JP2005036287A - Method for forming coating film having excellent durability, and metallic product with the coating film formed on the surface - Google Patents
Method for forming coating film having excellent durability, and metallic product with the coating film formed on the surface Download PDFInfo
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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Abstract
Description
本発明は、鉄、アルミニウム、マグネシウム、銅、亜鉛などの金属及びそれらの合金からなる各種金属製品に電着塗装を施した後にシリカ、アルミナ、チタニア、ジルコニアの微粒子の少なくとも１種類とアルコキシシラン化合物及び分子内にアルコキシシリル基を含有するアクリル樹脂とからなる無機系塗料組成物を塗装することで、かかる金属製品に優れた耐久性能を付与する塗装方法及びその塗装された金属製品に関するものである。 The present invention relates to an alkoxysilane compound and at least one kind of fine particles of silica, alumina, titania and zirconia after electrodeposition coating is performed on various metal products made of metals such as iron, aluminum, magnesium, copper and zinc and alloys thereof. In addition, the present invention relates to a coating method for imparting excellent durability performance to such a metal product by coating an inorganic coating composition comprising an acrylic resin containing an alkoxysilyl group in the molecule, and the coated metal product. .
鉄、アルミニウム、マグネシウム、銅、亜鉛などの金属及びそれらの合金からなる各種金属製品の内、防錆性能や耐酸性、耐アルカリ性、その他の耐薬品性等が要求される分野に使用される物には、一般に、その優れた性能と膜厚均一性及び塗装効率の観点から、電着塗装が行われる事が多い。たとえば、これら金属の表面処理に用いられる公知の電着塗装は、通常は被塗物を陽極にして塗装するアニオン型電着塗装と被塗物を陰極にして塗装するカチオン型電着塗装がある。アニオン型電着塗装に関しては、特許文献１や、特許文献２に詳細に記載されており、塗料の具体例としては、エスビアＥＤ ＡＬ−５０、エスビアＥＤ ＡＬ−９６０１（いずれも神東塗料（株）製アクリル系アニオン電着塗料）等が挙げられる。カチオン型電着塗装に関しては、特許文献３、特許文献４や特許文献５に詳細に記載されており、塗料の具体例としては、ＳＵＣＣＥＤ＃３０００（神東塗料（株）製アクリル／エポキシハイブリッド系カチオン電着塗料）、ＳＵＣＣＥＤ＃８０（神東塗料（株）製エポキシ系カチオン電着塗料）等が挙げられる。 Among various metal products made of metals such as iron, aluminum, magnesium, copper, and zinc and their alloys, those used in fields that require rust prevention performance, acid resistance, alkali resistance, and other chemical resistance In general, electrodeposition coating is often performed from the viewpoint of its excellent performance, film thickness uniformity and coating efficiency. For example, known electrodeposition coatings used for the surface treatment of these metals are usually anionic electrodeposition coating in which the object to be coated is applied as an anode and cationic electrodeposition coating in which the object is applied as a cathode. . The anionic electrodeposition coating is described in detail in Patent Document 1 and Patent Document 2, and specific examples of paints include Svia ED AL-50 and Svia ED AL-9601 (both Shinto Paint Co., Ltd.). ) Acrylic anion electrodeposition paint)). The cationic electrodeposition coating is described in detail in Patent Document 3, Patent Document 4 and Patent Document 5, and examples of the paint include SUCCED # 3000 (acrylic / epoxy hybrid system manufactured by Shinto Paint Co., Ltd.). Cationic electrodeposition paint), SUCCED # 80 (Epoxy cationic electrodeposition paint manufactured by Shinto Paint Co., Ltd.) and the like.
近年、省資源、省エネルギー、地球環境保全の観点から工業製品の長寿命化が望まれており、かかる製品についても従来以上の耐久性が要求されてきている。特に耐候性、耐傷性、耐磨耗性、耐汚染性と言った品質の向上が強く望まれてきている。 In recent years, it has been desired to extend the life of industrial products from the viewpoints of resource saving, energy saving, and global environmental protection, and such products have been required to have durability higher than before. In particular, improvements in quality such as weather resistance, scratch resistance, abrasion resistance, and contamination resistance have been strongly desired.
