2 で150秒間加熱圧着した。圧着完了後、
塗装鋼板から静電記録紙を剥離した。なお、ほぼ同様の
条件で昇華するシアン色,マゼンタ色,イエロー色の染
料の耐光性を比較すると、最も耐光性が低いものはシア
ン色であった。そこで、紫外線吸収剤及び光安定剤の添
加効果を、シアン色の耐光性で比較した。
Transfer of Pattern Using Sublimation Dye Cyan sublimation dye (RTB3 manufactured by Mitsubishi Chemical Corporation)
1 C. I. Using a sublimation dye toner (toner for sublimation printing manufactured by Nippon Steel Chemical Co., Ltd.) prepared from Disperse Blue 26), an electrostatic recording type image print system (Juna manufactured by Exis) A solid pattern was output. The obtained electrostatic recording paper is polymerized on the coated surface of the coated steel sheet, and the temperature is 165 ° C. and the pressure is 0.5.
It was thermocompression-bonded at 150 kg / cm 2 for 150 seconds. After crimping,
The electrostatic recording paper was peeled off from the coated steel plate. When the cyan, magenta, and yellow dyes that sublimate under almost the same conditions were compared in terms of light resistance, the one with the lowest light resistance was cyan. Therefore, the effect of adding the ultraviolet absorber and the light stabilizer was compared by the light resistance of cyan color.

【0023】実施例2(本発明例10〜14,比較例7
〜9)下地金属板として使用する塗装鋼板の製造 トリアジン系紫外線吸収剤に替えてベンゾトリアゾール
系紫外線吸収剤(チバガイギー社製 TINUVIN
384)を塗料揮発分に対して0〜20重量%配合し、
ヒンダートアミン系光安定剤(チバガイギー社製 TI
NUVIN123)の配合量を1.5重量%の一定に維
持した外は、実施例1の塗装鋼板を同じものを使用し
た。なお、ベンゾトリアゾール系紫外線吸収剤は、熱重
量分析の結果、空気雰囲気中,昇温速度5℃/分の加熱
条件下、300℃で重量減少が5.0重量%であった。昇華性染料を使用した模様の転写 実施例1と同じ昇華性染料を使用し、同様な方法で塗装
鋼板に模様を転写した。
Example 2 (Invention Examples 10 to 14 and Comparative Example 7)
~ 9) Manufacture of a coated steel sheet used as a base metal plate. Instead of the triazine-based UV absorber, a benzotriazole-based UV absorber (TINUVIN manufactured by Ciba-Geigy)
384) in an amount of 0 to 20% by weight based on the volatile content of the paint,
Hindered amine light stabilizer (TIVA manufactured by Ciba Geigy)
The same coated steel sheet of Example 1 was used except that the compounding amount of NUVIN 123) was kept constant at 1.5% by weight. As a result of thermogravimetric analysis, the benzotriazole-based ultraviolet absorber had a weight loss of 5.0% by weight at 300 ° C. in an air atmosphere under heating conditions of 5 ° C./min. Transfer of Pattern Using Sublimation Dye The same sublimation dye as in Example 1 was used and a pattern was transferred to a coated steel sheet by the same method.

