JPS6227469A - Fluororesin paint composition - Google Patents
Fluororesin paint compositionInfo
- Publication number
- JPS6227469A JPS6227469A JP16595885A JP16595885A JPS6227469A JP S6227469 A JPS6227469 A JP S6227469A JP 16595885 A JP16595885 A JP 16595885A JP 16595885 A JP16595885 A JP 16595885A JP S6227469 A JPS6227469 A JP S6227469A
- Authority
- JP
- Japan
- Prior art keywords
- fluororesin
- coupling agent
- paint
- titanate
- film
- 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.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、フッ素樹脂塗料組成物に係り、特に金属板に
塗装されるフッ素樹脂塗料組成物の塗膜物性を改善した
ものに関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a fluororesin coating composition, and particularly to a fluororesin coating composition coated on a metal plate with improved coating film properties.
従来の技術
各種金属板、例えば亜鉛メッキ鋼板、A I! −Zn
合金メッキ網板、ステンレス鋼板、アルミニューム板等
はいろいろな分野で使用されているが、これらの金属板
にフッ素樹脂塗料を塗布すると、屋外耐候性、曲げ加工
性、耐薬品性、耐溶剤性、耐摩耗性等の諸物性が良くな
るので、フッ素樹脂塗膜で被覆した金属板が各分野で利
用されている。Prior Art Various metal plates, such as galvanized steel plates, AI! -Zn
Alloy-plated mesh plates, stainless steel plates, aluminum plates, etc. are used in a variety of fields, but applying fluororesin paint to these metal plates improves their outdoor weather resistance, bending workability, chemical resistance, and solvent resistance. Metal plates coated with fluororesin coatings are used in various fields because of their improved physical properties such as abrasion resistance.
特に建築資材分野に使用さている着色鋼板の超耐久性保
護膜として利用されている。In particular, it is used as an ultra-durable protective film for colored steel plates used in the construction material field.
ところで、フッ素樹脂塗料で例えば亜鉛メ、7キ鋼板を
塗装するには、まず鋼板の表面をリン酸塩又はクロム酸
塩処理を施し乾燥させてその表面の錆等を除くとともに
防錆処理を行ない、ついでフッ素樹脂塗膜は金属に対し
て密着性が良くないのでこの表面処理を行なったものに
エポキシ樹脂を骨格基体樹脂とする下塗り塗料を乾燥膜
厚が3〜12μになるように塗布して金属表面温度が1
60°C〜220℃になるように焼付は乾燥する。つい
でフッ素樹脂塗料を乾燥膜厚が15〜35μになるよう
に塗布した後、金属表面温度が220〜260°Cにな
るように焼付は乾燥する。このように下塗り塗料、フッ
素樹脂塗料を併用するが、これらの下塗り、上塗り塗料
をそれぞれ例えばロール塗装方式で塗布し、ついで焼付
は乾燥すると、いわゆる2コ一ト2ベーク方式でフッ素
樹脂被覆銀1仮が得られる。By the way, in order to paint, for example, a galvanized steel plate or a 7-metal steel plate with a fluororesin paint, the surface of the steel plate is first treated with phosphate or chromate and dried to remove rust etc. on the surface and to perform rust prevention treatment. Next, since fluororesin coatings do not have good adhesion to metals, an undercoat with an epoxy resin as the skeleton base resin is applied to the surface treated surface to a dry film thickness of 3 to 12 μm. Metal surface temperature is 1
Baking is dried at a temperature of 60°C to 220°C. Next, a fluororesin paint is applied so that the dry film thickness is 15 to 35 μm, and then baked and dried so that the metal surface temperature is 220 to 260°C. In this way, an undercoat and a fluororesin paint are used in combination, and these undercoat and topcoat are each applied, for example, by a roll coating method, and then baked to dry. Temporary is obtained.