一方、電着塗装とは別に、高耐久性の塗料として、アルコキシシラン化合物、コロイダルシリカ、アルミナ等の無機材料を用いた無機系塗料の提案がなされている（例えば特許文献６、特許文献７、特許文献８）。この無機系塗料は塗膜の耐候性や耐傷性や耐汚染性等の性質は従来の有機塗膜に比べ優れている為、その応用として例えば電着塗装の上にこれら無機系の塗装を行うことで、電着塗膜が持つ、優れた耐薬品性、素地密着性、防錆性能及び、その膜厚均一性により複雑な形状の被塗物のどの部位でもこれらの性能が安定的に得られるといった性能に、無機系塗膜の優れた耐久性（耐候性や耐傷性等）が加えられる事が期待される。
しかるに、従来の無機系塗料は電着塗膜への密着性が十分でなく、上記の優れた耐薬品性、素地密着性、防錆性能及び、その膜厚均一性により複雑な形状の被塗物のどの部位でもこれらの性能が安定的に得られた上に、無機系塗膜の優れた耐久性が付与された金属製品が得られないという問題があった。 However, conventional inorganic coatings do not have sufficient adhesion to electrodeposition coatings, and the above-mentioned excellent chemical resistance, substrate adhesion, rust prevention performance, and coating thickness of complex shapes due to the film thickness uniformity. There was a problem in that these performances were stably obtained at any part of the product, and a metal product to which excellent durability of the inorganic coating film was imparted could not be obtained.
本発明者らは、この問題点に対し、無機系材料にアルコキシシラン含有アクリル樹脂を組み合わせることで、その優れた耐久性を損なうことなく電着塗膜と良好な密着性を持たせる事が可能なことを見出し、従来の電着塗装を施した後に、本発明の無機系塗料を塗装することで、今までに無い優れた耐候性、硬さ、耐傷性、耐汚染性、耐薬品性、防錆性を持った金属製品が得られることを提案するものである。すなわち本発明は、シリカ、アルミナ、チタニア、ジルコニアの微粒子の少なくとも１種類とアルコキシシラン化合物及び分子内にアルコキシシリル基を含有するアクリル樹脂とからなる塗料組成物を塗布し乾燥硬化させた金属製品に関するものである。 In order to solve this problem, the present inventors can provide an electrodeposition coating film with good adhesion without impairing its excellent durability by combining an alkoxysilane-containing acrylic resin with an inorganic material. After applying the conventional electrodeposition coating, by applying the inorganic paint of the present invention, excellent weather resistance, hardness, scratch resistance, contamination resistance, chemical resistance, It is proposed that a metal product having rust prevention properties can be obtained. That is, the present invention relates to a metal product obtained by applying a coating composition comprising at least one kind of fine particles of silica, alumina, titania, and zirconia, an alkoxysilane compound, and an acrylic resin containing an alkoxysilyl group in the molecule and drying and curing the coating composition. Is.
本発明の塗装を施す事で、従来に無い優れた耐候性、硬さ、耐傷性、耐汚染性、耐薬品性、防錆性を持った鉄、アルミニウム、マグネシウム、銅、亜鉛などの金属及びそれらの合金で作られた金属パネル、カーテンウォール、サッシ、エアコンの屋外機ケース、配電盤ボックス、街灯用カバー、冷蔵庫や洗濯機などのケース、自動車のタイヤホイール等といった金属製品が得られる。 By applying the coating of the present invention, iron, aluminum, magnesium, copper, zinc and other metals having excellent weather resistance, hardness, scratch resistance, contamination resistance, chemical resistance, rust resistance, and Metal products such as metal panels, curtain walls, sashes, outdoor unit cases for air conditioners, switchboard boxes, streetlight covers, refrigerators and washing machines, automobile tire wheels, etc. made of these alloys can be obtained.