【0024】実施例3(比較例10〜13)下地金属板として使用する塗装鋼板の製造 トリアジン系紫外線吸収剤に替えてベンゾフェノン系紫
外線吸収剤(共同薬品株式会社製 Viosorb13
0)を塗料不揮発分に対して0〜10重量%配合し、ヒ
ンダートアミン系光安定剤(チバガイギー社製 TIN
UVIN123)の配合量を1.5重量%の一定に維持
した外は、実施例1と同じ塗装鋼板を使用した。なお、
ベンゾフェノン系紫外線吸収剤は、熱重量分析の結果、
空気雰囲気中,昇温速度5℃/分の加熱条件下、300
℃で重量減少が33重量%であった。昇華性染料を使用した模様の転写 実施例1と同じ昇華性染料を使用し、同様な方法で塗装
鋼板に模様を転写した。
Example 3 (Comparative Examples 10 to 13) Production of Painted Steel Sheet Used as Base Metal Sheet A benzophenone type ultraviolet absorber (Kyoyaku Co., Ltd., Biosorb 13) was used in place of the triazine type ultraviolet absorber.
0) in an amount of 0 to 10% by weight based on the nonvolatile content of the paint, and a hindered amine light stabilizer (TIN manufactured by Ciba Geigy).
The same coated steel sheet as in Example 1 was used except that the compounding amount of UVIN123) was kept constant at 1.5% by weight. In addition,
Benzophenone-based UV absorbers are the result of thermogravimetric analysis,
300 in an air atmosphere at a heating rate of 5 ° C / min.
The weight loss at 0 ° C was 33% by weight. Transfer of Pattern Using Sublimation Dye The same sublimation dye as in Example 1 was used and a pattern was transferred to a coated steel sheet by the same method.

【0025】以上のように製造した各印刷塗装金属板に
対して耐光性,塗膜密着性,加工性,耐湿性,耐汚染性
及び耐疵付き性を調査した。調査結果を表1(本発明
例)及び表2(比較例)に示す。表1及び表2における
各性質は、次のように試験し評価した。 耐光性試験 試験温度を63℃に設定したサンシャインカーボンアー
クウエザメータ(60分照射中に12分間清水吹付け)
中で240時間経過後の試験板と未照射試験板との色差
ΔEを表示した。なお、240時間後の色差ΔE≧7で
は内装用として実用に供することが難しい。 塗膜密着性試験 碁盤目エリクセン(JIS G3320に規定されてい
る碁盤目を入れ、6mm押し出す)試験を行い、粘着性
テープの剥離に伴って剥離した塗膜を5段階評価した。
The light resistance, coating adhesion, workability, moisture resistance, stain resistance, and scratch resistance of each of the printing-coated metal plates produced as described above were investigated. The results of the investigation are shown in Table 1 (invention example) and Table 2 (comparative example). Each property in Table 1 and Table 2 was tested and evaluated as follows. Light resistance test Sunshine carbon arc weather meter with test temperature set at 63 ° C (spraying with fresh water for 12 minutes during irradiation for 60 minutes)
The color difference ΔE between the test plate and the non-irradiated test plate after 240 hours was displayed. If the color difference ΔE ≧ 7 after 240 hours, it is difficult to put it into practical use for interior use. Coating-Film Adhesion Test A cross-cut Erichsen (a cross-cut specified in JIS G3320 is inserted and extruded by 6 mm) test was carried out, and the coating film peeled along with the peeling of the adhesive tape was evaluated on a five-point scale.

