JPH05138122A - Production of decorative metallic plate - Google Patents
Production of decorative metallic plateInfo
- Publication number
- JPH05138122A JPH05138122A JP30906591A JP30906591A JPH05138122A JP H05138122 A JPH05138122 A JP H05138122A JP 30906591 A JP30906591 A JP 30906591A JP 30906591 A JP30906591 A JP 30906591A JP H05138122 A JPH05138122 A JP H05138122A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- coating
- coating film
- pigment
- 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
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、貼紙あるいは落書等を
人為的に容易に剥すことが可能で、かつ高硬度で、曲げ
加工性等に優れた意匠柄仕上げの化粧金属板の製造方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a decorative metal sheet having a design pattern finish, which is capable of easily peeling off a paper sticker or a letter, and has a high hardness and excellent bending workability. It is a thing.
【0002】[0002]
【従来の技術】従来、車輌等の内壁、天井への落書によ
る汚染を防止する手段として、その素材である金属板を
成形加工した後、ホ−ロ−仕上げする方法、もしくは無
機塗料あるいは特開昭55−132662号公報に見ら
れるように貼紙防止塗料を塗装する方法がとられてい
た。2. Description of the Related Art Conventionally, as a means for preventing contamination by accidental writing on the inner wall or ceiling of a vehicle or the like, a method of forming a metal plate, which is a material thereof, and then hollow-finishing it, or an inorganic coating or As seen in Japanese Patent Laid-Open No. 55-132662, a method of applying an anti-paper-sticking paint has been used.
【0003】[0003]
【発明が解決しようとする課題】しかしながら、上記従
来技術によれば、金属板を成形加工した後に塗装を行な
うため、塗装作業性が悪く、また切断あるいはわずかな
曲げ加工によっても塗膜のワレやハガレが生じやすく、
さらに平滑性のある塗膜が形成しにくく、意匠柄仕上げ
も困難であった。また、特公平3−44820号公報に
見られるような高硬度で、曲げ加工性等に優れたプレコ
−トメタルの製造方法も開発されてきているが、この場
合もメラミン化粧板の如き意匠柄仕上げが困難であると
いう問題点があった。However, according to the above-mentioned prior art, since the coating is performed after the metal plate is formed, the workability of the coating is poor, and even if the coating is broken or slightly bent, the coating film may be broken. Easy to peel off,
Further, it was difficult to form a coating film having smoothness, and it was also difficult to finish the design pattern. Further, a method for producing a pre-coated metal having a high hardness as shown in Japanese Patent Publication No. 3-44820 and excellent in bending workability has also been developed. In this case as well, a design pattern finish such as a melamine decorative board is finished. There was a problem that it was difficult.
【0004】本発明はこのような現状に鑑みて鋭意研究
したもので、塗装作業性がよく、また切断、曲げ加工時
にも塗膜のワレやハガレを生じにくく、かつ貼紙あるい
は落書等を人為的に容易に剥すことができる塗膜を有す
る意匠柄仕上げが可能となる化粧金属板の製造方法を提
供することを目的とする。The present invention has been earnestly studied in view of such a situation as described above, has good coating workability, is less likely to cause cracks or peeling of a coating film even during cutting or bending, and is not suitable for paper sticking or lettering. An object of the present invention is to provide a method for producing a decorative metal plate that enables a design pattern finish having a coating film that can be easily peeled off.
【0005】[0005]
【課題を解決するための手段】上記目的を達成するため
本発明に係る化粧金属板の製造方法は、必要に応じ化成
処理等の下地処理を行なった金属板上に、ガラス転移温
度5〜70℃、数平均分子量4500〜35000のポ
リエステル樹脂と硬化剤であるアミノプラスト樹脂と、
前記ポリエステル樹脂及び硬化剤の合計量100重量部
に対し、顔料30〜100重量部と有機溶剤必要量とか
らなり、顔料分散度がグラインドゲ−ジA法15μm以
下の下塗塗料を乾燥膜厚3〜10μmになるように塗装
し、焼付乾燥し、次いで、ガラス転移温度60〜200
℃、数平均分子量5000〜100000、重量平均分
子量20000〜150000のアクリル樹脂と硬化剤
であるアミノプラスト樹脂と、前記アクリル樹脂及び硬
化剤の合計量100重量部に対し、着色顔料50〜15
0重量部、平均粒径5μm以下の硬質体質顔料5〜50
重量部及び高沸点エ−テルアルコ−ル類を含む有機溶剤
必要量とからなり、顔料分散度がグラインドゲ−ジA法
15μm以下の中塗塗料を乾燥膜厚10〜30μmにな
るように塗装し、次いで、中塗塗膜上に、模様状印刷を
全面もしくは部分的に施し、焼付乾燥し、次いで、全面
に、ガラス転移温度60〜200℃、数平均分子量15
000〜100000、重量平均分子量20000〜1
50000のアクリル樹脂と硬化剤であるアミノプラス
ト樹脂と、前記アクリル樹脂及び硬化剤の合計量100
重量部に対し、平均粒径30μm以下の硬質体質顔料3
0〜80重量部、シリコ−ン油0.01〜10重量部及
び高沸点エ−テルアルコ−ル類を含む有機溶剤必要量と
からなるクリヤ−塗料を乾燥膜厚10〜30μmになる
よう塗装し、焼付乾燥して、硬度9H以上の塗膜を有す
る化粧金属板を製造するものである。In order to achieve the above object, a method for producing a decorative metal plate according to the present invention is such that a glass transition temperature of 5 to 70 is applied to a metal plate which has been subjected to a surface treatment such as chemical conversion treatment if necessary. C., a polyester resin having a number average molecular weight of 4,500 to 35,000 and an aminoplast resin as a curing agent,
Based on 100 parts by weight of the total amount of the polyester resin and the curing agent, 30 to 100 parts by weight of the pigment and the necessary amount of the organic solvent are used, and the degree of dispersion of the pigment is 15 μm or less of the Grindage A method. Painted to 10 μm, baked and dried, then glass transition temperature 60-200
50 ° C., a color pigment of 50 to 15 per 100 parts by weight of the acrylic resin having a number average molecular weight of 5,000 to 100,000 and a weight average molecular weight of 20,000 to 150,000 and a curing agent, aminoplast resin, and the acrylic resin and the curing agent.
0 parts by weight, hard extender pigment having an average particle size of 5 μm or less 5 to 50
And a necessary amount of an organic solvent containing a high boiling point ether alcohol, and a pigment dispersity is applied so that a dry film thickness of 10 to 30 μm is obtained by applying an intermediate coating composition having a pigment dispersity of 15 μm or less. Then, the intermediate coating film is subjected to pattern printing on the entire surface or a part thereof and baked and dried, and then the entire surface is subjected to a glass transition temperature of 60 to 200 ° C. and a number average molecular weight of 15
000 to 100,000, weight average molecular weight 20,000 to 1
50,000 acrylic resin and aminoplast resin which is a curing agent, and the total amount of the acrylic resin and the curing agent is 100.
Hard extender pigment 3 having an average particle size of 30 μm or less with respect to parts by weight
A clear coating composition consisting of 0 to 80 parts by weight, 0.01 to 10 parts by weight of silicone oil, and a necessary amount of an organic solvent containing high boiling ether alcohols is applied to a dry film thickness of 10 to 30 μm. Then, it is baked and dried to produce a decorative metal plate having a coating film having a hardness of 9H or more.
【0006】以下、本発明の構成をさらに詳細に説明す
る。本発明において使用する下塗塗料は、ポリエステル
樹脂、硬化剤でアミノプラスト樹脂、顔料及び有機溶剤
を主成分とし、さらに必要に応じ各種添加剤、改質剤等
からなるもので、化粧金属板の塗膜の加工性と密着性を
高めるためのものである。The structure of the present invention will be described in more detail below. The undercoat paint used in the present invention comprises a polyester resin, a curing agent, an aminoplast resin, a pigment and an organic solvent as main components, and if necessary, various additives and modifiers. This is for improving the workability and adhesion of the film.
