JP2000033324A - Coating method - Google Patents
Coating methodInfo
- Publication number
- JP2000033324A JP2000033324A JP20500898A JP20500898A JP2000033324A JP 2000033324 A JP2000033324 A JP 2000033324A JP 20500898 A JP20500898 A JP 20500898A JP 20500898 A JP20500898 A JP 20500898A JP 2000033324 A JP2000033324 A JP 2000033324A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- resin
- paint
- coating film
- aqueous dispersion
- 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)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は塗装方法に関し、よ
り詳しくは、成膜時に塗膜に割れが発生せず、塗膜性能
も良好であり、且つ、平滑性のある均一な塗膜の形成が
可能である塗装方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating method, and more particularly, to the formation of a uniform coating film having no cracking during coating, good coating performance, and smoothness. A coating method that is possible.
【０００２】[0002]
【従来の技術】従来、水性分散塗料として、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た
溶剤型塗料から有機溶剤分を除去して塗料樹脂粒子を作
成させ、その後、その塗料樹脂粒子を水中に分散させて
スラリ−塗料化する技術である。この技術では、溶剤型
塗料を調製し、有機溶剤分を除去するために溶液型塗料
を水中に強制乳化させ、有機溶剤分を除去して固形の塗
料樹脂粒子を作成し、この塗料樹脂粒子を水中に分散さ
せる必要があり、即ち、多数の工程が必要であり、更
に、水中から有機溶剤を回収する必要があった。2. Description of the Related Art Conventionally, a slurry paint prepared by a phase inversion method has been known as an aqueous dispersion paint. The preparation of slurry paint by the phase inversion method involves removing the organic solvent from a solvent-type paint using a water-soluble organic solvent to form paint resin particles, and then dispersing the paint resin particles in water to form a slurry paint. Technology. In this technique, a solvent-type paint is prepared, a solution-type paint is forcibly emulsified in water to remove an organic solvent component, and a solid paint resin particle is formed by removing the organic solvent component. It had to be dispersed in water, that is, a number of steps were required, and further, it was necessary to recover the organic solvent from the water.
【０００３】また、溶液型塗料から直接有機溶剤分を除
去する方法では、加温と減圧によって除去する場合に
は、除去の終点近くでは不揮発分濃度、樹脂成分濃度が
高くなり、その高濃度の樹脂成分により粘度が大きくな
り、そのため、有機溶剤分を完全に除去するために多大
のエネルギーを必要とした。その上の問題は、有機溶剤
分を除去して得られる塗料樹脂は塊状となるため、水に
安定に分散させるためには、微粉砕することが不可欠で
あった。この微粉砕に付随して生じる問題点は、目的と
する樹脂微粉の粒子径が小さくなればなるほど、微粉砕
に要するエネルギーの効率が悪くなると共に、微粉の捕
集にも特別の技術を要するようになることである。In the method of directly removing an organic solvent from a solution type paint, when the removal is performed by heating and reducing the pressure, the concentration of the nonvolatile components and the concentration of the resin component become high near the end point of the removal. The viscosity was increased by the resin component, so that a great amount of energy was required to completely remove the organic solvent component. Another problem is that the coating resin obtained by removing the organic solvent is in a lump, and it is essential to finely pulverize the resin in order to stably disperse it in water. The problem that accompanies this pulverization is that the smaller the particle size of the target resin fine powder, the lower the energy efficiency required for the fine pulverization and the special technique required for collecting the fine powder. It is to become.
【０００４】更に、上記技術の水性分散塗料は、一般的
には、ポリカルボン酸をアンモニアやアミン類で中和し
て得られる増粘剤を使用して安定化させた塗料である。
このような塗料においては、被塗装物に塗布して乾燥さ
せる際に、塗料中のそれらの中和剤は塗料樹脂粒子表面
付近で蒸発、飛散し易く、その結果として、ポリカルボ
ン酸はそのカルボキシル基による水素結合によって塗料
樹脂粒子表面を覆う強固な膜となる。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。この
対策として、中和剤の飛散を防止するため、非飛散性の
中和剤である苛性ソーダで中和する方法などが提案され
てきた。しかし、この中和剤は、飛散防止や塗膜の形成
性の点では優れているが、塗膜中に強塩基が残留するこ
ととなるため、塗膜性能の点で劣り、塗膜の耐水性試
験、耐湿性試験、塩水噴霧試験などで悪い結果となり、
即ち低い性能しか発揮できなかった。[0004] Further, the aqueous dispersion paint of the above technique is generally a paint stabilized using a thickener obtained by neutralizing a polycarboxylic acid with ammonia or amines.
In such paints, when applied to an object to be coated and dried, those neutralizing agents in the paint are liable to evaporate and scatter around the surface of the paint resin particles, and as a result, the polycarboxylic acid has its carboxyl group. Hydrogen bonding by the groups results in a strong film covering the surface of the coating resin particles. 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. As a countermeasure, a method of neutralizing with a non-scattering neutralizing agent such as caustic soda has been proposed in order to prevent the neutralizing agent from scattering. However, this neutralizer is excellent in terms of preventing scattering and forming a coating film, however, since a strong base remains in the coating film, the neutralizing agent is inferior in coating film performance, and the water resistance of the coating film is poor. Poor results in water resistance test, moisture resistance test, salt spray test, etc.
That is, only low performance could be exhibited.
【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膜の形成方法、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、微粉の捕集の手間も必要とせず、比較的簡単な操作
で、低コストで製造される安定な水性分散塗料を用い
て、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 method for forming a coating film and a coating method which do not cause the above-mentioned problems, that is, it does not require the use of an organic solvent, Using a stable water-dispersed paint that is manufactured at a low cost with relatively simple operation without the need for collection work, the coating film cracks or lacks smoothness during film formation. It is an object of the present invention to provide a coating method for forming a coating film having excellent coating film performance without using the same.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を達成するために鋭意研究を行った結果、特定の塗膜構
成成分原料を用い、混合、溶融練合、冷却固化、粗粉
砕、湿式粉砕からなる特定の処理工程によって製造され
た水性分散塗料を被塗装体表面に塗布し、水分の蒸発工
程、塗料樹脂粒子層の形成工程、塗料樹脂粒子を溶融、
融着させる工程を連続的又は段階的に実施して塗膜を形
成することにより、上記のような諸問題の生じることの
ない塗装方法が得られることを見出し、本発明を完成し
た。Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above-mentioned object, and as a result, using a specific coating component material, mixing, melting and kneading, cooling and solidifying, and coarse pulverization. Applying an aqueous dispersion paint produced by a specific treatment process consisting of wet pulverization to the surface of the object to be coated, evaporating water, forming a paint resin particle layer, melting the paint resin particles,
It has been found that a coating method free from the above-mentioned problems can be obtained by performing the step of fusing continuously or stepwise to form a coating film, and completed the present invention.