ところが、このフッ素樹脂塗膜の焼付は過程において塗
料の塗布段階では隈なく塗布された塗料が鋼板の端縁部
の0.1〜51鳳の範囲の幅でその塗膜が形成されない
部分が生じ、下塗りの塗膜が露出する現象を生しる。こ
のようなフッ素樹脂塗膜で被覆されない部分が生じると
、金属塗装板として外観上好ましくないのみならず、も
っと重大なことは、このフッ素樹脂で被覆されないとこ
ろから錆が発生し易くなったり、下塗り塗膜にワレが発
生し易くなって建築資材としての耐久寿命を縮めること
になる。そのため、フッ素樹脂塗膜で被覆されない部分
は鋼板を建築の所定箇所に組み込み施工を行った後、人
手により熱可塑性アクリルラッカーの如き他の塗料を塗
布するなどして補修しており、そのための作業には多大
な経費が必要になっていた。However, during the baking process of this fluororesin coating, there are areas where the coating film is not formed on the edge of the steel plate in a width range of 0.1 to 51mm. , which causes the undercoat film to be exposed. If there are areas that are not covered with such a fluororesin coating, it will not only be unfavorable in terms of appearance as a metal-coated plate, but more importantly, rust will easily occur from the areas that are not covered with the fluororesin, and the undercoat will deteriorate. The paint film is prone to cracking, which shortens its useful life as a building material. Therefore, the parts that are not covered by the fluororesin coating are repaired by installing steel plates in designated parts of the building and then manually applying other paints such as thermoplastic acrylic lacquer. required a huge amount of expense.
このように塗料の塗布段階で塗布された塗膜が焼付は乾
燥の後にはその塗膜がなく、その塗膜で被覆されないで
下塗り塗膜が露出する現象が起こるのは、高分子量フッ
素樹脂塗料はその溶剤溶解性が良くないので溶剤にフッ
素樹脂を分散させた、いわゆる溶剤型ディスバージョン
オルガノヅルとして使用されるため、その塗布後は焼付
は乾燥を行なって塗膜を溶融し、連続皮膜を形成する必
要があるが、その過程で塗膜の収縮が起こりこれに原因
があるものと考えられる。この収縮の原因にはフッ素樹
脂が結晶性熱可塑性樹脂であるため、溶融して連続膜を
形成し冷却されるときに結晶化することが考えられ、こ
の際下地との密着力より結晶化の力が強いほど塗膜の収
縮が起こり易いと考えられる。This phenomenon occurs when the paint film applied at the paint application stage is baked and dried, and the undercoat film is exposed without being covered by the paint film. Because of its poor solubility in solvents, it is used as a so-called solvent-type dispersion organ nodule, in which fluororesin is dispersed in a solvent. This is thought to be due to the fact that the coating film shrinks during this process. The reason for this shrinkage is that the fluororesin is a crystalline thermoplastic resin, so it is thought that it melts to form a continuous film and crystallizes when it is cooled. It is thought that the stronger the force, the more likely the coating film will shrink.
このようにフッ素樹脂塗膜の収縮により下塗り塗膜が露
出する現象は金属板の端部に限らず、フッ素樹脂塗料を
例えばロール塗装する際にロール表面の傷、塗料に生じ
た泡、あるいは塗料に混入した異物等により金属板表面
に均一な塗膜が形成されないときにも、これをそのまま
焼付は乾燥する際その不均一な塗膜の部分でワレを発生
するときにも生じる。This phenomenon in which the undercoat film is exposed due to shrinkage of the fluororesin paint film is not limited to the edges of the metal plate, but can also be caused by scratches on the roll surface, bubbles formed in the paint, or paint when applying the fluororesin paint by roll. Baking also occurs when a uniform coating film is not formed on the surface of the metal plate due to foreign matter mixed in with the metal plate, and when the uneven coating film cracks during drying.
このワレは上記したように塗布さたフッ素樹脂の粒子が
溶融され連続膜を形成する造膜過程で高分子の結晶化が
起こることにも原因があるが、これを防ぐには、従来分
散媒である有機溶剤に蒸発速度が遅い高沸点溶剤を使用
したり、可塑剤を多く含有させることが一般に行なわれ
ている。しかし、高沸点溶剤や可塑剤の添加量を多くす
ることは、塗料にチキソトロピー的挙動が強く現れて塗
装適性を害したり、また、残留可塑剤が塗膜よりにしみ
出てゴミが付いて汚(なったり、塗膜を軟化させる等の
塗膜欠陥を生じたりする欠点がある。This cracking is also caused by crystallization of the polymer during the film-forming process in which the applied fluororesin particles are melted to form a continuous film as described above. Generally, a high boiling point solvent with a slow evaporation rate is used as the organic solvent, or a large amount of plasticizer is added to the organic solvent. However, increasing the amount of high-boiling solvents or plasticizers may cause the paint to exhibit strong thixotropic behavior, impairing its suitability for painting, or the residual plasticizer may seep out of the paint film, causing dirt to form and stain the paint. (This has the drawback of causing paint film defects such as softening of the paint film and softening of the paint film.