【0007】前記ポリエステル樹脂は、多価カルボン酸
類と多価アルコ−ル類とを公知の方法で重合することに
より得られるものである。多価カルボン酸としては、例
えばアジピン酸、テレフタル酸、イソフタル酸、無水フ
タル酸、ヘキサヒドロ無水フタル酸、無水トリメリット
酸、無水マレイン酸、無水コハク酸などが使用され、ま
た多価アルコ−ルとしては、例えばネオペンチルグリコ
−ル、エチレングリコ−ル、プロピレングリコ−ル、ジ
エチレングリコ−ル、グリセリン、トリメチロ−ルプロ
パン、トリメチロ−ルエタン、ペンタエリスリト−ル、
ビスフェノ−ルAなどが使用される。このポリエステル
樹脂は、ガラス転移温度(以下、単にTgという)が5
〜70℃、好ましくは15〜65℃、数平均分子量(以
下、単にMnという)は4500〜35000、好まし
くは5000〜20000のものが好適である。なお、
上記Tgが5℃未満では、密着性が不十分となり、かつ
上塗後の塗膜硬度が低くなり、またTgが70℃を越え
る場合及びMnが4500未満の場合では、後加工時、
特に切断時において端部の塗膜がハガレ易くなり、また
Mnが35000を越えると、有機溶剤に溶解しにくく
なり平滑な塗膜が得にくくなるため、いずれの場合も好
ましくない。また、ポリエステル樹脂の酸価は、5以
下、水酸基価10〜50のものが好適で、この範囲で加
工性、密着性、耐食性等の優れた塗膜が得られる。The polyester resin is obtained by polymerizing a polyvalent carboxylic acid and a polyvalent alcohol by a known method. As the polyvalent carboxylic acid, for example, adipic acid, terephthalic acid, isophthalic acid, phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, maleic anhydride, succinic anhydride, etc. are used, and as the polyvalent alcohol. Are, for example, neopentyl glycol, ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol,
Bisphenol A or the like is used. This polyester resin has a glass transition temperature (hereinafter, simply referred to as Tg) of 5
The number average molecular weight (hereinafter, simply referred to as Mn) is preferably from 4500 to 35000, and more preferably from 5000 to 20000. In addition,
If the Tg is less than 5 ° C, the adhesion will be insufficient and the hardness of the coating film after topcoating will be low, and if the Tg exceeds 70 ° C and the Mn is less than 4500, the post-processing will be
In particular, at the time of cutting, the coating film on the end portion is easily peeled off, and when Mn exceeds 35000, it is difficult to dissolve in an organic solvent and it is difficult to obtain a smooth coating film. The acid value of the polyester resin is preferably 5 or less and the hydroxyl value is 10 to 50, and in this range, a coating film having excellent processability, adhesion, corrosion resistance and the like can be obtained.
【0008】前記アミノプラスト樹脂は、メラミン、尿
素、ベンゾグアナミン等のアミノ化合物とアルデヒド化
合物との縮合生成物あるいは該縮合生成物をさらにメタ
ノ−ル、ブタノ−ル等のアルコ−ルでエ−テル化したも
のである。ポリエステル樹脂とアミノプラスト樹脂の固
形分配合割合は重量比で(70/30〜85/15)が
適当で、この範囲で本来の樹脂特性を発揮することがで
きる。The aminoplast resin is a condensation product of an amino compound such as melamine, urea or benzoguanamine and an aldehyde compound, or the condensation product is further etherified with an alcohol such as methanol or butanol. It was done. The solid content ratio of the polyester resin and the aminoplast resin is appropriately (70/30 to 85/15) by weight ratio, and the original resin characteristics can be exhibited in this range.
【0009】前記顔料は、酸化チタン、ベンガラ、フタ
ロシアニンブル−等の通常の塗料用着色顔料、カオリ
ン、沈降性硫酸バリウム、タルク等の通常の塗料用体質
顔料を使用でき、さらに防錆性を付加するためにクロム
酸ストロンチウム等の通常の塗料用防錆顔料も併用する
ことが望ましい。この顔料は、前記ポリエステル樹脂及
び硬化剤の合計量100重量部に対し30〜100重量
部配合するのが望ましく、そのうち防錆顔料を5〜10
重量部配合するのが望ましい。As the above-mentioned pigment, a usual coloring pigment for paints such as titanium oxide, red iron oxide, phthalocyanine blue and the like, an extender pigment for usual paints such as kaolin, barium sulfate precipitating and talc can be used, and rust preventive property is added. Therefore, it is desirable to use an ordinary rust preventive pigment for paint such as strontium chromate. This pigment is preferably added in an amount of 30 to 100 parts by weight, based on 100 parts by weight of the total amount of the polyester resin and the curing agent.
It is desirable to blend in parts by weight.
【0010】前記有機溶剤は、トルエン、キシレン、メ
チルイソブチルケトン、セロソルブ、エチレングリコ−
ルモノブチルエ−テル、シクロヘキサノン等の通常塗料
用に使用されているものを使用できる。この有機溶剤
は、塗装作業性に合せて下塗塗料の粘度が40〜120
秒(フォ−ドカップ#4/室温)になるように配合す
る。The organic solvent is toluene, xylene, methyl isobutyl ketone, cellosolve, ethylene glycol-
What is normally used for paints, such as rumonobutyl ether and cyclohexanone, can be used. This organic solvent has a viscosity of 40 to 120 depending on the coating workability.
Blend for seconds (Food cup # 4 / room temperature).
【0011】本発明で使用する下塗塗料は以上の構成成
分からなり、この塗料は練合分散し、顔料分散度がグラ
インドゲ−ジA法15μm以下とする。なお、15μm
を越えると塗膜にブツの発生等が見られるようになるの
で好ましくない。なお、本発明において下塗塗料とし
て、アクリル樹脂系あるいはエポキシ樹脂系塗料も検討
したが、切断加工時あるいは曲げ加工時に塗膜のワレ,
ハガレが生じやすいので不適当であった。The undercoat paint used in the present invention comprises the above-mentioned constituents. This paint is kneaded and dispersed so that the pigment dispersity is 15 μm or less by the Grindge A method. 15 μm
If it exceeds the range, it is not preferable because the coating film is likely to have spots. In the present invention, an acrylic resin-based or epoxy resin-based coating was also examined as the undercoating paint, but cracks in the coating film during cutting or bending,
It was unsuitable because peeling easily occurred.
【0012】次に、本発明において使用する中塗塗料
は、アクリル樹脂、硬化剤であるアミノプラスト樹脂、
着色顔料、硬質体質顔料及び有機溶剤を主成分とし、さ
らに必要に応じ各種添加剤、改質剤等からなるものであ
る。Next, the intermediate coating used in the present invention is an acrylic resin, a curing agent such as aminoplast resin,
The main component is a coloring pigment, a hard extender pigment, and an organic solvent, and if necessary, various additives and modifiers.
