JP4726226B2 - Coating method - Google Patents
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- JP4726226B2 JP4726226B2 JP2006172847A JP2006172847A JP4726226B2 JP 4726226 B2 JP4726226 B2 JP 4726226B2 JP 2006172847 A JP2006172847 A JP 2006172847A JP 2006172847 A JP2006172847 A JP 2006172847A JP 4726226 B2 JP4726226 B2 JP 4726226B2
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Description
本発明は、加工性、下塗り塗料との密着性、耐侯性さらには耐汚染性に優れる塗膜形成方法に関する。 The present invention relates to a method for forming a coating film that is excellent in workability, adhesion to an undercoat paint, weather resistance, and stain resistance.
近年、建造物の屋根材や外壁材、建築物の内外壁材等に用いられている塗装金属板については、メンテナンスフリーで長期間の使用に耐え得るようにするため、下塗り塗料との密着性や耐侯性、さらには耐汚染性の向上が求められている。 In recent years, coating metal sheets used for building roofing materials and exterior wall materials, and interior and exterior wall materials for buildings, etc., are maintenance-free and adhere to undercoating paints to withstand long-term use. There is also a need for improved weather resistance and contamination resistance.
従来、金属板の少なくとも一方の面に、化成処理皮膜と下塗り塗膜と、ポリエステル樹脂系中塗り塗膜とが順次形成され、さらにその上に、水酸基を有するアクリル−シロキサン複合樹脂にブロックイソシアネート化合物及び／又はメラミン樹脂を配合した塗料組成物を塗布し、焼き付けして形成した上塗り塗膜を有することを特徴とするプレコート金属板に関する発明が開示されている（特許文献１）。 Conventionally, a chemical conversion film, an undercoat film, and a polyester resin-based intermediate coat film are sequentially formed on at least one surface of a metal plate, and a block isocyanate compound is added to an acrylic-siloxane composite resin having a hydroxyl group thereon. And the invention regarding the precoat metal plate characterized by having the top coat film formed by apply | coating the coating composition which mix | blended the melamine resin, and baking was disclosed (patent document 1).
他に、表面処理が施された帯状金属板の表面に、リニアポリエステル樹脂又はエポキシ変性ポリエステル樹脂を主成分とする下塗り塗膜層を形成し、下塗り塗膜層の外表面には、アクリルポリマーとシロキサンポリマーと、ブロックイソシアネート樹脂とメラミン
樹脂の何れか１つ又は両方からなる架橋剤が配合された上塗り塗膜層を形成しているプレコートメタルに関する発明が開示されている（特許文献２）。
In addition, an undercoat coating layer mainly composed of a linear polyester resin or an epoxy-modified polyester resin is formed on the surface of the band-shaped metal plate that has been subjected to surface treatment. On the outer surface of the undercoat coating layer, acrylic polymer and The invention regarding the precoat metal which forms the top coat film layer by which the crosslinking agent which consists of any one or both of a siloxane polymer, a block isocyanate resin, and a melamine resin is disclosed is disclosed (patent document 2).
特許文献１においては、塗装する塗膜が多い為、塗装に多くの工数がかかるという問題があった。特許文献２においては、下塗り塗膜を硬化させてから上塗り塗膜を塗り重ねており、加工性や下塗り塗膜との密着性において満足するものでなかった。 In patent document 1, since there are many coating films to paint, there existed a problem that a lot of man-hours required for painting. In Patent Document 2, the topcoat film is repeatedly applied after the undercoat film is cured, and the processability and the adhesion with the undercoat film are not satisfactory.
本発明の目的は、加工性、下層塗料との密着性、耐侯性に優れる塗膜形成方法を提供することである。 The objective of this invention is providing the coating-film formation method which is excellent in workability, adhesiveness with a lower layer coating material, and weather resistance.
本発明者らは、表面に化成処理が施されていてもよい金属板上に、少なくとも１層の下層塗料（Ｉ）の半硬化塗膜を形成し、該半硬化塗膜上に、特定組成の上塗塗料（II）を塗装して加熱硬化してなる塗膜形成方法によって、加工性、下層塗膜との密着性及び耐侯性に優れる塗膜を形成できることを見出し、本発明を完成するに至った。 The inventors of the present invention form a semi-cured coating film of at least one lower layer coating (I) on a metal plate whose surface may be subjected to chemical conversion treatment, and a specific composition on the semi-cured coating film. In order to complete the present invention, it has been found that a coating film that is excellent in processability, adhesion to the lower layer coating film and weather resistance can be formed by a coating film forming method obtained by coating and heat-curing an overcoat paint (II) It came.
本発明の、表面に化成処理が施されていてもよい金属板上に、少なくとも１層の下層塗料（Ｉ）の半硬化塗膜を形成し、該半硬化塗膜上に、上層塗料（II）として特定組成の上塗塗料を塗装して加熱硬化してなる塗膜形成方法によって、加工性、下塗り塗膜との密着性及び耐侯性に優れたプレコート鋼板が得られる。 A semi-cured coating film of at least one layer of the lower coating material (I) is formed on the metal plate which may be subjected to chemical conversion treatment on the surface, and the upper coating material (II ), A precoated steel sheet excellent in workability, adhesion to the undercoat film and weather resistance can be obtained by a coating film forming method in which an overcoat paint having a specific composition is applied and heat-cured.
本発明は、表面に化成処理が施されていてもよい金属板上に、下層塗料（Ｉ）の半硬化塗膜を形成し、該半硬化塗膜上に、上層塗料（II）を塗装して塗膜を形成し、次いで加熱硬化することを特徴とする塗膜形成方法である。以下、詳細に述べる。 In the present invention, a semi-cured coating film of a lower coating material (I) is formed on a metal plate whose surface may be subjected to chemical conversion treatment, and an upper coating material (II) is applied on the semi-curing coating film. Forming a coating film, followed by heat curing. Details will be described below.
［塗膜形成方法］
素材：
本発明に用いる素材としては、冷延鋼板、溶融亜鉛メッキ鋼板、電気亜鉛メッキ鋼板、鉄−亜鉛、ニッケル−亜鉛、亜鉛−アルミニウムなどの合金メッキ鋼板、アルミニウム板、ステンレス鋼板、銅板、銅メッキ鋼板、錫メッキ鋼板等の金属類、等が挙げられる。
金属類に塗装する場合に被塗装材である金属表面が油等汚染物質で汚染されていなければそのまま塗装してもかまわないが、塗膜との間の付着性、耐食性を改善するために公知の金属表面処理を施すのが望ましい。これら公知の表面処理方法としてリン酸塩系表面処理、クロム酸塩系表面処理、さらにはクロム酸系塗装剤による塗布処理が挙げられる。
[Coating film forming method]
Material:
The materials used in the present invention include cold-rolled steel sheets, hot-dip galvanized steel sheets, electrogalvanized steel sheets, alloy-plated steel sheets such as iron-zinc, nickel-zinc, and zinc-aluminum, aluminum plates, stainless steel plates, copper plates, and copper-plated steel plates. And metals such as tin-plated steel sheets.
When painting on metals, the metal surface, which is the material to be coated, may be painted as it is if it is not contaminated with oil or other pollutants, but it is well known for improving adhesion and corrosion resistance with the coating film. It is desirable to apply a metal surface treatment. These known surface treatment methods include phosphate surface treatment, chromate surface treatment, and coating treatment with a chromic acid coating agent.
下層塗料（Ｉ）：
次いで、少なくとも１層の下層塗料（Ｉ）を塗装する。下層塗料（Ｉ）としては、例えば着色カラー鋼板塗装分野、産業用機械塗装分野、金属部品塗装分野などで用いられている、従来から公知のプライマー塗料や着色塗料が適用できる。
プライマー塗料は、被塗装材の種類、金属表面処理の種類によって適宜選択されるが、特にエポキシ樹脂系のプライマー、ポリエステル樹脂系のプライマー及びそれらの変性プライマーが好適であり、加工性が特に要求される場合はポリエステル樹脂系のプライマーが好適である。
Lower layer paint (I):
Next, at least one lower layer paint (I) is applied. As the lower layer coating (I), conventionally known primer coatings and coloring coatings that are used, for example, in the colored color steel sheet coating field, the industrial machine coating field, and the metal part coating field can be applied.