【0026】加工性試験 20℃の室内で0〜6tの180度折り曲げ加工(試験
片と同じ厚みの板を1枚挟んだ場合が1)を施し、曲げ
の程度に応じた塗膜のクラック発生状況を調査した。塗
膜にクラックが発生しなかったもの及び0〜2tで塗膜
にクラックが発生したものを◎,3〜4tで塗膜にクラ
ックが発生したものを○,5tで塗膜にクラックが発生
したものを△,6tで塗膜にクラックが発生したものを
×として評価した。なお、○以上であれば、プレコート
用鋼板として実用に供しえる。 耐疵付き性試験 JIS K5400−8.4に基づき、鉛筆(三菱鉛筆
株式会社製 三菱ユニ)を用いた疵付き法で評価した。
評価は、疵が付かない限界の鉛筆硬度で表示した。 耐汚染製試験 油性のマジックペン(赤,黒)で線を描き、20℃で2
4時間放置した後、メタノールで拭き取り、痕跡が全く
ないものを5,痕跡が若干残るものを3,痕跡が著しい
ものを1として5段階評価した。なお、油性の赤マジッ
クペンで2点以上であれば、プレコート用鋼板として実
用に供しえる。
Workability test A 0 ° to 6t 180 ° bending process (1 when one plate having the same thickness as the test piece is sandwiched) was performed in a room at 20 ° C., and cracks in the coating film depending on the degree of bending. I investigated the situation. Those with no cracks in the coating film and those with cracks in the coating film at 0 to 2t are ⊚, those with cracks in the coating film with 3 to 4t are ◯, cracks in the coating film at 5t The sample was evaluated as Δ, and the sample having cracks in the coating film was evaluated as x, and evaluated as x. If it is ◯ or more, it can be put to practical use as a steel sheet for precoating. Scratch resistance test Based on JIS K5400-8.4, it was evaluated by a scratching method using a pencil (Mitsubishi Uni from Mitsubishi Pencil Co., Ltd.).
The evaluation is indicated by the pencil hardness, which is the limit without scratches. Draw a line with a stain-resistant test oil-based magic pen (red, black), and 2 at 20 ℃
After leaving it for 4 hours, it was wiped off with methanol, and a sample having no trace was evaluated as 5, a sample having a slight trace was 3, and a sample having a remarkable trace was 1 as 5 grades. In addition, if it is two or more points with an oil-based red magic pen, it can be practically used as a precoat steel plate.

【0027】耐湿性 JIS Z0208に準拠し、試験温度49℃に設定し
た湿潤試験を500時間継続し、塗膜にフクレが発生し
ないものを◎,発生したものを×として評価した。 塗装外観 平滑で一様な外観が得られることを指標にして、非常に
よいものを◎,問題のないものを○,多少の柚肌又は色
ムラ,曇り等があるものを△,明確な柚肌又は色ムラ,
曇り等があるものを×として評価した。
Moisture resistance According to JIS Z0208, a wetting test set at a test temperature of 49 ° C. was continued for 500 hours, and the case where no blistering occurred in the coating film was evaluated as ⊚, and the case where it occurred was evaluated as x. Appearance of the coating is very good, ◎, there is no problem, ○, there is some yuzu skin or color unevenness, cloudiness etc. △, clear yuzu Uneven skin or color,
Those with cloudiness were evaluated as x.

【0028】 [0028]

【0029】 [0029]

【0030】表1と表2との対比から明らかなように、
本発明に従った表1では、耐光性,塗膜密着性,加工
性,耐疵付き性,耐湿性等については何れも十分満足す
る特性を呈した。耐汚染性は、紫外線吸収剤の配合量が
多くなるに従って劣化する傾向が示されたが、過酷な耐
汚染性が要求される用途でない限り十分使用可能なレベ
ルにあった。これに対し、表2の比較例では、No.1〜
3,7,8,10〜13が耐光性に劣り、サンシャイン
カーボンアークウエザメータ240時間経過時点でシア
ン色の色差ΔEが8以上であった。紫外線吸収剤を20
重量%配合したNo.4,9では、耐汚染性,塗装外観が
大幅に低下した。光安定剤を5〜7重量%配合したNo.
5,6では、塗膜性能に関する要求が満足されるもの
の、塗装外観が悪く、塗膜表面に柚肌状の凹凸が観察さ
れた。また、光安定剤の配合割合を5〜7重量%に増加
したことによる耐光性向上効果がほとんど観察されなか
った。ベンゾフェノン系紫外線吸収剤を3〜12重量%
配合したNo.10〜13は、何れも耐光性に劣り、サン
シャインカーボンアークウエザメータ240時間経過時
点でシアン色の色差ΔEが17以上であった。また、塗
膜外観も極端に悪く、塗膜の黄変及び柚肌状の凹凸が観
察された。更に、塗膜焼成及び模様転写時の加熱によっ
て塗膜中から紫外線吸収剤の昇華が観察された。
As is clear from the comparison between Table 1 and Table 2,
In Table 1 according to the present invention, all of the light resistance, coating adhesion, workability, scratch resistance, moisture resistance, etc. exhibited sufficiently satisfactory characteristics. The stain resistance tended to deteriorate as the blending amount of the ultraviolet absorber increased, but it was at a level at which it could be used unless the application requires severe stain resistance. On the other hand, in the comparative example of Table 2, No. 1-
3, 7, 8, 10 to 13 were inferior in light resistance, and the cyan color difference ΔE was 8 or more after 240 hours of sunshine carbon arc weather meter. 20 UV absorbers
In No. 4 and 9 which were blended by weight, the stain resistance and the coating appearance were significantly deteriorated. No. containing 5 to 7 wt% of light stabilizer.
In Nos. 5 and 6, the requirements for coating film performance were satisfied, but the coating appearance was poor, and rugged skin-like irregularities were observed on the coating film surface. In addition, almost no effect of improving the light resistance due to the increase of the compounding ratio of the light stabilizer to 5 to 7% by weight was observed. 3-12% by weight of benzophenone UV absorber
All of the blended Nos. 10 to 13 were inferior in light resistance, and the color difference ΔE of the cyan color was 17 or more after 240 hours of sunshine carbon arc weather meter. In addition, the appearance of the coating film was extremely poor, and yellowing of the coating film and ruggedness like citrus were observed. Further, sublimation of the ultraviolet absorber was observed in the coating film by baking the coating film and heating during pattern transfer.

