JP2000225371A - Coating method of powder paint - Google Patents
Coating method of powder paintInfo
- Publication number
- JP2000225371A JP2000225371A JP11027361A JP2736199A JP2000225371A JP 2000225371 A JP2000225371 A JP 2000225371A JP 11027361 A JP11027361 A JP 11027361A JP 2736199 A JP2736199 A JP 2736199A JP 2000225371 A JP2000225371 A JP 2000225371A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- powder coating
- aqueous dispersion
- resin
- stabilizer
- 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
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- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は粉体塗料の塗装方法
に関し、より詳しくは、前補正や導電性塗膜の形成等を
目的として第１層として特定の分散安定剤を使用した水
性分散粉体塗料を塗装し、第２層として粉体塗料又は特
定の分散安定剤を使用した水性分散粉体塗料を塗装して
均一な組成の塗膜及び／又は異なった組成の２層の塗膜
を形成する塗装方法、又は特定の分散安定剤を使用した
水性分散粉体塗料（ａ）を前補正として部分的に塗装
し、その後、粉体塗料（ｂ）又は特定の分散安定剤を使
用した水性分散粉体塗料（ｃ）を塗装する塗装方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for applying a powder coating, and more particularly, to an aqueous dispersion powder using a specific dispersion stabilizer as a first layer for the purpose of pre-correction and formation of a conductive coating film. Body paint, and as the second layer, a powder paint or an aqueous dispersion powder paint using a specific dispersion stabilizer to paint a coating film having a uniform composition and / or a two-layer coating film having different compositions. A coating method to be formed, or an aqueous dispersion powder coating (a) using a specific dispersion stabilizer is partially applied as a pre-correction, and then an aqueous dispersion powder coating (b) or an aqueous dispersion using a specific dispersion stabilizer is used. The present invention relates to a coating method for coating the dispersed powder coating (c).
【０００２】[0002]
【従来の技術】従来、水可溶性塗料や有機溶剤型塗料を
下地として塗装し、その上に粉体塗料等を塗装して塗膜
を形成する技術は知られている。ところが、近年、環境
問題等から有機溶剤の大気中への拡散を防止するため
に、有機溶剤を使用しない塗装システムが要求されてき
ている。この要求を満たす塗料としては、粉体塗料、あ
るいは粉体塗料を水中に分散させた水性分散粉体塗料が
最適であることが判明し、開発を重ねてきた。2. Description of the Related Art Conventionally, there has been known a technique in which a water-soluble paint or an organic solvent-based paint is applied as a base, and a powder paint or the like is applied thereon to form a coating film. However, in recent years, a coating system that does not use an organic solvent has been required in order to prevent the organic solvent from diffusing into the atmosphere due to environmental problems and the like. As a coating material satisfying this requirement, a powder coating material or an aqueous dispersion powder coating material obtained by dispersing the powder coating material in water has been found to be optimal, and development has been repeated.
【０００３】なお、この粉体塗料を水中に分散させた水
性分散粉体塗料に非常に良く似ている塗料として相転換
法で作成されるスラリー塗料が知られている。相転換法
によるスラリー塗料の調製は、水可溶性有機溶剤を使用
して溶剤型塗料を調製し、有機溶剤分を除去するために
溶剤型塗料を水中に強制乳化させ、有機溶剤分を除去し
て固形の塗料樹脂粒子（樹脂成分だけでなく、顔料、添
加剤等を含むもの、以下、塗料樹脂粒子という）を作成
し、この塗料樹脂粒子を水中に分散させてスラリー塗料
化することにより実施される。即ち、相転換法によるス
ラリー塗料の調製においては、水中から有機溶剤を回収
する必要があった。A slurry paint prepared by a phase inversion method is known as a paint very similar to an aqueous dispersion powder paint obtained by dispersing the powder paint in water. Preparation of slurry paint by phase inversion method, prepare solvent type paint using water soluble organic solvent, forcibly emulsify solvent type paint in water to remove organic solvent component, remove organic solvent component It is carried out by preparing solid paint resin particles (containing not only resin components but also pigments and additives, hereinafter referred to as paint resin particles), dispersing the paint resin particles in water to form a slurry paint. You. That is, in preparing a slurry coating by the phase inversion method, it was necessary to recover the organic solvent from water.
【０００４】また、上記の相転換法で作成されるスラリ
ー塗料を下地として塗装し、その上に粉体塗料等を塗装
して塗膜を形成するには種々の問題があった。即ち、こ
のスラリー塗料は、塗料樹脂粒子の分散、安定化のため
に、主としてアニオン系の界面活性剤やポリカルボン酸
をアンモニアやアミン類で中和して得られる増粘安定剤
を使用しているため、このスラリー塗料を塗装した塗膜
中から水分が蒸発する際に塗料中の中和剤も蒸発・飛散
し、従って、塗膜中から水分が一旦蒸発すると塗膜中の
塗料樹脂粒子は中和剤を失ったアニオン樹脂となり、そ
の周りにポリカルボン酸のカルボキシル基による水素結
合によって形成される強固な被膜を持つこととなる。こ
の被膜は熱による溶融軟化性が乏しく、また粘着性も無
いため、塗料樹脂粒子を溶融、融着させることにより塗
膜を形成する際に塗膜形成を阻害することになる。この
ため、成膜時に塗膜に割れが生じたり、平滑性が不足し
たりした。従って、スラリー塗料は塗装後に一気に昇温
させて成膜させることが必要があり、スラリー塗料の上
に粉体塗料を塗装して同時に成膜させたり、スラリー塗
料の上に時間間隔を置いてスラリー塗料を塗装し、成膜
させたりすることはできなかった。[0004] In addition, there are various problems in forming a coating film by applying a slurry coating prepared by the above-mentioned phase inversion method as a base and then coating a powder coating or the like thereon. That is, this slurry coating uses a thickening stabilizer obtained by neutralizing an anionic surfactant or polycarboxylic acid with ammonia or amines, mainly for dispersion and stabilization of the coating resin particles. Therefore, when moisture evaporates from the paint film coated with the slurry paint, the neutralizing agent in the paint also evaporates and scatters, and therefore, once the moisture evaporates from the paint film, the paint resin particles in the paint film become It becomes an anion resin which has lost the neutralizing agent, and has a strong film formed around the resin by hydrogen bonding due to the carboxyl group of the polycarboxylic acid. Since this coating has poor melt softening properties due to heat and has no tackiness, the coating resin particles are melted and fused, thereby hindering the formation of the coating when forming the coating. For this reason, cracks occurred in the coating film during film formation and smoothness was insufficient. Therefore, it is necessary to raise the temperature of the slurry paint immediately after coating to form a film. A powder paint is applied on the slurry paint to form a film at the same time. It was not possible to apply paint and form a film.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記のよう
な諸問題の生じることのない塗装方法を提供すること、
即ち、有機溶剤を使用する必要がなく、低コストで製造
される安定な水性分散塗料を塗装を必要とする全部分又
は一部分に前補正として又は導電性塗膜の形成を目的と
して塗装し、次いで粉体塗料又は水性分散粉体塗料を塗
装しても、成膜時に塗膜に割れが生じたり、平滑性が不
足したりすることなしに塗膜性能に優れた均一な組成の
塗膜及び／又は異なった組成の２層の塗膜を形成する塗
装方法を提供することを課題としている。SUMMARY OF THE INVENTION The present invention provides a coating method which does not cause the above-mentioned problems.
That is, there is no need to use an organic solvent, and a stable aqueous dispersion paint manufactured at low cost is applied as a pre-correction to all or a part of the paint that needs painting, or for the purpose of forming a conductive coating film, Even if a powder coating or an aqueous dispersion powder coating is applied, a coating having a uniform composition and excellent coating performance without causing cracks in the coating at the time of film formation or lacking in smoothness. Another object of the present invention is to provide a coating method for forming two layers of coating films having different compositions.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、上記の課
題を解決するために鋭意検討した結果、水性分散粉体塗
料中の塗料樹脂粒子の分散、安定化のために、非揮発性
で、塗膜用樹脂と相溶し易いノニオン系の界面活性剤及
び／又はノニオン系の増粘安定剤を分散安定剤として使
用し、好ましくはその分散安定剤の一部又は全量を塗料
樹脂粒子の作成時に塗料樹脂粒子中に均一に配合分散さ
せて使用することにより上記の課題が解決されることを
見いだし、本発明を完成した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the dispersion and stabilization of the coating resin particles in the aqueous dispersion powder coating material require the use of a nonvolatile resin. A nonionic surfactant and / or a nonionic thickening stabilizer which is easily compatible with the resin for the coating film is used as a dispersion stabilizer, and preferably a part or all of the dispersion stabilizer is used as coating resin particles. It has been found that the above-mentioned problems can be solved by uniformly mixing and dispersing it in the coating resin particles at the time of preparation, and the present invention has been completed.
【０００７】即ち、本発明の粉体塗料の塗装方法は、下
層となる第１層として、ノニオン系界面活性剤及び／又
はノニオン系増粘安定剤を分散安定剤として使用した水
性分散粉体塗料（ａ）を塗装し、上層となる第２層とし
て、粉体塗料（ｂ）又は、ノニオン系界面活性剤及び／
又はノニオン系増粘安定剤を分散安定剤として使用した
水性分散粉体塗料（ｃ）を全面に又は必要とする部分に
塗装することを特徴とする。That is, in the method for coating a powder coating according to the present invention, an aqueous dispersion powder coating using a nonionic surfactant and / or a nonionic thickening stabilizer as a dispersion stabilizer as a lower first layer. (A) is applied, and a powder coating (b) or a nonionic surfactant and / or
Alternatively, an aqueous dispersion powder coating (c) using a nonionic thickening stabilizer as a dispersion stabilizer is coated on the entire surface or on a required portion.
【０００８】また、本発明の粉体塗料の塗装方法は、下
層となる第１層として、ノニオン系界面活性剤及び／又
はノニオン系増粘安定剤を分散安定剤として使用した水
性分散粉体塗料（ａ）を塗装し、塗装後塗膜中の水分に
よる導電性が消失する前に、上層となる第２層として、
粉体塗料（ｂ）又は、ノニオン系界面活性剤及び／又は
ノニオン系増粘安定剤を分散安定剤として使用した水性
分散粉体塗料（ｃ）を全面に又は必要とする部分に静電
塗装することを特徴とする。Further, in the method for coating a powder coating according to the present invention, an aqueous dispersion powder coating using a nonionic surfactant and / or a nonionic thickening stabilizer as a dispersion stabilizer as a lower first layer. (A) is applied, and before the conductivity due to moisture in the coating film is lost after coating, as a second layer to be an upper layer,
The powder coating (b) or the aqueous dispersion powder coating (c) using a nonionic surfactant and / or a nonionic thickening stabilizer as a dispersion stabilizer is electrostatically coated on the entire surface or on a necessary portion. It is characterized by the following.
【０００９】更に、本発明の粉体塗料の塗装方法は、ノ
ニオン系界面活性剤及び／又はノニオン系増粘安定剤を
分散安定剤として使用した水性分散粉体塗料（ａ）を前
補正として部分的に、即ち前補正を必要とする所定の部
分に塗装し、その後、粉体塗料（ｂ）又は、ノニオン系
界面活性剤及び／又はノニオン系増粘安定剤を分散安定
剤として使用した水性分散粉体塗料（ｃ）を塗装するこ
とを特徴とする。Further, the method of coating a powder coating according to the present invention is characterized in that the aqueous dispersion powder coating (a) using a nonionic surfactant and / or a nonionic thickening stabilizer as a dispersion stabilizer is partially corrected as a pre-correction. Specifically, that is, the aqueous dispersion using a powder coating (b) or a nonionic surfactant and / or a nonionic thickening stabilizer as a dispersion stabilizer is applied to a predetermined portion requiring pre-correction. It is characterized by applying a powder coating (c).
【００１０】[0010]
【発明の実施の形態】本発明の塗装方法においては、塗
布された水性分散粉体塗料（ａ）、及び粉体塗料（ｂ）
又は水性分散粉体塗料（ｃ）のそれぞれの塗料樹脂粒子
が加熱によって熱軟化又は溶融し、均質な塗膜となるこ
とが必要である。従って、本発明の塗装方法で用いる水
性分散粉体塗料又は粉体塗料を構成する塗料樹脂粒子の
軟化温度は好ましくは１０〜２５０℃、更に好ましくは
３０〜２００℃である。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the coating method of the present invention, the applied aqueous dispersion powder coating (a) and the powder coating (b)
Alternatively, it is necessary that each coating resin particle of the aqueous dispersion powder coating (c) is heat-softened or melted by heating to form a uniform coating film. Accordingly, the softening temperature of the aqueous dispersion powder coating or the coating resin particles constituting the powder coating used in the coating method of the present invention is preferably 10 to 250C, more preferably 30 to 200C.
