JP3349185B2 - Pigment dispersion for two-pack primary rust preventive paint composition and primary rust preventive paint composition of this dispersion - Google Patents
Pigment dispersion for two-pack primary rust preventive paint composition and primary rust preventive paint composition of this dispersionInfo
- Publication number
- JP3349185B2 JP3349185B2 JP01592193A JP1592193A JP3349185B2 JP 3349185 B2 JP3349185 B2 JP 3349185B2 JP 01592193 A JP01592193 A JP 01592193A JP 1592193 A JP1592193 A JP 1592193A JP 3349185 B2 JP3349185 B2 JP 3349185B2
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- dispersion
- rust preventive
- primary rust
- alkyl silicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】本願発明は、造船用鋼材などの２
液型一次防錆塗料組成物用顔料分散液及びこの分散液の
一次防錆塗料組成物に関するものである。BACKGROUND OF THE INVENTION The present invention relates to a method for manufacturing steel materials for shipbuilding.
The present invention relates to a liquid type primary rust preventive paint composition pigment dispersion and a primary rust preventive paint composition for this dispersion.
【０００２】[0002]
【従来の技術】近年、船舶塗装の合理化が、クローズア
ップされ、ハイソリッド化、速乾化、ライン塗装による
省力化が検討されている。その一環として塗膜性能に優
れた粉体塗料による造船用鋼材のプレコート方式が考え
られる。2. Description of the Related Art In recent years, the rationalization of marine coating has been highlighted, and efforts have been made to reduce labor through high solidification, quick drying, and line coating. As one of the measures, a pre-coating method of shipbuilding steel using powder coating with excellent coating performance can be considered.
【０００３】ところで、従来から造船用鋼材は、船の建
造の期間中の一次防錆のためショッププライマーが塗装
されるが、一次防錆性、溶接性、上塗り塗装後の塗装系
の耐久性などに優れる無機ジンクショッププライマー
（以下「ＩＺＰ」という）が広く用いられている。Conventionally, steel for shipbuilding has been coated with a shop primer for primary rust prevention during the construction of a ship. However, primary rust prevention, weldability, durability of the coating system after top coating, etc. Inorganic zinc shop primers (hereinafter referred to as "IZP") are widely used.
【０００４】[0004]
【発明が解決しようとする課題】ところが、従来のＩＺ
Ｐの上に粉体塗料を上塗りすると、粉体塗料の加熱硬化
時に発泡を生じたり、粉体塗膜の強靭な物性や硬化収縮
応力によってＩＺＰ層内で凝集破壊を生じるなどの不具
合があって、粉体塗料の性能を十分に発揮できない。However, the conventional IZ
When a powder coating is overcoated on P, there are problems such as foaming during heat curing of the powder coating and cohesive failure in the IZP layer due to the tough physical properties of the powder coating and curing shrinkage stress. However, the performance of the powder coating cannot be sufficiently exhibited.
【０００５】ＩＺＰの上の粉体塗膜の発泡は、加熱硬化
時のＩＺＰの空隙中の空気の膨脹が主原因と考えられ
る。従って、ＩＺＰの膜厚を低下させることによって改
善することができるが、従来のＩＺＰは薄膜に塗装する
と、カスレを生じ易く、防錆性が著しく低下して実用的
ではない。[0005] The foaming of the powder coating on the IZP is considered to be mainly caused by the expansion of air in the voids of the IZP during heat curing. Therefore, it can be improved by reducing the film thickness of IZP. However, when the conventional IZP is applied to a thin film, it is easy to cause abrasion, and the rust prevention is remarkably reduced, which is not practical.
【０００６】また、ＩＺＰはあらゆるショッププライマ
ーの中で最良の溶接性を有するものではあるが、造船工
程の効率化のためには更なる溶接性の向上が求められて
いる。これ等のＩＺＰの不具合や溶接性向上の限界は、
亜鉛末を主成分とする顔料の溶剤中への分散液（以下
「ペースト」という）中に添加された有機系添加剤が原
因と考えられる。すなわち、有機系添加剤のなかでケー
キング防止剤は、塗料液にチキソトロピックな性質を付
与するため、ＩＺＰを吹付塗装する際に、ウェット塗膜
のレベリング性を阻害し、薄膜となればなる程ウェット
被膜の連続性が損なわれることとなる。また、ケーキン
グ防止剤は、顔料粒子同士の接触を防止してケーキング
防止の目的を達成するものであり、防錆性の発揮に必要
な亜鉛末粒子の接触を少なからず阻害することとなる。
また、ＩＺＰの塗膜は、顔料粒子が結合剤であるアルキ
ルシリケートによって連続的に結合されて形成されるも
のであるが、ここでも顔料粒子の間に割り込んだ形で存
在する有機系ケーキング防止剤が、エチルシリケートに
よる顔料の結合を阻害し、塗膜強度を低下させることと
なる。また、有機系添加剤は溶接時の熱で分解してガス
を発生し、溶接を大きく阻害してきた。Although IZP has the best weldability among all shop primers, further improvement in weldability is required to improve the efficiency of the shipbuilding process. The disadvantages of these IZPs and the limitations of improving weldability are:
The cause is considered to be an organic additive added to a dispersion (hereinafter referred to as "paste") of a pigment containing zinc powder as a main component in a solvent. That is, among the organic additives, the anti-caking agent imparts a thixotropic property to the coating liquid. Therefore, when spray-coating IZP, the leveling property of the wet coating film is impaired, and the thinner the film becomes, the smaller the anti-caking agent becomes. The continuity of the wet coating will be impaired. Further, the anti-caking agent prevents the pigment particles from coming into contact with each other and achieves the purpose of preventing caking, and will hinder the contact of the zinc dust particles necessary for exhibiting the rust-proofing property to a considerable extent.
In addition, the coating film of IZP is formed by continuously binding pigment particles with an alkyl silicate as a binder, but here, too, an organic caking inhibitor present in a form interposed between the pigment particles. However, this inhibits the binding of the pigment with ethyl silicate, and lowers the strength of the coating film. In addition, organic additives have been decomposed by heat during welding to generate gas, which has greatly hindered welding.