発明が解決しようとする問題点
以上のように、従来のフッ素樹脂塗料は、その金属板上
の塗膜が端縁部で下塗り塗膜を露出させたり、不均一な
塗膜部分にワレを生じたりする問題点があり、その改善
が望まれていた。Problems to be Solved by the Invention As mentioned above, with conventional fluororesin paints, the paint film on the metal plate exposes the undercoat film at the edges, and cracks occur in uneven paint film areas. There were some problems, and improvements were desired.
問題点を解決するための手段
上記問題点を解決するために、本発明は、フッ素樹脂と
、シランカップリング剤及びチタネート系カップリング
剤のそれぞれ又は両者の1種又は2種以上をフッ素樹脂
100重量部に対して0.01〜10重量部含有するこ
とを特徴とするフッ素樹脂塗料組成物を提供するもので
ある。Means for Solving the Problems In order to solve the above problems, the present invention combines a fluororesin and one or more of each or both of a silane coupling agent and a titanate coupling agent into a fluororesin 100% The object of the present invention is to provide a fluororesin coating composition characterized in that it contains 0.01 to 10 parts by weight.
次に本発明の詳細な説明する。Next, the present invention will be explained in detail.
本発明のフッ素樹脂塗料組成物は、フッ素樹脂を主成分
とし、これにシランカップリング剤及びチタネート系カ
ップリング剤のそれぞれ又は両者の1種又は2種以上を
フッ素樹脂100重量部に対して0.01〜10重量部
含有させることを必須の構成要件にするが、さらにこれ
ら以外の成分としてアクリル樹脂等の熱可塑性樹脂、熱
硬化性アクリル樹脂、メラミン樹脂、尿素樹脂、イソシ
アネート化合物、着色顔料、体質顔料、可塑剤、有機溶
剤、界面活性剤、消泡割等一般に塗料に使用されている
添加剤も単独又は2種以上組み合わせて併用することも
できる。The fluororesin coating composition of the present invention has a fluororesin as a main component, and one or more of each or both of a silane coupling agent and a titanate coupling agent is added to the fluororesin in an amount of 0% per 100 parts by weight of the fluororesin. .01 to 10 parts by weight is an essential component, but further components other than these include thermoplastic resins such as acrylic resins, thermosetting acrylic resins, melamine resins, urea resins, isocyanate compounds, coloring pigments, Additives commonly used in paints, such as extender pigments, plasticizers, organic solvents, surfactants, and antifoaming agents, can also be used alone or in combination of two or more.
本発明において、フッ素樹脂としてはテトラフルオロエ
チレン(CFz=CFz) 、クロロトリフルオロエチ
レン(CI?2=CFCβ)、ヘキサフルオロプロピレ
ン(CF:1−CF=CF2)、トリフルオロエヂレン
(CIIF=CF2)、フッ化ビニル(C1lz=CH
F) 及ヒフソ化ビニリデン(CF、=CI+□)等の
含フツ素ポリマーの単独重合あるいは他のモノマーとの
共重合によって得られる含フツ素ポリマーの全てが含ま
れる。例えばポリフッ化ビニリデン、ポリフッ化ビニル
等が挙げられる。In the present invention, examples of fluororesins include tetrafluoroethylene (CFz=CFz), chlorotrifluoroethylene (CI?2=CFCβ), hexafluoropropylene (CF:1-CF=CF2), and trifluoroethylene (CIIF=CF2). ), vinyl fluoride (C1lz=CH
F) All fluorine-containing polymers obtained by homopolymerization of fluorine-containing polymers such as hyphrovinylidene (CF, = CI + □) or copolymerization with other monomers are included. Examples include polyvinylidene fluoride and polyvinyl fluoride.
また、熱可塑性アクリル樹脂としてはアクリル酸エステ
ル及びメタアクリル酸エステルの重合体あるいはこれら
の共重合体が挙げられる。この場合エステル基としては
メチル、エチル、プロピル、ブチル、イソブチル、n−
ヘキシル、ラウリル、ステアリル等が挙げられる。共重
合体中これらのエステル基は1種又は2種以上含まれて
いても良い。Examples of the thermoplastic acrylic resin include polymers of acrylic esters and methacrylic esters, and copolymers thereof. In this case, the ester groups include methyl, ethyl, propyl, butyl, isobutyl, n-
Examples include hexyl, lauryl, stearyl and the like. The copolymer may contain one or more of these ester groups.