本発明の詳細について以下に説明する。 Details of the present invention will be described below.
本発明の塗料組成物に用いるシリカ、アルミナ、チタニア、ジルコニアの微粒子は、平均粒子径が１μｍ以下、好ましくは３００ｎｍ以下であり、平均粒子径の下限は小さいほうが良いが、取扱い易さなどから１ｎｍ以上が好ましい。かかる微粒子は塩酸、硫酸、硝酸等の無機酸又は蟻酸、酢酸、プロピオン酸等の有機酸で中和安定化（邂逅）されて水中に分散されたものである。例えば、シリカの微粒子としては、日産化学（株）製スノーテックス２０、スノーテックス３０、スノーテックスＣ、スノーテックスＯ等、触媒化成工業（株）製Ｃａｔａｌｏｉｄ−Ｓ等が挙げられる。また、アルミナの微粒子としては、川研ファインケミカル（株）製ＣＳＡ−１１０ＡＤ、日産化学（株）製アルミナゾル−５２０等が挙げられる。また、チタニアの微粒子としては、石原産業（株）製のＳＴＳ−０１、ＳＴＳ−０２等、テイカ（株）製ＴＫＳ−２０１、ＴＫＳ−２０２等、チタン工業（株）製ＰＣ−２０１、ＰＣ−２０２等が挙げられる。また、ジルコニアの微粒子としては、日産化学（株）製のＮＺＳ−３０Ａ、ＮＺＳ-３０Ｂ等が挙げられる。但し、これら微粒子は上記の例に限定されるものではない。 The fine particles of silica, alumina, titania and zirconia used in the coating composition of the present invention have an average particle size of 1 μm or less, preferably 300 nm or less, and the lower limit of the average particle size is better. The above is preferable. Such fine particles are dispersed in water after being neutralized and stabilized with an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid or an organic acid such as formic acid, acetic acid or propionic acid. Examples of the silica fine particles include Snowtex 20, Snowtex 30, Snowtex C, Snowtex O, etc. manufactured by Nissan Chemical Co., Ltd., and Catalyst-S manufactured by Catalyst Kasei Kogyo Co., Ltd., and the like. Examples of the alumina fine particles include CSA-110AD manufactured by Kawaken Fine Chemical Co., Ltd., and Alumina Sol-520 manufactured by Nissan Chemical Co., Ltd. Further, as titania fine particles, STS-01 and STS-02 manufactured by Ishihara Sangyo Co., Ltd., TKS-201 and TKS-202 manufactured by Teika Co., Ltd., PC-201 manufactured by Titanium Industry Co., Ltd., and PC- 202 or the like. Examples of zirconia fine particles include NZS-30A and NZS-30B manufactured by Nissan Chemical Co., Ltd. However, these fine particles are not limited to the above examples.
また、本発明で用いるアルコキシシラン化合物としては、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ｎ−プロピルトリメトキシシラン、ｎ−プロピルトリエトキシシラン、イソプロピルトリメトキシシラン、イソプロピルトリエトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−クロロプロピルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−メタクリルオキシプロピルトリメトキシシラン、γ−メタクリルオキシプロピルトリエトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、３，４−エポキシシクロヘキシルエチルトリメトキシシラン、３，４−エポキシシクロヘキシルエチルトリエトキシシラン、ジメチルメトキシシラン、ジメチルジエトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジ−ｎ−プロピルジメトキシシラン、ジ−ｎ−プロピルジエトキシシラン、ジイソプロピルジメトキシシラン、ジイソプロピルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン等、更には、これらの部分加水分解性縮合物を挙げることができる。 Examples of the alkoxysilane compound used in the present invention include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, and n-propyl. Triethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoate Sisilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, dimethylmethoxysilane, dimethyldiethoxysilane , Diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, etc. Of the partial hydrolyzable condensate.