【００１１】塗料樹脂粒子の軟化温度が１０℃よりも低
い場合には、塗料の通常の保管温度においても、水性分
散粉体塗料中の塗料樹脂粒子が水性媒体中にあるにも拘
わらず凝集し易くなる傾向がある。その理由は、エマル
ション塗料等中の塗料樹脂粒子の大きさと比較して、粉
体塗料樹脂粒子の粒子径が１００倍から１０００倍大き
いためである。水性分散粉体塗料中の塗料樹脂粒子の平
均粒子径を小さくすればする程、軟化温度が低い塗料樹
脂粒子であっても、水性分散粉体塗料を安定に保つこと
ができる。しかし、この場合には水性分散粉体塗料中の
塗料樹脂粒子の合計表面積が大きくなるので、塗料樹脂
粒子を水媒体中に安定に分散させるために界面活性剤等
の湿潤剤を多く存在させることが必要となる。従って、
このような場合には、得られる塗膜の耐水性、光沢等の
性能が低下することになる。When the softening temperature of the coating resin particles is lower than 10 ° C., the coating resin particles in the aqueous dispersion powder coating agglomerate even at the ordinary storage temperature of the coating, despite being in the aqueous medium. Tends to be easier. The reason is that the particle diameter of the powder coating resin particles is 100 to 1000 times larger than the size of the coating resin particles in the emulsion coating or the like. The smaller the average particle diameter of the coating resin particles in the aqueous dispersion powder coating, the more stable the aqueous dispersion powder coating can be maintained, even if the coating resin particles have a lower softening temperature. However, in this case, the total surface area of the coating resin particles in the aqueous dispersion powder coating becomes large. Therefore, in order to stably disperse the coating resin particles in the aqueous medium, a large amount of a wetting agent such as a surfactant must be present. Is required. Therefore,
In such a case, the performance of the obtained coating film, such as water resistance and gloss, is reduced.
【００１２】また、塗料樹脂粒子の軟化温度が２５０℃
を超える場合には、塗膜を形成させるための加熱硬化に
２５０℃を超える温度が必要であり、そのような高温で
は塗膜が黄色に変色したり、塗膜が空気で酸化されて可
撓性を失ったりする傾向があるので好ましくない。その
ような現象の防止方法として、特殊な例としては、炭酸
ガス等の不活性ガス雰囲気中で成膜させる方法がある
が、この場合にはそのような不活性ガス雰囲気を形成す
るための装置が余分に必要になる。また、樹脂成分とし
てオレフィン樹脂や、高分子のフッ素樹脂を使用した塗
料を成膜させる場合にはそのような現象は生じにくい傾
向がある。The softening temperature of the coating resin particles is 250 ° C.
When the temperature exceeds 250 ° C, a temperature exceeding 250 ° C. is required for heat curing to form a coating film. At such a high temperature, the coating film turns yellow or the coating film is oxidized by air and becomes flexible. It is not preferable because the property tends to be lost. As a special example of a method for preventing such a phenomenon, there is a method of forming a film in an inert gas atmosphere such as carbon dioxide gas. In this case, an apparatus for forming such an inert gas atmosphere is used. Is needed. Further, such a phenomenon tends to hardly occur when forming a coating film using an olefin resin or a high-molecular fluorine resin as a resin component.
【００１３】上記のような塗料樹脂粒子の樹脂成分とし
て、アルキド樹脂、アクリル樹脂、ポリエステル樹脂、
エポキシ樹脂、メラミン樹脂、ブロックイソシアネート
樹脂、フッ素樹脂、シリコン樹脂、アミド樹脂、ＡＢＳ
樹脂等を挙げることができ、それらの樹脂成分は単独
で、又は、必要によって、任意の配合比率で組み合わせ
で使用することができる。更に必要に応じて、通常の塗
料に使用されている二塩基酸や多塩基酸、ポリアミド樹
脂等の硬化剤や、表面調整剤、硬化促進剤等の添加剤を
添加することもできる。Alkyd resin, acrylic resin, polyester resin,
Epoxy resin, melamine resin, blocked isocyanate resin, fluororesin, silicone resin, amide resin, ABS
Resins and the like can be mentioned, and those resin components can be used alone or, if necessary, in combination at an arbitrary mixing ratio. If necessary, a curing agent such as a dibasic acid or polybasic acid, a polyamide resin, and the like, which are used in ordinary coating materials, and an additive such as a surface conditioner and a curing accelerator can also be added.
【００１４】これらの樹脂、硬化剤等の外に、塗膜構成
成分として、着色顔料や防錆顔料、その他の機能を与え
るための添加剤等を加えることが有効である。これらの
着色顔料としては、黄色酸化鉄、チタン黄、ベンガラ、
酸化チタン、亜鉛華、リトポン、鉛白、硫化亜鉛、酸化
アンチモン等の無機系顔料や、ハンザイエロー５Ｇ、パ
ーマネントエローＦＧＬ、フタロシアニンブルー、イン
ダンスレンブルーＲＳ、パーマネントレッドＦ５ＲＫ、
ブリリアントファーストスカーレットＧ、パリオゲンレ
ッド３９１０等の有機顔料がある。In addition to these resins and curing agents, it is effective to add coloring pigments, rust-preventive pigments, additives for imparting other functions, etc. as coating film constituents. These coloring pigments include yellow iron oxide, titanium yellow, red iron oxide,
Inorganic pigments such as titanium oxide, zinc oxide, lithopone, lead white, zinc sulfide, antimony oxide, Hansa Yellow 5G, permanent yellow FGL, phthalocyanine blue, indanthrene blue RS, permanent red F5RK,
Organic pigments such as Brilliant First Scarlet G and Paliogen Red 3910.
【００１５】塗料樹脂粒子中へのこれら顔料の添加量
は、通常ＰＷＣで０．５〜６０％程度であるが、クリヤ
ー塗料の様に全く添加しない場合もある。ここで、ＰＷ
Ｃとは Pigment Weight Concentration （顔料重量濃
度）のことであり、下記の式により算出される。 ＰＷＣ＝［（含有顔料重量％）／（全塗料固形分重量
％）］×１００The amount of these pigments added to the coating resin particles is usually about 0.5 to 60% by PWC, but may not be added at all like clear coating. Where PW
C is Pigment Weight Concentration, which is calculated by the following equation. PWC = [(content pigment weight%) / (total paint solid content weight%)] × 100
【００１６】これらの顔料の添加量が多い場合には、特
に吸油量の高い顔料を用いる場合には、そのような塗料
を用いて塗膜を形成すると、塗膜の平滑性が損なわれる
傾向がある。その他に、塗膜の光沢値を調節したり、塗
膜の堅さを調節したりする目的で、体質顔料として、硫
酸バリウム、炭酸バリウム、炭酸カルシウム、クレー、
シリカ粉、微粉珪酸、珪藻土、タルク、塩基性炭酸マグ
ネシウム、アルミナホワイト等を添加することもでき
る。When a large amount of these pigments is added, particularly when a pigment having a high oil absorption is used, when a coating film is formed using such a paint, the smoothness of the coating film tends to be impaired. is there. In addition, for the purpose of adjusting the gloss value of the coating film or adjusting the hardness of the coating film, as an extender, barium sulfate, barium carbonate, calcium carbonate, clay,
Silica powder, finely divided silica, diatomaceous earth, talc, basic magnesium carbonate, alumina white, and the like can also be added.
【００１７】本発明の塗装方法においては、塗料中に光
輝性薄片状顔料を含有させてメタリック塗料とし、この
塗料を用いてデザイン的に有効な塗膜を形成させること
からなるメタリック塗装を実施することができる。この
ような光輝性薄片状顔料として、通常のアルミニウム顔
料、マイカ顔料、ブロンズ粉、銅粉、ステンレス粉や、
金属コーティングした硝子粉、金属コーティングしたマ
イカ粉、金属コーティングしたプラスチック粉等が使用
できる。In the coating method of the present invention, a metallic paint is formed by adding a glittery flaky pigment to the paint to form a metallic paint, and using this paint to form an effective coating film in terms of design. be able to. As such brilliant flaky pigments, ordinary aluminum pigments, mica pigments, bronze powder, copper powder, stainless steel powder,
Metal-coated glass powder, metal-coated mica powder, metal-coated plastic powder and the like can be used.
【００１８】水性分散粉体塗料の場合には、光輝性薄片
状顔料を塗料樹脂粒子中に含有させることもできるが、
好ましくは、水性分散粉体塗料の水媒体中に塗料樹脂粒
子とは別個に含有させることが好ましい。この添加方法
については特に制約されるものでは無いが、予め水可溶
性溶媒や界面活性剤で光輝性薄片状顔料表面を親水性に
し、更に必要なら水溶性樹脂や添加剤等を併用して加え
ることもできる。これらの光輝性薄片状顔料は、各々単
独で含有させることも、２種以上を同時に使用すること
も可能である。光輝性薄片状顔料の塗料中への添加量
は、全固形分の０．０５〜３０重量％程度であることが
好ましい。In the case of an aqueous dispersion powder coating, a glittery flaky pigment can be contained in the coating resin particles.
Preferably, it is preferably contained in the aqueous medium of the aqueous dispersion powder coating separately from the coating resin particles. There is no particular limitation on the method of addition, but the surface of the glittering flake pigment is made hydrophilic with a water-soluble solvent or a surfactant in advance, and if necessary, a water-soluble resin or an additive is added in combination. You can also. Each of these glittering flaky pigments can be used alone or in combination of two or more. The amount of the brilliant flaky pigment added to the paint is preferably about 0.05 to 30% by weight of the total solids.
【００１９】本発明の塗装方法により形成される塗膜の
ツヤを調製するために、塗料中にツヤ消し用顔料を加え
ることが可能である。また、塗料中の塗料樹脂粒子を２
種類以上の混合物とし、それらの塗料樹脂粒子間の相溶
性や反応速度の差でツヤを調整することもできる。これ
らのツヤ調整剤としては、塗料に通常使用されているコ
ロイダルシリカ、アルミナ、タルク等を使用することが
できる。In order to prepare the gloss of the coating film formed by the coating method of the present invention, it is possible to add a matting pigment to the paint. Also, the paint resin particles in the paint are
It is also possible to use a mixture of more than one kind, and to adjust the luster by the difference in compatibility or reaction rate between the coating resin particles. As these gloss control agents, colloidal silica, alumina, talc, and the like, which are commonly used in paints, can be used.
【００２０】本発明の塗装方法で用いる水性分散粉体塗
料（ａ）及び（ｃ）においては、塗料樹脂粒子を水媒体
中に安定に分散させるために分散安定剤を使用する必要
があり、本発明においては分散安定剤としてノニオン系
界面活性剤及び／又はノニオン系増粘安定剤を用いる。In the aqueous dispersion powder coatings (a) and (c) used in the coating method of the present invention, it is necessary to use a dispersion stabilizer to stably disperse the coating resin particles in an aqueous medium. In the present invention, a nonionic surfactant and / or a nonionic thickening stabilizer are used as the dispersion stabilizer.
【００２１】本発明で使用するノニオン系界面活性剤と
しては、ポリエチレングリコール型ノニオン界面活性
剤、多価アルコール型ノニオン界面活性剤等があり、ポ
リエチレングリコール型ノニオン界面活性剤としては、
ポリエチレングリコール型ノニオン界面活性剤、高級ア
ルコールエチレンオキサイド付加物、アルキルフェノー
ルエチレンオキサイド付加物、脂肪酸エチレンオキサイ
ド付加物、高級脂肪族アミンエチレンオキサイド付加
物、脂肪族アミドエチレンオキサイド付加物、ポリプロ
ピレングリコールエチレンオキサイド付加物等がある。
また、多価アルコール型ノニオン界面活性剤としては、
グリセリンの脂肪酸エステル、ペンタエリスリットの脂
肪酸エステル、ソルビットの脂肪酸エステル、ソルビタ
ンの脂肪酸エステル、脂肪酸アルカノールアミド等があ
る。The nonionic surfactant used in the present invention includes a polyethylene glycol type nonionic surfactant, a polyhydric alcohol type nonionic surfactant and the like. Examples of the polyethylene glycol type nonionic surfactant include:
Polyethylene glycol type nonionic surfactant, higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher aliphatic amine ethylene oxide adduct, aliphatic amide ethylene oxide adduct, polypropylene glycol ethylene oxide adduct Etc.