The primer paint is appropriately selected depending on the type of material to be coated and the type of metal surface treatment, and in particular, an epoxy resin-based primer, a polyester resin-based primer and a modified primer thereof are suitable, and workability is particularly required. In this case, a polyester resin primer is suitable.
着色塗料は、例えばポリエステル樹脂、アクリル樹脂、エポキシ樹脂、ポリウレタン樹脂等の水酸基含有樹脂、メラミン樹脂やブロックイソシアネート化合物等の架橋剤、着色顔料、アルミペースト、パール顔料等の光輝材、シリカ微粉末などの体質顔料、有機樹脂粉末、無機質骨材、消泡剤、レベリング剤、潤滑性付与剤、紫外線吸収剤、顔料分散剤等、従来から使用されている公知の材料も使用することができる。プライマーや着色塗料などによる下塗り塗膜は、通常、乾燥膜厚で１〜５０μｍ、好ましくは５〜３０μｍである。 Colored paints include, for example, hydroxyl group-containing resins such as polyester resins, acrylic resins, epoxy resins, polyurethane resins, crosslinking agents such as melamine resins and blocked isocyanate compounds, bright materials such as colored pigments, aluminum pastes and pearl pigments, silica fine powders, etc. Conventionally used materials such as extender pigments, organic resin powders, inorganic aggregates, antifoaming agents, leveling agents, lubricity-imparting agents, ultraviolet absorbers, and pigment dispersants can also be used. The undercoat film made of a primer or a colored paint is usually 1 to 50 μm, preferably 5 to 30 μm in dry film thickness.
上記の下層塗料（Ｉ）による塗膜は、素材到達最高温度が８０〜１９０℃、好ましくは１００〜１８０℃で２０〜９０秒間、好ましくは３０〜８０秒間加熱して、半硬化塗膜（注１）を形成する。次いで、半硬化状態の塗膜上に、上塗塗料（II）を塗装し、次いで下層塗料(Ｉ)の半硬化塗膜形成温度より素材到達最高温度が５℃以上高く、かつ素材到達最高温度が１６０〜２７０℃、好ましくは１７０〜２６０℃で、加熱時間２０〜９０秒間、好ましくは３０〜８０秒間加熱して、完全硬化させる塗膜形成方法である。なお、下層塗料（Ｉ）が未硬化状態の塗膜上に、上塗塗料（II）を塗装すると、仕上り性が低下することから好ましくない。 The coating film made of the lower layer coating (I) has a maximum material reaching temperature of 80 to 190 ° C., preferably 100 to 180 ° C., and is heated for 20 to 90 seconds, preferably 30 to 80 seconds. 1) is formed. Next, the top coating (II) is applied onto the semi-cured coating film, and then the material reaching maximum temperature is 5 ° C. higher than the semi-curing coating film forming temperature of the lower layer coating (I), and the material reaching maximum temperature is This is a coating film forming method in which the film is completely cured by heating at 160 to 270 ° C., preferably 170 to 260 ° C., for a heating time of 20 to 90 seconds, preferably 30 to 80 seconds. In addition, it is not preferable that the top coating (II) is applied onto the coating film in which the lower layer coating (I) is uncured, because the finish performance is lowered.
上記の塗膜形成方法について詳細は、下記の方法（１）〜方法（３）、
方法（１）：下層塗料（Ｉ）の半硬化塗膜上に、上塗塗料（II）を塗装し、加熱硬化してなる２コート１ベーク方式（２Ｃ１Ｂ）、方法（２）：下層塗料（Ｉ）の半硬化塗膜に、着色塗料を塗装し、該着色塗料の半硬化塗膜上に、さらに上塗塗料（II）を塗装し、加熱硬化してなる３コート１ベーク方式（３Ｃ１Ｂ）、方法（３）：下層塗料（Ｉ）の硬化塗膜上に、着色塗料を塗装し、該着色塗料の半硬化塗膜上に、さらに上塗塗料（II）を塗装し、加熱硬化してなる３コート２ベーク方式（３Ｃ２Ｂ）、が挙げられる。これらの塗膜形成方法によって、下層塗料（Ｉ）又は着色塗料の半硬化塗膜と上塗塗料（II）の塗膜が一部相溶し、いっそうの塗膜間密着性を向上することができることを見出せた。
For details on the coating film forming method, the following method (1) to method (3),
Method (1): Two-coat one-bake method (2C1B) obtained by coating the top-coat paint (II) on the semi-cured coating film of the lower-layer paint (I) and heat-curing, Method (2): Lower-layer paint (I 3 coating 1 baking system (3C1B), method in which a colored paint is applied to the semi-cured coating film of No. 3), and a top coating paint (II) is further applied on the semi-cured coating film of the colored paint and heat-cured. (3): 3 coats obtained by coating a colored coating on the cured coating of the lower coating (I), further coating the top coating (II) on the semi-cured coating of the colored coating, and heating and curing. 2 bake method (3C2B). By these coating film forming methods, the semi-cured coating film of the lower coating material (I) or the colored coating material and the coating film of the top coating material (II) are partially compatible to further improve the adhesion between the coating films. I was able to find.
（注１）半硬化塗膜：半硬化塗膜とは、塗膜面にキシレンを浸み込ませたガーゼを、ラビングテスターのＡＳＴＭ平面圧子に取付け、堅牢型試験機に取付け、試験板の塗膜面を荷重約１ｋｇ／ｃｍ２の圧力をかけて約５ｃｍ往復させて擦り、往復のこすり回数が５回以上で、かつ５０回未満で素材又は下塗り塗膜を溶解する塗膜をいう。 (Note 1) Semi-cured paint film: Semi-cured paint film is a gauze with xylene soaked in the paint film surface, attached to an ASTM flat indenter of a rubbing tester, attached to a robust tester, and coated with a test plate. The film surface is rubbed by reciprocating about 5 cm while applying a load of about 1 kg / cm 2 , and the number of reciprocating rubs is 5 times or more and less than 50 times to dissolve the material or the undercoat film.
上層塗料（II）：
下層塗料（Ｉ）の半硬化塗膜上に塗装される上層塗料（II）は、特定の組成（Ａ）と組成（Ｂ）を、組成（Ａ）と組成（Ｂ）の固形分合計１００質量部に基づいて、組成（Ａ）／組成（Ｂ）＝３０／７０〜８０／２０（質量部）で配合してなる塗料である。
Upper layer paint (II):
The upper layer paint (II) applied on the semi-cured coating film of the lower layer paint (I) has a specific composition (A) and composition (B), and the total solid content of the composition (A) and composition (B) is 100 mass. Based on the parts, it is a paint formed by blending the composition (A) / composition (B) = 30/70 to 80/20 (parts by mass).
組成（Ａ）：
組成（Ａ）は、１分子中に少なくとも２個のＳｉ−Ｈ結合を有するオルガノポリシロキサン（ａ１）と１分子中にアルケニル基を少なくとも１個有するオルガノポリシロキサン（ａ２）を含有する。
Composition (A):
The composition (A) contains an organopolysiloxane (a1) having at least two Si—H bonds in one molecule and an organopolysiloxane (a2) having at least one alkenyl group in one molecule.
オルガノポリシロキサン（ａ１）は、分子中に少なくとも２個のケイ素原子結合水素原子を有しているものである。オルガノポリシロキサン（ａ１）は、その分子構造に特に制限はなく、例えば鎖状、環状、分枝状構造等の各種のものが使用可能である。オルガノポリシロキサン（ａ１）の水素原子以外の置換基としては、アルケニル基、一価の炭化水素基、水酸基及びアルコキシル基が挙げられる。 The organopolysiloxane (a1) has at least two silicon-bonded hydrogen atoms in the molecule. The molecular structure of the organopolysiloxane (a1) is not particularly limited, and various types such as a chain, cyclic, and branched structures can be used. Examples of the substituent other than the hydrogen atom of the organopolysiloxane (a1) include an alkenyl group, a monovalent hydrocarbon group, a hydroxyl group, and an alkoxyl group.