本発明で用いる分子内にアルコキシシリル基を含有するアクリル樹脂は、アルコキシシリル基を含有するエチレン性不飽和モノマー及びその他のエチレン性不飽和モノマーの混合物をラジカル重合開始剤により溶液重合、エマルション重合、又は懸濁重合した物が挙げられる。 The acrylic resin containing an alkoxysilyl group in the molecule used in the present invention is a solution polymerization, emulsion polymerization, or a mixture of an ethylenically unsaturated monomer containing an alkoxysilyl group and another ethylenically unsaturated monomer using a radical polymerization initiator. Or the thing which carried out suspension polymerization is mentioned.
上記アルコキシシリル基を含有するエチレン性不飽和モノマーとしては、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルジメトキシフェニルシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（βメトキシエトキシ）シラン等が挙げられる。上記その他のエチレン性不飽和モノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート等の（メタ）アクリル酸アルキルエステル、例えばスチレン、メチルスチレン、酢酸ビニル、塩化ビニル等のビニル化合物、例えばアクリル酸、メタクリル酸、マレイン酸、イタコン酸等のカルボン酸類、例えば２−ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート等の（メタ）アクリル酸のヒドロキシアルキルエステル類、例えば、（メタ）アクリロニトリル等のニトリル類、例えば（メタ）アクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−イソプロピルアクリルアミドなどのアミド類、ジメチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリルアミド等のアミノ基含有モノマー等が挙げられ、これらの２種類以上が用いられる。そのなかでも、アルコキシシラン化合物との相溶性を良化し、平滑で高光沢の塗膜が得られる様にするために、上記のシリル基含有モノマーをエチレン性不飽和モノマーの合計重量中に１０〜６０％用いるのが特に好ましい。１０％未満ではアクリル樹脂とアルコキシシラン化合物や、微粒子の無機系材料との間に良好な相溶性が得られず混合後に白濁、沈殿が生じる。又、電着塗膜への密着性が得られない。６０％を超える場合は樹脂合成中にシリル基が反応してゲル化を起こし、目的とする樹脂が得られない。また、かかるアクリル樹脂の分子量は特に規定されるものではないが、混合のしやすさや粘度的な取り扱いやすさの点から１０００〜３００００が好ましい。 Examples of the ethylenically unsaturated monomer containing the alkoxysilyl group include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, and γ- (meth) acryloxypropyldimethoxyphenylsilane. , Γ- (meth) acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, and the like. Other ethylenically unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate and other (meth) acrylic acid alkyl esters, for example, styrene, methylstyrene, vinyl acetate, vinyl chloride and other vinyl compounds, for example acrylic Carboxylic acids such as acid, methacrylic acid, maleic acid, itaconic acid, such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate Hydroxyalkyl esters of (meth) acrylic acid such as, for example, nitriles such as (meth) acrylonitrile, amides such as (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, etc. And amino group-containing monomers such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylamide, and two or more of these are used. Among them, in order to improve the compatibility with the alkoxysilane compound and to obtain a smooth and high gloss coating film, the silyl group-containing monomer is added in an amount of 10 to 10% in the total weight of the ethylenically unsaturated monomer. It is particularly preferable to use 60%. In less than 10% and an acrylic resin and an alkoxysilane compound, white turbidity after mixing can not be obtained good compatibility between the inorganic material particles, precipitation occurs. Moreover, the adhesiveness to an electrodeposition coating film cannot be obtained. If it exceeds 60%, the silyl group reacts during resin synthesis to cause gelation, and the desired resin cannot be obtained. Further, the molecular weight of the acrylic resin is not particularly specified, but is preferably 1000 to 30000 from the viewpoint of easy mixing and viscosity handling.