【０００７】また、有機系添加剤を用いない場合は、ペ
ーストの貯蔵安定性が不良である。顔料粉末を、シリケ
ート液に使用直前に分散する方法も考えられるが，分散
不良となってチップに詰まりを生じたり、混合液に短時
間で沈降して塗装作業性が十分でない。[0007] When no organic additive is used, the storage stability of the paste is poor. A method of dispersing the pigment powder in the silicate solution immediately before use is also conceivable, but the dispersion becomes poor and the chips are clogged, or the pigment sediments in a mixed solution in a short time, and the coating workability is not sufficient.
【０００８】そこで本発明の目的は、粉体塗料の上塗り
に適し、さらに従来のＩＺＰよりも薄い膜厚で同等以上
の防食性を有し、溶接性が向上した２液型一次防錆塗料
組成物用顔料分散液及びこの分散液の一次防錆塗料組成
物を提供することにある。Accordingly, an object of the present invention is to provide a two-pack primary rust preventive paint composition which is suitable for overcoating of powder paints, has a thinner film thickness than conventional IZP, has the same or higher anticorrosion properties, and has improved weldability. It is an object of the present invention to provide a pigment dispersion for a product and a primary rust preventive coating composition of the dispersion.
【０００９】[0009]
【課題を解決するための手段】本発明にかかる亜鉛末を
主成分とする２液型一次防錆塗料組成物用顔料分散液の
第１の特徴は、加水分解されたアルキルシリケートの溶
液中に、亜鉛末を主成分とする顔料を分散させておき、
水の溶解度が１重量％以下の溶剤を添加して、アルキル
シリケート加水分解物を顔料表面に析出させることによ
って被覆処理したところにある。The first feature of the pigment dispersion for a two-part primary rust-preventive coating composition according to the present invention, which is mainly composed of zinc powder, is characterized in that it is contained in a solution of a hydrolyzed alkyl silicate. , Pigment containing zinc powder as a main component is dispersed,
The coating treatment is carried out by adding a solvent having a solubility of water of 1% by weight or less to precipitate an alkyl silicate hydrolyzate on the pigment surface.
【００１０】本発明にかかる２液型一次防錆塗料組成物
用顔料分散液の第２の特徴は、前記加水分解されたアル
キルシリケートが、高度に加水分解されたアルキルシリ
ケートであるところにある。A second feature of the pigment dispersion for a two-part primary rust preventive coating composition according to the present invention is that the hydrolyzed alkyl silicate is a highly hydrolyzed alkyl silicate.
【００１１】さらに、第３の特徴は、前記加水分解され
たアルキルシリケートの溶液中に、亜鉛末を主成分とす
る顔料を連続的に撹拌して浮遊させておき、水の溶解度
が１重量％以下の溶剤を徐々に添加して形成されたとこ
ろにある。さらに、第４の特徴は、ケーキング防止剤か
らなる有機系添加剤の含有率が、０．４重量％以下であ
るところにある。A third feature is that a pigment containing zinc powder as a main component is continuously stirred and suspended in the hydrolyzed alkyl silicate solution so that the solubility of water is 1% by weight. It is formed by gradually adding the following solvent. Further, a fourth feature is that the content of the organic additive composed of the anti-caking agent is 0.4% by weight or less.
【００１２】また、本発明にかかる一次防錆塗料組成物
の第１の特徴は、（Ａ）アルキルシリケートの部分加水
分解物を主たる成分とする主剤結合剤溶液と、（Ｂ）亜
鉛末を主成分とする顔料分散液と、からなる２液型塗料
組成物において、上記分散液（Ｂ）が、加水分解された
アルキルシリケートの溶液中に、亜鉛末を主成分とする
顔料を分散させておき、水の溶解度が１重量％以下の溶
剤を添加して、アルキルシリケート加水分解物を顔料表
面に析出させることによって被覆処理した亜鉛末を主成
分とする２液型一次防錆塗料組成物用顔料分散液である
ところにある。The first feature of the primary rust-preventive coating composition according to the present invention is that (A) a base binder solution containing a partial hydrolyzate of an alkyl silicate as a main component, and (B) a zinc powder. In a two-pack coating composition comprising a pigment dispersion as a component, the dispersion (B) is prepared by dispersing a pigment mainly composed of zinc powder in a solution of a hydrolyzed alkyl silicate. A pigment for a two-part primary rust-preventive coating composition containing zinc powder as a main component, which is coated by adding a solvent having a water solubility of 1% by weight or less to precipitate an alkyl silicate hydrolyzate on the surface of the pigment. Where it is a dispersion.
【００１３】さらに、この一次防錆塗料組成物の第２の
特徴は、上記分散液（Ｂ）の形成の加水分解されたアル
キルシリケートが、高度に加水分解されたアルキルシリ
ケートであるところにある。Further, a second feature of the primary rust preventive coating composition is that the hydrolyzed alkyl silicate forming the dispersion (B) is a highly hydrolyzed alkyl silicate.
【００１４】さらに、この一次防錆塗料組成物の第３の
特徴は、上記分散液（Ｂ）が、加水分解されたアルキル
シリケートの溶液中に、亜鉛末を主成分とする顔料を連
続的に撹拌して浮遊させておき、水の溶解度が１重量％
以下の溶剤を徐々に添加して形成されたものであるとこ
ろにある。Further, a third feature of the primary rust-preventive coating composition is that the dispersion (B) is obtained by continuously adding a pigment mainly composed of zinc powder to a solution of a hydrolyzed alkyl silicate. Stir and float, water solubility 1% by weight
It is formed by gradually adding the following solvent.
【００１５】さらに、第４の特徴は、上記分散液（Ｂ）
が、ケーキング防止剤からなる有機系添加剤の含有率
が、０．４重量％以下であるところにある。A fourth feature is that the dispersion (B)
However, the content of the organic additive composed of an anti-caking agent is 0.4% by weight or less.
【００１６】ところで、本願発明者は、有機系添加物を
用いずに貯蔵安定性の良好なペーストを製造する方法を
検討した結果、高度に加水分解されたアルキルシリケー
トを顔料粒子表面に析出・固着させてコーティング被膜
を形成すると、顔料粒子にケーキングが見られないこと
を見出し本発明を完成した。By the way, the present inventor studied a method for producing a paste having good storage stability without using an organic additive. As a result, highly hydrolyzed alkyl silicate was deposited and fixed on the surface of pigment particles. When a coating film was formed in this way, it was found that caking was not observed in the pigment particles, and the present invention was completed.