このオルガノポリシロキサン（ａ１）は、例えばオクタメチルシクロテトラシロキサン及び／またはテトラメチルシクロテトラシロキサンと、末端基となりうるヘキサメチルジシロキサンあるいは１，１−ジハイドロ−２,２,３,３−テトラメチルジシロキサン単位を含む化合物とを、触媒の存在下で、−１０℃〜４０℃程度の温度で平衡化反応させることによって得られる。このような、オルガノポリシロキサン（ａ１）の市販品としては、ＳＬＪ７２４１Ａ（旭化成ワッカーシリコーン社製、商品名）などが挙げられる。 The organopolysiloxane (a1) includes, for example, octamethylcyclotetrasiloxane and / or tetramethylcyclotetrasiloxane, and hexamethyldisiloxane or 1,1-dihydro-2,2,3,3-tetramethyl which can be a terminal group. It can be obtained by subjecting a compound containing a disiloxane unit to an equilibration reaction at a temperature of about -10 ° C to 40 ° C in the presence of a catalyst. Examples of such commercially available products of organopolysiloxane (a1) include SLJ7241A (trade name, manufactured by Asahi Kasei Wacker Silicone).
次に、オルガノポリシロキサン（ａ２）は、分子中に少なくとも１個のアルケニル基を有するオルガノポリシロキサンである。例えば下記の式（２）
Ｒa ＳｉＯ(４-ａ)／２・・・式（２）
（式中、Ｒは、同一でも異なってもいてもよく、少なくとも１個がアルケニル基であることを条件として、非置換または置換の一価炭化水素基、水酸基、及びアルコキシ基から選択された基であり、ａは、１．９〜２．４の数である）で表されるものが一般的に使用される。
Next, the organopolysiloxane (a2) is an organopolysiloxane having at least one alkenyl group in the molecule. For example, the following formula (2)
R a SiO (4-a) / 2 Formula (2)
Wherein R may be the same or different and is a group selected from an unsubstituted or substituted monovalent hydrocarbon group, a hydroxyl group, and an alkoxy group, provided that at least one is an alkenyl group. And a is a number from 1.9 to 2.4) is generally used.
上記式中の基Ｒの内、一価炭化水素基としては、メチル、エチル、プロピル等のアルキル基、ビニル、プロペニル、ブテニル等のアルケニル基、シクロヘキシル等のシクロアルキル基、フェニル、トリル、キシリル等のアリール基、ベンジル、フェニルエチル等のアラルキル基、及びこれらの基の水素原子の一部もしくは全部がハロゲン原子、シアノ基等で置換された基、例えば３,３,３-トリフルオロプロピル基等を例示することができる。
ケイ素原子に結合している置換基Ｒは、少なくも１個がアルケニル基であることを条件として、上記で例示した一価の炭化水素基や、水酸基、アルコキシ基の何れであってもよいが、アルケニル基としてはビニル基が好ましく、またそれ以外の基としては、メチル基及びフェニル基が好ましい。 また、これらのアルケニル基含有オルガノポリシロキサンは、直鎖状であってもよいし、分岐状であってもよい。このような、 オルガノポリシロキサン（ａ２）の市販品としては、ＳＬＪ７２４１Ｈ（旭化成ワッカーシリコーン社製、商品名）が挙げられる。
Among the groups R in the above formula, examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl and propyl, alkenyl groups such as vinyl, propenyl and butenyl, cycloalkyl groups such as cyclohexyl, phenyl, tolyl, xylyl and the like Aryl groups, aralkyl groups such as benzyl and phenylethyl, and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms, cyano groups, etc., such as 3,3,3-trifluoropropyl groups, etc. Can be illustrated.
The substituent R bonded to the silicon atom may be any of the monovalent hydrocarbon groups, hydroxyl groups and alkoxy groups exemplified above, provided that at least one is an alkenyl group. The alkenyl group is preferably a vinyl group, and the other groups are preferably a methyl group and a phenyl group. In addition, these alkenyl group-containing organopolysiloxanes may be linear or branched. Examples of such commercially available products of organopolysiloxane (a2) include SLJ7241H (trade name, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.).
オルガノポリシロキサン（ａ１）とオルガノポリシロキサン（ａ２）の反応は、適宜に触媒を加え、オルガノポリシロキサン（ａ１）とオルガノポリシロキサン（ａ２）とが付加反応によって架橋する。 In the reaction of the organopolysiloxane (a1) and the organopolysiloxane (a2), a catalyst is appropriately added, and the organopolysiloxane (a1) and the organopolysiloxane (a2) are crosslinked by an addition reaction.
組成（Ａ）におけるオルガノポリシロキサン（ａ１）とオルガノポリシロキサン（ａ２）の配合割合は、両成分の固形分合計に対して、オルガノポリシロキサン（ａ１）６０〜９５質量％、好ましくは７０〜９０質量％、オルガノポリシロキサン（ａ２）４０〜５質量％、好ましくは３０〜１０質量％の割合で混合することが、特に耐溶剤性と加工性向上の為にも好ましい。 The blending ratio of the organopolysiloxane (a1) and the organopolysiloxane (a2) in the composition (A) is 60 to 95% by mass, preferably 70 to 90%, based on the total solid content of both components. It is particularly preferable to mix in a proportion of 40% by mass and 40 to 5% by mass, preferably 30 to 10% by mass, especially for improving solvent resistance and workability.
組成（Ｂ）：
プレコートメタル用塗料における組成（Ｂ）は、下記式（１）で示されるオルガノポリシロキサン（ｂ１）と、加水分解性シリル基を有するオルガノポリシロキサン（ｂ２）を含有する。
Composition (B):
The composition (B) in the precoat metal paint contains an organopolysiloxane (b1) represented by the following formula (1) and an organopolysiloxane (b2) having a hydrolyzable silyl group.
Ｒ２ ａＳｉ（ＯＨ）ｂＯ（４−ａ−ｂ）／２・・・式（１）
（式中、Ｒ２は同一または異種の置換もしくは非置換の炭素数１〜８の１価炭化水素を示し、ａ及びｂは、０．２≦ａ≦２、０．１≦ｂ≦３、ａ＋ｂ＜４の関係を満たす）
Ｒ２は、好ましくは、炭素数１〜４のアルキル基、ビニル基、３−グリシドキシプロピル基〔γ−グリシドキシプロピル基とも言う〕、３−メタクリロイルオキシプロピル基〔γ−メタクリロイルオキシプロピル基とも言う〕、３−アミノプロピル基〔γ−アミノプロピル基とも言う〕、３，３，３−トリフルオロプロピル基などの置換炭化水素基、より好ましくはメチル基、エチル基等のアルキル基である。
R 2 a Si (OH) b O (4-ab) / 2 Formula (1)
(Wherein R 2 represents the same or different substituted or unsubstituted monovalent hydrocarbon having 1 to 8 carbon atoms, and a and b are 0.2 ≦ a ≦ 2, 0.1 ≦ b ≦ 3, a + b <4)
R 2 is preferably an alkyl group having 1 to 4 carbon atoms, a vinyl group, a 3-glycidoxypropyl group (also referred to as γ-glycidoxypropyl group), a 3-methacryloyloxypropyl group (γ-methacryloyloxypropyl). A substituted hydrocarbon group such as 3,3,3-trifluoropropyl group, more preferably an alkyl group such as a methyl group or an ethyl group. is there.