熱硬化性アクリル樹脂としては分子中に橋かけ構造を作
るような官能基(カルボキシル基、水酸基、アミノ基、
メチロール基、エポキシ基等)を持ったモノマー、例え
ばアクリル酸、メタクリル酸、アクリルアミド、メタク
リルアミド、N−メチロールアクリルアミド、アリルグ
リシジルエーテル、グリシジルメタクリレートの群と、
スチレン、アクリル酸エステル、メタクリル酸エステル
の群の2つの群から選ばれた2種以上のモノマーを共重
合して得られるポリマーが挙げられるがこれらに限定さ
れるものではない。Thermosetting acrylic resins contain functional groups (carboxyl groups, hydroxyl groups, amino groups,
methylol group, epoxy group, etc.), such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methylol acrylamide, allyl glycidyl ether, glycidyl methacrylate;
Examples include, but are not limited to, polymers obtained by copolymerizing two or more monomers selected from two groups of styrene, acrylic esters, and methacrylic esters.
本発明において、チクネート系カップリング剤としては
、イソプロピルトリイソステアロイルチタネート、イソ
プロピルトリドデシルベンゼンスルホニルチタネート、
イソプロピルトリス(ジオクチルパイロホスフェート)
チタネート、テトライソプロピルビス(ジオクチルホス
ファイト)チタネート、テトラオクチルビス(ジトリデ
シルホスファイl−)チタネート、テトラ(2,2−ジ
アリルオキシメチル−1−ブチル)ビス(ジ−トリデシ
ル)ホスファイトチタネート、ビス(ジオクチルパイロ
ホスフェート)オキシアセテートチタネート、ビス(ジ
オクチルパイロホスフェート)エチレンナタネート、イ
ソプロピルトリオクタノイルチクネート、イソプロピル
ジメタクリルイソステアロイルチタネート、イソプロピ
ルイソステアロイルジアクリルチタネート、イソプロピ
ルトリ (ジオクチルホスフェート)チタネート、イソ
プロピルトリクミルフェニールチタネート、イソプロピ
ルトリ (N−アミノエチル−アミノエチル)チタネー
ト、ジクミルフェニルオキシアセテートチタネート、ジ
イソステアロイルエチレンナタネート等が挙げられる。In the present invention, as the thicnate coupling agent, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate,
Isopropyl tris (dioctyl pyrophosphate)
Titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite l-) titanate, tetra(2,2-diallyloxymethyl-1-butyl) bis(di-tridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) ethylene natanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl trictinate Milphenyl titanate, isopropyltri(N-aminoethyl-aminoethyl)titanate, dicumylphenyloxyacetate titanate, diisostearoylethylenenathanate, and the like.
また、シランカップリング剤としては、ビニルトリクロ
ロシラン、ビニルトリスI・キンシラン、γ−クロロプ
ロピルトリメトキシシラン、γ−クロロプロピルメチル
ジクロロシラン、T−クロロプロピルメチルジメトキシ
シラン、T−クロロプロピルメチルジェトキシシラン、
γ−アミノプロピルトリエトキシシラン、N−(β−ア
ミノエチル)−γ−アミノプロピル1〜リメトキシシラ
ン、N−(β〜ルアミノエチル−γ−アミノプロピルメ
チルジメトキシシラン、γ−メルカプ1−プロピルトリ
メトキシシラン、T−グリシドキシプロピルトリメトキ
シシラン、T−グリシドキシプロビルメチルジメトキシ
シラン、T−メタクリロキシプロピルトリメトキシシラ
ン、γ−メタクリロキシプロピルメチルジメトキシシラ
ン、ビニルトリス(β−メトキシーエトキシ)シラン、
β−(3,4−エボキシシクロヘキソル)−エチルトリ
ノ!−キシシラン等が挙げられる。In addition, as a silane coupling agent, vinyltrichlorosilane, vinyltris I-quinsilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldichlorosilane, T-chloropropylmethyldimethoxysilane, T-chloropropylmethyljethoxysilane ,
γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyl 1-rimethoxysilane, N-(β-aminoethyl-γ-aminopropylmethyldimethoxysilane, γ-mercap 1-propyltrimethoxy Silane, T-glycidoxypropyltrimethoxysilane, T-glycidoxypropylmethyldimethoxysilane, T-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, vinyltris(β-methoxyethoxy)silane ,
β-(3,4-Eboxycyclohexol)-ethyltrino! -Xysilane and the like.
本発明の塗料組成物はフッ素樹脂100重量部に対し、
チタネート系カップリング剤あるいはシランカップリン
グ剤の1種又は2種以上を0.01〜10重量部含有す
るが、フッ素樹脂の溶融造膜過程における塗膜の収縮を
より良(防止する点からは0.1重世部以上が好ましく
、また、これが5重量部以上になると顕著な効果の差が
なくなるので、0.3〜2.0重量部が特に好ましい。The coating composition of the present invention contains, based on 100 parts by weight of fluororesin,
Although it contains 0.01 to 10 parts by weight of one or more titanate coupling agents or silane coupling agents, it is effective in improving (preventing) the shrinkage of the coating film during the melt coating process of fluororesin. It is preferably 0.1 parts by weight or more, and particularly preferably 0.3 to 2.0 parts by weight since there is no noticeable difference in effects when it is 5 parts by weight or more.