【０００７】即ち、本発明の塗装方法は、（ａ）軟化温
度が１０〜２５０℃である樹脂成分及びその他の塗膜構
成成分を混合して配合物を得る工程、（ｂ）該配合物を
該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、（ｃ）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（ｄ）該粗粒子を水性分散媒
体中で湿式粉砕して平均粒子径が１０μｍ以下の塗料樹
脂粒子を含む水性分散塗料を得る工程の各工程を含む製
造方法によって得られる水性分散塗料を被塗装体表面に
塗布し、次いで（Ａ）水分の蒸発工程、（Ｂ）塗料樹脂
粒子層の形成工程、及び（Ｃ）塗料樹脂粒子を溶融、融
着させる工程、の各工程を連続的又は段階的に実施する
ことによって塗膜を形成することを特徴とする。That is, the coating method of the present invention comprises: (a) a step of mixing a resin component having a softening temperature of 10 to 250 ° C. and other components of a coating film to obtain a compound; A step of obtaining a homogenized product by melt-kneading at a temperature equal to or higher than the softening temperature of the resin component, (c) a step of obtaining the coarse particles by cooling and solidifying the homogenized product to obtain coarse particles, and An aqueous dispersion paint obtained by a production method including each step of obtaining an aqueous dispersion paint containing paint resin particles having an average particle diameter of 10 μm or less by wet grinding in a dispersion medium is applied to the surface of the object to be coated, and then ( The coating film is formed by continuously or stepwise performing each of the steps of A) evaporating water, (B) forming a coating resin particle layer, and (C) melting and fusing the coating resin particles. It is characterized by forming.
【０００８】また、本発明の塗装方法は、好ましくは、
上記の塗装方法における配合物を得る工程（ａ）を、軟
化温度が１０〜２５０℃である樹脂成分及びその他の塗
膜構成成分、並びにノニオン系界面活性剤及びノニオン
系増粘安定剤を混合することにより実施すること、及び
／又は上記の塗装方法で用いる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、アミド樹脂及びＡＢＳ樹脂からなる
群から選ばれる少なくとも１種であることを特徴とす
る。[0008] The coating method of the present invention preferably comprises
In the step (a) of obtaining the compound in the above coating method, a resin component having a softening temperature of 10 to 250 ° C. and other components of the coating film, and a nonionic surfactant and a nonionic thickening stabilizer are mixed. By doing so, and / or the resin component used in the above coating method is an alkyd resin, acrylic resin, polyester resin, epoxy resin,
It is characterized by being at least one selected from the group consisting of a melamine resin, a blocked isocyanate resin, a fluororesin, a silicone resin, an amide resin and an ABS resin.
【０００９】[0009]
【発明の実施の形態】以下、本発明について詳細に説明
する。本発明で用いる水性分散塗料は、塗膜を形成し得
るためには、塗布された後の加熱によって塗料樹脂粒子
の樹脂成分が熱軟化または溶融し、均質な塗膜となるこ
とが必要である。このため、塗膜構成成分となる樹脂成
分の軟化温度は１０〜２５０℃であることが必要であ
る。更に好ましい軟化温度は３０〜２００℃である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In order to form a coating film, the aqueous dispersion paint used in the present invention is required to heat-soften or melt the resin component of the coating resin particles by heating after being applied to form a uniform coating film. . For this reason, it is necessary that the softening temperature of the resin component which is a component of the coating film is 10 to 250 ° C. A more preferred softening temperature is 30 to 200 ° C.
【００１０】樹脂成分の軟化温度が１０℃よりも低い場
合には、水性分散塗料の通常の保管温度においても、水
性分散塗料中の塗料樹脂粒子がその水性媒体中で凝集し
易くなる傾向がある。その理由は、エマルション塗料等
の塗料樹脂粒子の径と比較して、水性分散塗料中の塗料
樹脂粒子の径が１００倍から１０００倍大きいため、電
気２重層等の粒子間の電気的反発力等が重力に比べて著
しく小さくなるからである。水性分散塗料中の塗料樹脂
粒子の平均粒子径を小さくすればする程、軟化温度が低
い樹脂成分の塗料樹脂粒子であっても、水性分散塗料を
安定に保つことができる。しかしながら、この場合には
水性分散塗料中の塗料樹脂粒子の合計表面積が大きくな
るので、塗料樹脂粒子を水性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 resin component is lower than 10 ° C., the coating resin particles in the aqueous dispersion coating tend to agglomerate in the aqueous medium even at the ordinary storage temperature of the aqueous dispersion coating. . The reason is that the diameter of the paint resin particles in the aqueous dispersion paint is 100 to 1000 times larger than the diameter of the paint resin particles such as the emulsion paint. Is significantly smaller than gravity. The smaller the average particle size of the coating resin particles in the aqueous dispersion paint, the more stable the aqueous dispersion paint can be, even with a resin component having a low softening temperature. However, in this case, since the total surface area of the coating resin particles in the aqueous dispersion coating material becomes large, it is necessary to use a large amount of a wetting agent such as a surfactant to stably disperse the coating resin particles in the aqueous medium. Becomes Therefore, in such a case, the performance of the obtained coating film, such as water resistance and gloss, is reduced.
【００１１】また、樹脂成分の軟化温度が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２５
０℃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。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り、このような不活性ガス
雰囲気中での成膜は、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
合には有効である。しかし、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。When the softening temperature of the resin component is higher than 250 ° C., heat curing for forming a coating film is required.
Temperatures above 0 ° C are required, and at such high temperatures the coatings tend to turn yellow and the coatings tend to be oxidized by air and lose flexibility. As a special example of a method for preventing such a phenomenon, there is a method in which a film is formed in an inert gas atmosphere such as carbon dioxide gas. It is effective when forming a film using a resin or a paint using a high-molecular fluorine resin. However, in this case, an extra device for forming such an inert gas atmosphere is required.
【００１２】軟化温度が１０〜２５０℃である樹脂成分
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、Ａ
ＢＳ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、必要に応じて、任意の配合比率で組み合わ
せて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, fluorine resin, silicone resin, amide resin,
BS resin and the like can be mentioned, and those resin components can be used alone or, if necessary, in combination at an arbitrary mixing ratio. Further, if necessary, a curing agent such as a dibasic acid or a polybasic acid, a polyamide resin, or the like, which is commonly used in coating materials, and an additive such as a surface conditioner or a curing accelerator can be added.
【００１３】塗料樹脂粒子を調製する際に、これらの樹
脂成分、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ＦＧ
Ｌ、フタロシアニンブルー、インダンスレンブルーＲ
Ｓ、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
機顔料等がある。In preparing the coating resin particles, in addition to these resin components, curing agents, etc., coloring pigments, rust-preventive pigments, additives for imparting other functions, and the like are added as coating film constituents. Is valid. These pigments include inorganic pigments such as yellow iron oxide, titanium yellow, red iron oxide, titanium oxide, zinc white, lithopone, lead white, zinc sulfide, antimony oxide, Hansa Yellow 5G, permanent yellow FG
L, phthalocyanine blue, indanthrene blue R
And organic pigments such as S, permanent red F5RK, brilliant first scarlet G, and paliogen red 3910.
【００１４】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 brilliant flake 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.