このようなオルガノポリシロキサン（ｂ１）は、例えばメチルトリクロロシラン、ジメチルジクロロシラン、フェニルトリクロロシラン、ジフェニルジクロロシラン、もしくはこれらに対応するアルコキシシランの１種もしくは２種以上の混合物を公知の方法により大量の水で加水分解することによって得ることができる。このような、オルガノポリシロキサン（ｂ１）の市販品としては、ＫＲ−３１１、ＫＲ−２８２、ＫＲ−２７１（いずれも信越化学工業社製、商品名）が挙げられる。 Such an organopolysiloxane (b1) is, for example, methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, or one or a mixture of two or more alkoxysilanes corresponding to these in a large amount by a known method. It can be obtained by hydrolysis with water. Examples of such commercially available products of organopolysiloxane (b1) include KR-311, KR-282, and KR-271 (all manufactured by Shin-Etsu Chemical Co., Ltd., trade names).
オルガノポリシロキサン（ｂ２）は、分子の末端又は側鎖に加水分解性シリル基を有するオルガノポリシロキサンであって、分子中の加水分解性シリル基、例えばアルコキシシリル基が空気中の湿気や水分等に接触して加水分解されてシラノール基を形成する。オルガノポリシロキサン（ｂ２）は、常温で加水分解縮合するものであれば、それ自体既知の化合物を制限なく使用することができる。 The organopolysiloxane (b2) is an organopolysiloxane having a hydrolyzable silyl group at the end or side chain of the molecule, and the hydrolyzable silyl group in the molecule, such as an alkoxysilyl group, is moisture or moisture in the air. Is hydrolyzed to form silanol groups. As the organopolysiloxane (b2), a compound known per se can be used without limitation as long as it hydrolyzes and condenses at room temperature.
オルガノポリシロキサン（ｂ２）としては、一般に、重量平均分子量（注２）が２００〜３０，０００、特に３００〜２５，０００の範囲内にあるものが好適である。
（注２）重量平均分子量：ＪＩＳ Ｋ ０１２４−８３に準じて行ない、分離カラムにＴ
ＳＫ ＧＥＬ４０００ＨＸＬ+Ｇ３０００ＨＸＬ+Ｇ２５００ＨＸＬ+Ｇ２０００ＨＸＬ（東
ソー社製）を用いて４０℃で流速１．０ｍｌ／分、溶離液にＧＰＣ用テトラヒドロフランを用いて、ＲＩ屈折計で得られたクロマトグラフとポリスチレンの検量線から計算により求めた。以下の重量平均分子量は、（注２）の記載内容によるものである。
As the organopolysiloxane (b2), those having a weight average molecular weight (Note 2) in the range of 200 to 30,000, particularly 300 to 25,000 are generally suitable.
(Note 2) Weight average molecular weight: Measured according to JIS K 0124-83.
Chromatograph and polystyrene calibration curve obtained with RI refractometer using SK GEL4000HXL + G3000HXL + G2500HXL + G2000HXL (manufactured by Tosoh Corporation) at 40 ° C. with a flow rate of 1.0 ml / min and eluent with tetrahydrofuran for GPC. From the calculation. The following weight average molecular weight is based on the description in (Note 2).
オルガノポリシロキサン（ｂ２）の市販品としては、例えば、ＳＲ２４０６、ＳＲ２４１０、ＳＲ２４２０、ＳＲ２４１６、ＳＲ２４０２、ＡＹ４２−１６１（以上、東レ・ダウコーニング・シリコーン株式会社製、商品名）、ＦＺ−３７０４、ＦＺ−３５１１（以上、日本ユニカー社製、商品名）、ＫＣ−８９Ｓ、ＫＲ−５００、Ｘ−４０−９２２５、Ｘ−４０−９２４６、Ｘ−４０−９２５０、ＫＲ−２１７、ＫＲ−９２１８、ＫＲ−２１３、ＫＲ−５１０、Ｘ−４０−９２２７、Ｘ−４０−９２４７、Ｘ−４０−９２４７、Ｘ−４０−１０５３、Ｘ−４０−１０５６、Ｘ−４１−１０５３、Ｘ−４１−１０５６、Ｘ−４１−１８０５、Ｘ−４１−１８１０、Ｘ−４１−２６５１、Ｘ−４０−２３０８、Ｘ−４０−９２３８、Ｘ−４０−２２３９、Ｘ−４０−２３２７、ＫＲ−４００、Ｘ−４０−１７５、Ｘ−４０−９７４０（以上、信越化学工業株式会社製、商品名）等が挙げられ、これらはそれぞれ単独で又は２種以上組合せて用いることができる。 Examples of commercially available products of organopolysiloxane (b2) include SR2406, SR2410, SR2420, SR2416, SR2402, AY42-161 (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.), FZ-3704, FZ- 3511 (above, Nihon Unicar Co., Ltd., trade name), KC-89S, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-217, KR-9218, KR-213 , KR-510, X-40-9227, X-40-9247, X-40-9247, X-40-1053, X-40-1056, X-41-1053, X-41-1056, X-41 -1805, X-41-1810, X-41-2651, X-40-2308, X-40-9238, X-40- 239, X-40-2327, KR-400, X-40-175, X-40-9740 (above, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Can be used in combination.
組成（Ｂ）におけるオルガノポリシロキサン（ｂ１）とオルガノポリシロキサン（ｂ２）の配合割合は、両成分の固形分合計に対して、オルガノポリシロキサン（ｂ１）５０〜８０質量％、好ましくは５５〜７０質量％、オルガノポリシロキサン（ｂ２）５０〜２０質量％、好ましくは４５〜３０質量％の割合で混合することが、加工性、下塗り塗膜との密着性向上の為に好ましい。 The blending ratio of the organopolysiloxane (b1) and the organopolysiloxane (b2) in the composition (B) is 50 to 80% by mass, preferably 55 to 70% by weight, based on the total solid content of both components. Mixing at a ratio of mass%, organopolysiloxane (b2) 50 to 20 mass%, preferably 45 to 30 mass% is preferred for improving workability and adhesion with the undercoat film.
なお、オルガノポリシロキサン（ｂ１）とオルガノポリシロキサン（ｂ２）の反応は、
硬化触媒によって、オルガノポリシロキサン（ｂ１）の水酸基とオルガノポリシロキサン（ｂ２）のアルコキシ基とに基づき反応して硬化する。
The reaction between organopolysiloxane (b1) and organopolysiloxane (b2)
The curing catalyst reacts and cures based on the hydroxyl group of the organopolysiloxane (b1) and the alkoxy group of the organopolysiloxane (b2).
また、オルガノポリシロキサン（ａ１）における水素原子とオルガノポリシロキサン（ｂ１）の水酸基が、水分（例えば、加熱乾燥時に乾燥熱風中に含まれるの水分）によって反応が促進されて硬化に寄与するものと考える。このことによって、加工性や下塗り塗膜との密着性に優れた塗膜を得ることができると推察される。 Further, the hydrogen atom in the organopolysiloxane (a1) and the hydroxyl group of the organopolysiloxane (b1) are contributed to curing by the reaction being accelerated by moisture (for example, moisture contained in the dry hot air during heating and drying). Think. By this, it is speculated that a coating film excellent in processability and adhesion with the undercoat coating film can be obtained.
なお、上記組成（Ａ）と組成（Ｂ）の配合割合は、組成（Ａ）と組成（Ｂ）の固形分合計１００質量部に基づいて、組成（Ａ）／組成（Ｂ）＝３０／７０〜８０／２０（質量部）、好ましくは組成（Ａ）／組成（Ｂ）＝５０／５０〜８０／２０であることが、耐溶剤性、加工性及び塗り塗膜との密着性に優れた塗膜を得る為にも好ましい。 In addition, the blending ratio of the composition (A) and the composition (B) is based on the total solid content of 100 parts by mass of the composition (A) and the composition (B), and the composition (A) / composition (B) = 30/70. ~ 80/20 (parts by mass), preferably composition (A) / composition (B) = 50/50 to 80/20 is excellent in solvent resistance, workability and adhesion to the coating film It is also preferable for obtaining a coating film.