In addition, as a polyhydric alcohol type nonionic surfactant,
Examples include glycerin fatty acid ester, pentaerythrit fatty acid ester, sorbit fatty acid ester, sorbitan fatty acid ester, and fatty acid alkanolamide.
【００２２】これらノニオン系界面活性剤の中でも、水
性分散粉体塗料として塗料樹脂粒子を均一に湿潤、分散
させるためには、ＨＬＢが７以上の界面活性剤が好まし
い。しかし、ＨＬＢが２２を超える界面活性剤を用いる
と、勿論添加量にもよるが、塗膜の耐水性等の性能が低
下する傾向があるので好ましくない。更に好ましくはＨ
ＬＢが８〜１８程度の界面活性剤を用いる。Among these nonionic surfactants, surfactants having an HLB of 7 or more are preferred in order to uniformly wet and disperse the coating resin particles as an aqueous dispersion powder coating. However, it is not preferable to use a surfactant having an HLB of more than 22 because the performance such as the water resistance of the coating film tends to decrease, although it depends on the amount of addition. More preferably H
A surfactant having an LB of about 8 to 18 is used.
【００２３】塗料樹脂粒子及び／又は水媒体中に加える
界面活性剤の総量は、塗料樹脂粒子の重量の０．１〜５
重量％程度となる量にすることが好ましい。この場合、
塗料樹脂粒子内に加える添加量の割合を多くすると、水
媒体中にだけ加える場合に比べ、水性分散粉体塗料の全
体に必要な界面活性剤の総量を約２分の１とすることが
でき、この約２分の１の添加量で、水媒体中にだけ加え
る場合と同等以上の湿潤、分散性を得ることができる。
このため、塗膜性能、特に耐水性、光沢等の良好な塗膜
を形成することができる。The total amount of the surfactant added to the coating resin particles and / or the aqueous medium is 0.1 to 5% by weight of the coating resin particles.
It is preferable to set the amount to be about weight%. in this case,
When the ratio of the amount added to the coating resin particles is increased, the total amount of the surfactant required for the entire aqueous dispersion powder coating can be reduced to about one-half as compared with the case where the addition is performed only in the aqueous medium. With about half the amount of addition, it is possible to obtain wettability and dispersibility equal to or greater than that when only the aqueous medium is added.
For this reason, it is possible to form a coating film having good coating performance, particularly good water resistance and gloss.
【００２４】また、ノニオン系増粘安定剤としては、特
に、ポリエチレングリコール型増粘安定剤を挙げること
ができ、増粘安定効果の点では分子量の大きい増粘安定
剤が好ましい。しかし、分子量が１００万以上になる
と、水性分散粉体塗料の貯蔵安定性は良好であるが、エ
アースプレー塗装等におけるように微粒化して塗装する
方法では、塗装時、糸引き現象を発生する傾向があるの
で好ましくないが、プレコートメタルでの塗装の様に、
ロール塗装やフローコート塗装では、塗料の追随性や膜
形成性が良いので好ましい。As the nonionic thickening stabilizer, a polyethylene glycol type thickening stabilizer can be particularly mentioned, and a thickening stabilizer having a large molecular weight is preferable in terms of the thickening and stabilizing effect. However, when the molecular weight is 1,000,000 or more, the storage stability of the aqueous dispersion powder coating is good, but the method of atomizing and coating as in air spray coating tends to cause a stringing phenomenon at the time of coating. Although it is not preferable because there is, like painting with pre-coated metal,
Roll coating or flow coating is preferable because of good followability and film forming property of the paint.
【００２５】塗料樹脂粒子及び／又は水媒体中に加える
ノニオン系増粘安定剤の総量は、通常、エアースプレー
塗装、静電塗装、エアレス塗装、回転霧化型静電塗装に
使用する水性分散粉体塗料の場合で、分子量が数十万程
度のノニオン系増粘安定剤を用いる場合には、塗料樹脂
粒子の重量の０．３〜５重量％程度となる量にすること
が好ましい。また、ロール塗装やフローコート塗装に使
用する水性分散粉体塗料の場合で、分子量が数十万〜２
百万程度のノニオン系増粘安定剤を用いる場合には、塗
料樹脂粒子の重量の０．１〜５重量％程度となる量にす
ることが好ましい。The total amount of the nonionic thickening stabilizer to be added to the coating resin particles and / or the aqueous medium is usually the amount of the aqueous dispersion powder used for air spray coating, electrostatic coating, airless coating, and rotary atomizing electrostatic coating. In the case of a body paint, when a nonionic thickening stabilizer having a molecular weight of about several hundred thousand is used, the amount is preferably about 0.3 to 5% by weight of the paint resin particles. In the case of an aqueous dispersion powder coating used for roll coating or flow coating, the molecular weight is several hundred thousand to 2
When about one million nonionic thickening stabilizers are used, the amount is preferably about 0.1 to 5% by weight of the coating resin particles.
【００２６】本発明で用いる水性分散粉体塗料は、水媒
体中に上記の分散安定剤を溶解しておいてその中で塗料
樹脂粒子の原料を湿式粉砕する方法によっても製造する
ことができる。しかしながら、この方法では、湿式粉砕
の初期と終わりで、塗料樹脂粒子表面に吸着する分散安
定剤の濃度が異なり、特に塗料樹脂粒子の合計表面積が
多くなる湿式粉砕の終点においては、塗料樹脂粒子表面
に吸着された分散安定剤の希薄な塗料樹脂粒子が出来る
ためか、凝集し易くなる傾向があるので好ましくない。The aqueous dispersion powder coating used in the present invention can also be produced by dissolving the above-mentioned dispersion stabilizer in an aqueous medium and wet-grinding the raw material of the coating resin particles therein. However, in this method, the concentration of the dispersion stabilizer adsorbed on the surface of the coating resin particles differs between the beginning and the end of the wet grinding, and especially at the end point of the wet grinding where the total surface area of the coating resin particles increases, It is not preferable because dilute coating resin particles of the dispersion stabilizer adsorbed on the surface are formed, or they tend to be easily aggregated.
【００２７】本発明で用いる水性分散塗料を製造する際
に、好ましくは、これらの分散安定剤の一部または全量
を塗膜構成成分と一緒に混合し、溶融練合することによ
って塗料樹脂中に均一に分散させる。この塗料樹脂を冷
却固化後に粗砕し、その粗粒子を水性分散媒体中で湿式
粉砕すると、この粉砕によって新しく生成する塗料樹脂
粒子の表面には常に均一に分散安定剤が現れるのでその
塗料樹脂粒子は親水性になる。その結果、塗料塗料樹脂
粒子が微細に湿式粉砕されて表面積が増加しても、塗料
樹脂粒子の湿潤性や増粘安定性は一定に保たれる。更
に、塗料樹脂粒子が微細になるほど、通常は凝集し易く
なるが、分散安定剤を含有する塗料樹脂粒子の場合に
は、塗料樹脂粒子の表面特性が上記のように常に一定で
均一なため、塗料樹脂粒子は水性分散塗料中において安
定に分散する。従って、この場合には、前記したよう
に、分散安定剤を水媒体中にだけ加える場合に比べ、水
性分散粉体塗料の全体に必要な界面活性剤の総量を約２
分の１として、水媒体中にだけ加える場合と同等以上の
湿潤、分散性を得ることができるので、分散安定剤の配
合量が少なくなったことと、均一に分散していることの
ため、偏在が無く、塗膜性能も良好になる。しかし、一
番の相違点は、塗料のｐＨ依存性が無く、ｐＨが中和点
より低い３程度でも何ら支障無く塗布、成膜できる。In producing the aqueous dispersion paint used in the present invention, preferably, a part or all of these dispersion stabilizers are mixed together with the components of the coating film and melt-kneaded to form a resin in the paint resin. Disperse evenly. When the paint resin is cooled and solidified and then coarsely crushed, and the coarse particles are wet-pulverized in an aqueous dispersion medium, the dispersion stabilizer always appears uniformly on the surface of newly generated paint resin particles due to this pulverization. Becomes hydrophilic. As a result, even if the paint resin particles are finely wet-pulverized to increase the surface area, the wettability and the thickening stability of the paint resin particles are kept constant. Further, as the coating resin particles become finer, they usually tend to aggregate, but in the case of coating resin particles containing a dispersion stabilizer, the surface characteristics of the coating resin particles are always constant and uniform as described above, The paint resin particles are stably dispersed in the aqueous dispersion paint. Therefore, in this case, as described above, the total amount of the surfactant required for the entire aqueous dispersion powder coating is about 2 times as compared with the case where the dispersion stabilizer is added only to the aqueous medium.
As one part, we can obtain wetness and dispersibility equal to or higher than the case of adding only in an aqueous medium, so that the amount of the dispersion stabilizer is reduced and that the dispersion stabilizer is uniformly dispersed. There is no uneven distribution, and the coating film performance becomes good. However, the biggest difference is that there is no pH dependency of the coating material, and coating and film formation can be performed without any problem even when the pH is about 3 lower than the neutralization point.
【００２８】本発明の塗装方法においては、分散安定剤
としてノニオン系界面活性剤及び／又はノニオン系増粘
安定剤をするのであり、これらの分散安定剤は中和剤を
使用しないため、塗装後の水分の蒸発によっても塗料樹
脂粒子の熱軟化性や流動性があまり変化しない。従っ
て、水性分散粉体塗料の塗装後、その塗膜が湿潤状態で
あっても、完全に乾燥した状態であっても、その上に粉
体塗料や水性分散粉体塗料を塗装して加熱成膜させるこ
とができる。In the coating method of the present invention, a nonionic surfactant and / or a nonionic thickening stabilizer are used as dispersion stabilizers. Since these dispersion stabilizers do not use a neutralizing agent, they are used after coating. The heat softening property and fluidity of the coating resin particles do not change much even by evaporation of the water. Therefore, after the application of the water-based dispersed powder coating, the powder coating or the water-based dispersed powder coating is applied thereon, regardless of whether the coating film is wet or completely dried, and then heated. Can be filmed.
【００２９】本発明の塗装方法で用いる水性分散粉体塗
料は上記の特性を有しているので、前補正を目的として
第１層として上記の水性分散粉体塗料を塗装し、第２層
として粉体塗料又は水性分散粉体塗料を塗装するか、又
は非導電性素材に導電性塗膜を形成することを目的とし
て第１層として上記の水性分散粉体塗料を塗装し、第２
層として粉体塗料又は水性分散粉体塗料を静電塗装して
均一な組成の塗膜及び／又は異なった組成の２層の塗膜
を形成することができる。Since the aqueous dispersion powder coating used in the coating method of the present invention has the above-mentioned properties, the above-mentioned aqueous dispersion powder coating is applied as a first layer for the purpose of pre-correction, and as a second layer The above-mentioned aqueous dispersion powder coating is applied as a first layer for the purpose of applying a powder coating or an aqueous dispersion powder coating, or forming a conductive coating film on a non-conductive material;
A powder coating or an aqueous dispersion powder coating can be electrostatically applied as a layer to form a coating film having a uniform composition and / or two coating films having different compositions.
【００３０】例えば、箱物の内部を粉体塗料で塗装する
場合に、気流や電位の関係でコーナー部分の膜厚が薄く
なる傾向にある。この様なコーナー部分を予め水性分散
粉体塗料で前補正し、その後粉体塗料を塗装すること
で、コーナー部分まで確実に塗装することができる。即
ち、水性分散粉体塗料を前補正として部分的に、即ち前
補正を必要とする所定の部分に塗装し、その後、粉体塗
料又は水性分散粉体塗料を塗装することができる。For example, when the inside of a box is coated with a powder coating material, the thickness of the corners tends to be reduced due to the relationship between airflow and potential. Such a corner portion is pre-corrected with an aqueous dispersion powder coating in advance, and then the powder coating is applied, whereby the corner portion can be surely painted. That is, the aqueous dispersion powder coating can be partially applied as the pre-correction, that is, applied to a predetermined portion requiring the pre-correction, and then the powder coating or the aqueous dispersion powder coating can be applied.