【0013】前記アクリル樹脂は、官能基を有するモノ
マ−3〜40重量%と官能基を有しないモノマ−97〜
60重量%を通常の溶液重合法にて共重合させたものが
望ましい。なお、前者が40重量%を越えると硬化剤と
の反応が過大に起り、後工程の印刷工程での印刷適性が
悪くなったり、上塗クリヤ−塗膜との密着性が低下する
傾向にある。前記官能基を有するモノマ−としては、ア
クリル酸、メタクリル酸、アクリルアマイド、ブチルア
クリルアマイド、イソプロピルアクリルアマイド、イソ
ノニルアクリルアマイド、イソオクチルアクリルアマイ
ド、N−イソプロピルアクリルアマイド、N,Nジイソ
プロピルアクリルアマイド、N,Nジメチルアクリルア
マイド、N−メチル−N−フエニルアクリルアマイド、
モルフオリルアクリルアマイド、ピペリジルアクリルア
マイド、2ヒドロキシエチルメタクリレ−ト、2ヒドロ
キシプロピルメタクリレ−ト、4エトキシカルボニルフ
エニルアクリレ−ト、4メトキシカルボニルフエニルメ
タクリレ−ト、4−ブトキシカルボニルフエニルメタク
リルアマイド、4−カルボニルフエニルメタクリルアマ
イド、4−エトキシカルボニルフエニルメタクリルアマ
イド、4−メトキシカルボニルフエニルメタクリルアマ
イド、ブチルクロロアクリレ−ト、ブチルシアノアクリ
レ−ト、ヘキシルクロロアクリレ−ト、ペンタクロロフ
エニルアクリレ−ト、メトキシカルボニルフエニルアク
リレ−ト等が使用され、またスチレン系としては、2−
(2−ジメチルアミノエトキシカルボニ−ル)スチレ
ン、4−(2−ジメチルアミノエトキシカルボニル)ス
チレン、2−フエニルアミノカルボニルスチレン、2及
び4−プロポキシカルボニルスチレン、4−プロポキシ
メチルスチレン、4−プロポキシスルホニルスチレン等
が使用される。また非官能基モノマ−としては、4−ビ
フエニルアクリレ−ト、ブチルアクリレ−ト、ブチルフ
エニルアクリレ−ト、ヘキサデシルアクリレ−ト、イソ
ボミルアクリレ−ト、ナフチルアクリレ−ト、フエニル
アクリレ−ト、トリルアクリレ−ト、アダマンチルメタ
クリレ−ト、ベンチルメタクリレ−ト、t−ブチルメタ
クリレ−ト、エチルメタクリレ−ト、イソブチルメタク
リレ−ト、イソプロピルメタクリレ−ト、3,5ジメチ
ルラダマンチルメタクリレ−ト、3,3ジメチルブチル
メタクリレ−ト、3,3−ジメチル2−ブチルメタクリ
レ−ト、メチルメタクリレ−ト、トリメチルシリルメタ
クリレ−ト、フエニルメタクリレ−ト、プロピルメタク
リレ−ト等が使用され、またスチレン系としては、α−
メチルスチレン、2−メチルスチレン、3−メチルスチ
レン、4−メチルスチレン、ジメチルスチレン、トリメ
チルスチレン、4−フエニルスチレン、スチレン等が使
用される。The acrylic resin is a monomer having a functional group-3 to 40% by weight and a monomer having no functional group-97 to
It is desirable that 60% by weight is copolymerized by a normal solution polymerization method. If the amount of the former exceeds 40% by weight, the reaction with the curing agent will occur excessively, the printability in the subsequent printing step tends to deteriorate, and the adhesion with the clear top coat film tends to decrease. Examples of the monomer having a functional group include acrylic acid, methacrylic acid, acrylic amide, butyl acrylic amide, isopropyl acrylic amide, isononyl acrylic amide, isooctyl acrylic amide, N-isopropyl acrylic amide, N, N diisopropyl acrylic amide, N, N dimethyl acrylic amide, N-methyl-N-phenyl acrylic amide,
Morpholyl acrylate, piperidyl acrylate, 2 hydroxyethyl methacrylate, 2 hydroxypropyl methacrylate, 4 ethoxycarbonylphenyl acrylate, 4 methoxycarbonyl phenyl methacrylate, 4-butoxycarbonyl Phenyl methacrylic amide, 4-carbonyl phenyl methacrylic amide, 4-ethoxycarbonyl phenyl methacrylic amide, 4-methoxy carbonyl phenyl methacrylic amide, butyl chloro acrylate, butyl cyano acrylate, hexyl chloro acrylate , Pentachlorophenyl acrylate, methoxycarbonylphenyl acrylate, etc. are used.
(2-Dimethylaminoethoxycarbonyl) styrene, 4- (2-dimethylaminoethoxycarbonyl) styrene, 2-phenylaminocarbonylstyrene, 2 and 4-propoxycarbonylstyrene, 4-propoxymethylstyrene, 4-propoxy. Sulfonylstyrene and the like are used. As the non-functional group monomer, 4-biphenyl acrylate, butyl acrylate, butyl phenyl acrylate, hexadecyl acrylate, isobomyl acrylate, naphthyl acrylate. , Phenyl acrylate, tolyl acrylate, adamantyl methacrylate, benzyl methacrylate, t-butyl methacrylate, ethyl methacrylate, isobutyl methacrylate, isopropyl methacrylate, 3, 5 dimethyl radadamantyl methacrylate, 3,3 dimethyl butyl methacrylate, 3,3-dimethyl 2-butyl methacrylate, methyl methacrylate, trimethylsilyl methacrylate, phenyl methacrylate , Propyl methacrylate, etc. are used, and as the styrene type, α-
Methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, dimethylstyrene, trimethylstyrene, 4-phenylstyrene, styrene and the like are used.
【0014】上記したモノマ−組成により従来一般に行
なわれている溶液重合法にて重合されたアクリル樹脂
は、Tgが60〜200℃,好ましくは70〜160
℃、Mnが5000〜100000,好ましくは600
0〜80000、重量平均分子量(以下、単にMwとい
う)が20000〜150000,好ましくは2000
0〜80000のものが好適である。なお、Tgが60
℃未満では塗膜硬度が低く、逆に200℃を越えると塗
膜の平滑性が悪くなり、かつ切断時において塗膜がワレ
を生じやすくなるので好ましくない。また、Mnが50
00未満では塗膜硬度が低く、加工性においても低下傾
向に有り、逆に100000を越えると塗膜の平滑性が
悪くなるので好ましくない。さらにMwが20000未
満ではロ−ルコ−タ−塗装に必要なピックアップ特性
(ペイントパンよりピックアップロ−ルが塗料を持ち上
げる性質)が悪く、例えば30m/min以上の連続塗
装が不可能となり、逆に150000を越えると塗膜の
平滑性が悪くなるので好ましくない。The Tg of the acrylic resin polymerized by the heretofore commonly used solution polymerization method with the above-mentioned monomer composition is 60 to 200 ° C., preferably 70 to 160.
C, Mn of 5,000 to 100,000, preferably 600
0 to 80,000, weight average molecular weight (hereinafter, simply referred to as Mw) of 20,000 to 150,000, preferably 2,000
Those of 0 to 80,000 are preferable. In addition, Tg is 60
If the temperature is lower than 0 ° C, the hardness of the coating film is low. On the contrary, if the temperature exceeds 200 ° C, the smoothness of the coating film is deteriorated and the coating film is apt to crack during cutting, which is not preferable. Also, Mn is 50
If it is less than 00, the hardness of the coating film is low and the workability tends to decrease. On the contrary, if it exceeds 100,000, the smoothness of the coating film is deteriorated, which is not preferable. Further, if the Mw is less than 20000, the pick-up characteristics required for roll coater coating (the property that the pick-up roll lifts the paint from the paint pan) are poor, and continuous coating at a speed of 30 m / min or more becomes impossible. If it exceeds 150,000, the smoothness of the coating film deteriorates, which is not preferable.
【0015】また、アクリル樹脂は、酸価2〜15、水
酸基価15〜60のものが好適で、この範囲でアミノプ
ラスト樹脂との十分なる反応により硬度等のある塗膜が
得られる。前記アミノプラスト樹脂は、前記下塗塗料に
使用したものと同様のものを使用できるが、特にアクリ
ル樹脂との相溶性のよいヘキサメトキシメチルエテ−ル
化メラミン縮合物等が好ましい。市販品としては、例え
ば住友化学工業社製のスミマ−ル30S,40S,50
S;三井東圧化学社製のサイメル303,305,30
7,325,370;三和ケミカル社製のニカラックM
X45,ニカラック001;日立化成工業社製のメラン
230等が挙げられる。The acrylic resin preferably has an acid value of 2 to 15 and a hydroxyl value of 15 to 60. Within this range, a coating film having hardness and the like can be obtained by sufficient reaction with the aminoplast resin. As the aminoplast resin, the same ones as those used in the undercoat paint can be used, but hexamethoxymethyl etherified melamine condensate having a good compatibility with an acrylic resin is particularly preferable. Examples of commercially available products include Summar 30S, 40S, 50 manufactured by Sumitomo Chemical Co., Ltd.
S; Cymel 303, 305, 30 manufactured by Mitsui Toatsu Chemicals, Inc.
7,325,370; Sanwa Chemical Nikarac M
X45, Nikarac 001; Melan 230 manufactured by Hitachi Chemical Co., Ltd., and the like.
【0016】アクリル樹脂とアミノプラスト樹脂の固形
分配合割合は、重量比で(60/40〜80/20)が
適当で、この範囲で本来の樹脂特性を発揮することがで
きる。The mixing ratio of the solid contents of the acrylic resin and the aminoplast resin is appropriate (60/40 to 80/20) by weight ratio, and the original resin characteristics can be exhibited within this range.
【0017】前記着色顔料は、通常塗料用に使用されて
いる着色顔料を利用でき、その配合量は前記アクリル樹
脂及び硬化剤の合計量100重量部に対し、50〜15
0重量部が適当である。なお、着色顔料が前記範囲より
少ないと充分なる隠蔽力が得られず、逆に多過ぎると塗
面の平滑性が低下し、後工程における良好なる印刷が困
難となる。前記硬質体質顔料は、塗膜硬度を向上させる
ために配合するものであり、無水硅酸、炭化硅素、ガラ
ス、アルミナ等の平均粒径5μm以下のモ−ス硬度6.
5以上の体質顔料が適当である。硬質体質顔料は前記ア
クリル樹脂及び硬化剤の合計量100重量部に対し、5
〜50重量部が適当である。5重量部未満では塗膜硬度
向上への寄与が少なく、逆に50重量部を越えると塗面
の平滑性が低下し、後工程における良好なる印刷が困難
となる。As the color pigment, a color pigment usually used for paints can be used, and the compounding amount thereof is 50 to 15 with respect to 100 parts by weight of the total amount of the acrylic resin and the curing agent.