硬化触媒（Ｃ）：
さらに、本発明の塗膜形成方法の上層塗料（II）には、適宜必要に応じて、硬化触媒（Ｃ）を使用することができ、加工性や下塗り塗膜との密着性の向上に寄与することができる。
Curing catalyst (C):
Furthermore, a curing catalyst (C) can be used as needed in the upper layer coating material (II) of the coating film forming method of the present invention, contributing to improvement in workability and adhesion to the undercoat coating film. can do.
このような硬化触媒（Ｃ）としては、例えば、テトライソプロポキシチタン、テトラｎ−ブトキシチタン、テトラキス(２−エチルヘキソキシ)チタン、ジプロポキシビス(アセチルアセトナト)チタン、チタニウムイソプロポキシオクチレングリコール等のチタン酸エステルまたはチタンキレート化合物；ナフテン酸亜鉛、ステアリン酸亜鉛、亜鉛−２−エチルオクトエート、鉄−２−エチルヘキソエート、コバルト−２−エチルヘキソエート、マンガン−２−エチルヘキソエート、ナフテン酸コバルト、アルコキシアルミニウム化合物、ジブチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫ジオクトエート等のアルキル錫カルボキシレート化合物等の有機金属化合物；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−アミノプロピルトリメトキシシラン等のアミノアルキル基置換アルコキシシラン；ベンジルトリエチルアンモニウムアセテート等の第４級アンモニウム塩；酢酸カリウム、酢酸ナトリウム、蓚酸リチウム等のアルカリ金属の低級脂肪酸塩；ジメチルヒドロキシルアミン、ジエチルヒドロキシルアミン等のジアルキルヒドロキシルアミン；テトラメチルグアニジルプロピルトリメトキシシラン、テトラメチルグアニジルプロピルメチルジメトキシシラン、テトラメチルグアニジルプロピルトリス(トリメチルシロキシ)シラン等のグアニジル基を含有するシランまたはシロキサン化合物等が挙げられる。この中でも、亜鉛−２−エチルオクトエート、鉄−２−エチルヘキソエート、アルコキシアルミニウム化合物などが、硬化性向上の面から好ましい。 Examples of such a curing catalyst (C) include tetraisopropoxy titanium, tetra n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium, dipropoxy bis (acetylacetonato) titanium, titanium isopropoxy octylene glycol and the like. Titanic acid ester or titanium chelate compound; zinc naphthenate, zinc stearate, zinc-2-ethyl octoate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate , Organometallic compounds such as alkyl tin carboxylate compounds such as cobalt naphthenate, alkoxyaluminum compounds, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate; γ-aminopropyltriethoxysilane, N- (β-aminoethyl) An aminoalkyl group-substituted alkoxysilane such as γ-aminopropyltrimethoxysilane; a quaternary ammonium salt such as benzyltriethylammonium acetate; a lower fatty acid salt of an alkali metal such as potassium acetate, sodium acetate, lithium oxalate; dimethylhydroxylamine; Dialkylhydroxylamines such as diethylhydroxylamine; silanes containing guanidyl groups such as tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidylpropylmethyldimethoxysilane, tetramethylguanidylpropyltris (trimethylsiloxy) silane, or Examples thereof include siloxane compounds. Among these, zinc-2-ethyl octoate, iron-2-ethylhexoate, an alkoxyaluminum compound and the like are preferable from the viewpoint of improving curability.
これらの硬化触媒（Ｃ）は１種単独でも２種以上を組合わせても使用することができる。また配合量は、オルガノポリシロキサン（ａ１）とオルガノポリシロキサン（ａ２）
オルガノポリシロキサン（ｂ１）及びオルガノポリシロキサン（ｂ２）の固形分合計に対して０．０１〜１０質量％、好ましくは０.１〜５質量％程度が、塗料安定性と硬化性の面から好ましい。
These curing catalysts (C) can be used singly or in combination of two or more. The blending amounts are organopolysiloxane (a1) and organopolysiloxane (a2).
0.01 to 10% by weight, preferably about 0.1 to 5% by weight, based on the total solid content of the organopolysiloxane (b1) and the organopolysiloxane (b2) is preferable from the viewpoint of coating stability and curability. .
また、上塗塗料（II）には、従来から公知のその他の成分を添加することは任意で、例えば有機溶剤、潤滑性付与剤、紫外線吸収剤、光安定剤、消泡剤、塗面調整剤、シリカ微粉末及び着色顔料等を含有することができる。 In addition, it is optional to add other conventionally known components to the top coating (II), for example, organic solvents, lubricity-imparting agents, ultraviolet absorbers, light stabilizers, antifoaming agents, coating surface adjusting agents. In addition, fine silica powder and coloring pigments can be contained.
なお、上塗塗料（II）の塗装方法としては、特に制限はなく、カーテン塗装、ロール塗装、浸漬塗装及びスプレー塗装などが可能であり、通常、乾燥した後の塗膜厚が０．１〜２５μｍ、特に０．３〜１５μｍの範囲内となるように塗装される。 In addition, there is no restriction | limiting in particular as a coating method of top coating (II), Curtain coating, roll coating, immersion coating, spray coating, etc. are possible, and the coating-film thickness after drying is 0.1-25 micrometers normally. In particular, the coating is performed so as to be in the range of 0.3 to 15 μm.
プレコートメタル用塗料を塗装してなる塗膜は、プレコートメタル用塗膜側の下層塗料(Ｉ)の半硬化塗膜形成温度より素材到達最高温度が５℃以上高く、かつ素材到達最高温度１６０℃〜２７０℃、好ましくは１９０〜２６０℃の温度で、３０秒〜１２０秒間、好ましくは４５〜１００秒間加熱乾燥することによって硬化塗膜を得ることができる。 The coating film formed by applying the pre-coated metal paint has a maximum material reaching temperature of 5 ° C higher than the semi-cured coating film forming temperature of the lower layer coating (I) on the pre-coated metal coating side, and the material reaching maximum temperature of 160 ° C. A cured coating film can be obtained by heating and drying at a temperature of ˜270 ° C., preferably 190 to 260 ° C. for 30 seconds to 120 seconds, preferably 45 to 100 seconds.
以下、実施例により本発明をさらに具体的に説明する。なお、以下、「部」及び「％」はいずれも質量基準によるものとする。 Hereinafter, the present invention will be described more specifically with reference to examples. Hereinafter, both “parts” and “%” are based on mass.
製造例１ オルガノポリシロキサンＮｏ．１（式（１）に相当するオルガノポリシロキサン（ｂ１））
４つ口フラスコに、水１０００部、アセトン５０部を入れ、その混合溶液中に、メチルトリクロロシラン５９．７部（０．４モル）、ジメチルジクロロシラン５１．６部（０．４モル）、フェニルトリクロロシラン４２．３部（０．２モル）をトルエン２００部に溶解したものを攪拌下で滴下しながら加水分解した。
滴下終了から４０分後に攪拌を止め、反応液を分液ロートに移し入れて静置し、二層に分離したうちの下層を分液除去した。後に残った上層のオルガノポリシロキサンのトルエン溶液を減圧ストリッピングにかけ、この溶液中で残存している水と塩酸を過剰のトルエンとともに留去することにより、樹脂固形分１００％、重量平均分子量約３，０００のオルガノポリシロキサンＮｏ．１を得た。
Production Example 1 Organopolysiloxane No. 1 1 (organopolysiloxane (b1) corresponding to formula (1))
In a four-necked flask, 1000 parts of water and 50 parts of acetone are added, and in the mixed solution, 59.7 parts (0.4 mol) of methyltrichlorosilane, 51.6 parts (0.4 mol) of dimethyldichlorosilane, A solution obtained by dissolving 42.3 parts (0.2 mol) of phenyltrichlorosilane in 200 parts of toluene was hydrolyzed while being added dropwise with stirring.