【００３１】本発明の塗装方法においては、当然のこと
ではあるが、水性分散粉体塗料のみで全てを塗装して仕
上げる事も可能である。他方、第１層として塗装される
水性分散粉体塗料（ａ）に使用される塗料樹脂粒子の組
成と、第２層として塗装される粉体塗料（ｂ）又は水性
分散粉体塗料（ｃ）に使用される塗料樹脂粒子の組成と
は、同一の組成であっても、類似の組成であっても、ま
たは、全く異なる組成であってもよい。第１層に塗装す
る水性分散粉体塗料の塗料樹脂粒子の組成と第２層に塗
装する粉体塗料または水性分散粉体塗料の塗料樹脂粒子
の組成とが異なる場合には、連続的に、又は層状に異な
る樹脂組成の塗膜を容易に形成する事が出来る。In the coating method of the present invention, as a matter of course, it is also possible to finish all by applying only the aqueous dispersion powder coating. On the other hand, the composition of the coating resin particles used for the aqueous dispersion powder coating (a) applied as the first layer and the powder coating (b) or the aqueous dispersion powder coating (c) applied as the second layer The composition of the coating resin particles used in the above may be the same composition, a similar composition, or a completely different composition. When the composition of the coating resin particles of the aqueous dispersion powder coating applied to the first layer and the composition of the coating resin particles of the powder coating or aqueous dispersion powder coating applied to the second layer are different, Alternatively, coating films having different resin compositions can be easily formed in layers.
【００３２】＜水性分散粉体塗料（ａ）及び（ｃ）の製
造方法＞本発明で使用する水性分散粉体塗料（ａ）及び
（ｃ）は、（１）塗膜構成成分となる諸原料を混合して
配合物を得る工程、（２）該配合物を樹脂成分の軟化温
度以上の温度で溶融練合して均質化物を得る工程、
（３）該均質化物を冷却固化後に粗砕して粗粒子を得る
工程、及び（４）該粗粒子を水性分散媒中で湿式粉砕し
て平均粒子径が１０μｍ以下の微粒子を含む水性分散粉
体塗料を得る工程を順次実施することにより製造するこ
とができる。<Production Method of Aqueous Dispersion Powder Coatings (a) and (c)> The aqueous dispersion powder coatings (a) and (c) used in the present invention are prepared by (1) various raw materials to be constituents of a coating film (2) a step of melting and kneading the mixture at a temperature equal to or higher than the softening temperature of the resin component to obtain a homogenized product;
(3) a step of coarsely crushing the homogenized product after cooling and solidifying to obtain coarse particles, and (4) an aqueous dispersion powder containing fine particles having an average particle diameter of 10 μm or less by wet grinding the coarse particles in an aqueous dispersion medium. It can be manufactured by sequentially performing steps of obtaining a body paint.
【００３３】上記（１）の工程、即ち、塗膜構成成分と
なる諸原料を混合して配合物を得る工程においては、固
形の樹脂原料を中心に着色顔料、硬化剤、添加剤、更に
必要によっては少量の液状原料をできるだけ均質に混合
する。このための装置としては、粉体原料を混合する通
常の装置であるフラッシュミキサー、スクリューミキサ
ー、コニカルブレンダ、Ｖミキサー、タンブリングミキ
サー、ジェットミキサー、ニーダー、リボンミキサー等
が使用できる。これらの装置を用いて諸原料を混合配合
し、できるだけ均質にすることが好ましいが、諸原料の
合計量が少量である場合には、諸原料を袋の中で簡単に
混合し次の溶融練合工程で均質にすることもできる。特
に、塗料樹脂粒子を水媒体中に容易に分散させる働きを
する前記の分散安定剤の一部または全部をこの混合配合
工程において添加しておくと、後の湿式粉砕工程におい
て塗料樹脂粒子の新しく生成する粉砕表面も均しく親水
性であるので水性分散粉体塗料の生成が容易になる。In the step (1), that is, in the step of mixing various raw materials constituting the coating film to obtain a blend, a coloring pigment, a curing agent, additives, In some cases, a small amount of liquid raw material is mixed as homogeneously as possible. As a device for this, a flash mixer, a screw mixer, a conical blender, a V mixer, a tumbling mixer, a jet mixer, a kneader, a ribbon mixer, etc., which are ordinary devices for mixing powder raw materials, can be used. It is preferable to mix and mix the various raw materials using these devices and make them as homogeneous as possible.However, when the total amount of the various raw materials is small, the various raw materials are simply mixed in a bag and then melted and kneaded. It can be homogenized in the combined process. In particular, if a part or all of the dispersion stabilizer, which functions to easily disperse the coating resin particles in an aqueous medium, is added in this mixing and blending step, the coating resin particles will be newly added in the subsequent wet grinding step. Since the resulting pulverized surface is evenly hydrophilic, the production of the aqueous dispersion powder coating is facilitated.
【００３４】次に、上記（２）の工程、即ち、上記配合
物を上記樹脂成分の軟化温度以上の温度で溶融練合して
均質化物を得る工程を実施する。この工程は、塗料樹脂
粒子の原料である固形の樹脂原料、着色顔料、硬化剤、
添加剤などを数μｍ以下の程度まで均質に混合すること
を目的としている。本発明で使用する水性分散粉体塗料
の樹脂原料や硬化剤は、輸送や配合時の取り扱いを容易
にし且つ粉塵の舞い上がりが生じることのないようにす
る目的で、数ｍｍ程度のペレットに加工されている。こ
のペレットを破砕して数百μｍ程度の粒子からなる混合
物にし、これを樹脂成分の軟化温度以上に加温して機械
的に練合する。Next, the step (2), that is, the step of melting and kneading the compound at a temperature equal to or higher than the softening temperature of the resin component to obtain a homogenized product is performed. In this step, a solid resin raw material that is a raw material of the coating resin particles, a coloring pigment, a curing agent,
It is intended to uniformly mix additives and the like to a size of several μm or less. The resin raw material and the curing agent of the aqueous dispersion powder coating used in the present invention are processed into pellets of about several mm in order to facilitate handling during transportation and blending and to prevent dust from rising. ing. The pellets are crushed to form a mixture composed of particles of about several hundred μm, which are heated above the softening temperature of the resin component and mechanically kneaded.
【００３５】この練合に用いる装置として、ロールミ
ル、スクリューニーダー、マーラー、ニーダー等があ
る。特に好ましい装置は、作業性、取り扱い易さの点で
ロールミル、スクリューニーダーである。これらの装置
は、溶融練合後、練合物を速やかに装置より排出して冷
却することができる点で好ましい。特に、架橋型水性分
散粉体塗料の場合には塗料樹脂粒子中に硬化剤が含まれ
るものであり、それでこの溶融練合工程で樹脂成分、硬
化剤等が均質に混合され、この時、樹脂成分の軟化温度
以上に加熱されるので、練合する時の滞留時間が長くな
ると樹脂成分の一部が硬化剤と反応してしまい、その結
果として塗膜を形成する時に平滑にならなかったり、光
沢不足の欠陥を生じたりする傾向がある。従って、一方
向から供給し他方から連続的に排出する形式の装置を用
いることが好適である。As a device used for this kneading, there are a roll mill, a screw kneader, a mauler, a kneader and the like. Particularly preferred devices are a roll mill and a screw kneader in terms of workability and ease of handling. These devices are preferable in that after the melt-kneading, the kneaded material can be quickly discharged from the device and cooled. In particular, in the case of a crosslinked aqueous dispersion powder coating material, a curing agent is contained in the coating resin particles, so that in this melting and kneading step, a resin component, a curing agent, and the like are homogeneously mixed. Because the component is heated to a temperature higher than the softening temperature, a part of the resin component reacts with the curing agent when the residence time during kneading becomes longer, and as a result, it does not become smooth when forming a coating film, It tends to cause defects of insufficient gloss. Therefore, it is preferable to use an apparatus of a type in which the supply is performed from one direction and the discharge is continuously performed from the other.
【００３６】次に、上記（３）の工程、即ち、上記均質
化物を冷却固化後に粗砕して粗粒子を得る工程に入る。
この工程での処理は、前段の溶融練合工程でできる塗料
樹脂均質化物はそのままで冷却固化させると塊状になる
ので、これを次の湿式粉砕工程で処理し易い粗粒子にす
るための前処理である。粗砕するための装置の例として
はリングロールミル、エッジランナー、ロールクラッシ
ャー、ディスインテグレータ、ハンマクラッシャ、イン
ペラブレーカ、ジャイレトリークラッシャ、ジョウクラ
ッシャ等がある。Next, the process proceeds to the step (3), that is, a step of obtaining the coarse particles by crushing the homogenized product after cooling and solidifying.
In this process, the paint resin homogenized product formed in the preceding melt kneading process is cooled and solidified as it is to form a lump, so it is pre-processed to form coarse particles that can be easily processed in the next wet pulverization process It is. Examples of the apparatus for crushing include a ring roll mill, an edge runner, a roll crusher, a disintegrator, a hammer crusher, an impeller breaker, a gyratory crusher, and a jaw crusher.
【００３７】次に、上記（４）の工程、即ち、上記粗粒
子を水性分散媒中で湿式粉砕して平均粒子径が１０μｍ
以下の微粒子を含む水性分散粉体塗料を得る工程につい
て説明する。まず第一に、水性分散粉体塗料を受容する
タンクに必要量の水を準備する。必要に応じて、この水
に塗料樹脂粒子の湿潤のための界面活性剤や、沈殿防止
剤等を加え、混合して均質にする。この水媒体を循環ポ
ンプにより湿式粉砕機に循環させておく。この循環経路
の湿式粉砕機の入り口側に上記粗粒子の取り込み口を設
ける。ここに取り込まれた粗粒子は自重で水媒体中に混
合された後に湿式粉砕機の中へ入ってもよく、また、何
らかの攪拌混合機で湿潤された後に湿式粉砕機の中へ取
り込まれてもよい。Next, the above step (4), that is, the above coarse particles are wet-pulverized in an aqueous dispersion medium to have an average particle diameter of 10 μm
A process for obtaining the following aqueous dispersion powder coating containing fine particles will be described. First, a required amount of water is prepared in a tank for receiving the aqueous dispersion powder coating. If necessary, a surfactant for wetting the coating resin particles, a suspending agent, and the like are added to the water and mixed to make it homogeneous. This aqueous medium is circulated through a wet pulverizer by a circulation pump. An inlet for the coarse particles is provided on the inlet side of the wet pulverizer in this circulation path. The coarse particles taken in here may enter the wet pulverizer after being mixed into the aqueous medium by their own weight, or may be taken into the wet pulverizer after being wetted by any stirring mixer. Good.
【００３８】この場合に重要なことは、十分な量の水媒
体が湿式粉砕機中を循環して装置内の冷却と粉砕微粒子
の搬送とを十分に実行できることである。粉砕開始後の
初期段階においては循環水媒体中の塗料樹脂粒子の濃度
が低く、従ってその塗料樹脂粒子含有水媒体の粘度も低
いので、塗料樹脂粒子含有水媒体は循環しやすいが、順
次添加される粗粒子の湿式粉砕が進み、水媒体の循環が
繰り返されると循環水媒体中の塗料樹脂粒子の濃度が高
くなるので、循環と冷却とが次第に困難になってくる。
万が一水媒体の循環が停止すると、循環水媒体中に供給
された粗粒子及び循環していた塗料樹脂粒子が湿式粉砕
機中で粉砕エネルギーによって溶融し、装置の内面に固
着したりする危険がある。このため、目的とする水性分
散粉体塗料中の塗料樹脂粒子濃度、流動性の設定、水性
分散粉体塗料の循環量、温度の管理は重要である。通
常、循環量は容易に管理できるが、温度は、循環量が低
下すると急激に上昇するため、粗粒子の供給量と水媒体
の循環量、最終水性分散粉体塗料中の塗料樹脂粒子濃度
等は十分に管理する必要がある。What is important in this case is that a sufficient amount of aqueous medium can be circulated in the wet-type pulverizer to sufficiently cool the inside of the apparatus and transport the pulverized fine particles. In the initial stage after the commencement of pulverization, the concentration of the coating resin particles in the circulating aqueous medium is low, and thus the viscosity of the coating resin particle-containing aqueous medium is low. When the wet grinding of the coarse particles proceeds and the circulation of the aqueous medium is repeated, the concentration of the coating resin particles in the circulating aqueous medium increases, so that circulation and cooling gradually become difficult.
If the circulation of the aqueous medium is stopped, the coarse particles supplied into the circulating aqueous medium and the circulated paint resin particles may be melted by the grinding energy in the wet-type pulverizer and may adhere to the inner surface of the apparatus. . For this reason, it is important to control the concentration of the coating resin particles in the target aqueous dispersion powder coating, the fluidity, the circulation amount of the aqueous dispersion powder coating, and the temperature. Normally, the circulation amount can be easily controlled, but the temperature rises sharply as the circulation amount decreases, so the supply amount of coarse particles and the circulation amount of the aqueous medium, the concentration of the coating resin particles in the final aqueous dispersion powder coating, etc. Need to be well managed.