0 parts by weight is suitable. When the amount of the coloring pigment is less than the above range, sufficient hiding power cannot be obtained. On the contrary, when the amount of the coloring pigment is too large, the smoothness of the coated surface is deteriorated, and good printing in the subsequent step becomes difficult. The above-mentioned hard extender is blended to improve the hardness of the coating film, and the hardness of silicic acid anhydride, silicon carbide, glass, alumina or the like having an average particle size of 5 μm or less is 6.
Extender pigments of 5 or more are suitable. The hard extender pigment is 5 parts with respect to 100 parts by weight of the total amount of the acrylic resin and the curing agent.
-50 parts by weight is suitable. When the amount is less than 5 parts by weight, the contribution to the improvement of the coating film hardness is small. On the contrary, when the amount is more than 50 parts by weight, the smoothness of the coated surface is deteriorated and it becomes difficult to perform good printing in the subsequent step.
【0018】なお、本発明においてロ−ルコ−タ−塗装
の場合、ピックアップ特性を向上させるために中塗塗料
組成物中に、比表面積(BET法)50m2 /g以下,
平均粒径0.06μm以下の超微粒沈降性硫酸バリウム
を体質顔料として配合するのが望ましく、その配合量は
前記アクリル樹脂及び硬化剤の合計量100重量部に対
し、10〜30重量部が適当である。なお、前記超微粒
沈降性硫酸バリウムの市販品としては、例えば堺化学社
製のBF−1,10,20等がある。In the present invention, in the case of roll coater coating, a specific surface area (BET method) of 50 m 2 / g or less is contained in the intermediate coating composition in order to improve pickup characteristics.
It is desirable to add ultrafine precipitated barium sulfate having an average particle diameter of 0.06 μm or less as an extender pigment, and the amount thereof is 10 to 30 parts by weight per 100 parts by weight of the total amount of the acrylic resin and the curing agent. Is. Commercially available products of the ultrafine-grain precipitated barium sulfate include, for example, BF-1, 10, 20 manufactured by Sakai Chemical Co., Ltd.
【0019】前記有機溶剤は、塗装作業性に合せて中塗
塗料の粘度が40〜120秒(フォ−ドカップ#4/室
温)になるように通常塗料用に使用される有機溶剤を配
合する。本発明においては、有機溶剤として少くとも一
部に塗装後の平滑性を向上させるために高沸点エ−テル
アルコ−ル類を必須成分として使用している。その高沸
点エ−テルアルコ−ル類としては、エチレングリコ−ル
モノブチルエ−テル、ジエチレングリコ−ルモノブチル
エ−テル、エチレングリコ−ルモノエチルエ−テル、ジ
エチレングリコ−ルモノエチルエ−テル、エチレングリ
コ−ルモノメチルエ−テル、ジエチレングリコ−ルモノ
メチルエ−テル、エチレングリコ−ルモノプロピルエ−
テル、ジエチレングリコ−ルモノプロピルエ−テル等が
挙げられる。なお、上記高沸点エ−テルアルコ−ル類は
前記アクリル樹脂及び硬化剤合計量100重量部に対
し、約10〜50重量部配合することにより前記効果が
得られるが、過剰に配合すると、ハジキ等の塗膜欠陥の
原因となる場合があるので避ける必要がある。The organic solvent is blended with an organic solvent usually used for paints so that the viscosity of the intermediate coating paint is 40 to 120 seconds (fod cup # 4 / room temperature) in accordance with the coating workability. In the present invention, high boiling ether alcohols are used as an essential component as an organic solvent in order to improve smoothness after coating, at least in part. The high-boiling ether alcohols include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether. , Ethylene glycol monopropyl ether
Tellurium, diethylene glycol monopropyl ether and the like. The above-mentioned high boiling ether alcohols can achieve the above effects by blending about 10 to 50 parts by weight with respect to 100 parts by weight of the total amount of the acrylic resin and the curing agent. It may cause coating film defects in the above, and should be avoided.
【0020】本発明で使用する中塗塗料は以上の構成成
分からなり、この塗料は練合分散し、顔料分散度がグラ
インドゲ−ジA法15μm以下とする。なお、15μm
を越えると塗膜にブツの発生等が見られるようになるの
で好ましくない。The intermediate coating composition used in the present invention comprises the above-mentioned components. The coating composition is kneaded and dispersed so that the pigment dispersity is 15 μm or less by the Grindge A method. 15 μm
If it exceeds the range, it is not preferable because the coating film is likely to have spots.
【0021】次に、本発明において模様状印刷する際に
使用する印刷インキは、エポキシ樹脂(数平均分子量
(以下、Mnという)800〜3000)、アクリル樹
脂(Mn5000〜30000)またはポリエステル樹
脂(Mn2000〜20000)を主成分とし、該樹脂
固形分100重量部に対し、着色顔料5〜150重量
部、タルク,カオリン,炭酸カルシウム,硫酸バリウ
ム,無水硅酸等の体質顔料を0〜100重量部含有し、
また必要に応じてアミノプラスト樹脂等の架橋剤を樹脂
固形分100重量部に対し、1〜20重量部添加し、イ
ンキの硬度を上げることもできる。また顔料分散及び消
泡のために、アクリル系添加剤及びシリコ−ン油を0.
02〜1.0重量部配合する。市販のアクリル添加剤と
しては、モダフロ−(モンサント社製);ポリフロ−9
0,同85(共栄社油脂製);ディスバロン1980,
1982(楠本化成製)等を使用でき、シリコ−ン油と
しては、信越シリコンKP357,358,367;B
YK CHEMIE社製のBYK300,301,37
0,310;東レシリコン社製の東レシリコンS428
PA,SH29PA,SH30PA,SH34PH;ゴ
−ルドシュミット社製のテゴプレン等を使用できる。Next, the printing ink used for pattern printing in the present invention is an epoxy resin (number average molecular weight (hereinafter referred to as Mn) 800 to 3000), an acrylic resin (Mn 5000 to 30000) or a polyester resin (Mn 2000). .About.20000) as a main component, and based on 100 parts by weight of the resin solid content, 5 to 150 parts by weight of color pigments and 0 to 100 parts by weight of extender pigments such as talc, kaolin, calcium carbonate, barium sulfate and silicic acid anhydride. Then
If necessary, a crosslinking agent such as an aminoplast resin may be added in an amount of 1 to 20 parts by weight based on 100 parts by weight of the resin solid content to increase the hardness of the ink. In order to disperse the pigment and defoam, an acrylic additive and silicone oil should be added in an amount of 0.
Add from 02 to 1.0 parts by weight. Examples of commercially available acrylic additives include Modaflow (manufactured by Monsanto); Polyflo-9
0, 85 (manufactured by Kyoeisha Yushi); Disvalon 1980,
1982 (produced by Kusumoto Kasei Co., Ltd.) can be used, and as the silicone oil, Shin-Etsu Silicon KP357, 358, 367; B
BYK300, 301, 37 made by YK CHEMIE
0,310; Toray Silicon S428 manufactured by Toray Silicon Co., Ltd.
PA, SH29PA, SH30PA, SH34PH; Tegoprene manufactured by Goldschmidt, etc. can be used.
【0022】さらに、インキの乾燥性を補助するため
に、ニトロセルロ−スあるいは塩ビ,酢ビのホモポリマ
−またはコポリマ−を前述の樹脂固型分100重量部に
対し、5〜15重量部添加することが望ましい。なお、
本インキについては、通常塗料あるいはインキに用いら
れる溶剤を使用できるが、印刷適性を上げるために高沸
点溶剤、例えばジエチレングリコ−ル,イソホロン等を
0.1〜5重量部添加するのが望ましい。Further, in order to assist the drying property of the ink, 5 to 15 parts by weight of nitrocellulose or a homopolymer or copolymer of vinyl chloride or vinyl acetate is added to 100 parts by weight of the resin solid content. Is desirable. In addition,
For this ink, a solvent usually used for paints or inks can be used, but it is preferable to add 0.1 to 5 parts by weight of a high boiling point solvent such as diethylene glycol or isophorone in order to improve printability.