【００１７】本発明によるペーストについて具体的に説
明する。The paste according to the present invention will be specifically described.
【００１８】アルキルシリケートのアルコール溶液に、
酸触媒と水とを加えて高度に加水分解すると、アルコー
ルや親水性溶剤には溶解するが、疎水性溶剤に溶解し難
いポリヒドロキシシロキサンの溶液が得られる。この液
に、疎水性溶剤を加えるとカサ高いポリヒドロキシシロ
キサンが析出する。この現象を応用して、ポリヒドロキ
シシロキサンによる顔料の被覆処理を行なうことができ
る。すなわち、ポリヒドロキシシロキサンの溶液に、顔
料を強力に撹拌して分散した状態で疎水性溶剤を徐々に
加えて行くと、析出したポリヒドロキシシロキサンは、
顔料粒子の表面に付着してコーティング被膜を形成す
る。このようにしてコーティング処理された顔料ペース
トは、静置しておくと顔料が沈降して上澄みと分離する
が、比重が７．１もある亜鉛末でも沈降層が非常にカサ
高く、長時間放置していてもケーキングの徴候を示さ
ず、撹拌すると容易に再分散でき、極めて低粘度でチキ
ソトロピックな性質を示さない。In the alcohol solution of the alkyl silicate,
When highly hydrolyzed by adding an acid catalyst and water, a solution of a polyhydroxysiloxane which is soluble in an alcohol or a hydrophilic solvent but hardly soluble in a hydrophobic solvent is obtained. When a hydrophobic solvent is added to this solution, a high bulk polyhydroxysiloxane is deposited. By applying this phenomenon, a coating treatment of the pigment with polyhydroxysiloxane can be performed. That is, when the hydrophobic solvent is gradually added to the solution of the polyhydroxysiloxane while the pigment is vigorously stirred and dispersed, the precipitated polyhydroxysiloxane becomes
It adheres to the surface of the pigment particles to form a coating film. When the pigment paste coated in this way is allowed to stand, the pigment sediments and separates from the supernatant. However, even with zinc dust having a specific gravity of 7.1, the sedimentation layer is very high and the pigment paste is left for a long time. It does not show any signs of caking, can be easily redispersed upon stirring, does not exhibit very low viscosity and thixotropic properties.
【００１９】本発明に用いる疎水性溶剤としては、水の
溶解度が１重量％以下のものが好ましく、トルエン、キ
シレン等の芳香族系溶剤、ｎ−ヘキサン、燈油、タ−ペ
ン等の脂肪族系溶剤などが最も好ましい。水の溶解度が
１重量％よりも多いものを使用すると、ポリヒドロキシ
シロキサンの析出が不十分となって、経時とともに顔料
の２次凝集を生じて好ましくない。The hydrophobic solvent used in the present invention is preferably one having a solubility of water of 1% by weight or less, aromatic solvents such as toluene and xylene, and aliphatic solvents such as n-hexane, kerosene and tapene. Solvents and the like are most preferred. When the solubility of water is more than 1% by weight, the precipitation of the polyhydroxysiloxane becomes insufficient, and secondary aggregation of the pigment occurs over time, which is not preferable.
【００２０】コーティングに用いるポリヒドロキシシロ
キサンは、アルキルシリケートのアルコール溶液に、酸
と水とを加えて加温することによって、容易に調整する
ことができる。加える水の量は、アルキルシリケートの
有するアルコキシ基の７５％以上を分解するに要する量
が必要で、９０％以上がより好ましい。逆に、７５％未
満では、僅かに溶剤中に溶解したポリヒドロキシシロキ
サンが経時とともに架橋して、顔料の２次凝集を生じて
好ましくない。The polyhydroxysiloxane used for the coating can be easily adjusted by adding an acid and water to an alcohol solution of an alkyl silicate and heating. The amount of water to be added must be an amount required to decompose at least 75% of the alkoxy groups of the alkyl silicate, and is more preferably at least 90%. Conversely, if it is less than 75%, the polyhydroxysiloxane slightly dissolved in the solvent is cross-linked with the passage of time, and secondary aggregation of the pigment occurs, which is not preferable.
【００２１】本発明による顔料の分散方法がディスパー
による撹拌であるため、高度の分散を必要とする着色顔
料などは、少量のケーキング防止剤とともに別途ＳＧミ
ルなどで分散して、本発明によるコーティングされた顔
料液へ加えることが好ましい。有機系添加剤のなかで使
用するケーキング防止剤は、着色顔料の分散を助け、２
次凝集を防止するに必要な最少限で用いることが必要
で、ペースト中の全顔料に対して、０．４重量％以下で
使用されなければならない。Since the method of dispersing the pigment according to the present invention is agitation by a disper, a coloring pigment or the like which requires a high degree of dispersion is dispersed separately with a small amount of an anti-caking agent by an SG mill or the like to form a coating according to the present invention. It is preferable to add to the pigment liquid. The anti-caking agent used in the organic additives helps disperse the color pigment,
It must be used in the minimum amount necessary to prevent secondary agglomeration and must be used at no more than 0.4% by weight, based on the total pigment in the paste.
【００２２】本発明に用いるアルキルシリケートは、ペ
ースト中の顔料の被覆処理と結合剤の両方に用いられる
が、アルキル基の炭素数が１〜４のものが好適で、中で
もエチルシリケートが最も好適である。The alkyl silicate used in the present invention is used for both the coating treatment of the pigment in the paste and for the binder. The alkyl silicate having an alkyl group having 1 to 4 carbon atoms is preferred, and ethyl silicate is most preferred. is there.