【００３９】次に、この湿式粉砕工程で使用しうる湿式
粉砕機の例について述べる。使用可能な湿式粉砕機とし
ては、ディスクグラインダ、タワーミル、ボールミル、
振動ミル、エッジランナ、ロールミルなどがある。タワ
ーミル、ボールミル、振動ミルのように分散メジアを使
用する湿式粉砕機では、供給する粗粒子の大きさがメジ
アの粒子径より大きいと湿式粉砕の効率が著しく低下す
る。従って、分散メジアを使用する湿式粉砕機の場合に
は、粗粒子をメジアの粒子径に比べて十分に小さくして
供給する必要がある。ディスクグラインダ、ロールミル
のように粗粒子を回転体に鋏んで粉砕するタイプの湿式
粉砕機では、かなり大きい粗粒子でも粉砕することは容
易であるが、湿潤させる水媒体の循環量が不足したり、
部分的に偏ったりすると、発熱により塗料樹脂粒子が融
着し易い傾向がある。Next, an example of a wet pulverizer that can be used in this wet pulverization step will be described. Usable wet grinders include disc grinders, tower mills, ball mills,
Vibration mills, edge runners, roll mills, etc. In a wet mill using a dispersed media such as a tower mill, a ball mill, and a vibration mill, if the size of the coarse particles to be supplied is larger than the median particle diameter, the efficiency of the wet mill is significantly reduced. Therefore, in the case of a wet mill using a dispersed media, it is necessary to supply coarse particles sufficiently smaller than the particle diameter of the media. In a wet grinder of a type in which coarse particles are crushed by a scissor on a rotating body such as a disc grinder or a roll mill, it is easy to grind even large coarse particles, but the circulation amount of the aqueous medium to be wetted is insufficient,
If it is partially biased, the coating resin particles tend to fuse due to heat generation.
【００４０】湿式粉砕機の運転態様としては、塗料樹脂
粒子濃度を低濃度に維持して運転すると管理が容易であ
るので、必要に応じて、遠心濾過機、遠心分離機、デカ
ンタ等を用いて塗料樹脂粒子濃度を調整することが好ま
しい。湿式粉砕処理については、塗料樹脂粒子が一定の
大きさの粒子径になるまで数回湿式粉砕機を通過させる
ことも、また一定の大きさ以上の塗料樹脂粒子をフィル
ターや遠心分級機などで分離、除去することもできる。
塗料樹脂粒子濃度を所定の濃度に調整した後、後調整と
して防黴剤や消泡剤、粘性付与剤等の添加剤等を加えて
水性分散粉体塗料とする。As for the operation mode of the wet-type pulverizer, if the operation is performed while maintaining the coating resin particle concentration at a low concentration, it is easy to manage. Therefore, if necessary, a centrifugal filter, a centrifugal separator, a decanter or the like may be used. It is preferable to adjust the coating resin particle concentration. For wet pulverization, paint resin particles can be passed through a wet pulverizer several times until they reach a certain particle size, or paint resin particles of a certain size or more can be separated using a filter or centrifugal classifier. , Can also be removed.
After adjusting the concentration of the coating resin particles to a predetermined concentration, additives such as a fungicide, an antifoaming agent, and a viscosity imparting agent are added as a post-adjustment to obtain an aqueous dispersion powder coating.
【００４１】でき上がった水性分散粉体塗料は、その中
に分散している塗料樹脂粒子の平均粒径が１０μｍ以下
で、含有濃度が２０〜６０重量％程度のものである。こ
こで重要な特徴は、水媒体中で直接湿式粉砕して塗料化
するので、また、必要によっては、塗膜構成成分となる
諸原料中に予め水中分散用の水系界面活性剤や水系増粘
安定剤の一部または全部が添加されているので、塗料樹
脂粒子が容易に水媒体中に湿潤し、分散、安定化される
ことにある。この結果、従来の相転換法で作成されるス
ラリー塗料や、粉体塗料を更に微粉砕して得られる微粒
子を水性媒体中に湿潤させて得られる水性分散粉体塗料
に比べ、分散安定剤の必要量が少なく、かつ粒子径の小
さい塗料樹脂粒子の水性分散粉体塗料が容易に調製でき
る。The resulting aqueous dispersion powder coating has an average particle size of the coating resin particles dispersed therein of not more than 10 μm and a content of about 20 to 60% by weight. The important feature here is that it is directly wet-pulverized in an aqueous medium to form a coating, and if necessary, aqueous surfactants for aqueous dispersion or aqueous thickening are preliminarily incorporated into the various raw materials that constitute the coating film. Since part or all of the stabilizer is added, the coating resin particles are easily wetted in an aqueous medium, and are dispersed and stabilized. As a result, compared with the aqueous dispersion powder coating obtained by wetting fine particles obtained by further finely pulverizing the slurry coating or powder coating obtained by the conventional phase inversion method in an aqueous medium, the dispersion stabilizer An aqueous dispersion powder coating of coating resin particles having a small required amount and a small particle diameter can be easily prepared.
【００４２】＜粉体塗料の製造方法＞本発明で使用する
粉体塗料（ｂ）は、（１）塗膜構成成分となる諸原料を
混合して配合物を得る工程、（２）該配合物を樹脂成分
の軟化温度以上の温度で溶融練合して均質化物を得る工
程、（３）該均質化物を冷却固化後に粗砕して粗粒子を
得る工程、（４）該粗粒子を水性分散媒中で湿式粉砕し
て平均粒子径が１０μｍ以下の微粒子を含む水性分散液
を得る工程、及び（５）該水性分散液を脱水処理して粉
体塗料を得る工程を順次実施することにより製造するこ
とができる。<Production Method of Powder Coating> The powder coating (b) used in the present invention comprises: (1) a step of mixing various raw materials as constituents of a coating film to obtain a compound; Melt-kneading the product at a temperature equal to or higher than the softening temperature of the resin component to obtain a homogenized product, (3) cooling and solidifying the homogenized product to obtain coarse particles, and (4) preparing the coarse particles in an aqueous solution. A step of obtaining an aqueous dispersion containing fine particles having an average particle size of 10 μm or less by wet grinding in a dispersion medium, and (5) a step of obtaining a powder coating by dehydrating the aqueous dispersion. Can be manufactured.
【００４３】上記（１）〜（４）の工程は、前記した水
性分散粉体塗料の製造方法の（１）〜（４）の工程と同
じであるので説明は省略する。上記の（５）の工程、即
ち、上記の水性分散液を脱水処理して粉体塗料を得る工
程は、フィルタープレス、葉状濾過機、回転濾過機等の
ケーキ濾過機、遠心濾過機、遠心分離機等を用いて脱水
し、乾燥することによって実施される。このような脱
水、乾燥によって塗料樹脂微粒子は凝集するので乾燥後
に破砕処理して粉体塗料とする。The steps (1) to (4) are the same as the steps (1) to (4) of the above-mentioned method for producing an aqueous dispersion powder coating, and therefore description thereof is omitted. The step (5), that is, the step of dehydrating the aqueous dispersion to obtain a powder coating, includes a filter press, a leaf filter, a cake filter such as a rotary filter, a centrifugal filter, and a centrifuge. It is carried out by dehydrating and drying using a machine or the like. The coating resin fine particles are aggregated by such dehydration and drying, and after drying, crushing treatment is performed to obtain a powder coating.
【００４４】本発明の粉体塗料の塗装方法においては、
第１層として、又は前補正として部分的に水性分散粉体
塗料（ａ）を塗装する。この塗装方法としては、水系塗
料で採用される通常の塗装方法を採用することができ、
例えばエアースプレー塗装、静電塗装、ディップ塗装、
刷毛塗り塗装、ロール塗装やフローコート塗装を挙げる
ことができる。In the method for coating a powder coating according to the present invention,
An aqueous dispersion powder coating (a) is applied as a first layer or partially as a pre-correction. As this coating method, a normal coating method used in water-based paint can be adopted,
For example, air spray painting, electrostatic painting, dip painting,
Examples include brush coating, roll coating, and flow coating.
【００４５】該水性分散粉体塗料（ａ）においては、塗
布して未乾燥の状態では、塗膜内部にある水分は塗料樹
脂粒子の間を毛細管現象によって自由に移動できるの
で、乾燥過程において、塗膜内部に水分がある間、塗膜
表面で水が蒸発するにつれて、塗膜内部の水が塗料樹脂
粒子の間を毛細管現象によって自由に塗膜表面まで移動
する。この移動速度は乾燥過程の終わりにおいても十分
に速く、水溶性樹脂塗料やエマルション塗料の場合の塗
膜内部を水が拡散によって表面に供給される速度に比べ
てかなり大きく、従って、水は塗膜表面より一定の早い
速度で蒸発する。このため、加熱によって内部の水が沸
騰し、ピンホールを形成するようなことも少ない。この
ため、沸点調整用の高沸点溶剤を併用する必要も無く、
塗料のＶＯＣも極めて少なく、通常１％以下である水性
分散粉体塗料となる。In the aqueous dispersion powder coating (a), when it is applied and undried, the water present in the coating can move freely between the coating resin particles by capillary action. While water is present inside the coating film, as the water evaporates on the coating film surface, the water inside the coating film moves freely between the coating resin particles to the coating film surface by capillary action. This movement speed is sufficiently fast even at the end of the drying process, which is considerably higher than the speed at which water is supplied to the surface by diffusion through the coating in the case of water-soluble resin coatings and emulsion coatings, and therefore water Evaporates at a constant faster rate than the surface. For this reason, it is unlikely that the water inside is boiled by heating and pinholes are formed. Therefore, there is no need to use a high boiling point solvent for adjusting the boiling point,
The VOC of the paint is extremely low, and usually becomes an aqueous dispersion powder paint having 1% or less.
【００４６】該水性分散粉体塗料（ａ）を用いることに
よる塗膜形成は、（Ａ）水分の蒸発工程、塗料樹脂粒子
層の形成工程、（Ｂ）塗料樹脂粒子の溶融、融着工程を
経て、連続塗膜を形成する。The coating film formation by using the aqueous dispersion powder coating (a) comprises (A) a step of evaporating water, a step of forming a coating resin particle layer, and (B) a step of melting and fusing coating resin particles. After that, a continuous coating film is formed.
【００４７】上記の諸工程は、エマルション塗料や水溶
性塗料で加熱、成膜工程で必要な程度には、厳格に工程
を管理する必要はないが、膜厚が厚い場合には、水の沸
騰によるピンホールの発生を防止するため昇温速度の管
理に注意をすることが好ましい。上記の（Ａ）工程及び
（Ｂ）工程はそれらの工程の間に時間を置かないで連続
的に実施しても、あるいは時間を置いて段階的に実施し
ても良い。上記の（Ａ）工程及び（Ｂ）工程間に時間を
置いて段階的に実施しても、即ち、塗装後、室温にて放
置し、任意の時間経過後、加温して成膜させても、従来
のアニオン系添加剤を使用した塗料の場合に発生した様
な割れが塗膜に発生することはない。室温で長期間放置
した塗膜は、水が蒸発し、塗料樹脂粒子が析出して粉体
塗料を塗装した場合とほとんど同じ状態の成膜過程を経
て成膜する。In the above-mentioned steps, it is not necessary to control the steps strictly to the extent necessary in the heating and film-forming steps with an emulsion paint or a water-soluble paint, but when the film thickness is large, boiling of water is required. It is preferable to pay attention to the control of the heating rate in order to prevent the occurrence of pinholes due to the above. The above steps (A) and (B) may be carried out continuously without any time between them, or may be carried out stepwise with a time in between. Even if the step (A) and the step (B) are carried out stepwise with an interval between the steps (A) and (B), that is, the coating is allowed to stand at room temperature, and after an elapse of an arbitrary time, heated to form a film. However, cracks such as those generated in the case of a paint using a conventional anionic additive do not occur in the coating film. The coating film left at room temperature for a long time is formed through a film forming process in almost the same state as when a powder coating is applied by evaporating water and depositing coating resin particles.