［塗料の製造方法］
本発明の塗料組成物は、ディスパー等の攪拌混合機を用い、上記シリカ、アルミナ、チタニア、ジルコニアの微粒子の少なくとも１種類とアルキルアルコキシシラン化合物とその分子内にアルコキシシラン基を含有するアクリル樹脂をプラスチック又はステンレス製の容器中で攪拌混合して得る。
[Manufacturing method of paint]
The coating composition of the present invention uses an agitator / mixer such as a disper, and contains at least one kind of fine particles of silica, alumina, titania and zirconia, an alkylalkoxysilane compound, and an acrylic resin containing an alkoxysilane group in the molecule. It is obtained by stirring and mixing in a plastic or stainless steel container.
[塗装方法]
本発明の塗装方法は、金属に一般に公知の方法で電着塗装を施し、焼付け硬化させた後に、前述のアルミナ、シリカ、チタニア、ジルコニアの微粒子の少なくとも１種類とアルコキシシラン化合物及び分子内にアルコキシシリル基を含有するアクリル樹脂とからなる塗料組成物を塗装物品に応じ、ロール塗装、刷毛塗り、吹き付け塗装、浸漬塗装等を行い、室温〜２５０℃で所定の時間の乾燥硬化を行うものである。所定の時間は温度に応じて異なるが、室温〜６０℃では約7日、６０〜１２０℃では１〜２時間、１２０℃以上では３０分程度である。これらは、一般の塗料と同様に、その乾燥雰囲気の条件により最適化され得るものである。
[Coating method]
In the coating method of the present invention, after applying electrodeposition coating to a metal by a generally known method and baking and curing, at least one kind of the fine particles of alumina, silica, titania and zirconia, an alkoxysilane compound, and alkoxy in the molecule A coating composition comprising an acrylic resin containing a silyl group is subjected to roll coating, brush coating, spray coating, dip coating, etc., depending on the coated article, and dry-cured at room temperature to 250 ° C. for a predetermined time. . Although the predetermined time varies depending on the temperature, it is about 7 days at room temperature to 60 ° C, 1 to 2 hours at 60 to 120 ° C, and about 30 minutes at 120 ° C or more. These can be optimized according to the conditions of the dry atmosphere as in the case of general paints.
本発明の塗料組成物は必要に応じ、有機溶剤、着色顔料、体質顔料の他、紫外線吸収剤、光安定化剤、顔料分散剤、消泡剤、増粘剤、酸化防止剤、防腐剤、防かび剤等の添加剤を用いても良い。 The coating composition of the present invention, if necessary, in addition to organic solvents, colored pigments, extender pigments, UV absorbers, light stabilizers, pigment dispersants, antifoaming agents, thickeners, antioxidants, preservatives, Additives such as fungicides may be used.
以下、実施例及び比較例を挙げて本発明をさらに具体的に説明する。「部」及び「％」はそれぞれ「重量部」及び「重量％」を意味する。本発明はこれらの実施例に制限されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. “Parts” and “%” mean “parts by weight” and “% by weight”, respectively. The present invention is not limited to these examples.
［アクリル樹脂合成例１］
撹拌機、還流冷却器、滴下槽及び温度計を取り付けた反応容器にイソプロパノール１００部を投入し、内温を８０℃に調整しつつ、シクロヘキシルメタクリレート３０部、エチルアクリレート１０部、メタクリル酸１０部、γ―メタクリロキシプロピルトリメトキシシラン５０部、アゾビスメチルブチロニトリル５部の混合液を３時間かけて滴下した。滴下終了後内温を８５℃に調整しつつ３時間保ち、その後室温まで冷却し、平均分子量１２，０００、不揮発分５０％のアクリル樹脂Ａ−１を得た。
[Acrylic resin synthesis example 1]
Into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 100 parts of isopropanol was added, and while adjusting the internal temperature to 80 ° C., 30 parts of cyclohexyl methacrylate, 10 parts of ethyl acrylate, 10 parts of methacrylic acid, A mixed solution of 50 parts of γ-methacryloxypropyltrimethoxysilane and 5 parts of azobismethylbutyronitrile was added dropwise over 3 hours. After completion of dropping, the internal temperature was maintained at 85 ° C. for 3 hours, and then cooled to room temperature to obtain acrylic resin A-1 having an average molecular weight of 12,000 and a non-volatile content of 50%.