【００２３】本発明の一次防錆塗料組成物に用いる他の
原材料としては、従来のＩＺＰに用いられている原材料
を用いることができる。たとえば、ケーキング防止剤と
しては酸化ポリエチレン系、アマイド系、ポリエーテル
系、有機ベントナイト系、アルステ系、オルベンゲル系
などの有機系ケーキング防止剤や、アエロジル系、アス
ベスト系などの無機系ケーキング防止剤を、溶剤として
はアルコール系、芳香族系、エステル系、ケトン系、エ
チレングリコール系、脂肪族系などから選ばれた溶剤
を、顔料としては着色顔料、導電性顔料、体質顔料、溶
接性向上用顔料、その他の機能性顔料を適宜選定して用
いることができる。As other raw materials used in the primary rust preventive coating composition of the present invention, the raw materials used in conventional IZP can be used. For example, as an anti-caking agent, polyethylene oxide-based, amide-based, polyether-based, organic bentonite-based, Alste-based, or organic solvent such as orbengel-based, or aerosil-based, asbestos-based inorganic caking inhibitor, Solvents selected from alcohols, aromatics, esters, ketones, ethylene glycols, aliphatics, etc. as the solvent, and the pigments as color pigments, conductive pigments, extender pigments, pigments for improving weldability, Other functional pigments can be appropriately selected and used.
【００２４】本発明によるＩＺＰは、粉体塗装に適する
ものであるが、その強い塗膜強度によって従来のＩＺＰ
上に塗装できなかった厚膜で高強度の塗膜、例えばガラ
スフレーク入り塗料や無溶剤型エポキシ塗料などの塗装
も可能である。The IZP according to the present invention is suitable for powder coating.
It is also possible to apply a thick and high-strength coating film that could not be applied thereon, for example, a paint containing glass flakes or a solventless epoxy paint.
【００２５】[0025]
【実施例】以下実施例によって本発明をより具体的に説
明する。The present invention will be described more specifically with reference to the following examples.
【００２６】（主剤調整） エチルシリケート４０（日本コルコート製）３５０ｇ、
エタノール２００ｇ、水４０ｇ、３５％塩酸０．５ｇを
容器に仕込み、撹拌しながら５０〜５５℃に５時間保っ
た後、ＩＰＡを４０９．５ｇ加えて主剤を調整した。本
主剤を比較例−１，２、実施例−１，２に共通に用い
た。(Main agent preparation) 350 g of ethyl silicate 40 (manufactured by Nippon Colcoat)
200 g of ethanol, 40 g of water, and 0.5 g of 35% hydrochloric acid were charged into a container, and the mixture was maintained at 50 to 55 ° C. for 5 hours with stirring. Then, 409.5 g of IPA was added to prepare a main agent. This main agent was used commonly for Comparative Examples-1 and 2, and Examples-1 and 2.
【００２７】（塗料の調整） 比較例−１ シリカ末５０ｇ、亜鉛華３０ｇ、ルチルフラワー８０
ｇ、有機ベントナイト１０ｇ、酸化ポリエチレンペース
ト（２０％）１０ｇ、キシロール１２０ｇ、イソブチル
アルコール１２０ｇ、イソプロピルアルコール１００ｇ
を容器に仕込み、ガラスビースを加えてペイントシェー
カーで１時間振とうして分散した後、亜鉛末５００ｇを
加えてさらに５分間振とうしてペーストを調整した。こ
のペーストと主剤とを６５：３５に混合して比較例−１
の塗料を調整した。(Preparation of paint) Comparative Example-1 Silica powder 50 g, zinc white 30 g, rutile flower 80
g, organic bentonite 10 g, polyethylene oxide paste (20%) 10 g, xylol 120 g, isobutyl alcohol 120 g, isopropyl alcohol 100 g
Was charged into a container, glass beads were added, and the mixture was dispersed by shaking for 1 hour with a paint shaker. Then, 500 g of zinc dust was added, and the mixture was further shaken for 5 minutes to prepare a paste. This paste and the base material were mixed at a ratio of 65:35, and Comparative Example-1
The paint was adjusted.
【００２８】比較例−２ 亜鉛末、主剤、イソブチルアルコールを塗布直前に５０
０：３５０：１５０に混合して比較例−２の塗料を調整
した。混合直後よりただちに亜鉛末の沈澱が始まり、３
０分の放置で著しいケーキングが見られた。COMPARATIVE EXAMPLE 2 Zinc powder, a base material and isobutyl alcohol were applied 50
0: 350: 150 to prepare the coating material of Comparative Example-2. Immediately after mixing, the precipitation of zinc dust started immediately.
Significant caking was observed on standing for 0 minutes.
【００２９】実施例−１ エチルシリケート２５０ｇ、水７０ｇ、イソプロピルア
ルコール２５０ｇ、３５％塩酸０．１ｇを容器に仕込
み、撹拌しながら５０〜５５℃で３時間保った後、さら
に５０℃のオーブン内で１４時間エイジングし、イソプ
ロピルアルコール４３０ｇを加えて被覆処理液を調整し
た。この被覆処理液を実施例−１，２に共通して用い
た。Example 1 A container was charged with 250 g of ethyl silicate, 70 g of water, 250 g of isopropyl alcohol and 0.1 g of 35% hydrochloric acid, kept at 50 to 55 ° C. for 3 hours with stirring, and further placed in an oven at 50 ° C. After aging for 14 hours, 430 g of isopropyl alcohol was added to prepare a coating solution. This coating treatment liquid was used commonly in Examples-1 and 2.
【００３０】被覆処理液２０ｇ、イソブチルアルコール
２０ｇ、トルオール４０ｇを容器に仕込み、強く撹拌し
ながら亜鉛末５００ｇを分散し、続いてトルオールとキ
シロールの１：１の混合物８０ｇを３０分かけて滴下し
た。さらに０．１％のエチルアミンキシロール溶液２ｇ
を加えて塩酸を中和した。攪拌をさらに１時間継続して
亜鉛末の被覆処理液を調整した。20 g of the coating solution, 20 g of isobutyl alcohol, and 40 g of toluene were charged into a container, and 500 g of zinc dust was dispersed with vigorous stirring. Subsequently, 80 g of a 1: 1 mixture of toluene and xylol was added dropwise over 30 minutes. 2 g of 0.1% ethylamine xylol solution
Was added to neutralize the hydrochloric acid. Stirring was further continued for one hour to prepare a coating solution of zinc dust.