After 40 minutes from the end of dropping, the stirring was stopped, the reaction solution was transferred to a separatory funnel and allowed to stand, and the lower layer separated into two layers was separated and removed. The remaining toluene solution of the organopolysiloxane remaining behind is subjected to vacuum stripping, and water and hydrochloric acid remaining in this solution are distilled off together with excess toluene, whereby the resin solid content is 100% and the weight average molecular weight is about 3 1,000 organopolysiloxane No. 1 was obtained.
製造例２ オルガノポリシロキサンＮｏ．２（オルガノポリシロキサン（ｂ２））
攪拌機、加温ジャケット、コンデンサー、滴下ロート及び温度計を取付けた４つ口フラスコに、メチルトリメトキシシラン８０部及びジメチルジメトキシシラン２０部を加え、攪拌下０．０５Ｎ塩酸水１０部を滴下し、６８℃で１時間加水分解縮合をした。これを１２０℃まで加熱して副生メタノールを系外に留去して冷却し、ろ過を行って、樹脂固形分１００％、重量平均分子量約２，５００の加水分解性シリル基を有するオルガノポリシロキサンＮｏ．２を得た。
Production Example 2 Organopolysiloxane No. 2 (organopolysiloxane (b2))
To a four-necked flask equipped with a stirrer, heating jacket, condenser, dropping funnel and thermometer, 80 parts of methyltrimethoxysilane and 20 parts of dimethyldimethoxysilane were added, and 10 parts of 0.05N hydrochloric acid water was added dropwise with stirring. Hydrolysis condensation was performed at 68 ° C. for 1 hour. This is heated to 120 ° C. to distill off by-product methanol out of the system, cooled, filtered, and an organopolysiloxane having a hydrolyzable silyl group with a resin solid content of 100% and a weight average molecular weight of about 2,500. Siloxane No. 2 was obtained.
製造例３ プレコートメタル用塗料Ｎｏ．１の製造例
ＳＬＪ７２４１Ａ（注３）６０部（固形分）、ＳＬＪ７２４１Ａ（注４）４０部（固形分）、製造例１で得たオルガノポリシロキサンＮｏ．１を５０部（固形分）、製造例２で得たオルガノポリシロキサンＮｏ．２を５０部（固形分）、亜鉛−２−エチルオクトエートを１部（固形分）加えて攪拌し、次いで、サイロイド７４（注８）５部、ＣＲ−９７（注９）５０部を加え、均一に撹拌し、シクロヘキサンノン／ソルベッソ１５０（「ソルベッソ１５０」は、エッソ石油株式会社製、によって粘度８０秒（フォードカップ＃４、２５℃）に調整してプレコートメタル塗料Ｎｏ．１を得た。
Production Example 3 Pre-coated metal paint No. Production Example 1 SLJ7241A (Note 3) 60 parts (solid content), SLJ7241A (Note 4) 40 parts (solid content), organopolysiloxane No. 1 obtained in Production Example 1. 1 in 50 parts (solid content), organopolysiloxane No. 1 obtained in Production Example 2. 50 parts (solid content) of 2 and 1 part (solid content) of zinc-2-ethyl octoate were added and stirred, and then 5 parts of thyroid 74 (Note 8) and 50 parts of CR-97 (Note 9) were added. Then, the mixture was stirred uniformly and adjusted to a viscosity of 80 seconds (Ford Cup # 4, 25 ° C.) by using cyclohexanenon / sorbeso 150 (“Esso Petroleum 150” manufactured by Esso Petroleum Corporation) to obtain a pre-coated metal paint No. 1. .
製造例４〜１５ プレコートメタル用塗料Ｎｏ．２〜Ｎｏ．１３の製造例
表１の配合内容とする以外は、製造例３と同様にして、プレコートメタル用塗料Ｎｏ．２〜Ｎｏ．１３を得た。
Production Examples 4 to 15 Prepainted metal paint No. 2-No. Production Example 13 In the same manner as in Production Example 3 except that the blending contents shown in Table 1 were used, the precoat metal paint No. 13 was used. 2-No. 13 was obtained.
（注３）ＳＬＪ７２４１Ａ（旭化成ワッカーシリコーン社製、商品名、Ｓｉ−Ｈを有するオルガノポリシロキサン（ａ１）に相当、重量平均分子量約５，０００）
（注４）ＳＬＪ７２４１Ｈ（旭化成ワッカーシリコーン社製、商品名、アルケニル基を有するオルガノポリシロキサン（ａ２）に相当、重量平均分子量約５，０００）
（注５）ＫＲ−３１１（信越化学工業社製、商品名、ヒドロキシシリル基を有するオルガノポリシロキサン（ｂ１）に相当、重量平均分子量約３０，０００）
（注６）ＫＲ−５１０（信越化学工業社製、商品名、メトキシシリル基を有するオルガノポリシロキサン（ｂ２）に相当、重量平均分子量約３，０００）
（注７）ＣＡＴ．ＡＣ：信越化学工業社製、商品名、アルコキシアルミニウム化合物
（注８）サイロイド７４：富士デヴィゾン株式会社製、無定形シリカ微粉末
（注９）ＣＲ−９７：石原産業株式会社製、商品名、チタン白
（注１０）ＳＴ−２１:（石原産業株式会社、商品名、微粒子チタン白、光触媒）
(Note 3) SLJ7241A (Asahi Kasei Wacker Silicone, trade name, equivalent to organopolysiloxane (a1) having Si-H, weight average molecular weight of about 5,000)
(Note 4) SLJ7241H (manufactured by Asahi Kasei Wacker Silicone, trade name, equivalent to organopolysiloxane (a2) having an alkenyl group, weight average molecular weight of about 5,000)
(Note 5) KR-311 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, equivalent to organopolysiloxane (b1) having a hydroxysilyl group, weight average molecular weight of about 30,000)
(Note 6) KR-510 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, equivalent to organopolysiloxane (b2) having a methoxysilyl group, weight average molecular weight of about 3,000)
(Note 7) CAT. AC: Shin-Etsu Chemical Co., Ltd., trade name, alkoxyaluminum compound (Note 8) Thyroid 74: Fuji Devison Co., Ltd., amorphous silica fine powder (Note 9) CR-97: Ishihara Sangyo Co., Ltd., trade name, titanium White (Note 10) ST-21: (Ishihara Sangyo Co., Ltd., trade name, fine titanium white, photocatalyst)
［２層複層塗膜の形成］
実施例１
下記の工程（１）〜工程（４）によって試験板Ｎｏ．１を作成した。
工程１：鋼板（注１１）上に、プライマー塗料（注１２）を乾燥膜厚が５μｍになるように塗装する工程、
工程２：被塗物の素材到達最高温度が１８０℃で、５０秒間加熱乾して半硬化させた。耐溶剤性（注１４）の評価は、「△」であった。
工程３：該塗膜上に、製造例３で得られたプレコートメタル塗料Ｎｏ．１をバーコーターで乾燥膜厚１２μｍとなるように塗装した。
工程４：被塗物の素材到達最高温度が２３５℃となるように５０秒間焼付けて試験板Ｎｏ．１を得た。 耐溶剤性（注１４）の評価は、「○」であった。
[Formation of two-layer / multi-layer coating film]
Example 1
In accordance with the following steps (1) to (4), the test plate No. 1 was created.
Step 1: A step of applying a primer paint (Note 12) on a steel plate (Note 11) so that the dry film thickness is 5 μm.
Step 2: The material reaching maximum temperature of the object to be coated was 180 ° C. and heat-dried for 50 seconds to be semi-cured. The evaluation of solvent resistance (Note 14) was “Δ”.
Step 3: On the coating film, the precoat metal paint No. obtained in Production Example 3 was used. 1 was coated with a bar coater to a dry film thickness of 12 μm.
Process 4: Baking for 50 seconds so that the maximum material arrival temperature of the object to be coated is 235 ° C. 1 was obtained. The evaluation of solvent resistance (Note 14) was “◯”.