【００１５】水性分散塗料への光輝性薄片状顔料の添加
方法として、水性分散塗料の塗料樹脂粒子内に含有させ
る方法があるが、水性分散塗料の水性媒体中に塗料樹脂
粒子とは別に含有させる方法のほうが好ましい。この添
加方法については、特に制約されるものではないが、予
め水可溶性溶媒や界面活性剤で処理して光輝性薄片状顔
料表面を親水性にしてから添加し、更に必要ならば水溶
性樹脂や添加剤等を併用して加えることが好ましい。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（全塗膜
構成成分）の０．０５〜３０重量％程度であることが好
ましい。As a method of adding the glittering flaky pigment to the aqueous dispersion paint, there is a method of adding it to the paint resin particles of the aqueous dispersion paint. However, it is contained separately from the paint resin particles in the aqueous medium of the aqueous dispersion paint. The method is preferred. There is no particular limitation on the method of addition, but it is treated with a water-soluble solvent or a surfactant in advance to make the surface of the glittering flake pigment hydrophilic and then added. It is preferable to add additives in combination. 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 based on the total solids (all components of the coating film).
【００１６】本発明の塗装方法においては、塗膜のツヤ
を調整するために、水性分散塗料にツヤ消し用顔料を加
えることが可能である。また、水性分散塗料中の塗料樹
脂粒子を２種類以上にし、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。水
性分散塗料のツヤ調整剤としては、塗料に通常使用され
てるコロイダルシリカ、アルミナ、タルク等が使用でき
る。In the coating method of the present invention, it is possible to add a matting pigment to the aqueous dispersion paint in order to adjust the gloss of the coating film. Further, it is also possible to use two or more kinds of paint resin particles in the aqueous dispersion paint, and to adjust gloss by a difference in compatibility or reaction speed between the paint resin particles. Colloidal silica, alumina, talc, etc., which are commonly used in paints, can be used as a gloss control agent for the aqueous dispersion paint.
【００１７】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。In addition, barium sulfate, barium carbonate, calcium carbonate, clay, and the like may be used as extenders for the purpose of adjusting the gloss value of the coating film and adjusting the hardness of the coating film.
Silica powder, finely divided silica, diatomaceous earth, talc, basic magnesium carbonate, alumina white, and the like can also be added.
【００１８】塗料樹脂粒子中への上記の種々の顔料の添
加量は、通常ＰＷＣで０．５〜６０％程度であるが、ク
リヤー塗料のように全く添加しない場合もある。逆に、
これらの顔料の添加量が多い場合には、特に吸油量の高
い顔料の場合には、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ことになる。The amount of the various pigments to be added to the coating resin particles is usually about 0.5 to 60% by PWC, but may not be added at all like a clear coating. vice versa,
When a large amount of these pigments is added, particularly in the case of a pigment having a high oil absorption, if a coating film is formed using such a paint, the smoothness of the coating film will be impaired.
【００１９】これらの塗膜構成成分を含む塗料樹脂粒子
を水性媒体中に分散させ、安定化させるためには、水性
分散塗料中に界面活性剤や水系増粘安定剤を含有させる
ことが望ましい。従来は、これら添加剤を水性媒体中に
均一に溶解させ、その中に塗料樹脂粒子の微粉を投入
し、混合し、さらには分散させてスラリー塗料化してい
た。しかしながら、水性媒体中に界面活性剤や水系増粘
安定剤を溶解させ、その中に粗粒子を投入し、湿式粉砕
してスラリー塗料化する方法では、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界面活性剤や水系
増粘安定剤の濃度が異なってくる。特に、各々の塗料樹
脂粒子の表面積の総合計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界面活性剤や水
系増粘安定剤が希薄になるためか、塗料樹脂粒子が凝集
する傾向が著しくなる。In order to disperse and stabilize the coating resin particles containing these coating film components in an aqueous medium, it is desirable to include a surfactant or an aqueous thickening stabilizer in the aqueous dispersion coating. Conventionally, these additives have been uniformly dissolved in an aqueous medium, into which fine powder of paint resin particles has been introduced, mixed, and further dispersed to form a slurry paint. However, in a method in which a surfactant or an aqueous thickening stabilizer is dissolved in an aqueous medium, coarse particles are put therein, and wet pulverization is performed to form a slurry paint, paint resin particles are used at the beginning and end of wet pulverization. The concentration of the surfactant or the water-based thickening stabilizer adsorbed on the surface varies. In particular, at the end point of wet pulverization where the total surface area of each coating resin particle increases, probably because the surfactant and the water-based thickening stabilizer adsorbed on the coating resin particle surface become thin, The tendency to agglomerate becomes significant.
【００２０】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、これらの所望の界面活性剤、水系増粘
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界
面活性剤や水系増粘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、界面活性
剤や水系増粘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。In producing the aqueous dispersion paint used in the present invention, preferably, a part or all of these desired surfactants and water-based thickening stabilizers are mixed together with the constituents of the coating film and melt-kneaded. By mixing, they are uniformly dispersed in the coating resin. 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 surface of the newly formed paint resin particles formed by the pulverization is constantly uniformly coated with a surfactant and an aqueous thickening stabilizer. As they appear, the paint resin particles become 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. Furthermore, as the coating resin particles become finer, they usually tend to aggregate, but in the case of coating resin particles containing a surfactant or an aqueous thickening stabilizer, the surface characteristics of the coating resin particles are always as described above. Because it is constant and uniform, the coating resin particles are stably dispersed in the aqueous dispersion coating.
【００２１】塗料樹脂粒子中に含有させることのできる
界面活性剤、水系増粘安定剤は当業界において普通に用
いられているものである。界面活性剤として通常のアニ
オン系界面活性剤、カチオン系界面活性剤、ノニオン系
界面活性剤、両性界面活性剤等が使用できる。本発明の
好ましい実施態様においては、界面活性剤の一部又は全
量を塗料樹脂粒子中に含有させて使用するので、塗膜構
成樹脂成分や硬化剤と反応せず、それらの樹脂の架橋反
応を阻害しないもの、即ち、ノニオン系界面活性剤を使
用することが好ましい。しかし、塗膜形成時に樹脂成分
は全く反応せず、ただ樹脂成分を加熱することで溶融成
膜できるタイプの塗料の場合には、あるいは塗膜形成時
の樹脂の反応のタイプによっては、使用する界面活性剤
の種類については何ら制約されるものではない。The surfactant and the water-based thickening stabilizer which can be contained in the coating resin particles are those commonly used in the art. Usable surfactants include ordinary anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and the like. In a preferred embodiment of the present invention, since part or all of the surfactant is used by being contained in the coating resin particles, it does not react with the resin component or the curing agent constituting the coating film, and the crosslinking reaction of those resins is performed. It is preferable to use one that does not inhibit, that is, a nonionic surfactant. However, the resin component does not react at all during the formation of the coating film, and is used in the case of a type of coating that can be melted and formed simply by heating the resin component, or depending on the type of reaction of the resin at the time of forming the coating film. There is no restriction on the type of surfactant.