【0031】[0031]

【発明の効果】以上に説明したように、本発明の印刷塗
装金属板は、熱的特性の優れたトリアジン系紫外線吸収
剤又はベンゾトリアゾール系紫外線吸収剤を配合した透
明又は半透明の樹脂層に昇華性染料を浸透させて印刷模
様を形成している。そのため、耐光性に優れた印刷模様
が得られ、長期間にわたる紫外線照射に曝される環境に
おいても変色や褪色のない鮮明な模様が持続される。こ
のようにして得られた印刷塗装金属板は、意匠性に優れ
たフルカラー広告看板,装飾用内装材,電化製品や什器
の外板等として使用される。
As described above, the printed and coated metal sheet of the present invention has a transparent or semitransparent resin layer containing a triazine-based UV absorber or a benzotriazole-based UV absorber having excellent thermal properties. A sublimation dye is infiltrated to form a printed pattern. Therefore, a printed pattern having excellent light resistance can be obtained, and a clear pattern without discoloration or fading can be maintained even in an environment exposed to ultraviolet irradiation for a long period of time. The printed and coated metal plate thus obtained is used as a full-color advertising sign having excellent design, an interior material for decoration, an outer plate of electric appliances and furniture, and the like.

【図面の簡単な説明】[Brief description of drawings]

【図1】 本発明に従った印刷塗装金属板の表層部断面
を示し、ベースコート層上に昇華性染料染着層を設けた
例(a),プライマー層及びベースコート層上に昇華性
染料染着層を設けた例(b),下地金属板上に昇華性染
料染着層を直接設けた例(c)
FIG. 1 is a cross-sectional view of a surface layer portion of a printed and coated metal plate according to the present invention, showing an example (a) in which a sublimation dye dyeing layer is provided on a base coat layer, a sublimation dye dyeing on a primer layer and a base coat layer. Example (b) in which a layer is provided, and example (c) in which a sublimable dye dyeing layer is directly provided on a base metal plate

───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平7−31931(JP,A) 特開 平6−47338(JP,A) 実開 昭55−23770(JP,U) (58)調査した分野(Int.Cl.7,DB名) B05D 1/00 - 7/26 B32B 1/00 - 35/00 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-7-31931 (JP, A) JP-A-6-47338 (JP, A) Actual development Sho 55-23770 (JP, U) (58) Investigation Field (Int.Cl. 7 , DB name) B05D 1/00-7/26 B32B 1/00-35/00