【００３１】シリカ末５０ｇ、亜鉛華３０ｇ、ルチルフ
ラワー８０ｇ、酸化ポリエチレンペースト（２０％）１
０ｇ、トルオール５０ｇ、キシロール１１８ｇとガラス
ビーズを容器に仕込み、ペイントシェーカーで振とうし
て得た顔料スラリーに、先に被覆処理した亜鉛末分散液
６８０ｇを加えてペーストを調整した。このペーストと
主剤とを６５：３５に混合して実施例−１の塗料を得
た。１時間放置して顔料を沈澱させても軽く撹拌すれば
良好な分散ができた。Silica powder 50 g, zinc white 30 g, rutile flower 80 g, polyethylene oxide paste (20%) 1
A container was charged with 0 g, 50 g of toluene, 118 g of xylol, and glass beads, and 680 g of a zinc powder dispersion previously coated was added to a pigment slurry obtained by shaking with a paint shaker to prepare a paste. This paste and the base material were mixed at a ratio of 65:35 to obtain a coating material of Example-1. Even if the pigment was allowed to settle for 1 hour, good dispersion was achieved with gentle stirring.
【００３２】実施例−２ 実施例−１で調整した被覆処理液２０ｇ、イソブチルア
ルコール２０ｇ、トルオール４０ｇを容器に仕込み、強
く撹拌しながら亜鉛末４００ｇと亜鉛華３０ｇとを分散
し、トルオールとキシロールとの１：１の混合物８８ｇ
を３０分かけて滴下した。さらに０．１％のエチルアミ
ンキシロール溶液２ｇを加えて塩酸を中和した。撹拌を
さらに１時間継続して実施例−２のペーストを得た。１
時間放置して顔料を沈澱させても軽く攪拌すれば良好な
分散ができた。Example 2 20 g of the coating solution prepared in Example 1, 20 g of isobutyl alcohol and 40 g of toluene were charged into a container, and 400 g of zinc dust and 30 g of zinc white were dispersed with vigorous stirring. 88 g of a 1: 1 mixture of
Was added dropwise over 30 minutes. Further, 2 g of a 0.1% ethylamine xylol solution was added to neutralize hydrochloric acid. Stirring was continued for another hour to obtain a paste of Example-2. 1
Even if the pigment was allowed to settle after standing for a long time, a good dispersion could be obtained with gentle stirring.
【００３３】比較例−３ 実施例−１で調整した被覆処理液２０ｇ、イソブチルア
ルコール２０ｇ（イソブチルアルコールの水の溶解度：
１５％（２０℃））、トルオール４０ｇを容器に仕込
み、強く撹拌しながら亜鉛末５００ｇを分散し、続いて
イソブチルアルコール８０ｇを３０分かけて滴下した。
さらに、０．１％のエチルアミンイソブチルアルコール
溶液２ｇを加えて塩酸を中和した。撹拌をさらに１時間
継続し、亜鉛末の被覆処理液を調整した。この液を室内
で７日間放置後の状態を調べたところ、亜鉛末は沈殿
し、スプーンで撹拌しても分散できなかった。さらに、
１ヶ月放置後に状態を調べたところ、全体がゲル化して
いた。この被覆処理亜鉛末を用いて塗料調製をすること
はできなかった。 Comparative Example 3 20 g of the coating solution prepared in Example 1 and isobutyl alcohol
20 g of alcohol (solubility of water in isobutyl alcohol:
15% (20 ° C), 40g of toluene is charged in a container
And disperse 500 g of zinc powder with vigorous stirring.
80 g of isobutyl alcohol was added dropwise over 30 minutes.
In addition, 0.1% ethylamine isobutyl alcohol
Hydrochloric acid was neutralized by adding 2 g of the solution. Stir for another hour
Continuously, a coating treatment solution for zinc powder was prepared. Apply this liquid indoors
After checking the condition after standing for 7 days, the zinc dust precipitated
However, even if it was stirred with a spoon, it could not be dispersed. further,
When I checked the condition after leaving for one month, the whole gelled
Was. Preparation of paint using this coated zinc powder
Could not.
【００３４】比較例−４ 実施例−１で調整した被覆処理液２０ｇ、イソブチルア
ルコール２０ｇ、トルオール４０ｇを容器に仕込み、強
く撹拌しながら亜鉛末５００ｇを分散し、６０℃に加温
して３０分撹拌を継続し、０．１％のエチルアミンイソ
ブチルアルコール溶液２ｇを加えて撹拌を止めた。亜鉛
末の状態を調べたところ、亜鉛末が凝集してざらざらし
たスラリー状であった。これにトルエン、キシレン１：
１の混合物８０ｇを加えて再分散を試みたが、ざらざら
した状態は改善できず、塗料の顔料状態としては不適当
と判断した。この被膜処理亜鉛末を用いて塗料調製をす
ることはできなかった。 Comparative Example 4 20 g of the coating solution prepared in Example 1
Charge 20g of rucol and 40g of toluene into a container,
Disperse 500g of zinc dust while stirring well and heat to 60 ℃
And continue stirring for 30 minutes.
The stirring was stopped by adding 2 g of a butyl alcohol solution. zinc
When examining the state of the powder, the zinc powder aggregated and became rough
Slurry. Toluene and xylene 1:
80 g of the mixture of Example 1 was added, and re-dispersion was attempted.
Condition cannot be improved and is unsuitable as a paint pigment
Was determined. Use this coated zinc powder to prepare paint.
I couldn't do it.
【００３５】比較例−５ エチルシリケートの２５％イソプロピルアルコール２０
ｇ、イソブチルアルコール２０ｇ、トルオール４０ｇを
容器に仕込み、強く撹拌しながら亜鉛末５００ｇを分散
し、トルエン、キシレン１：１の混合物８０ｇを３０分
かけて滴下し、 さらに１時間撹拌して亜鉛末の被膜を試
みた。 Comparative Example 5 Ethyl silicate 25% isopropyl alcohol 20
g, isobutyl alcohol 20g, toluene 40g
Charge into a container and disperse 500g of zinc dust with vigorous stirring
Then, 80 g of a mixture of toluene and xylene 1: 1 was added for 30 minutes.
And stir for an additional hour to test the zinc dust coating.
saw.
【００３６】この亜鉛末分散液を、室内で一晩放置して
状態を調べたところ、透明な溶剤の上澄層と亜鉛末層に
分離し、亜鉛末は固くケーキングして分散困難であっ
た。上澄をガラス版に塗り広げて溶剤を蒸発させたとこ
ろ、やや粘着性のある薄いエチルシリケート層の存在を
認め、エチルシリケートが亜鉛末表面に十分に析出して
皮膜を形成していないことを確認した。この被膜処理亜
鉛末を用いて塗料調製をすることはできなかった。 This zinc powder dispersion is left in a room overnight.