【００２２】また、水性分散塗料がグリシジル基含有ア
クリル樹脂と二塩基酸との反応系よりなるアクリル樹脂
を主成分とする水性分散塗料である場合、水系増粘安定
剤としてポリカルボン酸を使用すると、中和剤のアミン
がアクリル樹脂中のグリシジル基と反応して消費され
る。その結果、水性分散塗料の粘度が低下したり、水系
増粘安定剤の効果が低下して塗料の安定性がなくなる傾
向がある。更に悪いことには、アクリル樹脂中の官能基
であるグリシジル基が開環してしまい、塗膜を形成する
時に架橋反応に寄与しなくなる傾向がある。その結果、
塗膜性能として強度が不足したり、塗膜光沢、耐食性が
不足したりすることがある。In the case where the aqueous dispersion paint is an aqueous dispersion paint mainly composed of an acrylic resin comprising a reaction system of a glycidyl group-containing acrylic resin and a dibasic acid, when a polycarboxylic acid is used as an aqueous thickening stabilizer, The neutralizer amine is consumed by reacting with the glycidyl group in the acrylic resin. As a result, the viscosity of the aqueous dispersion paint tends to decrease, and the effect of the water-based thickening stabilizer tends to decrease, and the stability of the paint tends to be lost. To make matters worse, the glycidyl group, which is a functional group in the acrylic resin, tends to be ring-opened and does not contribute to the crosslinking reaction when forming a coating film. as a result,
In some cases, the strength of the coating film is insufficient, and the gloss and corrosion resistance of the coating film are insufficient.
【００２３】本発明においては、上記のような問題が生
じないようにするため、塗料樹脂粒子中に含有させる水
系添加剤としてノニオン系添加剤を主体として使用する
ことが好ましい。本発明で用いることのできるノニオン
系界面活性剤としてはポリエチレングリコ−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。In the present invention, in order to prevent the above-mentioned problems from occurring, it is preferable to mainly use a nonionic additive as an aqueous additive contained in the coating resin particles. Nonionic surfactants that can be used in the present invention include polyethylene glycol-type nonionic surfactants, polyhydric alcohol-type nonionic surfactants, and the like, and polyethylene glycol-type nonionic surfactants include polyethylene glycol-type nonionic surfactants. 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,
There is a polypropylene glycol ethylene oxide adduct and the like. Examples of the polyhydric alcohol-type nonionic surfactant include fatty acid esters of glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbit,
Fatty acid esters of sorbitan, fatty acid alkanolamides and the like.
【００２４】塗料樹脂粒子を均一に湿潤させて安定な水
性分散塗料とするためには、ＨＬＢが７以上のノニオン
系界面活性剤を添加することが好ましい。しかし、ＨＬ
Ｂが２２以上の高いノニオン系界面活性剤を添加する
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。さらに好ましくは、ＨＬＢが８〜１
８程度のノニオン系界面活性剤を添加する。In order to uniformly wet the coating resin particles to form a stable aqueous dispersion coating, it is preferable to add a nonionic surfactant having an HLB of 7 or more. However, HL
When a nonionic surfactant having a high B of 22 or more is added, there is a tendency that the performance such as the water resistance of the coating film is lowered, though it depends on the amount of addition. More preferably, the HLB is 8 to 1
About 8 nonionic surfactants are added.
【００２５】本発明で用いる水性分散塗料においては、
塗料樹脂粒子中及び水性媒体中に含有させるノニオン系
界面活性剤の総量は樹脂成分の重量を基準にして０．１
〜５重量％程度であることが好ましい。塗料樹脂粒子中
に含有させるノニオン系界面活性剤の量（割合）を多く
すると、水性分散塗料全体（塗料樹脂粒子中及び水性媒
体中）に必要なノニオン系界面活性剤の総量は、ノニオ
ン系界面活性剤の全量を水性媒体中に加える場合に比
べ、約２分の１の量ですむ。このことにより、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。In the aqueous dispersion paint used in the present invention,
The total amount of the nonionic surfactant contained in the coating resin particles and the aqueous medium is 0.1% based on the weight of the resin component.
It is preferably about 5% by weight. When the amount (proportion) of the nonionic surfactant contained in the paint resin particles is increased, the total amount of the nonionic surfactant required for the entire aqueous dispersion paint (in the paint resin particles and in the aqueous medium) becomes larger. Only about one-half the amount of active agent added to the aqueous medium. This makes it possible to form a coating film having good coating film performance, particularly good water resistance and gloss.
【００２６】本発明で用いることのできるノニオン系増
粘安定剤としては、特に、分子量の大きいポリエチレン
グリコール型増粘安定剤が挙げられる。しかし、分子量
が１００万以上のものを用いると、水性分散塗料の貯蔵
安定性は良好であるが、エアースプレー塗装等のように
微粒子化して塗装する方法では、塗装時に糸引き現象が
発生する。一方で、プレコートメタルでの塗装のよう
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。慣例的には、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
用する水性分散塗料においては、分子量が数１０万程度
のノニオン系増粘安定剤を樹脂成分の重量を基準にして
０．３〜５重量％程度添加することが好ましい。一方、
ロール塗装やフローコート塗装に使用する水性分散塗料
においては、分子量が数１０万〜２００万程度のノニオ
ン系増粘安定剤を樹脂成分の重量を基準にして０．１〜
５重量％程度添加することが好ましい。As the nonionic thickening stabilizer which can be used in the present invention, in particular, a polyethylene glycol type thickening stabilizer having a large molecular weight can be mentioned. However, when a compound having a molecular weight of 1,000,000 or more is used, the storage stability of the aqueous dispersion paint is good, but a stringing phenomenon occurs at the time of coating in a method of applying fine particles such as air spray coating. On the other hand, roll coating or flow coating coating, such as coating with pre-coated metal, has good paint followability and film forming properties. Conventionally, in an aqueous dispersion coating used for air spray coating, electrostatic coating, airless coating, and rotary atomization type electrostatic coating, a nonionic thickening stabilizer having a molecular weight of about several hundred thousand is added to a resin component by weight. Is preferably added in an amount of about 0.3 to 5% by weight based on the weight. on the other hand,
In an aqueous dispersion paint used for roll coating or flow coat coating, a nonionic thickening stabilizer having a molecular weight of about several hundred thousand to about two million is used in an amount of 0.1 to 100% based on the weight of the resin component.
It is preferable to add about 5% by weight.
【００２７】前記したように、従来の技術のスラリー塗
料は、その製造において多数の工程が必要であり、また
操作が面倒であり且つ費用のかかるものであった。これ
に対して、本発明で用いる水性分散塗料の製造方法にお
いては、湿式粉砕を採用することにより、エネルギー効
率が良く、目的とする塗料樹脂粒子を水中に直接分散さ
せることで安定性の良い水性分散塗料を製造することが
できる。As mentioned above, prior art slurry coatings required a number of steps in their manufacture, and were cumbersome and expensive to operate. On the other hand, in the method for producing the aqueous dispersion paint used in the present invention, by employing wet pulverization, energy efficiency is good, and the target paint resin particles are directly dispersed in water to obtain a stable aqueous dispersion. Dispersed paints can be produced.