本発明の塗料組成物は上記のフッ素樹脂、チタネート系
カップリング剤あるいはシランカップリング剤を必須成
分にするが、その塗装適性を考えると、フッ素樹脂に例
えばポリフッ化ビニリデン樹脂を使用するときには、そ
の100重量部に対し熱可塑性樹脂あるいは熱硬化性ア
クリル樹脂を10〜60重量部加えることが好ましい。The coating composition of the present invention contains the above-mentioned fluororesin, titanate coupling agent, or silane coupling agent as essential components, but considering its coating suitability, when using polyvinylidene fluoride resin as the fluororesin, for example, It is preferable to add 10 to 60 parts by weight of thermoplastic resin or thermosetting acrylic resin per 100 parts by weight.
この際、塗料の適度な流動性を保つために種々な可塑剤
を添加することもできる。At this time, various plasticizers may be added to maintain appropriate fluidity of the paint.
また、本発明の組成物を溶剤型ディスバージョンオルガ
ノヅル塗料として供給するときには、溶剤が加えられる
が、この溶剤組成は塗装適性を決めるフッ素樹脂の分散
、塗料の粘度、流動特性や、塗料の長期保存性を示す塗
料の貯蔵安定性(樹脂の粒子が分散媒に安定に分散して
いて凝集しない性質)及び造膜性能を示す塗膜形成能等
に与える影響が大きい。一般には、ケトン系あるいはエ
ステル系溶剤のような極性基を持った溶剤と芳香族炭化
水素系溶剤が併用される。Furthermore, when the composition of the present invention is supplied as a solvent-based dispersion organo-nodule paint, a solvent is added, and the composition of this solvent is determined by the dispersion of the fluororesin, the viscosity and flow characteristics of the paint, and the long-term properties of the paint. It has a large influence on the storage stability of the paint, which indicates storage stability (the property that resin particles are stably dispersed in a dispersion medium and does not aggregate), and the coating film-forming ability, which indicates film-forming performance. Generally, a solvent having a polar group such as a ketone or ester solvent and an aromatic hydrocarbon solvent are used in combination.
本発明の塗料組成物に加えることかできる着色剤につい
ては、あらゆる顔料の使用が可能であるが、フッ素樹脂
の耐熱性、耐薬品性、屋外耐候性等の特性を活かすため
にはこれらと同じ特性を有する顔料を使用することが好
ましく、その使用に当たっては例えばボリフフ化ビニリ
デン100重量部に対して5〜240重量部加えること
ができる。As for the colorant that can be added to the coating composition of the present invention, any pigment can be used, but in order to take advantage of the properties of fluororesin such as heat resistance, chemical resistance, outdoor weather resistance, etc. It is preferable to use a pigment having specific properties, and when using it, for example, 5 to 240 parts by weight can be added to 100 parts by weight of vinylidene borifuff.
本発明の塗料組成物は、ロール塗装方式、カーテン=X
方式、スプレー塗装方式等が使用されるが、前二者につ
いてはフッ素樹脂としてポリフッ化ビニリデン、ポリフ
ッ化ビニルを用いた塗料が一般に使用され、スプレー塗
装方式については上記したテトラフルオロエチレン等の
単独又は共重合体の塗料が使用さる。The coating composition of the present invention can be applied using a roll coating method, curtain=X
For the former two, paints using polyvinylidene fluoride or polyvinyl fluoride as the fluororesin are generally used, and for the spray painting method, paints using the above-mentioned tetrafluoroethylene, etc. alone or Copolymer paints are used.
本発明の塗料が使用される被塗装体としては従来からフ
ッ素樹脂塗料が用いられていた上記した金属板に限らず
、他の金属その他のものが含まれる。The objects to be coated to which the paint of the present invention is applied are not limited to the above-mentioned metal plates on which fluororesin paints have conventionally been used, but also include other metals and other objects.
実施例 以下本発明を実施例により詳細に説明する。Example The present invention will be explained in detail below with reference to Examples.