【００４８】第１層の塗装後又は前補正としての部分的
な塗装後に、第２層として又は前補正のない部分につい
ては仕上層として（以下、これらを総称して第２層と記
載する）粉体塗料（ｂ）又は水性分散粉体塗料（ｃ）を
塗装する。第２層の塗装方法としては、通常の塗装方法
を採用することができ、粉体塗料（ｂ）においては、例
えば静電塗装等を挙げることができる。また、水性分散
粉体塗料（ｃ）においては、例えば、エアースプレー塗
装、静電塗装、ディップ塗装、刷毛塗り塗装、ロール塗
装やフローコート塗装を挙げることができる。After coating the first layer or after partial coating as a pre-correction, the second layer or a part without the pre-correction is used as a finishing layer (hereinafter, these are collectively referred to as a second layer). The powder coating (b) or the aqueous dispersion powder coating (c) is applied. As the coating method of the second layer, a normal coating method can be adopted, and in the case of the powder coating (b), for example, electrostatic coating and the like can be mentioned. Examples of the aqueous dispersion powder coating (c) include air spray coating, electrostatic coating, dip coating, brush coating, roll coating, and flow coating.
【００４９】本発明の粉体塗料の塗装方法においては、
第１層の塗膜の乾燥状態によらずに第２層を塗装するこ
とができる。即ち、第１層を塗装した後、直ちに、又は
しばらく放置した後に第２層を塗装し、第１層と第２層
とを同時に硬化、成膜させることが可能であり、あるい
は第１層を塗装し、硬化、成膜させた後に、第２層を塗
装し、硬化、成膜させることも可能である。このため、
第１層として、水性分散粉体塗料（ａ）を塗装し、塗装
後水分による導電性が消失する前に、第２層として、粉
体塗料（ｂ）又は、水性分散粉体塗料（ｃ）を静電塗装
することも可能である。In the method for applying a powder coating according to the present invention,
The second layer can be applied irrespective of the drying state of the coating film of the first layer. That is, after coating the first layer, immediately or after leaving it for a while, the second layer is coated, and the first layer and the second layer can be simultaneously cured and formed, or the first layer can be formed. After coating, curing, and forming a film, the second layer can be coated, cured, and formed into a film. For this reason,
As the first layer, an aqueous dispersion powder coating (a) is applied, and before the conductivity due to moisture disappears after the application, as the second layer, the powder coating (b) or the aqueous dispersion powder coating (c) Can be electrostatically coated.
【００５０】本発明の粉体塗料の塗装方法においては、
水により吸着力等の強い力で塗料樹脂粒子が被塗装物に
付着しているため、プラスチック等の付着力の弱い被塗
装物の場合でも落下することはない。従って、塗装後の
放置時間は任意であるが、埃等の付着や、塗装ラインの
長さ、保管場所等の有効利用を考慮すると、塗装後でき
るだけ短時間に乾燥、加熱し成膜させることが好まし
い。In the powder coating method of the present invention,
Since the coating resin particles adhere to the object to be coated with a strong force such as an adsorption force by water, even if the object to be coated such as plastic has a weak adhesive force, it does not fall. Therefore, the time for leaving after painting is arbitrary, but in consideration of the adhesion of dust and the like, the effective use of the painting line length, storage place, etc., it is possible to dry and heat as soon as possible after painting to form a film. preferable.
【００５１】短時間に成膜させる場合には、塗膜形成工
程（Ｂ）の塗料樹脂粒子の溶融、融着工程に入る際に、
水の沸騰温度である１００℃まで被塗装物を加熱し、昇
温させるのに２０秒以上の時間をかけることが好まし
い。通常、１００℃に達する時間が１分〜３分程度とな
るような加温速度で昇温させ、１００℃を越した時点に
おいては所定の反応温度まで任意に昇温させ、その温度
に保持して塗膜を架橋成膜させる。従って、エマルショ
ン塗料や水溶性塗料を加熱、成膜させる時に要求され
る、８０〜１００℃で５分〜１０分加熱し、その後所定
の温度に昇温して硬化させるという工程は不要である。In the case of forming a film in a short time, when the coating resin particles are melted and fused in the coating film forming step (B),
It is preferable that the object to be coated is heated to 100 ° C., which is the boiling temperature of water, and it takes more than 20 seconds to raise the temperature. Normally, the temperature is raised at a heating rate such that the time to reach 100 ° C. is about 1 to 3 minutes, and when the temperature exceeds 100 ° C., the temperature is arbitrarily raised to a predetermined reaction temperature and maintained at that temperature. To form a crosslinked film. Therefore, there is no need for the step of heating at 80 to 100 ° C. for 5 to 10 minutes, and then raising the temperature to a predetermined temperature and curing, which is required when heating and forming a film of an emulsion paint or a water-soluble paint.
【００５２】[0052]
【実施例】次に、本発明を実施例及び比較例によって更
に詳細に説明する。尚、以下の記載において「部」は重
量部を示す。 ＜エポキシ／ポリエステル樹脂水性分散粉体塗料＞の調
製 軟化温度１２０℃、酸価４５のポリエステル樹脂３２
部、エポキシ当量９１０のビスフェノールＡタイプのエ
ポキシ樹脂３２部、チタン顔料２５部、カーボンブラッ
ク０．１部、その他酸化鉄系顔料０．１部、表面調整剤
６部、紫外線吸収剤２部、酸化防止剤１部、硬化促進剤
１部、ＨＬＢ１２のノニオン系界面活性剤０．８部、及
び分子量３０万のノニオン系増粘安定剤０．８部をスク
リューミキサー中で配合し、さらにフラッシュミキサー
で均一に混合した。Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following description, "parts" indicates parts by weight. Preparation of <Epoxy / Polyester Resin Aqueous Dispersion Powder Coating> Polyester resin 32 having a softening temperature of 120 ° C. and an acid value of 45
Parts, bisphenol A type epoxy resin having an epoxy equivalent of 910, 32 parts, titanium pigment 25 parts, carbon black 0.1 part, other iron oxide pigment 0.1 part, surface conditioner 6 parts, ultraviolet absorber 2 parts, oxidation 1 part of an inhibitor, 1 part of a curing accelerator, 0.8 part of a nonionic surfactant of HLB12, and 0.8 part of a nonionic thickening stabilizer having a molecular weight of 300,000 are compounded in a screw mixer, and further mixed with a flash mixer. Mix evenly.
【００５３】一方、溶融練合機として２軸スクリューニ
ーダーを用い、それを１１５℃に加温し、溶融練合機の
先端に、圧延冷却用の２本ロール冷却機を設け、その先
にハンマクラッシャを設置して練合と粗砕の準備をし
た。また、ステンレス製塗料タンクに水２２０部を入
れ、更にＨＬＢ１２のノニオン系界面活性剤０．２部及
び分子量８０万のノニオン系増粘安定剤０．２部を配合
し、溶解して水性媒体とした。この水性媒体を循環ポン
プで、ディスクグラインダに循環するように設定して湿
式粉砕の準備した。On the other hand, a twin screw kneader was used as a melt kneading machine, which was heated to 115 ° C., and a two-roll cooler for rolling and cooling was provided at the tip of the melt kneading machine. A crusher was installed to prepare for kneading and crushing. In addition, 220 parts of water was put into a stainless steel paint tank, and 0.2 part of a nonionic surfactant of HLB12 and 0.2 part of a nonionic thickening stabilizer having a molecular weight of 800,000 were blended, dissolved, and dissolved in an aqueous medium. did. This aqueous medium was set to be circulated to a disk grinder by a circulation pump to prepare for wet grinding.
【００５４】フラッシュミキサーで混合した配合物を２
軸スクリューニーダーのフィーダーに供給した。その配
合物は、フィーダーより供給された後約２０秒間滞留し
て溶融練合処理された後、約１２０℃の粘性液体（均質
化物）として２軸スクリューニーダーの先端から２本ロ
ール冷却機の圧延ロールに落ち、圧延され、約１０秒で
常温近くまで冷却された。この板状の塗料樹脂粒子用原
料をハンマクラッシャで約０．５ｍｍの大きさの粗粒子
に一次粉砕した。この一次粉砕した粗粒子を、ディスク
グラインダに循環している水性媒体中に、ディスクグラ
インダの入り口直前で連続的に入れ、ディスクグライン
ダに導入した。ディスクグラインダは、グラインダの間
隙２５０μｍ、回転数１２００ｒｐｍで運転し、粗粒子
を湿式粉砕処理をした。配合物の溶融練合が終了し、水
性媒体中への粗粒子の供給が終了した後、それらの粗粒
子及び一部分湿式粉砕された物の全体を更に同一条件で
ディスクグラインダを通過させて湿式粉砕した。The mixture mixed with the flash mixer was mixed with 2
It was supplied to the feeder of the shaft screw kneader. After being supplied from the feeder, the mixture is retained for about 20 seconds and melted and kneaded, and then, as a viscous liquid (homogenized product) at about 120 ° C., is rolled from the tip of a twin-screw kneader using a two-roll cooler. It was rolled, rolled, and cooled to near room temperature in about 10 seconds. The plate-like raw material for coating resin particles was primarily pulverized by a hammer crusher into coarse particles having a size of about 0.5 mm. The primary ground coarse particles were continuously introduced into the aqueous medium circulating in the disk grinder immediately before the entrance of the disk grinder, and introduced into the disk grinder. The disc grinder was operated at a grinder gap of 250 μm and a rotation speed of 1200 rpm, and the coarse particles were subjected to wet pulverization. After the completion of the melt kneading of the mixture and the supply of the coarse particles into the aqueous medium, the whole of the coarse particles and the partially wet-pulverized product is further passed through a disk grinder under the same conditions, and wet-pulverized. did.
【００５５】できた水性分散液を４００メッシュの振動
篩を通過させた。篩のステンレス製金網の上には、ほと
んど何も残留しなかった。この後、水を若干補充し、防
黴剤、消泡剤、粘性付与剤を添加して、不揮発分４５重
量％、ＰＨ５．８の水性分散塗料とした。この水性分散
塗料中の塗料樹脂粒子径は、粒度分布測定の結果、平均
粒子径６μｍであった。The resulting aqueous dispersion was passed through a 400-mesh vibrating sieve. Almost nothing remained on the stainless steel wire mesh of the sieve. Thereafter, water was slightly replenished, and a fungicide, an antifoaming agent, and a viscosity-imparting agent were added to obtain an aqueous dispersion paint having a nonvolatile content of 45% by weight and a pH of 5.8. The particle diameter of the paint resin in the aqueous dispersion paint was 6 μm as a result of the particle size distribution measurement.
【００５６】この塗料を、燐酸亜鉛系化成処理した鋼板
上に通常のエアースプレー塗装で膜厚５μｍ〜８０μｍ
の種々の段階的な厚さに塗布し、塗布後、室温で、相対
湿度７５％で１０分間放置した。この段階で、塗布膜厚
が５μｍ〜５０μｍの塗布膜厚の薄い各々の塗板では、
水分は完全に蒸発し、外観上は粉体塗料を極めて緻密に
塗布したような状態であった。又、塗布膜厚が７０μｍ
以上の塗布膜厚の厚い塗板では、塗板の外周部分は半乾
燥状態で艶が引けつつある状態であり、塗膜の中心部分
は水分があり艶のある状態であった。これらの塗板を乾
燥炉で３分間で１００℃まで昇温させ、その後２分間で
１７０℃まで昇温させ、昇温後その温度に２０分間保持
して、各種膜厚の塗膜を得た。塗膜外観については、塗
布膜厚５μｍの塗板では、多少つながりの不良による凹
凸が見られたが、塗布膜厚８μｍ以上８０μｍまでは全
く異常は認められず、平滑性のある均一な塗膜であっ
た。この塗膜の光沢値は９０、鉛筆硬度はＨで、デュポ
ン衝撃試験（５００ｇ、３０ｃｍ）も全ての膜厚の塗膜
で合格であった。This paint is applied to a zinc phosphate-based chemical conversion treated steel sheet by ordinary air spray coating to a film thickness of 5 μm to 80 μm.
And then left at room temperature for 10 minutes at a relative humidity of 75% after application. At this stage, in each coated plate having a coating thickness of 5 μm to 50 μm,
The water was completely evaporated, and the appearance was as if the powder coating had been applied very finely. The coating thickness is 70 μm
In the coated plate having the thick coating film described above, the outer peripheral portion of the coated plate was in a semi-dry state and was glossy, and the central portion of the coating film was moist and glossy. These coated plates were heated in a drying oven to 100 ° C. in 3 minutes, then to 170 ° C. in 2 minutes, and then kept at that temperature for 20 minutes to obtain coating films of various thicknesses. Regarding the appearance of the coating film, in the case of a coating plate having a coating film thickness of 5 μm, irregularities due to some poor connection were observed, but no abnormality was observed at all from a coating film thickness of 8 μm to 80 μm. there were. The gloss value of this coating film was 90, the pencil hardness was H, and the DuPont impact test (500 g, 30 cm) passed all coating films of all film thicknesses.