［アクリル樹脂合成例２］
撹拌機、還流冷却器、滴下槽及び温度計を取り付けた反応容器にイソプロパノール１００部を投入し、内温を８０℃に調整しつつ、シクロヘキシルメタクリレート１０部、エチルアクリレート１０部、２−ヒドロキシエチルメタクリレート１０部、メタクリル酸１０部、γ―メタクリロキシプロピルトリメトキシシラン２５部、γ―メタクリロキシプロピルメチルジメトキシシラン２５部、アゾビスメチルブチロニトリル６部の混合液を３時間かけて滴下した。滴下終了後内温を８５℃に調整しつつ３時間保ち、その後室温まで冷却し、分子量１０，０００、不揮発分５０％のアクリル樹脂Ａ−２を得た。
[Acrylic resin synthesis example 2]
Into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 100 parts of isopropanol was added, and while adjusting the internal temperature to 80 ° C., 10 parts of cyclohexyl methacrylate, 10 parts of ethyl acrylate, 2-hydroxyethyl methacrylate A mixed solution of 10 parts, 10 parts of methacrylic acid, 25 parts of γ-methacryloxypropyltrimethoxysilane, 25 parts of γ-methacryloxypropylmethyldimethoxysilane, and 6 parts of azobismethylbutyronitrile was added dropwise over 3 hours. After completion of dropping, the internal temperature was kept at 85 ° C. for 3 hours, and then cooled to room temperature to obtain an acrylic resin A-2 having a molecular weight of 10,000 and a nonvolatile content of 50%.
［電着塗装板の製造例１］
幅７０ｍｍ、長さ１５０ｍｍ、厚さ１．５ｍｍのＡ６０６３アルミニウム板に陽極酸化により７μｍのアルマイト処理を施したパネルに、エスビアＥＤ ＡＬ−５０（神東塗料（株）製アクリル系アニオン型電着塗料）を焼き付け後の塗膜厚さが１０μｍになるように電着塗装し、１８０℃で２５分間の焼付けを行った。
[Production Example 1 of Electrodeposited Plate]
A panel of A6063 aluminum plate 70mm wide, 150mm long and 1.5mm thick and anodized with 7μm alumite, Svia ED AL-50 (acrylic anionic electrodeposition paint by Shinto Paint Co., Ltd.) ) Was electrodeposited so that the coating thickness after baking was 10 μm, and baked at 180 ° C. for 25 minutes.
［電着塗装板の製造例２］
幅７０ｍｍ、長さ１５０ｍｍ、厚さ０．８ｍｍの鋼板に、ＳＵＣＣＥＤ＃３０００（神東塗料（株）製アクリル／エポキシハイブリッド系カチオン型電着塗料）を焼き付け後の塗膜厚さが１０μｍになるように電着塗装し、１８０℃で２５分間の焼付けを行った。
[Production Example 2 of Electrodeposited Plate]
SUCCED # 3000 (acrylic / epoxy hybrid cationic electrodeposition paint manufactured by Shinto Paint Co., Ltd.) is applied to a steel sheet having a width of 70 mm, a length of 150 mm, and a thickness of 0.8 mm. Thus, electrodeposition was applied, and baking was performed at 180 ° C. for 25 minutes.