【００２８】次に、本発明で用いる水性分散塗料の製造
方法について具体的に述べる。本発明においては、
（ａ）軟化温度が１０〜２５０℃である樹脂成分及びそ
の他の塗膜構成成分を混合して配合物を得る工程、
（ｂ）該配合物を該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、（ｃ）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（ｄ）該粗
粒子を、例えば分散用水溶液の循環している湿式摩砕機
に投入して、水性分散媒体中で湿式粉砕して平均粒子径
が１０μｍ以下の塗料樹脂粒子を含む水性分散塗料を得
る工程を順次実施し、塗料樹脂粒子の捕集と微粒子化、
分散安定化を同時に実施することで、良好なエネルギー
効率、資源効率で、且つ産業廃棄物を出さないで水性分
散塗料を製造することができる。Next, a method for producing the aqueous dispersion paint used in the present invention will be specifically described. In the present invention,
(A) a step of mixing a resin component having a softening temperature of 10 to 250 ° C. and other coating film components to obtain a blend;
(B) 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; (c) a step of obtaining the coarse particles by crushing the homogenized product after cooling and solidifying; d) The coarse particles are charged into, for example, a wet mill in which an aqueous solution for dispersion is circulated, and wet-ground in an aqueous dispersion medium to obtain an aqueous dispersion paint containing paint resin particles having an average particle diameter of 10 μm or less. The process is performed sequentially to collect and micronize paint resin particles,
By simultaneously carrying out dispersion stabilization, an aqueous dispersion paint can be produced with good energy efficiency and resource efficiency and without producing industrial waste.
【００２９】上記（ａ）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
は必要に応じて一部液状原料を、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。In the step (a), that is, in the step of mixing the various raw materials to be the constituents of the coating film to obtain a compound, a color pigment, a curing agent, an additive, If necessary, partially liquid materials are 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.
【００３０】これらの混合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、塗料樹脂粒子を水性媒体中に容易に分散させ
る働きをする界面活性剤や増粘安定剤、特にノニオン系
界面活性剤やノニオン系増粘安定剤の一部又は全量をこ
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
均しく親水性になるので水性分散塗料の作成が容易であ
る。It is preferable to mix and mix the various raw materials using these mixing apparatuses 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. In the next melt-kneading step, it can be made homogeneous. In particular, in this mixing and blending step, a part or all of a surfactant or a thickening stabilizer which functions to easily disperse the coating resin particles in an aqueous medium, particularly a nonionic surfactant or a nonionic thickening stabilizer is used. If added, the newly formed pulverized surface of the coating resin particles in the subsequent wet pulverization step becomes evenly hydrophilic, so that it is easy to prepare an aqueous dispersion coating.
【００３１】次に、上記（ｂ）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。本発明に用いられる水性分散塗料の
製造方法に使用される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
の粒子からなる配合物にし、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 (b), that is, the step of melting and kneading the compound at a temperature not lower than the softening temperature of the resin component to obtain a homogenized product is carried out. 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 used in the method for producing the aqueous dispersion coating used in the present invention have a size of about several mm for the purpose of facilitating transportation and handling during compounding and preventing dust from rising. Processed into pellets. The pellets are crushed to form a composition comprising particles of about several hundred μm, and the mixture is heated to a temperature higher than the softening temperature of the resin component and mechanically kneaded.
【００３２】この溶融練合のため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。特にロールミル、スクリューニーダーは、作業
性、取り扱い易さの点で、また溶融練合後、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特に
好ましい。架橋型水性分散塗料の場合には、塗料樹脂粒
子中に硬化剤が含まれるものであり、本溶融練合工程で
均質に混合されるが、この時、樹脂成分の軟化温度以上
に加熱されるので、溶融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
から上記配合物を供給し、他方から均質化物を連続的に
速やかに排出する装置が好適である。As a device used for the melting and kneading, there are a roll mill, a screw kneader, a Mahler kneader and the like. In particular, roll mills and screw kneaders are particularly preferred in terms of workability and ease of handling, and that after kneading, the kneaded material can be quickly discharged from the apparatus and cooled. In the case of a crosslinked aqueous dispersion paint, a curing agent is contained in the paint resin particles, and is uniformly mixed in the present melt kneading step, but at this time, the resin component is heated to a softening temperature or higher. Therefore, if the residence time during melt-kneading becomes longer, a part of the resin component reacts with the curing agent, and as a result, it does not become smooth when forming a coating film, or a defect of insufficient gloss occurs. Tend. Therefore, a device that supplies the above-mentioned composition from one side and discharges the homogenized product continuously and quickly from the other side is preferable.
【００３３】次に、上記（ｃ）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。
この粗砕工程での処理は、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れると塊状に
なるので、この塊状物を次段の湿式粉砕工程で処理し易
い大きさの粗粒子に粗砕するための前処理である。従っ
て、この塊状物が湿式粉砕機の受け入れ可能な最大の大
きさ（粒径）よりも小さくなっていれば、この粗砕工程
は必ずしも必要ではない。塊状物を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 (c), that is, a step of obtaining the coarse particles by crushing the homogenized product after cooling and solidifying it.
In the crushing process, the homogenized paint resin produced in the melt-kneading process in the previous stage is cooled and solidified as it is to form a lump, so that the lump can be easily processed in the next wet crushing process. This is a pretreatment for crushing into coarse particles. Therefore, if the agglomerate is smaller than the maximum size (particle size) that can be accepted by the wet mill, the crushing step is not always necessary. Examples of the apparatus for crushing a lump include a ring roll mill, an edge runner, a roll crusher, a disintegrator, a hammer crusher, an impeller breaker, a gyratory crusher,
There is a jaw crusher.
【００３４】次に、上記（ｄ）の工程、即ち、上記粗粒
子を水性分散媒中で湿式粉砕し平均粒子径１０μｍ以下
の塗料樹脂粒子を含む水性分散液を得る工程について説
明する。まず第一に、水性分散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
脂粒子を湿潤させるため界面活性剤や増粘安定剤、好ま
しくはノニオン系界面活性剤やノニオン系増粘安定剤、
等の水系添加剤を加え、混合して均質にする。この水性
媒体を循環ポンプにより湿式粉砕機に循環させておく。Next, the step (d), that is, the step of wet-grinding the coarse particles in an aqueous dispersion medium to obtain an aqueous dispersion containing coating resin particles having an average particle diameter of 10 μm or less will be described. First, a required amount of water is prepared in a tank for receiving the aqueous dispersion paint. If necessary, a surfactant or a thickening stabilizer to wet the coating resin particles in the water, preferably a nonionic surfactant or a nonionic thickening stabilizer,
And other aqueous additives and mix to homogenize. This aqueous medium is circulated through a wet pulverizer by a circulation pump.
【００３５】この湿式粉砕を断続的に実施する場合に
は、前段で得た粗粒子を塗料受けタンクに一旦集め、次
いで湿式粉砕の工程に送る。このように粗粒子を塗料受
けタンクに一旦集める場合には、この粗粒子の粒子径が
大きいので沈降し易い。このため、塗料受けタンク内を
常に攪拌するか、湿式粉砕の工程に送る前に攪拌して流
動性を与えることが必要になる。When the wet pulverization is carried out intermittently, the coarse particles obtained in the preceding stage are once collected in a paint receiving tank and then sent to the wet pulverization step. When the coarse particles are once collected in the paint receiving tank as described above, the coarse particles have a large particle diameter, and thus easily settle. For this reason, it is necessary to constantly stir the inside of the paint receiving tank, or to impart fluidity by stirring before sending to the wet pulverization step.