実施例1
2度塗り2回焼付型着色亜鉛鉄板製造ラインでリン酸亜
鉛系化成処理(表面処理)を施された厚さ0.6ua、
幅9201mのコイル状亜鉛メッキ鋼板に下塗り塗料と
してNo、23プライマー(エポキシ樹脂系下塗り防錆
塗料:大日本インキ化学工業■製)を乾燥膜厚が5μに
なるようにロール塗装し、直ちに長さ4010の下塗り
塗料乾燥オーブンにて最高金属表面温度が180℃にな
るように40秒間焼付乾燥を行なった。ついでポリフッ
化ビニリデン(カイチー500=ベンウオル14t!!
!り100重量部、チタぶ一ト系カップリング剤(プレ
ン°7クト38S1味の素C4@製)0.5重量部、P
肘A(大日本インキ化学工業0@製アクリル樹脂)16
重量部、二酸化チタン(タイベークCR−95、石原産
業0′@製)70重量部、イソボロン40重景部、メチ
ルイソブチルケトン25重量部、セロソルブアセテート
10重量部、トルエン30重量部からなる上塗りフッ素
樹脂塗料を乾燥膜厚が20μになるようにロール塗装し
、直ちに長さ50mの上塗り塗料乾燥オーブンにて最高
金属温度が260℃になるように50秒間焼付乾燥を行
なった。Example 1 Thickness 0.6 ua, subjected to zinc phosphate chemical conversion treatment (surface treatment) on a two-coating, two-time baking type colored galvanized iron plate manufacturing line.
A coiled galvanized steel plate with a width of 9201 m was coated with No. 23 Primer (epoxy resin-based anti-rust undercoat paint: manufactured by Dainippon Ink & Chemicals) as an undercoat to a dry film thickness of 5 μm, and immediately the length was Baking drying was performed for 40 seconds in a 4010 undercoat drying oven so that the maximum metal surface temperature was 180°C. Next, polyvinylidene fluoride (Kaichi 500 = Benwall 14t!!
! 100 parts by weight, 0.5 parts by weight of titanium-based coupling agent (manufactured by Plen°7ct38S1 Ajinomoto C4@), P
Elbow A (acrylic resin manufactured by Dainippon Ink & Chemicals 0@) 16
Parts by weight, 70 parts by weight of titanium dioxide (Tie Bake CR-95, manufactured by Ishihara Sangyo 0'@), 40 parts by weight of isoboron, 25 parts by weight of methyl isobutyl ketone, 10 parts by weight of cellosolve acetate, and 30 parts by weight of toluene. The paint was roll coated to a dry film thickness of 20 μm, and immediately baked in a 50 m long top coat drying oven for 50 seconds at a maximum metal temperature of 260°C.
実施例2
実施例1において、チタネート系カップリング剤0.5
重量部の代わりにシランカップリング剤(TSL−83
50、東芝シリコーン社製)1.0重量部を使用する以
外は同様にしてフッ素樹脂塗料を作成し、実施例1と同
様の方法で塗装焼付けを行なった。Example 2 In Example 1, titanate coupling agent 0.5
Silane coupling agent (TSL-83
A fluororesin paint was prepared in the same manner as in Example 1, except that 1.0 part by weight of 50 (manufactured by Toshiba Silicone Co., Ltd.) was used, and the coating was baked in the same manner as in Example 1.
実施例3
実施例1において、フッ素樹脂塗料中にさらにシランカ
ップリング剤(TSL−8350、東芝シリコーン社製
)1.0重■部加えた以外は同様にしてフッ素樹脂塗料
を作成し、実施例1と同様の方法で塗装焼付けを行なっ
た。Example 3 A fluororesin paint was prepared in the same manner as in Example 1 except that 1.0 parts by weight of a silane coupling agent (TSL-8350, manufactured by Toshiba Silicone Co., Ltd.) was further added to the fluororesin paint. Paint baking was performed in the same manner as in 1.
比較例1
実施例1において、チタネート系カンプリング剤0.5
重量部を除いた以外は同様にしてフッ素樹脂塗料を作成
し、実施例1と同様な方法で塗装焼付けを行なった。Comparative Example 1 In Example 1, 0.5 titanate camping agent
A fluororesin paint was prepared in the same manner except for the parts by weight, and the coating was baked in the same manner as in Example 1.
実施例1〜3及び比較例で得た塗装鋼板の評価試験を行
なった。その結果を表に示す。Evaluation tests were conducted on the coated steel plates obtained in Examples 1 to 3 and Comparative Example. The results are shown in the table.