【００５７】＜エポキシ／ポリエステル樹脂粉体塗料＞
の調製 上記の＜エポキシ／ポリエステル樹脂水性分散粉体塗料
＞の調製で用いた水性分散粉体塗料のための添加剤、ノ
ニオン系界面活性剤及びノニオン系増粘安定剤を配合し
なかった以外は、上記の＜エポキシ／ポリエステル樹脂
水性分散粉体塗料＞の調製の場合と全く同じ原料をスク
リューミキサー中で配合し、さらにフラッシュミキサー
で均一に混合した。この混合物を、更にエポキシ／ポリ
エステル樹脂水性分散粉体塗料の粗砕塗料樹脂粒子の調
製と同様に２軸スクリューニーダーで溶融練合し、圧延
冷却、粗砕した。この粗砕塗料樹脂粒子１００部に流動
性改質剤として微粉シリカを０．６部添加し、粉砕機で
平均粒子径２５μｍの粉体塗料とした。<Epoxy / polyester resin powder coating>
Preparation of the above-mentioned <Epoxy / polyester resin aqueous dispersion powder coating> The additive for the aqueous dispersion powder coating used in the preparation of the above, except that the nonionic surfactant and the nonionic thickening stabilizer were not blended. The same raw materials as in the preparation of the above <Epoxy / polyester resin aqueous dispersion powder coating> were blended in a screw mixer, and further uniformly mixed with a flash mixer. This mixture was further melt-kneaded with a twin-screw kneader in the same manner as in the preparation of the crushed coating resin particles of the aqueous dispersion powder coating of an epoxy / polyester resin, roll-cooled, and crushed. To 100 parts of the crushed paint resin particles, 0.6 part of fine powder silica was added as a fluidity modifier, and a powder paint having an average particle diameter of 25 μm was obtained using a pulverizer.
【００５８】この粉体塗料を通常の静電塗装機で、燐酸
亜鉛系化成処理した鋼板に膜厚３μｍから１２０μｍま
で段階的に塗装し、１７０℃で２０分間保持して、各種
膜厚の塗膜を得た。塗膜外観は、塗布膜厚５〜２０μｍ
の範囲内の塗板では、膜厚が薄くなるに従って多少凹凸
になる傾向が見られたが、ピンホール等は無く、良好で
あった。塗布膜厚５μｍ未満では膜厚が薄くなる程ピン
ホールの数が多くなった。塗布膜厚２０μｍ〜１２０μ
ｍまでは全く異常は認められず、平滑性のある均一な塗
膜であった。この塗膜の光沢値は９０、鉛筆硬度Ｈで、
デュポン衝撃試験（５００ｇ、３０ｃｍ）も全ての膜厚
の塗膜で合格であり、塗膜性状は＜エポキシ／ポリエス
テル樹脂水性分散粉体塗料＞とほぼ同一であった。This powder coating is applied stepwise to a zinc phosphate chemical conversion-treated steel sheet from a film thickness of 3 μm to 120 μm by a usual electrostatic coating machine, and kept at 170 ° C. for 20 minutes to obtain various coating films. A membrane was obtained. Appearance of coating film is 5-20μm
In the coated plate in the range of 傾向, the tendency to be slightly uneven as the film thickness was reduced was observed, but there was no pinhole or the like, and the result was good. When the coating film thickness is less than 5 μm, the number of pinholes increases as the film thickness decreases. Coating thickness 20μm ~ 120μ
No abnormality was observed at all up to m, and the coating film was smooth and uniform. The gloss value of this coating film is 90, pencil hardness H,
The DuPont impact test (500 g, 30 cm) was also passed for the coating films of all film thicknesses, and the coating film properties were almost the same as <Epoxy / Polyester resin aqueous dispersion powder coating>.
【００５９】＜エポキシ樹脂水性分散粉体塗料＞の調製 エポキシ当量４５０〜５２５、樹脂軟化温度６４〜７６
℃のエポキシ樹脂（商品名：エピコート１００１；油化
シェル化学（株）製）８３部、２−フェニルイミダゾー
ル１部、テトラハイドロフタリックアンハイドライド１
３部、チタン白２１部及びカーボンブラック１部を配合
し、＜エポキシ／ポリエステル樹脂粉体塗料＞の調製の
場合と同様に溶融練合し、更に、＜エポキシ／ポリエス
テル樹脂水性分散粉体塗料＞の調製の場合と同様に水媒
体、添加剤を加え、後処理をして＜エポキシ樹脂水性分
散粉体塗料＞とした。Preparation of <Epoxy resin aqueous dispersion powder coating> Epoxy equivalent 450 to 525, resin softening temperature 64 to 76
83 ° C. epoxy resin (trade name: Epicoat 1001; manufactured by Yuka Shell Chemical Co., Ltd.), 1 part of 2-phenylimidazole, 1 part of tetrahydrophthalic anhydride 1
3 parts, 21 parts of titanium white and 1 part of carbon black are blended and melt-kneaded in the same manner as in the preparation of <Epoxy / Polyester resin powder coating>, and then <Epoxy / Polyester resin aqueous dispersion powder coating> In the same manner as in the preparation of the above, an aqueous medium and additives were added, and post-treatment was carried out to obtain <epoxy resin aqueous dispersion powder coating>.
【００６０】＜アクリル樹脂粉体塗料＞の調製 メチルメタクレート６０部、ブチルアクリレート６部、
グリシジルメタクレート３３部及びアゾイソブチロニト
リル１部を均一に溶解して得た溶液を滴下槽に入れた。
反応槽にキシロール１００部を仕込み、１２０℃に加温
し、攪拌しながら、該滴下槽に入れた溶液を該反応槽に
１時間かけて滴下し、２時間保持した。その後、更にア
ゾイソブチロニトリル０．３部を加え、１５０℃で約４
時間保持し、重合反応させて樹脂溶液を得た。薄膜、減
圧乾燥機を用いてこの樹脂溶液から溶剤を除去して固形
のアクリル樹脂を得た。このアクリル樹脂は軟化温度約
５５℃、エポキシ当量４３０、分子量約７０００であっ
た。Preparation of <Acrylic Resin Powder Coating> 60 parts of methyl methacrylate, 6 parts of butyl acrylate,
A solution obtained by uniformly dissolving 33 parts of glycidyl methacrylate and 1 part of azoisobutyronitrile was put into a dropping tank.
The reaction tank was charged with 100 parts of xylol, heated to 120 ° C., and while stirring, the solution placed in the dropping tank was dropped into the reaction tank over 1 hour and held for 2 hours. Thereafter, 0.3 parts of azoisobutyronitrile is further added, and at 150 ° C., about 4 parts.
The resin solution was obtained by holding for a time and performing a polymerization reaction. The solvent was removed from the resin solution using a thin film and a vacuum drier to obtain a solid acrylic resin. This acrylic resin had a softening temperature of about 55 ° C., an epoxy equivalent of 430, and a molecular weight of about 7,000.
【００６１】このアクリル樹脂７７部、ドデカンジカル
ボン酸１９部、表面調整剤１部及び流展性付与剤３部を
配合し、溶融練合し、粉砕、分級、表面処理をしてアク
リル樹脂クリヤー粉体塗料の塗料樹脂粒子を作成した。
この塗料樹脂粒子９３部に、アルミニウム顔料（粒子径
３０μｍ、アスペクト比約１０）６部をドライブレンド
し、更に微粉シリカ１部を追加し、均一に混合して＜ア
クリル樹脂粉体塗料＞とした。This acrylic resin (77 parts), dodecanedicarboxylic acid (19 parts), a surface conditioner (1 part) and a flowability imparting agent (3 parts) are blended, melt-kneaded, pulverized, classified, and surface-treated to give an acrylic resin clear powder. Paint resin particles for body paint were prepared.
To 93 parts of the paint resin particles, 6 parts of an aluminum pigment (particle size: 30 μm, aspect ratio: about 10) were dry-blended, and 1 part of fine silica was further added and uniformly mixed to obtain <acrylic resin powder paint>. .
【００６２】＜ポリエステル樹脂粉体塗料＞の調製 ポリエステル樹脂（商品名：ファインディックＭ８０２
３、大日本インキ化学工業（株）製、軟化温度１１０
℃、水酸基価４０）５６部、ブロックイソシアネート樹
脂（商品名：ＩＰＤＩ−Ｂ１５３０、ダイセルヒュルス
社製）１１部、表面調整剤１部、流展性付与剤２部、酸
化チタン２９部及びカーボンブラック１部を配合し、＜
エポキシ／ポリエステル樹脂粉体塗料＞の調製の場合と
同様に溶融練合し、平均粒子径１５μｍに粉砕し、分級
し、更にまた＜エポキシ／ポリエステル樹脂粉体塗料＞
の調製の場合と同様に後処理をして＜ポリエステル樹脂
粉体塗料＞とした。Preparation of <Polyester Resin Powder Coating> Polyester resin (trade name: Finedick M802)
3. Dainippon Ink and Chemicals, softening temperature 110
56 ° C., hydroxyl value 40), 11 parts of blocked isocyanate resin (trade name: IPDI-B1530, manufactured by Daicel Huls), 1 part of surface conditioner, 2 parts of flowability imparting agent, 29 parts of titanium oxide, and carbon black 1 part, <
Epoxy / polyester resin powder coating> Melt-kneaded in the same manner as in the preparation of above, pulverized to an average particle diameter of 15 μm, classified, and further <Epoxy / polyester resin powder coating>
Was subjected to post-treatment in the same manner as in the case of the preparation of <Polyester resin powder coating>.
【００６３】＜アクリル樹脂メタリック水性分散粉体塗
料＞の調製 前記した＜アクリル樹脂粉体塗料＞の調製で作成したア
クリル樹脂粉体塗料の塗料樹脂粒子を用い、前記した＜
エポキシ／ポリエステル樹脂水性分散粉体塗料＞の調製
の場合と同様に水媒体、添加剤を加え、後処理をしてア
クリル樹脂水性分散粉体塗料を作成した。この水性分散
粉体塗料９３部にアルミニウム顔料（粒子径３０μｍ、
アスペクト比約１０）４部、水３部を加え、均一に混合
して＜アクリル樹脂メタリック水性分散粉体塗料＞とし
た。Preparation of <Acrylic Resin Aqueous Dispersion Powder Coating> Preparation of the acrylic resin powder coating prepared in the above <Acrylic resin powder coating>
Aqueous medium and additives were added in the same manner as in the preparation of <Epoxy / Polyester Resin Aqueous Dispersion Powder Coating>, and post-treatment was carried out to prepare an acrylic resin aqueous dispersion powder coating. An aluminum pigment (particle diameter: 30 μm,
4 parts of an aspect ratio of about 10) and 3 parts of water were added and uniformly mixed to obtain <Acrylic resin metallic aqueous dispersion powder coating>.
【００６４】実施例１ 脱脂、燐酸亜鉛被膜処理したスチール製の内装家具の組
立部材の粉体塗料で塗装し難い内部に、前記の＜エポキ
シ／ポリエステル樹脂水性分散粉体塗料＞を用いてロボ
ットで静電塗装した。この塗装後、塗膜中に一部水分が
残っている状態で内装家具を自転搬送しながら、＜エポ
キシ／ポリエステル樹脂粉体塗料＞を用いて粉体塗料用
静電塗装機を上下にレシプロさせて粉体塗装し、外部の
膜厚として３０μｍになるように塗装した。Example 1 A robot using the above-mentioned <epoxy / polyester resin aqueous dispersion powder coating> inside a degreasing, zinc phosphate coating-treated steel interior furniture assembly member that is difficult to apply with powder coating. Electrostatic coating. After this coating, the interior furniture is rotated and transported in a state where some moisture remains in the coating film, and the electrostatic coating machine for powder coating is reciprocated up and down using <epoxy / polyester resin powder coating>. Then, powder coating was performed so that the external film thickness was 30 μm.