【００３６】このため、次に記すように、できるだけ連
続的に処理して湿式粉砕することが好ましいが、このこ
とは本発明を何ら制約するものではない。湿式粉砕を連
続的に実施する場合には、循環経路の入り口側に前段で
得た粗粒子の取り込み口を設ける。ここで取り込まれた
粗粒子は自重で水性媒体中に混合された後に湿式粉砕機
の中へ入っても、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良い。For this reason, as described below, it is preferable to treat as continuously as possible and wet-pulverize, but this does not limit the present invention at all. When performing wet grinding continuously, an inlet for the coarse particles obtained in the preceding stage is provided at the entrance side of the circulation path. The coarse particles captured here may enter the wet pulverizer after being mixed in the aqueous medium by their own weight, or may be taken into the wet pulverizer after being wetted by any stirring mixer. .
【００３７】これらの場合に重要なことは、十分な量の
水性媒体が湿式粉砕機中を循環して装置内の冷却と微粉
砕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性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性媒体
の粘度も低いので、塗料樹脂粒子含有水性媒体は循環し
易いが、順次添加される粗粒子の湿式粉砕がすすみ、水
性媒体の循環が繰り返されると循環水性媒体中の塗料樹
脂粒子の濃度が高くなり、循環と冷却とが次第に困難に
なってくる。万が一水性媒体の循環が停止すると、循環
水性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。What is important in these cases is that a sufficient amount of aqueous medium can be circulated in the wet mill to sufficiently cool the apparatus and transport the finely ground 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 therefore the viscosity of the coating resin particle-containing aqueous medium is low. When wet grinding of 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, and circulation and cooling gradually become difficult. If the circulation of the aqueous medium is stopped, there is a danger that the coarse particles supplied into the circulating aqueous medium and the circulated paint resin particles are melted by the pulverizing energy in the wet pulverizer and adhere to the inner surface of the apparatus. .
【００３８】このような危険を未然に防止するために
は、目的とする水性分散塗料中の塗料樹脂粒子の濃度、
流動性の設定、水性分散塗料の循環量、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
量と水性媒体の循環量、最終水性分散塗料中の塗料樹脂
粒子の濃度等は十分に管理する必要がある。In order to prevent such danger beforehand, the concentration of the coating resin particles in the intended aqueous dispersion coating,
It is important to set the fluidity, circulate the aqueous dispersion paint, and control the temperature. In general, the circulation amount can be easily controlled, but the temperature rises sharply as the circulation amount decreases.Therefore, the supply amount of the coarse particles, the circulation amount of the aqueous medium, the concentration of the coating resin particles in the final aqueous dispersion coating, and the like are sufficient. Need to be 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
供給することが望ましい。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容易に粉砕す
ることができるが、湿潤させる水性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
粒子が融着しやすい傾向がある。Next, an example of a wet pulverizer that can be used in this wet pulverization step will be described. Usable wet grinding machines include a disc grinder, a tower mill, a ball mill, a vibration mill, an edge runner, a roll mill, and the like. 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 pulverizer using a dispersed media, it is desirable to supply coarse particles sufficiently smaller than the particle diameter of the media. A wet grinder of the type in which coarse particles are crushed by a rotating body such as a disc grinder or a roll mill can grind easily 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
粒子濃度を低濃度で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の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。塗料樹脂粒子の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
加えて水性分散塗料とすることもできる。As the operation mode of the wet mill, it is easy to control the operation while maintaining the coating resin particle concentration at a low concentration, and therefore, if necessary, a centrifugal filter, a centrifugal separator, a decanter or the like may be used. It is preferable to adjust the concentration of the coating resin particles. Regarding the wet pulverization process, the coating resin particles can be passed through a wet pulverizer several times until they reach a certain particle size, or the coating resin particles having a certain size or more can be filtered or centrifugally classified. It can also be separated and removed. After adjusting the concentration of the coating resin particles to a predetermined concentration, additives such as an antifungal agent, an antifoaming agent, and a viscosity-imparting agent may be added as a post-adjustment to obtain an aqueous dispersion coating.
【００４１】でき上がった水性分散塗料は、その中に分
散している塗料樹脂粒子の平均径が１０μｍ以下で、含
有濃度としては２０〜６０重量％程度となる。本発明で
用いる水性分散塗料の製造方法の重要な特徴は、水性媒
体中で直接湿式粉砕して塗料化するので、また、所望に
応じて、塗膜構成成分となる諸原料中に予め水中分散用
の界面活性剤や増粘安定剤、好ましくはノニオン系界面
活性剤やノニオン系増粘安定剤等の水系添加剤の一部又
は全量が添加されているので、塗料樹脂粒子が容易に水
性媒体中に湿潤し、分散、安定化されることにある。そ
の結果、従来の相転換法で作成されるスラリー塗料や、
微粉に粉砕した粉体塗料を更に微粉砕して得られる塗料
樹脂粒子を水性媒体中に湿潤させて得られる水性分散塗
料に比べ、水性湿潤剤の必要量が少なく、且つ粒子径の
小さい塗料樹脂粒子の水性分散塗料が容易に調製でき
る。また、水性分散塗料の製造過程において塗膜構成成
分が粉塵や微粉として製造装置外に持ち出されることこ
とは全くなく、また過剰の水性媒体も次回の水性分散塗
料の製造に再使用することで有効に使用できる。The resulting aqueous dispersion paint has an average particle size of the paint resin particles dispersed therein of not more than 10 μm and a concentration of about 20 to 60% by weight. An important feature of the method for producing the aqueous dispersion paint used in the present invention is that it is directly wet-pulverized in an aqueous medium to make a paint, and if necessary, dispersed in water in various raw materials to be constituents of a coating film in advance. A part or all of the water-based additives such as surfactants and thickening stabilizers, preferably nonionic surfactants and nonionic thickening stabilizers are added, so that the coating resin particles can be easily dispersed in the aqueous medium. Wetting, dispersion and stabilization. As a result, slurry paints created by conventional phase inversion methods,
A coating resin that requires a smaller amount of an aqueous wetting agent and has a smaller particle size than an aqueous dispersion coating obtained by wetting the coating resin particles obtained by further finely pulverizing a powder coating into fine powder into an aqueous medium. An aqueous dispersion coating of particles can be easily prepared. Also, in the production process of the aqueous dispersion paint, the components of the coating film are never taken out of the production equipment as dust or fine powder, and the excess aqueous medium can be effectively reused for the next production of the aqueous dispersion paint. Can be used for
【００４２】本発明の塗装方法においては、以上に説明
した製造方法により水性分散塗料を製造し、この水性分
散塗料を水系塗料による塗装に採用されている通常の塗
装方法、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
によって被塗装体表面に塗布し、次いで、（Ａ）水分の
蒸発工程、（Ｂ）塗料樹脂粒子層の形成工程、及び
（Ｃ）塗料樹脂粒子を溶融、融着させる工程、の各工程
を連続的又は段階的に実施する。ここでいう「連続的」
とは、任意の２工程の間に時間を置くことなく、任意の
２工程又は全工程を連続的に行うことを意味し、「段階
的」とは、任意の２工程の間に適当な時間を設けて実施
することを意味する。In the coating method of the present invention, an aqueous dispersion paint is manufactured by the above-described manufacturing method, and the aqueous dispersion paint is used in a usual coating method used for coating with an aqueous paint, for example, air spray coating, static coating. Electrocoating, dip coating, brush coating, roll coating or flow coating is applied to the surface of the object to be coated, then (A) a step of evaporating water, (B) a step of forming a coating resin particle layer, and (C) The steps of melting and fusing the coating resin particles are performed continuously or stepwise. "Continuous" here
The term “stepwise” means that any two steps or all steps are continuously performed without leaving a time between any two steps, and “stepwise” means that an appropriate time is set between any two steps. Means to implement.