Examination of the condition revealed that the clear solvent was a supernatant layer and a zinc powder layer.
Separated and the zinc dust was hard caked and difficult to disperse.
Was. The supernatant was spread on a glass plate and the solvent was evaporated.
Of course, the presence of a slightly sticky thin ethyl silicate layer
Recognized, ethyl silicate was sufficiently deposited on the zinc powder surface
It was confirmed that no film was formed. This coating treatment
A paint could not be prepared using lead powder.
【００３７】評価 ペーストの安定性； 比較例−１、実施例−１，２のペーストを密閉容器に入
れ、５０℃で１ヵ月保った後、ケーキングの状態を調べ
た。次のとおり評価した。 ○ ： 容易に均質化できる。 △ ： 沈澱がやや硬く、均質化に時間がかかる。 × ： 沈澱が硬く、均質化が困難。 塗装性； 比較例−１，２、実施例−１，２の塗料を７０×１５０
×０．８ｍｍｔのミガキ軟鋼板に乾燥膜厚が６μ，１０
μ，１５μとなるようにエアスプレ−にて塗付し、塗膜
の状態を調べた。次のとおり評価した。 ○ ： 塗膜が均質でスケがない。 △ ： スケはないが、表面がザラザラしている。 × ： ザラザラしてスケが多い。 防錆性； ７０×１５０×３．２ｍｍｔのショットブラスト板に比
較例−１，２、実施例−１，２の塗料を乾燥膜厚が６
μ，１０μ，１５μとなるようにエアスプレーにて塗付
し、室内で７日間乾燥して試験片とした。Evaluation Stability of Paste: The pastes of Comparative Example-1, Example-1 and Example-2 were placed in a closed container, kept at 50 ° C. for one month, and the state of the caking was examined. The evaluation was as follows. ：: Easy homogenization. Δ: Precipitation is slightly hard, and it takes time to homogenize. ×: Precipitation is hard and homogenization is difficult. Paintability: 70 × 150 of the paints of Comparative Examples-1 and 2 and Examples-1 and 2
Dry film thickness of 6μ, 10
μ and 15 μ were applied by air spray, and the state of the coating film was examined. The evaluation was as follows. ：: The coating film is homogeneous and there is no scale. Δ: There is no invisibility, but the surface is rough. ×: There are many rough and rough. Rust resistance; 70% x 150mm x 3.2mmt shot blast plates were coated with the paints of Comparative Examples-1 and 2 and Examples-1 and 2 to a dry film thickness of 6
μ, 10 μ, and 15 μ were applied by air spray and dried in a room for 7 days to obtain test pieces.
【００３８】これ等の試験片を海浜地区の屋外に南面４
５°に固定された台に設置して３ヵ月間バクロし、発錆
の状況を調べた。次のとおり評価した。 ○ ： 全く発錆の徴候なし。 △ ： 点さび。 × ： 著しい発錆。 粉体塗料の上塗り適性； 防食性の評価で用いた試験片と同様にして調整した試験
片に、硬化膜厚が１００ミクロンとなるようにエポキシ
系粉体塗料を静電塗装し、２００℃に調整した熱風炉中
で１０分間硬化させて、粉体塗膜の発泡の状況と付着力
を調べた。These test pieces were placed outside the beach area on the south side 4
It was set on a table fixed at 5 ° and baked for 3 months to check the state of rusting. The evaluation was as follows. : No sign of rusting. Δ: dot rust. ×: remarkable rusting. Top coating suitability of powder coating; Epoxy powder coating was electrostatically applied to a test piece prepared in the same manner as the test piece used for the evaluation of anticorrosion so that the cured film thickness became 100 microns, and heated to 200 ° C. After curing for 10 minutes in the adjusted hot-blast furnace, the state of foaming and adhesion of the powder coating film were examined.
【００３９】発泡については肉眼判定で、次のとおり評
価した。 ○ ： 表面が平滑で発泡がみられない。 △ ： 小さい泡の先端が表面にみられるがピンホール
はない。 × ： 大きい泡の先端が表面にみられ、一部ははじけ
てクレーター状の凹凸となっている。 付着力については、ドーリーをエポキシ接着剤で取り付
け、垂直に引張って破断に要した力（Ｋｇｆ／平方ｃ
ｍ）と剥離の状況を記録した。 溶接性； サイズ１００×５００×１２ｍｍｔのサンドブラスト処
理した鋼材に、防錆性の評価で用いた試験片と同様の方
法で塗装した。The foaming was evaluated by the naked eye as follows. : The surface is smooth and no foaming is observed. Δ: The tip of a small bubble is seen on the surface, but there is no pinhole. ×: The tip of a large bubble is seen on the surface, and a part of the bubble pops out to form crater-like irregularities. Regarding the adhesive force, the dolly was attached with an epoxy adhesive and pulled vertically to break (Kgf / square c).
m) and the state of peeling were recorded. Weldability: A steel material having a size of 100 × 500 × 12 mmt and subjected to sand blasting was coated in the same manner as the test piece used for the evaluation of rust prevention.
【００４０】そして、図１に示すように、立板１と水平
板２とを組み合わせて水平隅肉溶接３を実施した。この
立板とこの水平板の上面を塗装し塗膜４を形成し、立板
の端面の塗装は行なわなかった。実験の精度を高めるた
め、端面は機械加工によって平滑にし、水平板と立板の
仮付溶接の際、クサビを打込んで固定して、隙間がない
ように配慮した。その他の溶接条件を表１に示す。Then, as shown in FIG. 1, horizontal fillet welding 3 was performed by combining the standing plate 1 and the horizontal plate 2. The upper surface of the standing plate and the horizontal plate was painted to form a coating film 4, and the end surface of the standing plate was not painted. In order to increase the precision of the experiment, the end face was smoothed by machining, and wedges were driven in and fixed during temporary tack welding of the horizontal plate and the standing plate so that there was no gap. Table 1 shows other welding conditions.
【００４１】[0041]
【表１】 溶接第２ビート（後行ビート）について、ピットの発生
数と破断面のブローホールの発生率を調べて記録した。
以上の評価結果をまとめて表２に示す。[Table 1] The number of pits generated and the occurrence rate of blowholes in the fractured surface were examined and recorded for the second beat of the welding (the succeeding beat).