表中、塗膜のフクレ評価はASTM D−714により
、折り曲げ加工性(万力折曲げ性)は加工部に塗膜の傷
を起こさないためには何枚挟まなければならないか、そ
の必要枚数で示す。(Tは一枚の厚さで0.6脂鳳)
上記の試験の結果から、実施例1〜3の塗料を用いた塗
装鋼板にはその端縁部には下塗り塗膜の露出は見られな
かったが、比較例の塗装鋼板にはその両端縁部に0.5
〜2.010幅で連続して下塗り塗膜の露出が見られた
。In the table, the blistering evaluation of the paint film is based on ASTM D-714, and the bending workability (vise bendability) is based on the number of sheets that must be sandwiched in order to prevent the paint film from being scratched in the processed area. Indicated by (T is 0.6 thickness of one sheet) From the above test results, no exposed undercoat film was observed on the edges of the coated steel sheets using the paints of Examples 1 to 3. However, the painted steel plate of the comparative example had a coating of 0.5 on both edges.
Exposure of the undercoat film was observed in a continuous width of ~2.010 mm.
また、実施例1〜3の塗料を用いた塗装鋼板は比較例の
ものと比較して塩水噴霧試験による塗膜のフクレ、煮沸
後の塗膜のフクレ及び折り曲げ加工性が改善されている
ことが明らかであり、これらは従来のフッ素樹脂塗膜の
不均一な部分におけるワレによる下地の露出が起こり難
いことを示しているのみならず、さらに一層の塗膜物性
の向上を示している。In addition, the coated steel plates using the paints of Examples 1 to 3 were found to have improved coating film blistering in the salt spray test, coating film blistering after boiling, and bending workability compared to those of the comparative examples. It is clear that these results not only indicate that exposure of the underlying layer due to cracking in non-uniform areas of conventional fluororesin coatings is less likely to occur, but also indicate further improvement in the physical properties of the coating.
このようにチタネート系カンプリング剤、シランカップ
リング剤のフッ素樹脂に対する作用については、塗料に
おける分散安定性等に関する作用によりゃ装適性を良好
ならしめる作用と、下塗り塗膜に対する接着性の向上、
フッ素樹脂自体に対する補強効果等の塗膜物性上の作用
が考えられるが、いずれにせよ塗膜の収縮防止以外に耐
塩水噴霧性能、耐煮沸性能及び耐折り曲げ性能等の金属
被覆塗膜物性が従来のフッ素樹脂塗料組成物と比較して
改善される。In this way, the effects of titanate-based camping agents and silane coupling agents on fluororesins include effects related to dispersion stability in paints, which improves suitability for coating, and improvements in adhesion to the undercoat film.
It is thought that the effect on the physical properties of the coating film, such as a reinforcing effect on the fluororesin itself, is considered, but in any case, in addition to preventing shrinkage of the coating film, the physical properties of the metal coating coating film, such as salt spray resistance, boiling resistance, and bending resistance, are improved compared to fluororesin coating compositions.
発明の詳細
な説明したように、本発明によれば、フッ素樹脂塗料に
チタネート系カップリング剤、シランカップリング剤の
いずれか又は両方を含有させたので、これを金属板に傳
布し、焼イ・]け乾燥を行なってもその収縮により金属
板の端部に下地が露出するようなことがないのみならず
、塗膜の不均一部分に生じ易いワレの現象もなく、さら
に塩水噴霧性能、耐煮沸性能、耐折り曲げ性能等の各種
塗膜物性の一層の改善が図られ、フッ素樹脂の特性を隈
なく活かし、耐久寿命の長い塗装板を提供でき、その建
築上の施工上、耐用年数上の経費も軽減できる多大な効
果をもたらすことができる。As described in detail, according to the present invention, a fluororesin paint contains either a titanate coupling agent or a silane coupling agent, or both, and is applied to a metal plate and baked.・Even when drying is performed, the substrate will not be exposed at the edges of the metal plate due to shrinkage, and there will be no cracking that tends to occur in uneven areas of the coating, and it has excellent salt spray performance. Various physical properties of the coating film, such as boiling resistance and bending resistance, have been further improved, making full use of the characteristics of fluororesin, and providing coated panels with a long durable life. This can have a significant effect of reducing costs.
Claims (1)
ート系カップリング剤のそれぞれ又は両者の1種又は2
種以上をフッ素樹脂100重量部に対して0.01〜1
0重量部含有することを特徴とするフッ素樹脂塗料組成
物。(1) A fluororesin and one or both of a silane coupling agent and a titanate coupling agent, or both.