Claims (3)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 空気雰囲気中、昇温速度5℃/分の加熱
条件下、300℃で重量減少が10重量%以下である熱
安定性及び溶解性の良好なトリアジン系紫外線吸収剤
を、塗料不揮発分に対して6〜18重量%の割合で含有
させた透明又は半透明樹脂のトップ塗膜層が形成されて
おり、該トップ塗膜層に昇華性染料を浸透させた印刷塗
装金属板。
1. A heating rate of 5 ° C./min in an air atmosphere
Heat that loses less than 10% by weight at 300 ° C under conditions
Triazine UV absorber with good stability and solubility
Containing 6 to 18% by weight with respect to the nonvolatile content of the paint.
Transparent or top coating layer of a translucent resin is formed, printed coated metal sheet impregnated with sublimable dyes to the top coating layer was.
【請求項2】 空気雰囲気中、昇温速度5℃/分の加熱
条件下、300℃で重量減少が10重量%以下である熱
安定性及び溶解性の良好なベンゾトリアゾール系紫外線
吸収剤を、塗料不揮発分に対して6〜18重量%の割合
で含有させた透明又は半透明樹脂のトップ塗膜層が形成
されており、該トップ塗膜層に昇華性染料を浸透させた
印刷塗装金属板。
2. A heating rate of 5 ° C./min in an air atmosphere
Heat that loses less than 10% by weight at 300 ° C under conditions
Benzotriazole-based UV rays with good stability and solubility
Absorbent in a proportion of 6 to 18% by weight with respect to the nonvolatile content of the paint
The top coating layer of transparent or translucent resin contained in
A printing coated metal plate having a sublimable dye penetrated into the top coating layer .
【請求項3】 空気雰囲気中、昇温速度5℃/分の加熱
条件下、300℃で重量減少が10重量%以下である熱
安定性及び溶解性の良好なトリアジン系紫外線吸収剤と
空気雰囲気中、昇温速度5℃/分の加熱条件下、300
℃で重量減少が10重量%以下である熱安定性及び溶解
性の良好なベンゾトリアゾール系紫外線吸収剤を、複合
して塗料不揮発分に対して6〜18重量%の割合で含有
させた透明又は半透明樹脂のトップ塗膜層が形成されて
おり、該トップ塗膜層に昇華性染料を浸透させた印刷塗
装金属板。
3. A heating rate of 5 ° C./min in an air atmosphere
Heat that loses less than 10% by weight at 300 ° C under conditions
Triazine-based UV absorber with good stability and solubility
300 in an air atmosphere under heating conditions of a heating rate of 5 ° C / min.
Thermal stability and dissolution with weight loss of less than 10% by weight at ℃
A benzotriazole type UV absorber with good properties
And contained in a proportion of 6 to 18% by weight based on the nonvolatile content of the paint.
The top coating layer of transparent or translucent resin is formed
And a printing-coated metal plate in which a sublimable dye is impregnated into the top coating film layer .
JP04055696A 1996-02-02 1996-02-02 Printed metal plate with excellent light resistance Expired - Fee Related JP3468970B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP04055696A JP3468970B2 (en) 1996-02-02 1996-02-02 Printed metal plate with excellent light resistance

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP04055696A JP3468970B2 (en) 1996-02-02 1996-02-02 Printed metal plate with excellent light resistance

Publications (2)

Publication Number Publication Date
JPH09206678A JPH09206678A (en) 1997-08-12
JP3468970B2 true JP3468970B2 (en) 2003-11-25

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
JP04055696A Expired - Fee Related JP3468970B2 (en) 1996-02-02 1996-02-02 Printed metal plate with excellent light resistance

Country Status (1)

Country Link
JP (1) JP3468970B2 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5990188A (en) * 1996-08-15 1999-11-23 General Electric Company Radiation curable coatings with improved weatherability
US6746986B1 (en) 2000-04-24 2004-06-08 Nisshin Steel Co., Ltd. Painted metal sheet for printing with a sublimation dye
JP4843852B2 (en) * 2001-02-28 2011-12-21 旭硝子株式会社 Paint composition

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