Table 2 summarizes the above evaluation results.
【００４２】[0042]
【表２】 [Table 2]
【００４３】[0043]
【発明の効果】１．本発明による方法で調整されたペー
ストは、有機系ケーキング防止剤を用いずとも安定性が
良好である。 ２．アルキルシリケート液と本発明によるペーストとを
混合したものを吹付塗装すると、スプレーミストの微粒
化とウェット塗膜の流動性、つまりレベリング性が良好
で、薄膜塗装性が向上した。 ３．塗膜中の顔料粒子は、結合剤であるアルキルシリケ
ートによって強固に結合され、粉体塗料の強靭な塗膜強
度や硬化収縮応力に対抗できる塗膜強度が確保でき、凝
集破壊が防止できる。 ４．塗膜中の顔料粒子、特に亜鉛末が密に接触すること
ができるため、防錆性が著しく向上する。 ５．薄膜塗装が実用化できたことにより、塗膜空隙の空
気の膨脹による粉体塗膜の焼付け時の発泡が防止でき
る。 ６．薄膜塗装であること、および塗膜中に加熱により分
解する有機物がほとんどないため、溶接欠陥が大幅に減
少する。Advantages of the Invention The paste prepared by the method according to the present invention has good stability without using an organic caking inhibitor. 2. When the mixture of the alkyl silicate solution and the paste according to the present invention was spray-coated, the spray mist was atomized and the fluidity of the wet coating film, that is, the leveling property was good, and the thin film coating property was improved. 3. The pigment particles in the coating film are firmly bound by the alkyl silicate as a binder, and the tough coating film strength of the powder coating and the coating film strength that can withstand the curing shrinkage stress can be secured, and cohesive failure can be prevented. 4. Since the pigment particles, particularly zinc dust, in the coating film can come into close contact with each other, the rust prevention is significantly improved. 5. The practical application of the thin film coating can prevent foaming during baking of the powder coating film due to expansion of air in the coating film voids. 6. Since it is a thin film coating and there is almost no organic matter decomposed by heating in the coating film, welding defects are greatly reduced.
【図１】この実施例の溶接性を調べるための立板と水平
板の接合の様子を示す断面図である。FIG. 1 is a cross-sectional view showing a state of joining a vertical plate and a horizontal plate for examining weldability of this embodiment.
フロントページの続き (72)発明者 原田 伸 広島県広島市中区吉島東１丁目15番２号 中国塗料株式会社船舶塗料本部技術部 内 (72)発明者 田辺 真一 広島県広島市中区吉島東１丁目15番２号 中国塗料株式会社船舶塗料本部技術部 内 (56)参考文献 特開 昭63−17976（ＪＰ，Ａ) 特開 昭60−51756（ＪＰ，Ａ) 特開 昭54−112936（ＪＰ，Ａ) 特開 昭61−204282（ＪＰ，Ａ) 特開 昭50−145340（ＪＰ，Ａ) 特開 昭60−112870（ＪＰ，Ａ) 特開 平４−46932（ＪＰ，Ａ) 特開 昭60−168772（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C09D 183/02 B05D 7/14 C09C 3/06 C09C 3/12 C09D 5/08 Continuation of the front page (72) Inventor Shin Harada 1-15-2 Yoshishima Higashi, Naka-ku, Hiroshima-shi, Hiroshima Pref. China Paint Co., Ltd. Ship Paint Headquarters Technical Department (72) Inventor Shinichi Tanabe Hiroshima-shi, Hiroshima 1-15-2 Chugoku Paint Co., Ltd. Ship Paint Division Technical Department (56) References JP-A-63-17976 (JP, A) JP-A-60-51756 (JP, A) JP-A-54-112936 ( JP, A) JP-A-61-204282 (JP, A) JP-A-50-145340 (JP, A) JP-A-60-112870 (JP, A) JP-A-4-46932 (JP, A) 60-168772 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C09D 183/02 B05D 7/14 C09C 3/06 C09C 3/12 C09D 5/08
Claims (8)
液中に、亜鉛末を主成分とする顔料を分散させておき、
水の溶解度が１重量％以下の溶剤を添加して、アルキル
シリケート加水分解物を顔料表面に析出させることによ
って被覆処理したことを特徴とする亜鉛末を主成分とす
る２液型一次防錆塗料組成物用顔料分散液。1. A pigment mainly composed of zinc powder is dispersed in a solution of a hydrolyzed alkyl silicate,
A two-pack type primary rust preventive paint containing zinc powder as a main component, which is coated by adding a solvent having a water solubility of 1% by weight or less and depositing an alkyl silicate hydrolyzate on the pigment surface. A pigment dispersion for a composition.
高度に加水分解されたアルキルシリケートであることを
特徴とする請求項１に記載された２液型一次防錆塗料組
成物用顔料分散液。2. The hydrolyzed alkyl silicate is
2. The pigment dispersion for a two-part primary rust preventive coating composition according to claim 1, which is a highly hydrolyzed alkyl silicate.
液中に、亜鉛末を主成分とする顔料を連続的に撹拌して
浮遊させておき、水の溶解度が１重量％以下の溶剤を徐
々に添加して形成されたことを特徴とする請求項１また
は２に記載された２液型一次防錆塗料組成物用顔料分散
液。3. A pigment mainly composed of zinc powder is continuously stirred and suspended in a solution of the hydrolyzed alkyl silicate, and a solvent having a water solubility of 1% by weight or less is gradually added. The pigment dispersion for a two-component primary rust-preventive coating composition according to claim 1, wherein the pigment dispersion is formed by:
の含有率が、０．４重量％以下であることを特徴とする
請求項１〜３のいずれか１に記載の２液型一次防錆塗料
組成物用顔料分散液。4. The two-component primary rust preventive according to claim 1, wherein the content of the organic additive comprising an anti-caking agent is 0.4% by weight or less. Pigment dispersion for coating composition.