【0023】次に、本発明において使用する上塗クリヤ
−塗料はアクリル樹脂、硬化剤であるアミノプラスト樹
脂、硬質体質顔料、シリコ−ン油及び高沸点エ−テルア
ルコ−ル類を含む有機溶剤を主成分とし、さらに必要に
応じ、下層の意匠柄印刷面の視認性が低下しない程度の
少量の着色顔料、体質顔料、各種添加剤、改質剤等から
なるものである。Next, the clear topcoat paint used in the present invention is mainly composed of an acrylic resin, a curing agent such as aminoplast resin, a hard extender pigment, silicone oil and an organic solvent containing high boiling ether alcohols. As a component, it further comprises, if necessary, a small amount of a coloring pigment, an extender pigment, various additives, a modifier, etc., to the extent that the visibility of the design pattern printing surface of the lower layer is not deteriorated.
【0024】前記アクリル樹脂は、前記中塗塗料に使用
したアクリル樹脂とほぼ同様なものを使用できるが、M
nは塗膜硬度を所定以上とするために15000以上の
ものを使用する必要がある。The acrylic resin may be substantially the same as the acrylic resin used in the intermediate coating paint, but M
For n, it is necessary to use one having a hardness of 15,000 or more so that the coating film hardness is not less than a predetermined value.
【0025】前記アミノプラスト樹脂は、前記中塗塗料
に使用したアミノプラスト樹脂と同様なものが使用でき
る。なお、アクリル樹脂とアミノプラスト樹脂の固形分
配合割合は重量比で(60/40〜80/20)が適当
である。The aminoplast resin may be the same as the aminoplast resin used in the intermediate coating composition. In addition, the mixing ratio of the solid content of the acrylic resin and the aminoplast resin is preferably 60/40 to 80/20 by weight.
【0026】前記硬質体質顔料は、前記中塗塗料に使用
した硬質体質顔料とほぼ同様なものを使用できるが、そ
の平均粒径は30μm以下で、その配合割合は、前記ア
クリル樹脂及び硬化剤の合計量100重量部に対し、3
0〜80重量部が適当である。なお、粒径が30μmを
越えると、塗膜にザラツキ感を生じ、化粧板として不適
である。また配合割合が30重量部未満では、塗膜硬度
の向上への寄与が少なく、逆に80重量部を越えると、
塗面が多孔質になりやすく、防汚性が悪くなるだけでな
く、透明感がうすれて意匠性が悪くなるので好ましくな
い。The hard extender pigment may be substantially the same as the hard extender pigment used in the intermediate coating composition, but its average particle size is 30 μm or less, and the mixing ratio thereof is the sum of the acrylic resin and the curing agent. 3 for 100 parts by weight
0 to 80 parts by weight is suitable. If the particle size exceeds 30 μm, the coating film will have a rough feel, and is not suitable as a decorative plate. Further, if the blending ratio is less than 30 parts by weight, the contribution to the improvement of the coating film hardness is small, and conversely if it exceeds 80 parts by weight,
It is not preferable because the coated surface tends to be porous, the antifouling property is deteriorated, and the transparency is weakened to deteriorate the design.
【0027】前記シリコ−ン油は、塗膜に対する付着物
を剥れ易くする機能を補助し、また塗膜の平滑性を向上
させるために配合するものであり、市販品としては、例
えば信越化学工業社製の信越シリコンKP357,35
8,367;BYK CHEMIE社製のBYK30
0,301,320,370;東レシリコン社製の東レ
シリコンSH28PA,SH29PA,SH30PA,
SH34PA,ST92PA;ゴ−ルドシュミット社製
のテゴプレン等が挙げられる。このシリコ−ン油の配合
量は、前記アクリル樹脂及び硬化剤の合計量100重量
部に対し、0.01〜10重量部配合するのが適当であ
る。なお、配合量が0.01重量部未満では前記効果を
十分に発揮できず、逆に10重量部を越えると、安定な
分散を得ることができず、ハジキ等の塗膜欠陥が発生し
やすくなるので好ましくない。The silicone oil is added in order to assist the function of facilitating the removal of deposits on the coating film and to improve the smoothness of the coating film. Examples of commercially available products include Shin-Etsu Chemical. Shin-Etsu Silicon KP357,35 made by Kogyo Co., Ltd.
8,367; BYK30 manufactured by BYK CHEMIE
0,301,320,370; Toray Silicon SH28PA, SH29PA, SH30PA, manufactured by Toray Silicon Co., Ltd.
SH34PA, ST92PA; Tegoprene manufactured by Goldschmidt, and the like. It is suitable that the silicone oil is blended in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the acrylic resin and the curing agent. If the blending amount is less than 0.01 parts by weight, the above effect cannot be sufficiently exhibited, and conversely if it exceeds 10 parts by weight, stable dispersion cannot be obtained, and coating film defects such as cissing tend to occur. Therefore, it is not preferable.
【0028】前記有機溶剤は、塗装作業性に合せて上塗
クリヤ−塗料の粘度が40〜120秒(フォ−ドカップ
#4/室温)になるように通常塗料用に使用される有機
溶剤を配合する。本発明においては、有機溶剤として少
なくとも一部に前記シリコ−ン油の分散効果を向上させ
るために前記中塗塗料に使用した同様の高沸点エ−テル
アルコ−ル類を必須成分として使用している。なお、高
沸点エ−テルアルコ−ル類は前記アクリル樹脂及び硬化
剤の合計量100重量部に対し、約10〜50重量部配
合することにより、前記の効果が得られるが、過剰に配
合すると、ハジキ等の塗膜欠陥の原因となるので避ける
必要がある。また、必要に応じて、普通の塗料に用いら
れる有機ベントナイト、シリカ等の沈殿防止剤をアクリ
ル樹脂及び硬化剤の合計量100重量部に対し、0.1
〜2.0重量部添加するのが望ましい。The above-mentioned organic solvent is blended with an organic solvent usually used for coating so that the viscosity of the top coating clear coating is 40 to 120 seconds (Food cup # 4 / room temperature) according to the coating workability. .. In the present invention, the same high boiling point ether alcohols used in the intermediate coating composition for improving the dispersion effect of the silicone oil are used at least partially as the organic solvent as an essential component. It should be noted that the high-boiling ether alcohols can achieve the above effect by blending about 10 to 50 parts by weight with respect to 100 parts by weight of the total amount of the acrylic resin and the curing agent, but if blended in excess, It causes coating defects such as cissing and must be avoided. In addition, if necessary, an organic bentonite used in ordinary paints, a precipitation inhibitor such as silica, or the like may be used in an amount of 0.1 parts by weight per 100 parts by weight of the total amount of the acrylic resin and the curing agent.
It is desirable to add ~ 2.0 parts by weight.
【0029】本発明は使用する上塗クリヤ−塗料は、以
上の構成成分からなり、この塗料は混合分散し、顔料分
散度をグラインドゲ−ジA法30μm以下とした透明な
いしは半透明の塗料である。The clear coating composition for top coating used in the present invention is a transparent or semi-transparent coating composition comprising the above-mentioned components, which is mixed and dispersed to obtain a pigment dispersity of 30 μm or less by the Grindage A method. ..
【0030】次に、本発明の化粧金属板の製造方法につ
いて説明する。亜鉛メッキ鋼板,アルミニウム板,不銹
鋼板等の従来常用されているシ−ト状もしくはコイル状
金属板表面に対し必要に応じ化成処理等の通常の下地処
理をした後、下塗塗料を乾燥膜厚が3〜10μmになる
ように塗装し、最高板温(以下、単にPMTという)約
180〜230℃で30〜70秒の短時間焼付を行ない
下塗塗膜を形成する。なお、膜厚が前記範囲より薄いと
充分な防食性が得られず、逆に厚くなると上塗後の塗膜
硬度が低下するので好ましくない。また、塗装手段はロ
−ルコ−タ−,フロ−コ−タ−等の通常のコイル塗装手
段を利用できるが、本発明においては、膜厚調整が容易
なロ−ルコ−ターの使用が特に好適である。Next, a method for manufacturing the decorative metal plate of the present invention will be described. The surface of conventionally used sheet-like or coil-like metal sheets such as galvanized steel sheets, aluminum sheets, and stainless steel sheets is subjected to ordinary base treatment such as chemical conversion treatment, if necessary, and then the undercoat paint is dried to a dry film thickness. Coating is performed so as to have a thickness of 3 to 10 μm, and baking is performed at a maximum plate temperature (hereinafter, simply referred to as PMT) of about 180 to 230 ° C. for a short time of 30 to 70 seconds to form an undercoat coating film. If the film thickness is smaller than the above range, sufficient corrosion resistance cannot be obtained, and conversely, if the film thickness is larger, the hardness of the coating film after top coating is lowered, which is not preferable. Further, as the coating means, an ordinary coil coating means such as a roll coater or a flow coater can be used, but in the present invention, the use of a roll coater whose film thickness can be easily adjusted is particularly preferable. It is suitable.