【００４３】前記の水性分散塗料の塗布して未乾燥の状
態では、未乾燥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。従って、乾燥
過程において未乾燥塗膜内部に水分がある間、未乾燥塗
膜表面から水が蒸発するにつれて、未乾燥塗膜内部の水
が塗料樹脂粒子の間を毛細管現象によって自由に通過し
て未乾燥塗膜表面まで移動し、引き続いて水が蒸発す
る。水溶性樹脂塗料やエマルション塗料の場合には乾燥
過程の終わり近くにおいては塗膜内部の水が拡散によっ
て表面に供給されるので水の移動速度が極めて遅いが、
上記の水性分散塗料の場合には上記のように水の移動速
度は乾燥過程の終わり近くにおいても十分に早く、水は
未乾燥塗膜表面から一定の速度で蒸発する。その結果と
して、その後の加熱工程において内部の水が沸騰してピ
ンホールを形成するようなことも少ない。よって、沸点
調整用の高沸点溶剤を併用する必要も無く、塗料中のＶ
ＯＣも極めて少なく、通常は１％以下で済む。In the undried state after the application of the aqueous dispersion paint, the moisture inside the undried paint film can freely move between the paint resin particles by capillary action. Therefore, during the drying process, while water is present inside the wet coating, as the water evaporates from the wet coating surface, the water inside the wet coating freely passes between the coating resin particles by capillary action. It travels to the wet coating surface and the water evaporates subsequently. In the case of water-soluble resin paints and emulsion paints, near the end of the drying process, the water inside the coating film is supplied to the surface by diffusion, so the water movement speed is extremely slow,
In the case of the above-mentioned aqueous dispersion paint, as described above, the movement speed of water is sufficiently fast even near the end of the drying process, and water evaporates at a constant rate from the surface of the wet coating film. As a result, in the subsequent heating step, the water inside is less likely to boil to form pinholes. Therefore, there is no need to use a high boiling point solvent for adjusting the boiling point, and the V
The OC is also very low, usually less than 1%.
【００４４】本発明の塗装方法においては、エマルショ
ン塗料や水溶性塗料を用いる塗装の場合のように加熱工
程、成膜工程を厳格に管理することは必要ではないが、
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
防止するように注意をすることが好ましい。前記の水性
分散塗料を用いる場合には、塗布後、室温に放置し、任
意の時間経過後に加温して成膜させても、従来のポリカ
ルボン酸系増粘安定剤を使用した塗料の場合に発生した
ような割れが塗膜に発生することがない。In the coating method of the present invention, it is not necessary to strictly control the heating step and the film forming step as in the case of coating using an emulsion paint or a water-soluble paint.
When the film thickness is large, it is preferable to take care to prevent the generation of pinholes due to boiling of water. When using the water-based dispersion coating, after application, leave at room temperature, even after heating to form a film after the elapse of an arbitrary time, in the case of a coating using a conventional polycarboxylic acid thickening stabilizer No cracks such as those generated in the coating film are generated.
【００４５】工程（Ａ）として、室温で長期間放置し、
水分を蒸発させた未硬化塗膜は、原料である塗料樹脂粒
子を粉体塗料として塗布した場合とほとんど同じ成膜過
程を経て成膜することができる。ただ、異なる点は、粉
体塗料の場合には、静電気で被塗装物に付着しているた
め、時間の経過と共に静電気による付着力が低下し、粉
体塗料の塗料樹脂粒子が重力に負け、落下する場合があ
る。本発明の塗装方法場合には、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。したがって、工程（Ａ）において、水分
を蒸発させるため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、塗布後できるだけ短時間に水分を蒸発させるこ
とが好ましく、また、以降の工程もできるだけ短時間に
完了させることが好ましい。In step (A), the mixture is left at room temperature for a long time,
The uncured coating film from which the moisture has been evaporated can be formed through almost the same film forming process as when the coating resin particles as the raw material are applied as a powder coating. However, the difference is that, in the case of powder coatings, since the powder coating adheres to the object to be coated with static electricity, the adhesive force due to static electricity decreases over time, and the coating resin particles of the powder coating lose the gravity, May fall. In the case of the coating method of the present invention, since the coating resin particles adhere to the object to be coated with a strong force such as adsorption force by water, the object does not fall even in the case of the object to be coated having low adhesion such as plastic. . Therefore, in the step (A), the leaving time for evaporating water is arbitrary, but in consideration of the adhesion of dust and the like, the length of the coating line, the effective use of the storage space, etc., the time is as short as possible after the application. It is preferable to evaporate the water, and it is preferable to complete the subsequent steps in as short a time as possible.
【００４６】工程（Ｂ）及び（Ｃ）において、塗料樹脂
粒子層を形成させ、塗料樹脂粒子を溶融、融着させるた
めに加熱する際の温度と時間については、水の沸点であ
る１００℃まで２０秒以上かけて昇温させ、例えば毎秒
４℃以下の昇温速度で加熱することが好ましい。通常
は、１００℃まで１〜３分かけて昇温させ、例えば毎秒
０．４〜１．３℃の昇温速度で加熱する。１００℃を越
したあとは、所定の反応温度まで任意の加温速度で加熱
し、その温度に保持して、塗膜内の樹脂成分を溶融、融
着させ、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用いる塗装の場合の加熱、成膜時に
要求されるような８０〜１００℃で５〜１０分間加熱し
その後所定の温度に昇温して硬化させる工程は不要であ
る。In the steps (B) and (C), the temperature and the time when the coating resin particle layer is formed and the coating resin particles are heated for melting and fusing are up to 100 ° C. which is the boiling point of water. Preferably, the temperature is raised over 20 seconds or more, for example, at a temperature rising rate of 4 ° C. or less per second. Usually, the temperature is raised to 100 ° C. over a period of 1 to 3 minutes, for example, at a rate of 0.4 to 1.3 ° C. per second. After the temperature exceeds 100 ° C., the resin is heated to a predetermined reaction temperature at an arbitrary heating rate, and is kept at that temperature to melt and fuse the resin components in the coating film to form a cross-linked film of the coating film. Therefore, there is no need for heating in the case of coating using an emulsion paint or a water-soluble paint, a step of heating at 80 to 100 ° C. for 5 to 10 minutes as required at the time of film formation, and then raising the temperature to a predetermined temperature and curing. is there.
【００４７】本発明の塗装方法を採用して塗装すること
により、成膜時に塗膜に割れが生じることがなく、塗膜
性能も良好であり、塗料のｐＨ依存性もなく、ｐＨが中
和点より低い５程度でも何等支障無く塗布でき、且つ、
平滑性のある均一な塗膜を形成することができる。By coating using the coating method of the present invention, the coating film does not crack at the time of film formation, the coating film performance is good, there is no pH dependency of the coating material, and the pH is neutralized. It can be applied without any trouble even about 5 lower than the point, and
A uniform coating film having smoothness can be formed.