（注１１）鋼板：クロメート処理された厚さ０．５ｍｍの溶融亜鉛メッキ鋼板、亜鉛目付量６０ｇ／ｍ２
（注１２）プライマー塗料：ＫＰカラー８６３０プライマー、関西ペイント社製、商品名、エポキシ変性ポリエステル系プライマー。
(Note 11) Steel sheet: 0.5 mm thick hot-dip galvanized steel sheet treated with chromate, zinc basis weight 60 g / m 2
(Note 12) Primer paint: KP color 8630 primer, manufactured by Kansai Paint Co., Ltd., trade name, epoxy-modified polyester primer.
実施例２〜８
表２の塗料種及び工程（１）〜工程（４）とする以外は、実施例１と同様にして、試験板Ｎｏ．２〜Ｎｏ．８を得た。
Examples 2-8
A test plate No. 1 was prepared in the same manner as in Example 1 except that the coating types in Table 2 and the steps (1) to (4) were used. 2-No. 8 was obtained.
比較例１〜８
表３の塗料種及び工程（１）〜工程（４）とする以外は、実施例１と同様にして、試験板Ｎｏ．９〜Ｎｏ．１７を得た。
これらの試験板Ｎｏ．１〜Ｎｏ．１７を下記試験条件に従って試験に供した結果を併せて、表２及び表３に示す。
Comparative Examples 1-8
A test plate No. 1 was prepared in the same manner as in Example 1 except that the coating types in Table 3 and the steps (1) to (4) were used. 9-No. 17 was obtained.
These test plates No. 1-No. The results obtained by subjecting 17 to the test according to the following test conditions are shown in Table 2 and Table 3.
[３層複層塗膜の形成]
実施例９
工程１：鋼板（注１１）上に、プライマー塗料（注１２）を乾燥膜厚が５μｍになるように塗装する工程、
工程２：被塗物の素材到達最高温度が２１０℃となるように５０秒間焼付けて硬化させた。耐溶剤性（注１４）の評価は、「○」であった。
工程３：カラーコート（注１３）を乾燥膜厚が１５μｍになるように塗装する工程、
工程４：被塗物の素材到達最高温度が１８０℃となるように５０秒間焼付けて半硬化させた。耐溶剤性（注１４）の評価は、「△」であった。
工程５：該塗膜上に、製造例３で得られたプレコートメタル塗料Ｎｏ．１をバーコーターで乾燥膜厚２μｍとなるように塗装した。
工程６：被塗物の素材到達最高温度が２３５℃となるように５０秒間焼付けて試験板Ｎｏ．９を得た。 耐溶剤性（注１４）の評価は、「○」であった。
[Formation of a three-layer coating film]
Example 9
Step 1: A step of applying a primer paint (Note 12) on a steel plate (Note 11) so that the dry film thickness is 5 μm.
Process 2: It was baked and hardened for 50 seconds so that the material arrival maximum temperature of a to-be-coated object might be 210 degreeC. The evaluation of solvent resistance (Note 14) was “◯” .
Step 3: A step of coating the color coat (Note 13) so that the dry film thickness is 15 μm.
Process 4: Baking was carried out for 50 seconds so that the highest material arrival temperature of the object to be coated was 180 ° C., and semi-cured. The evaluation of solvent resistance (Note 14) was “△” .
Step 5: On the coating film, the precoat metal paint No. obtained in Production Example 3 was used. 1 was coated with a bar coater so as to have a dry film thickness of 2 μm.
Step 6: Baking for 50 seconds so that the maximum material arrival temperature of the object to be coated is 235 ° C. 9 was obtained. The evaluation of solvent resistance (Note 14) was “◯”.
（注１３）カラーコート：ＫＰカラー１５９３アイボリー、関西ペイント社製、商品名、ポリエステル系着色塗料。 (Note 13) Color coat: KP color 1593 ivory, manufactured by Kansai Paint Co., Ltd., trade name, polyester colored paint.
実施例１０〜１４
表４の塗料種及び工程（１）〜工程（６）とする以外は、実施例９と同様にして、試験板Ｎｏ．１８〜Ｎｏ．２３を得た。
Examples 10-14
Test plate No. 5 was prepared in the same manner as in Example 9 except that the coating type and the steps (1) to (6) in Table 4 were used. 18-No. 23 was obtained.
比較例１０〜１３
表５の塗料種及び工程（１）〜工程（６）とする以外は、実施例９と同様にして、試験板Ｎｏ．２４〜Ｎｏ．２７を得た。
これらの試験板Ｎｏ．１〜Ｎｏ．１７を下記試験条件に従って試験に供した結果を併せて、表４及び表５に示す。
Comparative Examples 10-13
Test plate No. 5 was prepared in the same manner as in Example 9 except that the coating material types in Table 5 and the steps (1) to (6) were used. 24-No. 27 was obtained.
These test plates No. 1-No. The results obtained by subjecting 17 to the test according to the following test conditions are shown in Table 4 and Table 5.
（注１４）耐溶剤性：試験板の塗膜面にキシレンを浸み込ませたガーゼを、学振型摩擦堅牢度試験器を用いて、塗膜面を荷重約１ｋｇ／ｃｍ２の圧力をかけて、金属面又は下層面が出るまで約５ｃｍ往復させて擦り、下記基準で評価した。
◎：１００回以上擦って問題なし
○：往復の擦り回数が５０回以上で、かつ１００回未満で塗膜が溶解する
△：往復の擦り回数が５回以上で、かつ５０回未満で塗膜を溶解する（半硬化状態） ×：往復の擦り回数が５回未満で塗膜を溶解する。
(Note 14) Solvent resistance: Gauze in which xylene is impregnated into the coating surface of the test plate is applied to the coating surface with a load of about 1 kg / cm 2 using a Gakushin friction fastness tester. Then, it was rubbed by reciprocating about 5 cm until the metal surface or lower layer surface appeared, and evaluated according to the following criteria.
◎: No problem with rubbing 100 times or more ○: The coating film dissolves when the number of reciprocating rubs is 50 times or more and less than 100 times
(Triangle | delta): A coating film is melt | dissolved when the frequency | count of reciprocation is 5 times or more and less than 50 times (semi-hardened state) x: A coating film is melt | dissolved when the frequency | count of reciprocation is less than 5 times.
（注１５）密着性：ＪＩＳ Ｋ ５６００−５−６：付着性（クロスカット法）に準拠して、試験板の塗膜表面にカッターナイフで素地に到達するように、直交する縦横１１本ずつの平行な直線を１ｍｍ間隔で引いて、１ｍｍ×１ｍｍのマス目を１００個作成した。その表面にセロハンテープ（登録商標）を密着させ、テ−プを急激に剥離した際のマス目の剥れ程度を観察し下記基準で評価した。
○：塗膜の剥離が全く認められない
△：塗膜がわずかに剥離したが、マス目は９０個以上残存
×：塗膜が剥離し、マス目の残存数は５０個未満。
(Note 15) Adhesion: JIS K 5600-5-6: In accordance with adhesion (cross-cut method), eleven orthogonally crosswise vertically and horizontally so as to reach the substrate with a cutter knife on the coating film surface of the test plate 100 parallel lines were drawn at intervals of 1 mm to create 100 squares of 1 mm × 1 mm. Cellophane tape (registered trademark) was closely adhered to the surface, and the degree of peeling of the cells when the tape was peeled off rapidly was observed and evaluated according to the following criteria.
○: No peeling of the coating film is observed Δ: The coating film is slightly peeled, but 90 or more cells remain. ×: The coating film peels and the number of remaining cells is less than 50.
（注１６）加工性：各試験板の塗膜表面を外側にして折曲げ、その内側に同じ厚さの鋼板を１枚挟み、記塗装板を万力にて１８０度折曲する１Ｔ折曲げ加工を行ったときの折曲げ部の塗膜状態を下記基準にて評価した。試験は塗装板の温度が５℃で行った。
◎：塗膜にワレ、ハガレなどの異常が認められない
○：塗膜にワレが僅かに認められる
△：塗膜にワレがかなり認められる
×：塗膜にワレが著しく認められる。
(Note 16) Workability: 1T bend in which the coating film surface of each test plate is bent outward, one steel plate of the same thickness is sandwiched inside, and the coated plate is bent 180 degrees in a vise The coating state of the bent part when processing was evaluated according to the following criteria. The test was performed at a coated plate temperature of 5 ° C.