解物を主たる成分とする主剤結合剤溶液と、 （Ｂ）亜鉛末を主成分とする顔料分散液と、 からなる２液型塗料組成物において、 上記分散液（Ｂ）が、加水分解されたアルキルシリケー
トの溶液中に、亜鉛末を主成分とする顔料を分散させて
おき、水の溶解度が１重量％以下の溶剤を添加して、ア
ルキルシリケート加水分解物を顔料表面に析出させるこ
とによって被覆処理した亜鉛末を主成分とする２液型一
次防錆塗料組成物用顔料分散液であることを特徴とする
一次防錆塗料組成物。5. A two-pack coating composition comprising: (A) a base binder solution containing a partial hydrolyzate of alkyl silicate as a main component; and (B) a pigment dispersion containing zinc powder as a main component. The dispersion (B) is prepared by dispersing a pigment mainly composed of zinc powder in a solution of a hydrolyzed alkyl silicate, and adding a solvent having a solubility of water of 1% by weight or less to an alkyl. A primary rust preventive paint composition, which is a pigment dispersion for a two-part primary rust preventive paint composition containing zinc powder as a main component and coated by depositing a silicate hydrolyzate on the pigment surface.
たアルキルシリケートが、高度に加水分解されたアルキ
ルシリケートであることを特徴とする請求項５に記載さ
れた一次防錆塗料組成物。6. The primary rust preventive coating composition according to claim 5, wherein the hydrolyzed alkyl silicate forming the dispersion (B) is a highly hydrolyzed alkyl silicate. .
ルキルシリケートの溶液中に、亜鉛末を主成分とする顔
料を連続的に撹拌して浮遊させておき、水の溶解度が１
重量％以下の溶剤を徐々に添加して形成されたものであ
ることを特徴とする請求項５または６に記載された一次
防錆塗料組成物。7. The dispersion (B) is prepared by continuously stirring and suspending a pigment mainly composed of zinc powder in a solution of a hydrolyzed alkyl silicate so that the solubility of water is 1%.
7. The primary rust preventive coating composition according to claim 5, wherein the composition is formed by gradually adding a solvent of not more than weight%.
からなる有機系添加剤の含有率が、０．４重量％以下で
あることを特徴とする請求項５〜７のいずれか１に記載
された一次防錆塗料組成物。8. The method according to claim 5, wherein the dispersion (B) has a content of an organic additive comprising an anti-caking agent of 0.4% by weight or less. The described primary rust preventive paint composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01592193A JP3349185B2 (en) | 1993-01-05 | 1993-01-05 | Pigment dispersion for two-pack primary rust preventive paint composition and primary rust preventive paint composition of this dispersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01592193A JP3349185B2 (en) | 1993-01-05 | 1993-01-05 | Pigment dispersion for two-pack primary rust preventive paint composition and primary rust preventive paint composition of this dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06210240A JPH06210240A (en) | 1994-08-02 |
| JP3349185B2 true JP3349185B2 (en) | 2002-11-20 |
Family
ID=11902252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01592193A Expired - Lifetime JP3349185B2 (en) | 1993-01-05 | 1993-01-05 | Pigment dispersion for two-pack primary rust preventive paint composition and primary rust preventive paint composition of this dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3349185B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5325398B2 (en) * | 2007-06-25 | 2013-10-23 | 日本ペイント株式会社 | Method for producing inorganic-organic composite coating composition |
| JP5048407B2 (en) * | 2007-07-10 | 2012-10-17 | 日本ペイント株式会社 | Inorganic organic composite coating composition |
| CN104968740B (en) * | 2013-02-04 | 2016-11-02 | 关西涂料株式会社 | Anticorrosive coating composition and the application steel structure of application said composition |
| JP6767150B2 (en) * | 2016-04-08 | 2020-10-14 | 中国塗料株式会社 | Manufacturing method of steel sheet with rust preventive coating |
| KR102237993B1 (en) * | 2020-01-31 | 2021-04-08 | 주식회사 켐프 | Method for surface treatment of galvanized metal for surface coloring, surface repairing and improving corrosion resistance |
| KR102237992B1 (en) * | 2020-01-31 | 2021-04-08 | 주식회사 켐프 | Cr-FREE SURFACE TREATMENT COMPOSITION HAVING HIGH CORROSION RESISTANCE FOR SURFACE COLORING AND SURFACE REPAIRING, AND METHOD FOR APPLYING THE SAME |
-
1993
- 1993-01-05 JP JP01592193A patent/JP3349185B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06210240A (en) | 1994-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2729935B2 (en) | Sealing treatment method for thermal spray coating and sealing material | |
| US6541540B2 (en) | Powder coating compositions, method for preparing them and method for forming films | |
| JP3184614B2 (en) | Corrosion protection coating method for steel | |
| JPS63176453A (en) | Production of thermally sprayed metal film | |
| JP4350182B2 (en) | Anticorrosion paint composition, anticorrosion coating film, and method for anticorrosion of metal substrate surface | |
| JP3349185B2 (en) | Pigment dispersion for two-pack primary rust preventive paint composition and primary rust preventive paint composition of this dispersion | |
| JP2752337B2 (en) | Method of forming metal spray coating | |
| JPH11343422A (en) | Rust-preventive pigment for rust-preventive organic coating | |
| JPH11279488A (en) | Heat-resistant coating composition | |
| TWI731335B (en) | Coating with oxidation resistance at high temperature and method for coating surface of carbon steel | |
| JPS58142948A (en) | Zinc-rich paint composition | |
| JPS6212266B2 (en) | ||
| JPH0328507B2 (en) | ||
| JPS6257670B2 (en) | ||
| JPS6034588B2 (en) | Steel plate pretreatment method | |
| JP2001295071A (en) | Pretreatment method for steel sheet | |
| JP2002212508A (en) | Method for producing powdered coating, powdered coating and anticorrosion-treated steel material | |
| JPH069903A (en) | Zinc shop primer | |
| JPS58196872A (en) | Chipping-resistive coating method | |
| JP3582818B2 (en) | Ship heat-resistant paint | |
| KR101708151B1 (en) | High heat-resistant and corrosion-resistant thin film inorganic zinc coating composition and a manufacturing method thereof | |
| JPH08302241A (en) | Powdery coating material | |
| JPH11323184A (en) | Coating composition | |
| JPS61123674A (en) | Flaky zinc powder composition | |
| JPS62141075A (en) | Primary rust-preventive coating composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20020205 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20020806 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080913 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090913 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100913 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110913 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120913 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130913 Year of fee payment: 11 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130913 Year of fee payment: 11 |