0.01 to 1 or more seeds per 100 parts by weight of fluororesin
A fluororesin coating composition containing 0 parts by weight.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16595885A JPS6227469A (en) | 1985-07-29 | 1985-07-29 | Fluororesin paint composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16595885A JPS6227469A (en) | 1985-07-29 | 1985-07-29 | Fluororesin paint composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6227469A true JPS6227469A (en) | 1987-02-05 |
Family
ID=15822246
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16595885A Pending JPS6227469A (en) | 1985-07-29 | 1985-07-29 | Fluororesin paint composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6227469A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63196644A (en) * | 1987-02-12 | 1988-08-15 | Dainippon Ink & Chem Inc | Curable resin composition |
JPS63210157A (en) * | 1987-02-27 | 1988-08-31 | Dainippon Ink & Chem Inc | Curable resin composition |
JPH03195757A (en) * | 1989-12-26 | 1991-08-27 | Asahi Glass Co Ltd | Fluorine-containing polymer composition for coating and use thereof |
KR100342680B1 (en) * | 1999-05-04 | 2002-07-03 | 이승열 | Method of producing a stain-proofing agent |
JP2011256689A (en) * | 2010-06-10 | 2011-12-22 | Marukou Rezin Co Ltd | Interval holding rod for concrete form |
CN103694882A (en) * | 2013-11-29 | 2014-04-02 | 蚌埠市正园电子科技有限公司 | Fluororesin oil paint with weather resistance, temperature resistance and color retention |
CN104059476A (en) * | 2013-05-03 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Antirust surface chemical treatment agent, preparation method and application thereof, and hot-dipped metal material |
CN104059412A (en) * | 2013-05-03 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Sealing agent and preparation method and use thereof, and hot-dip plated metal material |
WO2015145514A1 (en) * | 2014-03-27 | 2015-10-01 | 日新製鋼株式会社 | Chemical conversion coated steel sheet, and manufacturing method and chemical conversion solution therefor |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5136226A (en) * | 1975-07-10 | 1976-03-27 | Daikin Ind Ltd | FUTSUSOJUSHITOSOYOSOSEIBUTSU OYOBI SONOTOSOHOHO |
JPS5236135A (en) * | 1975-09-18 | 1977-03-19 | Uetsuzu:Kk | Coating compounds for spray coaring |
JPS5825368A (en) * | 1981-08-07 | 1983-02-15 | Daikin Ind Ltd | Electrically conductive coating composition |
JPS5883066A (en) * | 1981-11-12 | 1983-05-18 | Daikin Ind Ltd | Non-tacky, electrically conductive fluororubber paint |
-
1985
- 1985-07-29 JP JP16595885A patent/JPS6227469A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5136226A (en) * | 1975-07-10 | 1976-03-27 | Daikin Ind Ltd | FUTSUSOJUSHITOSOYOSOSEIBUTSU OYOBI SONOTOSOHOHO |
JPS5236135A (en) * | 1975-09-18 | 1977-03-19 | Uetsuzu:Kk | Coating compounds for spray coaring |
JPS5825368A (en) * | 1981-08-07 | 1983-02-15 | Daikin Ind Ltd | Electrically conductive coating composition |
JPS5883066A (en) * | 1981-11-12 | 1983-05-18 | Daikin Ind Ltd | Non-tacky, electrically conductive fluororubber paint |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63196644A (en) * | 1987-02-12 | 1988-08-15 | Dainippon Ink & Chem Inc | Curable resin composition |
JPS63210157A (en) * | 1987-02-27 | 1988-08-31 | Dainippon Ink & Chem Inc | Curable resin composition |
JPH03195757A (en) * | 1989-12-26 | 1991-08-27 | Asahi Glass Co Ltd | Fluorine-containing polymer composition for coating and use thereof |
KR100342680B1 (en) * | 1999-05-04 | 2002-07-03 | 이승열 | Method of producing a stain-proofing agent |
JP2011256689A (en) * | 2010-06-10 | 2011-12-22 | Marukou Rezin Co Ltd | Interval holding rod for concrete form |
CN104059476A (en) * | 2013-05-03 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Antirust surface chemical treatment agent, preparation method and application thereof, and hot-dipped metal material |
CN104059412A (en) * | 2013-05-03 | 2014-09-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Sealing agent and preparation method and use thereof, and hot-dip plated metal material |
CN103694882A (en) * | 2013-11-29 | 2014-04-02 | 蚌埠市正园电子科技有限公司 | Fluororesin oil paint with weather resistance, temperature resistance and color retention |
WO2015145514A1 (en) * | 2014-03-27 | 2015-10-01 | 日新製鋼株式会社 | Chemical conversion coated steel sheet, and manufacturing method and chemical conversion solution therefor |
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