A: Abnormalities such as cracks and peelings are not observed in the coating film
○: Slight cracking is observed in the coating film
Δ: Slight cracking in coating film
X: A crack is recognized remarkably in a coating film.
（注１７）耐衝撃性：各試験板を、温度２０±１℃、湿度７５±２％の恒温恒湿室に２４時間置いたのち、デュポン衝撃試験器に規定の大きさの受台と撃心を取り付け、試験板の塗面を上向きにして、その間に挟み、次に５００ｇの重さのおもり撃心の上に落とし、衝撃による塗膜にワレ、ハガレがない最大高さ（ｃｍ）を測定した。 (Note 17) Impact resistance: After each test plate is placed in a constant temperature and humidity chamber at a temperature of 20 ± 1 ° C and a humidity of 75 ± 2% for 24 hours, a Dupont impact tester with a cradle of a specified size and an impact Attach the heart, put the test plate face up, pinch it in between, then drop it on the weight of the weight of 500g, and make the maximum height (cm) where there is no cracking or peeling on the coating film due to impact It was measured.
（注１８）耐候性：各試験板の光沢を、ＪＩＳ Ｈ ８６０２ ５．１２（１９９
２）に準拠（水スプレー時間１２分間、ブラックパネル温度６０℃）し、カーボンアーク灯式促進耐候性試験機サンシャインウェザオメーターを使用して測定して、暴露試験前の光沢に対する光沢保持率が８０％を割る時間を測定した。さらに塗膜表面を目視により観察した。
◎：光沢保持率が８０％を割る時間が１，５００時間を越える
○：光沢保持率が８０％を割る時間が１，０００時間以上、かつ２，５００時間未満
△：光沢保持率が８０％を割る時間が５００時間以上、かつ１，０００時間未満
×：光沢保持率が８０％を割る時間５００時間未満。
(Note 18) Weather resistance: The gloss of each test plate was measured according to JIS H 8602 5.12 (199
2) (water spray time 12 minutes, black panel temperature 60 ° C), measured using a sunshine weatherometer with a carbon arc lamp type accelerated weathering tester, and the gloss retention ratio against gloss before the exposure test is The time to divide 80% was measured. Furthermore, the coating film surface was observed visually.
A: Time for gloss retention to break 80% exceeds 1,500 hours B: Time for gloss retention to break 80% is 1,000 hours or more and less than 2,500 hours Δ: Gloss retention is 80% The time for cracking is 500 hours or more and less than 1,000 hours x: The time for the gloss retention to break 80% is less than 500 hours.
（注１９）耐汚染性：各試験板にマジックインキで線を引き、エタノールを染み込ませた布で拭き取る。
◎：全く問題なくきれいに拭き取れる。
○：ほとんど問題なくきれいに拭き取れる。
△：ややマジックの跡が見られる
×：マジック跡がはっきりみえる。
(Note 19) Contamination resistance: Draw a line on each test plate with magic ink and wipe with a cloth soaked in ethanol.
A: It can be wiped clean without any problems.
○: Wipe cleanly with almost no problems.
Δ: Somewhat magical marks can be seen
×: The magic mark is clearly visible.
加工性、下層塗膜との密着性及び耐候性に優れるプレコートメタル鋼板が得られる。 A precoated metal steel sheet excellent in workability, adhesion with the lower layer coating film and weather resistance is obtained.
Claims (4)
上塗塗料（ＩＩ）：下記の組成（Ａ）と組成（Ｂ）を、組成（Ａ）と組成（Ｂ）の固形分合計１００質量部に基づいて、組成（Ａ）／組成（Ｂ）＝３０／７０〜８０／２０（質量部）で含有する上塗塗料であって、
組成（Ａ）：１分子中に少なくとも２個のＳｉ−Ｈを有するオルガノポリシロキサン（ａ１）と１分子中にアルケニル基を少なくとも１個有するオルガノポリシロキサン（ａ２）を、オルガノポリシロキサン（ａ１）とオルガノポリシロキサン（ａ２）の固形分合計に対して、オルガノポリシロキサン（ａ１）６０〜９５質量％、オルガノポリシロキサン（ａ２）５〜４０質量％含有する組成物
組成（Ｂ）：下記式（１）で示されるオルガノポリシロキサン（ｂ１）と加水分解性シリル基を有するオルガノポリシロキサン（ｂ２）を、オルガノポリシロキサン（ｂ１）とオルガノポリシロキサン（ｂ２）固形分合計に対して、オルガノポリシロキサン（ｂ１）５０〜８０質量％、オルガノポリシロキサン（ｂ２）２０〜５０質量％含有する組成物
Ｒ２ ａＳｉ（ＯＨ）ｂＯ（４−ａ−ｂ）／２・・・式（１）
（式中、Ｒ２は同一または異種の置換もしくは非置換の炭素数１〜８の１価炭化水素を示し、ａ及びｂは、０．２≦ａ≦２、０．１≦ｂ≦３、ａ＋ｂ＜４の関係を満たす） On the metal plate whose surface may be subjected to chemical conversion treatment, (1) a semi-cured coating film of a lower layer coating (I) -1 comprising a polyester resin primer coating and a modified primer coating thereof is formed; A semi-cured coating of (2) the lower coating (I) -1 is formed on the cured coating, and a semi-curing coating of the lower coating (I) -2 comprising a polyester-based colored coating is formed on the semi-cured coating. A film is formed on the semi-cured coating film, or (3) a cured coating film of the lower coating material (I) -1 is formed, and the semi-curing coating film of the lower coating material (I) -2 is formed on the cured coating film. A coating film forming method comprising: coating a semi-cured coating film with a top coating (II) having the following composition, followed by heat curing.
Top coating (II): Composition (A) / Composition (B) = 30, based on 100 parts by mass of the total solid content of composition (A) and composition (B). / 70 to 80/20 (parts by weight) containing a top coating,
Composition (A): Organopolysiloxane (a1) having at least two Si—H in one molecule and organopolysiloxane (a2) having at least one alkenyl group in one molecule, organopolysiloxane (a1) Composition composition (B) containing 60 to 95% by mass of organopolysiloxane (a1) and 5 to 40% by mass of organopolysiloxane (a2) with respect to the total solids content of organopolysiloxane (a2): The organopolysiloxane (b1) represented by 1) and the organopolysiloxane (b2) having a hydrolyzable silyl group are mixed with the organopolysiloxane (b1) and the organopolysiloxane (b2) in the total solid content. (B1) 50-80% by weight, organopolysiloxane (b2) 20-50% by weight Object R 2 a Si (OH) b O (4-a-b) / 2 ··· Equation (1)
(Wherein R 2 represents the same or different substituted or unsubstituted monovalent hydrocarbon having 1 to 8 carbon atoms, and a and b are 0.2 ≦ a ≦ 2, 0.1 ≦ b ≦ 3, a + b <4)
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| JP2006172847A JP4726226B2 (en) | 2006-06-22 | 2006-06-22 | Coating method |
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| JP4726226B2 true JP4726226B2 (en) | 2011-07-20 |
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| JP4849186B2 (en) | 2009-10-28 | 2012-01-11 | Ｊｆｅスチール株式会社 | Hot pressed member and method for manufacturing the same |
| US10030290B2 (en) | 2012-10-31 | 2018-07-24 | Jfe Steel Corporation | Steel sheet for hot press-forming, hot press-formed part, and method of producing hot press-formed part |
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| JPH09141193A (en) * | 1995-11-24 | 1997-06-03 | Matsushita Electric Works Ltd | Coated plate with high resistance to pollution |
| JPH1088010A (en) * | 1996-09-17 | 1998-04-07 | Nippon Paint Co Ltd | Curable resin composition |
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