【００４８】[0048]
【実施例】以下、本発明について実施例により詳細に説
明する。尚、実施例中の「部」は重量部である。 ＜実施例＞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、表面調
整剤６部、紫外線吸収剤２．２部、酸化防止剤１部、硬
化促進剤１部、ＨＬＢ＝１２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、更にフラッシュ
ミキサーで均一に混合した。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. Incidentally, "parts" in the examples are parts by weight. <Examples> 32 parts of a polyester resin having a softening temperature of 120 ° C. and an acid value of 45, 32 parts of a bisphenol A type epoxy resin having an epoxy equivalent of 910, 25 parts of titanium pigment, 6 parts of a surface conditioner, 2.2 parts of an ultraviolet absorber, 1 part of antioxidant, 1 part of curing accelerator, 0.8 part of nonionic surfactant having HLB = 12, and 0.3 part of nonionic thickening stabilizer having a molecular weight of 300,000.
Eight parts were compounded in a screw mixer and further uniformly mixed with a flash mixer.
【００４９】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ＨＬＢ＝１２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 cooling machine for rolling and cooling was provided at the tip of the melt kneading machine, and a hammer was provided at the tip. 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 having an HLB of 12 and 0.2 part of a nonionic thickening stabilizer having a molecular weight of 800,000 were blended and dissolved. Medium. This aqueous medium was set to be circulated to a disk grinder by a circulation pump to prepare for wet grinding.
【００５０】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.
【００５１】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
％、ＰＨ＝５．８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 an antifungal agent, an antifoaming agent, and a viscosity-imparting agent were added.
%, PH = 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.
【００５２】この塗料を、アルミニウム板上に通常のエ
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〜５
０μｍ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１６０℃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（５
００ｇ、３０ｃｍ）も全ての膜厚の塗膜で合格であっ
た。The paint was applied on an aluminum plate by ordinary air spray coating in various step thicknesses of 5 μm to 80 μm, and then left at room temperature at a relative humidity of 75% for 10 minutes. At this stage, the coating thickness is 5 μm to 5 μm.
In each of the coating plates having a thin coating thickness of 0 μm, the moisture was completely evaporated, and the appearance was such that the powder coating was applied very densely. On the other hand, in the case of a coated plate having a coated film thickness of 70 μm or more, the outer peripheral portion of the coated plate is in a semi-dry state and is glossy, and the central portion of the coated film is moist and glossy. Was. These coated plates were heated in a drying oven to 100 ° C. in 3 minutes, then to 160 ° C. in 2 minutes, and then kept at that temperature for 20 minutes to obtain coating films of various thicknesses. Regarding the coating film appearance, the coating film thickness was 5 μm
In the coated plate, irregularities due to some poor connection were observed, but no abnormality was observed at all from the coating film thickness of 8 μm to 80 μm, and the coating film was smooth and uniform. The gloss value of this coating film was 90, the pencil hardness was H, and the DuPont impact test (5
(00 g, 30 cm).
【００５３】[0053]
【発明の効果】本発明の塗装方法においては、成膜時に
塗膜に割れが生じず、塗膜性能も良好であり、塗料のｐ
Ｈ依存性もなく、ｐＨが中和点よりも低い５程度でも何
等支障無く塗布でき、且つ、平滑性のある均一な塗膜の
形成が可能である。According to the coating method of the present invention, the coating film does not crack at the time of film formation, the coating film performance is good, and the p
There is no dependency on H, and the coating can be applied without any trouble even if the pH is about 5 lower than the neutralization point, and a uniform coating film having smoothness can be formed.
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Claims (3)
脂成分及びその他の塗膜構成成分を混合して配合物を得
る工程、 （ｂ）該配合物を該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、 （ｃ）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 （ｄ）該粗粒子を水性分散媒体中で湿式粉砕して平均粒
子径が１０μｍ以下の塗料樹脂粒子を含む水性分散塗料
を得る工程の各工程を含む製造方法によって得られる水
性分散塗料を被塗装体表面に塗布し、次いで （Ａ）水分の蒸発工程、 （Ｂ）塗料樹脂粒子層の形成工程、及び （Ｃ）塗料樹脂粒子を溶融、融着させる工程、の各工程
を連続的又は段階的に実施することによって塗膜を形成
することを特徴とする塗装方法。(1) a step of mixing a resin component having a softening temperature of 10 to 250 ° C. and other components of a coating film to obtain a blend; and (b) mixing the blend with a softening temperature of the resin component or higher. Melt-kneading at a temperature of to obtain a homogenized product; (c) a step of coarsely crushing the homogenized material after cooling and solidifying to obtain coarse particles; and (d) wet-grinding the coarse particles in an aqueous dispersion medium. The aqueous dispersion paint obtained by the production method including the steps of obtaining an aqueous dispersion paint containing paint resin particles having an average particle diameter of 10 μm or less is applied to the surface of the object to be coated, and then (A) a water evaporation step, (B) a step of forming a coating resin particle layer; and (C) a step of melting and fusing the coating resin particles. Painting method.
０〜２５０℃である樹脂成分及びその他の塗膜構成成
分、並びにノニオン系界面活性剤及びノニオン系増粘安
定剤を混合することにより実施することを特徴とする請
求項１記載の塗装方法。2. The method according to claim 1, wherein the step (a) of obtaining the blend is carried out at a softening temperature of
The coating method according to claim 1, wherein the coating method is carried out by mixing a resin component and other coating film components at 0 to 250 ° C, a nonionic surfactant and a nonionic thickening stabilizer.
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、
アミド樹脂及びＡＢＳ樹脂からなる群から選ばれる少な
くとも１種であることを特徴とする請求項１又は２記載
の塗装方法。3. The resin component is an alkyd resin, an acrylic resin,
Polyester resin, epoxy resin, melamine resin, block isocyanate resin, fluororesin, silicone resin,
The coating method according to claim 1, wherein the coating method is at least one selected from the group consisting of an amide resin and an ABS resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20500898A JP4111287B2 (en) | 1998-07-21 | 1998-07-21 | Painting method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20500898A JP4111287B2 (en) | 1998-07-21 | 1998-07-21 | Painting method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000033324A true JP2000033324A (en) | 2000-02-02 |
| JP4111287B2 JP4111287B2 (en) | 2008-07-02 |
Family
ID=16499932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20500898A Expired - Fee Related JP4111287B2 (en) | 1998-07-21 | 1998-07-21 | Painting method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4111287B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009503168A (en) * | 2005-07-25 | 2009-01-29 | ビーエーエスエフ ソシエタス・ヨーロピア | Solid pigment preparations containing water-soluble surfactant aids and antioxidants |
-
1998
- 1998-07-21 JP JP20500898A patent/JP4111287B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009503168A (en) * | 2005-07-25 | 2009-01-29 | ビーエーエスエフ ソシエタス・ヨーロピア | Solid pigment preparations containing water-soluble surfactant aids and antioxidants |
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| Publication number | Publication date |
|---|---|
| JP4111287B2 (en) | 2008-07-02 |
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