【0031】上記のような下塗塗膜を施した後、該塗膜
上に中塗塗料を同様な塗装手段により乾燥膜厚が10〜
30μm、好ましくは15〜25μmになるように塗装
し、PMT約170〜220℃で、20〜100秒の短
時間焼付を行ない中塗塗膜を形成する。After applying the undercoat coating film as described above, an intermediate coating composition is applied onto the coating film by a similar coating method to give a dry film thickness of 10 to 10.
It is coated so as to have a thickness of 30 μm, preferably 15 to 25 μm, and is baked at PMT of about 170 to 220 ° C. for a short time of 20 to 100 seconds to form an intermediate coating film.
【0032】上記の中塗塗膜を施した後、該塗膜上に、
グラビア印刷、グラビアオフセット印刷、フレキソ印
刷、スクリ−ン印刷等の印刷手段により、任意の意匠柄
を全面もしくは部分的に施す。この印刷は、乾燥膜厚が
約1〜10μmになるように施し、次いで、全面に上塗
クリヤ−塗料を下塗、中塗と同様な塗装手段により乾燥
膜厚が10〜30μm、好ましくは15〜25μmにな
るように塗装し、PMT約220〜250℃で、30〜
100秒間焼付を行ない、硬度9H以上のクリヤ−塗膜
を形成して、化粧金属板を製造する。なお、硬度が9H
未満であると、耐摩耗性が不充分であり落書を除去する
際のウェスあるいはブラシ等での傷がつきやすくなり、
好ましくない。前記印刷インキは、必要ならば、PMT
約170〜220℃で、20〜100秒焼付けて上塗り
クリヤ−塗料を塗装してもよい。After applying the above-mentioned intermediate coating film, on the coating film,
An arbitrary design pattern is entirely or partially applied by printing means such as gravure printing, gravure offset printing, flexographic printing, screen printing. This printing is carried out so that the dry film thickness is about 1 to 10 μm, then the entire surface is undercoated with a clear coating, and the dry film thickness is adjusted to 10 to 30 μm, preferably 15 to 25 μm by the same coating means as the intermediate coating. And PMT at 220 ~ 250 ℃, 30 ~
Baking is performed for 100 seconds to form a clear coating film having a hardness of 9H or more, and a decorative metal plate is manufactured. The hardness is 9H
If it is less than, abrasion resistance is insufficient and scratches easily occur with a waste cloth or a brush when removing a missing letter,
Not preferable. If necessary, the printing ink may be PMT.
The top clear coating composition may be applied by baking at about 170 to 220 ° C. for 20 to 100 seconds.
【0033】[0033]
【実施例】以下、本発明の実施例について説明する。な
お、「部」、「%」は重量基準で示す。 <下塗塗料の調製>表1に示すポリエステル樹脂溶液
(固形分60%;有機溶剤イソホロン,ソルベッソ15
0(シェル社製の商品名),酢酸エチレングリコ−ルモ
ノエチルエ−テルの1:1:1からなる混合溶剤)、メ
ラミン樹脂〔「サイメル303」(三井東圧化学社製商
品名);固形分100%〕及び顔料を練合分散し、次い
でパラトルエンスルホン酸及び有機溶剤(イソホロンと
キシレンの1:1からなる混合溶剤)を添加し、顔料分
散度がグラインドゲ−ジA法15μm以下の下塗塗料を
調製した。なお、実施例および比較例では、塗装直前に
希釈溶剤(キシレンと酢酸エチレングリコ−ルモノエチ
ルエ−テル,シクロヘキサノンの3:1:1からなる混
合溶剤)にて塗装粘度50秒(フォ−ドカップ#4/2
0℃)になるように調製した下塗塗料を使用した。EXAMPLES Examples of the present invention will be described below. In addition, "part" and "%" are shown by weight. <Preparation of Undercoat Paint> Polyester resin solution shown in Table 1 (solid content 60%; organic solvent isophorone, Solvesso 15)
0 (trade name manufactured by Shell Co.), a mixed solvent of ethylene glycol monoethyl ether acetate (1: 1: 1), melamine resin [“Cymel 303” (trade name manufactured by Mitsui Toatsu Chemicals, Inc.); solid content 100 %] And a pigment are kneaded and dispersed, and then paratoluenesulfonic acid and an organic solvent (a mixed solvent of isophorone and xylene are mixed at a ratio of 1: 1) are added to the undercoat paint having a pigment dispersity of 15 μm or less by the Grindage A method Was prepared. In each of the examples and comparative examples, a coating solvent having a viscosity of 50 seconds (foad cup # 4 / fused with a diluting solvent (mixed solvent of xylene and ethylene glycol monoethyl ether acetate / cyclohexanone 3: 1: 1) was used immediately before coating. Two
An undercoat paint prepared to have a temperature of 0 ° C. was used.
【0034】<中塗塗料の調製>表2に示すアクリル樹
脂溶液(固形分50%;有機溶剤ソルベッソ#150,
エチレングリコ−ルモノブチルエ−テルの4:1からな
る混合溶剤)、メラミン樹脂溶液〔「サイメル370」
(三井東圧化学社製商品名);固形分88%;有機溶剤
イソブタノ−ルとイソプロパノ−ルの1:1からなる混
合溶剤〕及び顔料を練合分散し、次いでパラトルエンス
ルホン酸及び有機溶剤(エチレングリコ−ルモノブチル
エ−テル,イソブタノ−ル,ソルベッソ#150の1:
1:3からなる混合溶剤)を添加し、顔料分散度がグラ
インドゲ−ジA法15μm以下の中塗塗料を調製した。
なお、実施例および比較例では、塗装直前に希釈溶剤
(ソルベッソ#150,イソブタノ−ル,ジエチレング
リコ−ルモノブチルエ−テルの7:2:1からなる混合
溶剤)にて塗装粘度80秒になるように調製した中塗塗
料を使用した。<Preparation of Intermediate Coating Composition> Acrylic resin solution shown in Table 2 (solid content 50%; organic solvent Solvesso # 150,
Ethylene glycol monobutyl ether 4: 1 mixed solvent), melamine resin solution ["Cymel 370"
(Mitsui Toatsu Chemical Co., Ltd. product name); solid content 88%; organic solvent: a mixed solvent of isobutanol and isopropanol 1: 1] and a pigment are kneaded and dispersed, and then paratoluenesulfonic acid and an organic solvent. (Ethylene glycol monobutyl ether, isobutanol, Solvesso # 150 1:
A mixed solvent of 1: 3) was added to prepare an intermediate coating composition having a pigment dispersity of 15 μm or less by the method of Grindge A.
In the Examples and Comparative Examples, a coating viscosity of 80 seconds was prepared with a diluting solvent (solvent of Solvesso # 150, isobutanol, diethylene glycol monobutyl ether 7: 2: 1) immediately before coating. The used intermediate coating paint was used.
【0035】<インキの調製>ポリエステル樹脂溶液
[アルマテックスP646(三井東圧化学社製商品
名),Mn2700〜3000,固形分60%,有機溶
剤ソルベッソ#100,メチルイソブチルケトンの9:
1からなる混合溶剤]、メラミン樹脂溶液〔コ−バン1
28(三井東圧化学社製商品名);固形分60%;有機
溶剤キシロ−ル,ノルマルブタノ−ル4:6からなる混
合溶剤〕をそれぞれ167重量部及び17重量部と、顔
料として酸化チタン100重量部,カ−ボンブラック
0.5重量部、さらに分散剤及び消泡剤としてディスパ
ロン1980(楠本化成社製商品名)を0.2部投入
後、練合分散し、別途メチルエチルケトンにて18%溶
液に調製した[エスレックA(塩ビ,酢ビコポリマ−;
積水化成品社製商品名)]を固形分として7重量部、ジ
エチレングリコ−ルを3重量部、及びソルベッソ100
/キシロ−ル/イソブタノ−ル=7/2/1からなる混
合溶剤を40重量部添加して、グラインドゲ−ジA法1
5μm以下のインキを調製した。なお、実施例および比
較例では、印刷直前にソルベッソ#100,イソブタノ
−ル,ジエチレングリコ−ルモノブチルエ−テルの6:
3:1からなる混合溶剤で粘度60秒になるように調製
したインキを使用した。<Preparation of Ink> Polyester resin solution [ALMATEX P646 (trade name, manufactured by Mitsui Toatsu Chemicals, Inc.), Mn 2700 to 3000, solid content 60%, organic solvent Solvesso # 100, 9 of methyl isobutyl ketone:
1 mixed solvent], melamine resin solution [Coban 1
28 (trade name, manufactured by Mitsui Toatsu Chemicals, Inc.); solid content 60%; mixed solvent consisting of organic solvent xylol and normal butanol 4: 6 parts by weight, 167 parts by weight and 17 parts by weight, respectively, and titanium oxide 100 as a pigment. Parts by weight, 0.5 parts by weight of carbon black, 0.2 parts of Disparlon 1980 (trade name of Kusumoto Kasei Co., Ltd.) as a dispersant and an antifoaming agent, and then kneaded and dispersed. Separately, 18% with methyl ethyl ketone. Prepared into a solution [Eslec A (vinyl chloride, vinegar bicopolymer;
Sekisui Plastics Co., Ltd.)] as solid content, 7 parts by weight, diethylene glycol 3 parts by weight, and Solvesso 100.