【００６５】この部材を１７０℃に保持した乾燥炉に搬
送し、乾燥炉中で移動させながら、２０分間保持し、そ
の後冷却して製品とした。この製品の内部も外部も完全
に塗装され、塗膜の境界も均一で全く判別ができなかっ
た。また、塗膜性能も前記した＜エポキシ／ポリエステ
ル樹脂水性分散粉体塗料＞を単独で用いた場合の塗膜性
能及び＜エポキシ／ポリエステル樹脂水性分散粉体塗料
＞を単独で用いた場合の塗膜性能と同様に良好であっ
た。This member was conveyed to a drying oven maintained at 170 ° C., and was moved for 20 minutes while being moved in the drying oven, and then cooled to obtain a product. Both the inside and the outside of this product were completely painted, and the boundaries of the coating film were uniform and could not be distinguished at all. In addition, the coating film performance was also obtained when the above-described <Epoxy / polyester resin aqueous dispersion powder coating> was used alone and the coating film obtained when <Epoxy / polyester resin aqueous dispersion powder coating> was used alone. It was as good as the performance.
【００６６】実施例２ 脱脂、燐酸亜鉛被膜処理したスチール製の自動車用鉄ホ
イールに防錆塗膜として＜エポキシ樹脂水性分散粉体塗
料＞を用いて膜厚が１５μｍになるように静電塗装し
た。特に打ち抜き部分や合わせ目は重点的に塗装して全
面塗装した。この防錆層を塗装したホイールの表面部分
と裏面の意匠部分だけ、更に＜アクリル樹脂粉体塗料＞
でシルバー色にメタリック塗装した。この２層の塗膜を
同時に１８０℃３０分間焼付硬化させて製品とした。Example 2 A steel automobile wheel made of degreased and zinc phosphate was subjected to electrostatic coating using an <epoxy resin aqueous dispersion powder coating> as a rust preventive coating so as to have a thickness of 15 μm. . In particular, the punched parts and seams were painted with emphasis. Only the surface part and the design part on the back side of the wheel coated with this rust preventive layer, and also <Acrylic resin powder coating>
Was painted in metallic silver. The two coating films were simultaneously baked and cured at 180 ° C. for 30 minutes to obtain a product.
【００６７】このホイールの塗膜性能は、従来の電着塗
膜＋溶剤型上塗塗膜の２コート２ベーク方式による塗膜
と比較して、塗膜の仕上がり外観、塗膜の耐食性、耐チ
ッピング性等何ら劣る点は無く、むしろ耐腐食性試験に
おいては優れた点が多々あった。また、塗装における生
産性については、従来の２コート２ベーク方式に比べ
て、塗膜の塗装、乾燥時間が約半分になり、エネルギー
コスト、生産速度とも大きく改善できた。The coating performance of this wheel was compared with that of a conventional electrodeposition coating + solvent-type top coating in a two-coat two-bake coating system, in which the finished appearance of the coating, corrosion resistance of the coating, and chipping resistance were compared. There were no inferior points such as properties, and rather, there were many excellent points in the corrosion resistance test. As for the productivity in the coating, the time for coating and drying the coating film was reduced to about half as compared with the conventional two-coat two-bake method, and the energy cost and the production speed were greatly improved.
【００６８】実施例３ 無処理のアルミニウム板を清浄化し、その上に＜エポキ
シ樹脂水性分散粉体塗料＞を用いてフローコータで膜厚
が１０μｍになるように塗布し、直ちにその上に＜ポリ
エステル樹脂粉体塗料＞を用いて膜厚が２５μｍになる
ように静電塗装した。この塗膜を２２０℃１分間加熱し
て塗膜とした。この塗膜は、平滑性、耐食性とも良好
で、ＰＣＭ塗膜として十分に使用可能な製品となった。Example 3 An untreated aluminum plate was cleaned, and was coated thereon with an aqueous epoxy resin powder coating so as to have a film thickness of 10 μm using a flow coater. Resin powder coating> was used for electrostatic coating so that the film thickness became 25 μm. This coating film was heated at 220 ° C. for 1 minute to form a coating film. This coating film was good in both smoothness and corrosion resistance, and was a product that could be sufficiently used as a PCM coating film.
【００６９】実施例４ 実施例２と同様に、脱脂、燐酸亜鉛被膜処理したスチー
ル製の自動車用鉄ホイールに防錆塗膜として＜エポキシ
樹脂水性分散粉体塗料＞を用いて膜厚が１０μｍになる
ように静電塗装した。特に打ち抜き部分や合わせ目は重
点的に塗装して全面塗装し、水分が５％以下になるよう
に８０℃で５分間プレベークした。この防錆層を塗装し
たホイールの表面部分と裏面の意匠部分だけ、更に＜ア
クリル樹脂メタリック水性分散粉体塗料＞を膜厚が３０
μｍとなるようにメタリック塗装した。この２層の塗膜
を同時に乾燥炉で１００℃まで３分、その後１８０℃ま
で昇温し、昇温後３０分間焼付硬化させた。仕上がった
製品は、シルバー色の均一な色をした良好な外観であっ
た。Example 4 In the same manner as in Example 2, an iron wheel for automobiles made of degreased and zinc phosphate was treated with an epoxy resin aqueous dispersion powder coating as a rust-preventive coating film to a film thickness of 10 μm. Electrostatic coating was performed as follows. In particular, the punched portions and seams were painted with emphasis on the entire surface and prebaked at 80 ° C. for 5 minutes so that the water content was 5% or less. Only the surface part and the design part of the back surface of the wheel coated with this rust-proof layer are further coated with <Acrylic resin metallic aqueous dispersion powder coating> to a film thickness of 30.
Metallic coating was performed to a thickness of μm. The two coating films were simultaneously heated in a drying furnace to 100 ° C. for 3 minutes, then to 180 ° C., and baked and cured for 30 minutes after the temperature was raised. The finished product had a good appearance with a uniform silver color.
【００７０】比較例１ 従来から使用しているスラリー塗料を電着塗装し、該電
着塗膜が乾燥する前に前記の＜アクリル樹脂粉体塗料
＞、＜ポリエステル樹脂粉体塗料＞、＜エポキシ／ポリ
エステル樹脂水性分散粉体塗料＞、＜エポキシ／ポリエ
ステル樹脂粉体塗料＞をそれぞれ塗装し、焼付硬化させ
て４種の塗膜を作製した。この結果、いずれも塗膜は形
成されるが、ピンホールが発生したり、塗膜の平滑性が
劣っていた。これは、電着塗膜中にわずかに残留する水
分の影響か、あるいは塗膜の硬化性、あるいは電着塗膜
がフロー性を持たないことが原因と考えられる。Comparative Example 1 A slurry coating conventionally used was electrodeposited, and before the electrodeposited film was dried, the above-mentioned <acrylic resin powder coating>, <polyester resin powder coating>, <epoxy / Aqueous dispersion of polyester resin powder coating> and <Epoxy / Polyester resin powder coating> were applied and baked and cured to prepare four types of coating films. As a result, although a coating film was formed in each case, pinholes were generated and the smoothness of the coating film was poor. This is considered to be due to the effect of moisture remaining in the electrodeposited coating film, the curability of the coating film, or the lack of flowability of the electrodeposited coating film.
【００７１】[0071]
【発明の効果】本発明の塗装方法によれば、最初に塗布
した塗膜の乾燥状態によらずにその上に次の塗膜を塗装
することができ、割れのない、平滑性のある塗膜を形成
させることが可能となる。また、例えば、箱物の内部の
コーナー部分を前補正塗装し、次いで全体を塗装するこ
とや、非導電性素材に導電層を形成し、次いで静電塗装
をすることができる。According to the coating method of the present invention, the next coating film can be coated on the first coating film irrespective of the drying state of the coating film, and the coating film has no cracks and is smooth. A film can be formed. Further, for example, it is possible to perform pre-correction painting on the inside corner portion of the box and then paint the whole, or to form a conductive layer on a non-conductive material and then apply electrostatic painting.
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Claims (7)
／又はノニオン系増粘安定剤を分散安定剤として使用し
た水性分散粉体塗料（ａ）を塗装し、第２層として、粉
体塗料（ｂ）又は、ノニオン系界面活性剤及び／又はノ
ニオン系増粘安定剤を分散安定剤として使用した水性分
散粉体塗料（ｃ）を塗装することを特徴とする粉体塗料
の塗装方法。An aqueous dispersion powder coating (a) using a nonionic surfactant and / or a nonionic thickening stabilizer as a dispersion stabilizer is applied as a first layer, and a powder is used as a second layer. A method for coating a powder coating, which comprises coating a coating (b) or an aqueous dispersion powder coating (c) using a nonionic surfactant and / or a nonionic thickening stabilizer as a dispersion stabilizer.
／又はノニオン系増粘安定剤を分散安定剤として使用し
た水性分散粉体塗料（ａ）を塗装し、塗装後塗膜中の水
分による導電性が消失する前に、第２層として、粉体塗
料（ｂ）又は、ノニオン系界面活性剤及び／又はノニオ
ン系増粘安定剤を分散安定剤として使用した水性分散粉
体塗料（ｃ）を静電塗装することを特徴とする粉体塗料
の塗装方法。2. An aqueous dispersion powder coating (a) using a nonionic surfactant and / or a nonionic thickening stabilizer as a dispersion stabilizer is applied as the first layer, and the water content in the coating film after coating is applied. As the second layer before the conductivity of the aqueous dispersion powder coating (b) or an aqueous dispersion powder coating (c) using a nonionic surfactant and / or a nonionic thickening stabilizer as a dispersion stabilizer A) a method for applying a powder coating, which comprises electrostatically applying
系増粘安定剤を分散安定剤として使用した水性分散粉体
塗料（ａ）を前補正として部分的に塗装し、その後、粉
体塗料（ｂ）又は、ノニオン系界面活性剤及び／又はノ
ニオン系増粘安定剤を分散安定剤として使用した水性分
散粉体塗料（ｃ）を塗装することを特徴とする粉体塗料
の塗装方法。3. An aqueous dispersion powder coating (a) using a nonionic surfactant and / or a nonionic thickening stabilizer as a dispersion stabilizer is partially applied as a pre-correction, and then the powder coating ( b) Or a method of applying a powdery coating material, which comprises applying an aqueous dispersion powder coating material (c) using a nonionic surfactant and / or a nonionic thickening stabilizer as a dispersion stabilizer.
体塗料（ｂ）又は水性分散粉体塗料（ｃ）の樹脂組成と
が同一あるいは類似の組成であることを特徴とする請求
項１〜３の何れかに記載の塗装方法。4. The resin composition of the aqueous dispersion powder coating (a) and the resin composition of the powder coating (b) or the aqueous dispersion powder coating (c) are the same or similar. The coating method according to claim 1.
体塗料（ｂ）又は水性分散粉体塗料（ｃ）の樹脂組成と
が異なる組成であることを特徴とする請求項１〜３の何
れかに記載の粉体塗料の塗装方法。5. The resin composition of the aqueous dispersion powder coating (a) is different from the resin composition of the powder coating (b) or the aqueous dispersion powder coating (c). 4. The method for coating a powder coating material according to any one of claims 3 to 3.
塗料（ｂ）又は水性分散粉体塗料（ｃ）の塗装層とを同
時に硬化、成膜させることを特徴とする請求項１〜５の
何れかに記載の塗装方法。6. A coating layer of the aqueous dispersion powder coating (a) and a coating layer of the powder coating (b) or the aqueous dispersion powder coating (c) are simultaneously cured and formed into a film. Item 6. The coating method according to any one of Items 1 to 5.
粉体塗料（ｂ）の樹脂成分が、アルキド樹脂、アクリル
樹脂、ポリエステル樹脂、エポキシ樹脂、メラミン樹
脂、ブロックイソシアネート樹脂、フッ素樹脂、シリコ
ン樹脂、アミド樹脂、ＡＢＳ樹脂からなる群より選ばれ
る１種又は２種以上の組合せよりなることを特徴とする
請求項１〜６の何れかに記載の粉体塗料の塗装方法。7. The resin component of the aqueous dispersion powder coatings (a) and (c) and the powder coating (b) is an alkyd resin, an acrylic resin, a polyester resin, an epoxy resin, a melamine resin, a block isocyanate resin, a fluororesin. The method for coating a powder coating according to any one of claims 1 to 6, comprising one or a combination of two or more selected from the group consisting of silicone resin, amide resin and ABS resin.
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|---|---|---|---|
| JP02736199A JP4111295B2 (en) | 1999-02-04 | 1999-02-04 | How to apply powder paint |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02736199A JP4111295B2 (en) | 1999-02-04 | 1999-02-04 | How to apply powder paint |
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| Publication Number | Publication Date |
|---|---|
| JP2000225371A true JP2000225371A (en) | 2000-08-15 |
| JP4111295B2 JP4111295B2 (en) | 2008-07-02 |
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