/ Xylol / Isobutanol = 7/2/1 (40 parts by weight) was added to the mixture to prepare a Grindage A method 1
An ink of 5 μm or less was prepared. In the examples and comparative examples, immediately before printing, Solvesso # 100, isobutanol, and diethylene glycol monobutyl ether (6: 6) were used.
An ink prepared to have a viscosity of 60 seconds with a mixed solvent of 3: 1 was used.
【0036】<上塗クリヤ−塗料の調製>表3に示すア
クリル樹脂溶液(固形分50%;有機溶剤ソルベッソ#
150,エチレングリコ−ルモノブチルエ−テルの4:
1からなる混合溶剤)、メラミン樹脂溶液〔「サイメル
370」(三井東圧化学社製商品名);固形分88%;
有機溶剤イソブタノ−ルとイソプロパノ−ルの1:1か
らなる混合溶剤〕及び硬質体質顔料を混合分散し、次い
でパラトルエンスルホン酸及び有機溶剤(エチレングリ
コ−ルモノブチルエ−テル,イソブタノ−ル,ソルベッ
ソ#150の1:1:3からなる混合溶剤)を添加し、
顔料分散度がグラインドゲ−ジA法30μm以下の上塗
クリヤ−塗料を調製した。なお、実施例および比較例で
は、塗装直前に希釈溶剤(ソルベッソ#150,イソブ
タノ−ル,ジエチレングリコ−ルモノブチルエ−テルの
7:2:1からなる混合溶剤)にて塗装粘度80秒にな
るように調製した上塗クリヤ−塗料を使用した。<Preparation of Topcoat Clear Paint> Acrylic resin solutions shown in Table 3 (solid content 50%; organic solvent Solvesso #
150, ethylene glycol monobutyl ether 4:
1), a melamine resin solution [“Cymel 370” (trade name, manufactured by Mitsui Toatsu Chemicals, Inc.); solid content 88%;
Organic solvent isobutanol and isopropanol 1: 1 mixed solvent) and a hard extender pigment are mixed and dispersed, and then paratoluenesulfonic acid and an organic solvent (ethylene glycol monobutyl ether, isobutanol, Solvesso # 150). Mixed solvent consisting of 1: 1: 3 of
A clear top coat paint having a pigment dispersity of 30 μm or less by the Grindge A method was prepared. In the Examples and Comparative Examples, a coating viscosity of 80 seconds was prepared with a diluting solvent (solvent of Solvesso # 150, isobutanol, diethylene glycol monobutyl ether 7: 2: 1) immediately before coating. A clear topcoat paint was used.
【0037】〔実施例1〜7及び比較例1〜8〕リン酸
亜鉛系化成処理を施した亜鉛メッキ鋼板(0.5mm厚)
にリバ−ス方式ロ−ルコ−タ−〔周速比(バックアップ
ロ−ルの周速:コ−ティングロ−ルの周速:ピックアッ
プロ−ルの周速)1:1.4:0.4〕にてライン速度
35m/minの条件下で前記下塗塗料を塗装し、PM
T210℃で40秒間焼付けた。[Examples 1 to 7 and Comparative Examples 1 to 8] Galvanized steel sheet (0.5 mm thick) which has been subjected to zinc phosphate chemical conversion treatment.
Reversing type roll coater [peripheral speed ratio (peripheral speed of backup roll: peripheral speed of coating roll: peripheral speed of pickup roll) 1: 1.4: 0.4 ], The above undercoat paint was applied under the condition of a line speed of 35 m / min.
It was baked at T210 ° C. for 40 seconds.
【0038】次いで、リバ−ス方式ロ−ルコ−タ−〔周
速比(バックアップロ−ルの周速:コ−ティングロ−ル
の周速:ピックアップロ−ルの周速)1:1.2:0.
3〕にてライン速度35m/minの条件下で前記中塗
塗料を塗装し、PMT200℃で40秒間焼付けた。Next, a reverse type roll coater [peripheral speed ratio (peripheral speed of backup roll: peripheral speed of coating roll: peripheral speed of pickup roll) 1: 1.2 : 0.
3], the intermediate coating composition was applied under the condition of the line speed of 35 m / min and baked at PMT 200 ° C. for 40 seconds.
【0039】次いで、グラビア印刷にて前記インキを用
いてプリント印刷し、PMT200℃、60秒間焼付け
た。Then, the above ink was used for gravure printing, and printing was carried out, followed by baking at PMT 200 ° C. for 60 seconds.
【0040】次いで、中塗と同様な条件下で前記上塗ク
リヤ−塗料を塗装し、PMT241℃で40秒間焼付け
た。なお、35m/minの速度で塗装し得ないものは
その最高速度で得られた塗膜につき硬度,防汚性,曲げ
性,外観の試験をし、その結果を表4に示した。Next, the above-mentioned clear topcoat paint was applied under the same conditions as the intermediate coat and baked at PMT 241 ° C. for 40 seconds. For the coatings that could not be coated at a speed of 35 m / min, the coating film obtained at the maximum speed was tested for hardness, stain resistance, bendability, and appearance, and the results are shown in Table 4.
【0041】また、中塗塗料によるリバ−ス方式ロ−ル
コ−タ−〔周速比1:1.2:0.3〕の最高ライン速
度の試験をし、その結果を表2下段に示した。なお、試
験方法は次の通り行った。 硬 度……JIS K−5400に準ずる。 防汚性……アクリルラッカ−(黒)を塗り、該塗膜の剥
れ易さを判定した。 (A)セロハンテ−プによる剥離 5:100%剥離、 4:80〜99%剥離、 3:50〜79%剥離、 2:10〜49%剥離、 1:10%未満。 (B)ベンゼンをしみこませたガーゼのラビングによる
剥離 5:剥離回数5回以内、 4:剥離回数6〜15回、 3:剥離回数16〜30回, 2:剥離回数31〜100回, 1:剥離回数101回以上。 曲げ性……20mmφの180°折り曲げを行ない塗膜
状態を観察した。 ○:塗膜異常なし Х:塗膜にクラック,ワレもしくはハガレが生じる。 中塗の最高ライン速度……ピックアップ性が不充分とな
り塗膜にスケムラが生じる限界のライン速度(m/mi
n)を測定した。Further, the maximum line speed of a reverse type roll coater [peripheral speed ratio 1: 1.2: 0.3] with an intermediate coating was tested, and the results are shown in the lower row of Table 2. .. The test method was as follows. Hardness: According to JIS K-5400. Antifouling property ... Acrylic lacquer (black) was applied and the ease of peeling of the coating film was evaluated. (A) Peeling by cellophane tape 5: 100% peeling, 4:80 to 99% peeling, 3:50 to 79% peeling, 2:10 to 49% peeling, less than 1: 10%. (B) Peeling by rubbing gauze soaked with benzene 5: Peeling times within 5 times, 4: Peeling times 6 to 15 times, 3: Peeling times 16 to 30 times, 2: Peeling times 31 to 100 times, 1: Peeling frequency is 101 times or more. Bendability: A coating film state was observed by bending 180 ° of 20 mmφ. ○: No abnormality in coating film Х: Crack, crack or peeling occurs in coating film. Maximum line speed of middle coating: Pickup property is insufficient and the coating film becomes uneven, which is the limit line speed (m / mi
n) was measured.
【0042】表4および表2からも明らかな通り本発明
の方法により得られた実施例の塗膜性能、意匠性は優れ
ており、また塗装ライン速度も実用的なものであった。As is clear from Tables 4 and 2, the coating film performance and design of the examples obtained by the method of the present invention were excellent, and the coating line speed was also practical.
【0043】一方、Tgの低いポリエステル樹脂を使用
した比較例1は、硬度が低く、また逆にTgの高いポリ
エステル樹脂を使用した比較例2は、加工性が悪く、ま
た硬質体質顔料の少ない上塗クリヤ−塗料を使用した比
較例3は硬度が低く、またTgの低いアクリル樹脂を使
用した比較例4は防汚性が悪く、かつ硬度も低い。また
分子量の低いアクリル樹脂を使用した比較例5は加工性
が悪く、また硬質体質顔料を配合しない比較例6は硬度
が低く、また逆に硬質体質顔料を過剰に配合した比較例
7は、加工性、意匠性が悪く、またシリコ−ン油を配合
しない比較例8は防汚性が悪かった。On the other hand, Comparative Example 1 using a polyester resin having a low Tg has a low hardness, and conversely Comparative Example 2 using a polyester resin having a high Tg has a poor processability and a topcoat having a small amount of a hard extender pigment. Comparative Example 3 using the clear paint has a low hardness, and Comparative Example 4 using an acrylic resin having a low Tg has a poor antifouling property and a low hardness. Further, Comparative Example 5 using an acrylic resin having a low molecular weight is poor in processability, Comparative Example 6 in which a hard extender pigment is not mixed has low hardness, and conversely, Comparative Example 7 in which a hard extender pigment is excessively mixed is processed. Comparative Example 8 in which the silicone oil was not mixed was poor in antifouling property.
【0044】[0044]
【発明の効果】以上のように、本発明によれば、貼紙あ
るいは落書き等を人為的に容易に剥がすことが可能な平
滑な塗膜を塗装作業性よく形成することができるととも
に、化粧板を切断、折曲げ加工等の成形加工に供して
も、ワレや剥離などを生じにくい優れた塗膜を維持する
ことができ、したがって、意匠柄仕上げの良好な化粧金
属板を得ることができる。As described above, according to the present invention, it is possible to form a smooth coating film capable of easily artificially peeling off a paper sticker, graffiti, etc., with good coating workability, and at the same time, to obtain a decorative board. Even when subjected to a forming process such as cutting or bending, it is possible to maintain an excellent coating film that is unlikely to cause cracking or peeling, and thus it is possible to obtain a decorative metal plate having a good design pattern finish.
【0045】[0045]
【表1】 [Table 1]
【0046】[0046]
【表2】 [Table 2]
【0047】[0047]
【表3】 [Table 3]
【0048】[0048]
【表4】 [Table 4]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 B05D 7/24 302 V 8616−4D S 8616−4D P 8616−4D (72)発明者 赤井田 夏彦 大阪府大阪市中央区南本町4丁目1番1号 株式会社淀川製鋼所内 (72)発明者 寺尾 修 大阪府大阪市旭区太子橋1丁目22ー10 (72)発明者 山口 貴司 兵庫県神戸市兵庫区平野町249ー6─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical display location B05D 7/24 302 V 8616-4D S 8616-4D P 8616-4D (72) Inventor Natsuhiko Akita 4-1-1 Minamihonmachi, Chuo-ku, Osaka-shi, Osaka Prefecture Inside the Yodogawa Steel Works (72) Inventor Osamu Terao 1-22-10 Taishibashi, Asahi-ku, Osaka-shi, Osaka (72) Takashi Yamaguchi Kobe-shi, Hyogo Prefecture Hyogo Prefecture 249-6 Hirano-cho, Tokyo
Claims (1)
℃、数平均分子量4500〜35000のポリエステル
樹脂と硬化剤であるアミノプラスト樹脂と、前記ポリエ
ステル樹脂及び硬化剤の合計量100重量部に対し、顔
料30〜100重量部と有機溶剤必要量とからなり、顔
料分散度がグラインドゲ−ジA法15μm以下の下塗塗
料を乾燥膜厚3〜10μmになるように塗装し、焼付乾
燥し、次いで、 ガラス転移温度60〜200℃、数平均分子量5000
〜100000、重量平均分子量20000〜1500
00のアクリル樹脂と硬化剤であるアミノプスト樹脂
と、前記アクリル樹脂及び硬化剤の合計量100重量部
に対し、着色顔料50〜150重量部、平均粒径5μm
以下の硬質体質顔料5〜50重量部及び高沸点エ−テル
アルコ−ル類を含む有機溶剤必要量とからなり、顔料分
散度がグラインドゲ−ジA法15μm以下の中塗塗料を
乾燥膜厚10〜30μmになるように塗装し、次いで、 中塗塗膜上に、模様状印刷を全面もしくは部分的に施
し、焼付乾燥し、次いで、 全面に、ガラス転移温度60〜200℃、数平均分子量
15000〜100000、重量平均分子量20000
〜150000のアクリル樹脂と硬化剤であるアミノプ
ラスト樹脂と、前記アクリル樹脂及び硬化剤の合計量1
00重量部に対し、平均粒径30μm以下の硬質体質顔
料30〜80重量部、シリコ−ン油0.01〜10重量
部及び高沸点エテ−ルアルコ−ル類を含む有機溶剤必要
量とからなるクリヤ−塗料を乾燥膜厚10〜30μmに
なるよう塗装し、焼付乾燥する硬度9H以上の塗膜を有
する化粧金属板の製造方法。1. A glass transition temperature of 5 to 70 on a metal plate.
C., consisting of a polyester resin having a number average molecular weight of 4500 to 35000, an aminoplast resin which is a curing agent, and 30 to 100 parts by weight of a pigment and 100 parts by weight of an organic solvent based on 100 parts by weight of the total amount of the polyester resin and the curing agent. An undercoat paint having a pigment dispersity of 15 μm or less in the Grindage A method is applied to a dry film thickness of 3 to 10 μm, baked and dried, and then the glass transition temperature is 60 to 200 ° C. and the number average molecular weight is 5000.
~ 100,000, weight average molecular weight 20000-1500
No. 00 acrylic resin and aminoplast resin which is a curing agent, and 50 to 150 parts by weight of a color pigment, and an average particle diameter of 5 μm with respect to 100 parts by weight of the total amount of the acrylic resin and the curing agent.
It comprises 5 to 50 parts by weight of the following hard extender pigments and the required amount of an organic solvent containing high boiling ether alcohols, and the degree of dispersion of the pigment is an intermediate coating composition of 15 μm or less of the Grindage A method. 30 μm, then the intermediate coating film is subjected to pattern printing on the entire surface or a part thereof, and baked and dried. Then, the entire surface has a glass transition temperature of 60 to 200 ° C. and a number average molecular weight of 15,000 to 100,000. , Weight average molecular weight 20000
~ 150,000 acrylic resin and aminoplast resin which is a curing agent, and the total amount of the acrylic resin and the curing agent is 1
It is composed of 30 to 80 parts by weight of a hard extender pigment having an average particle diameter of 30 μm or less, 0.01 to 10 parts by weight of silicone oil, and a required amount of an organic solvent containing high boiling point ether alcohols, relative to 00 parts by weight. A method for producing a decorative metal plate having a coating film having a hardness of 9H or more, which is obtained by applying a clear coating material to a dry film thickness of 10 to 30 µm and baking and drying.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30906591A JPH0632775B2 (en) | 1991-11-25 | 1991-11-25 | Method for manufacturing decorative metal plate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30906591A JPH0632775B2 (en) | 1991-11-25 | 1991-11-25 | Method for manufacturing decorative metal plate |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05138122A true JPH05138122A (en) | 1993-06-01 |
JPH0632775B2 JPH0632775B2 (en) | 1994-05-02 |
Family
ID=17988462
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30906591A Expired - Fee Related JPH0632775B2 (en) | 1991-11-25 | 1991-11-25 | Method for manufacturing decorative metal plate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0632775B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1034823A (en) * | 1996-07-25 | 1998-02-10 | Nisshin Steel Co Ltd | Precoating steel sheet with excellent stain resistance and nonstickiness |
JP2004075054A (en) * | 2002-07-30 | 2004-03-11 | Yokohama Seiki Kk | Lightweight interior trimming panel for vehicle |
JP2004216789A (en) * | 2003-01-17 | 2004-08-05 | Yodogawa Steel Works Ltd | Scribble-proof metal plate |
-
1991
- 1991-11-25 JP JP30906591A patent/JPH0632775B2/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1034823A (en) * | 1996-07-25 | 1998-02-10 | Nisshin Steel Co Ltd | Precoating steel sheet with excellent stain resistance and nonstickiness |
JP2004075054A (en) * | 2002-07-30 | 2004-03-11 | Yokohama Seiki Kk | Lightweight interior trimming panel for vehicle |
JP2004216789A (en) * | 2003-01-17 | 2004-08-05 | Yodogawa Steel Works Ltd | Scribble-proof metal plate |
Also Published As
Publication number | Publication date |
---|---|
JPH0632775B2 (en) | 1994-05-02 |
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