スノーテックＯ（コロイダルシリカ、固形分２０％：日産化学（株）製）２０部、ＡＳ５２０（アルミナゾル、固形分２０％：日産化学（株）製）1２０部、イソプロピルアルコール５７部、水２０部、メチルトリメトキシシラン７０部、ジメチルジメトキシシラン２６部、アクリル樹脂Ａ−１（合成例１） ３６部、ジブチル錫ジラウレート１部をステンレス容器中でディスパーにより２５℃で２時間撹拌混合する。保持後、上記電着塗装板の製造例１で示した塗装アルミニウム板に、乾燥膜厚で１５μｍになる様スプレー塗装し、１５０℃で３０分間焼付け乾燥して試験体を得た。この試験体に下記試験を行い、結果を表１に示した。 Snowtec O (Colloidal silica, solid content 20%: manufactured by Nissan Chemical Co., Ltd.) 20 parts, AS520 (alumina sol, solid content 20%: manufactured by Nissan Chemical Co., Ltd.) 120 parts, 57 parts of isopropyl alcohol, 20 parts of water, 70 parts of methyltrimethoxysilane, 26 parts of dimethyldimethoxysilane, 36 parts of acrylic resin A-1 (Synthesis Example 1), and 1 part of dibutyltin dilaurate are stirred and mixed in a stainless steel container at 25 ° C. for 2 hours. After holding, spray coating was performed on the coated aluminum plate shown in Production Example 1 of the above-mentioned electrodeposited coated plate so that the dry film thickness was 15 μm, and baked and dried at 150 ° C. for 30 minutes to obtain a test specimen. The following tests were conducted on this test body, and the results are shown in Table 1.
ＡＳ５２０（アルミナゾル、固形分２０％：日産化学（株）製）１６０部、イソプロピルアルコール４８部、水１８部、メチルトリメトキシシラン６４部、ジメチルジメトキシシラン１５部、γ―グリシドキシプロピルトリメトキシシラン１４部、アクリル樹脂Ａ−１（合成例１） ３０部、ジブチル錫ジラウレート１部を２５℃で２時間混合した。その後、上記電着塗装板の製造例１で示した塗装アルミニウム板に乾燥膜厚１５μｍになる様にスプレー塗装し、１１０℃にて４０分間焼付乾燥して試験体を得た。この試験体に下記試験を行い、結果を表１に示した。 AS520 (alumina sol, solid content 20%: manufactured by Nissan Chemical Co., Ltd.) 160 parts, isopropyl alcohol 48 parts, water 18 parts, methyltrimethoxysilane 64 parts, dimethyldimethoxysilane 15 parts, γ-glycidoxypropyltrimethoxysilane 14 parts, 30 parts of acrylic resin A-1 (Synthesis Example 1) and 1 part of dibutyltin dilaurate were mixed at 25 ° C. for 2 hours. Thereafter, the coated aluminum plate shown in Production Example 1 of the electrodeposition coated plate was spray-coated so as to have a dry film thickness of 15 μm, and baked and dried at 110 ° C. for 40 minutes to obtain a test specimen. The following tests were conducted on this test body, and the results are shown in Table 1.
スノーテックＯ（コロイダルシリカ、固形分２０％：日産化学（株）製）２０部、ＳＴＳ−０１（チタニアゾル、固形分３０％：石原産業（株）製）１００部、イソプロピルアルコール３５部、水１４部、メチルトリメトキシシラン７６部、アクリル樹脂Ａ−２（合成例２） ５４部、ジブチル錫ジラウレート１部を２５℃で２時間ディスパーで撹拌混合した。その後、上記電着塗装板の製造例２で示した塗装鋼板に乾燥膜厚１５μｍになる様にスプレー塗装し、１５０℃にて２５分間焼付乾燥して試験体を得た。この試験体に下記試験を行い、結果を表１に示した。 Snowtec O (colloidal silica, solid content 20%: manufactured by Nissan Chemical Co., Ltd.) 20 parts, STS-01 (titania sol, solid content 30%: manufactured by Ishihara Sangyo Co., Ltd.) 100 parts, isopropyl alcohol 35 parts, water 14 Part, methyltrimethoxysilane 76 parts, acrylic resin A-2 (Synthesis Example 2) 54 parts, and dibutyltin dilaurate 1 part were stirred and mixed with a disper at 25 ° C. for 2 hours. Thereafter, the coated steel plate shown in Production Example 2 of the electrodeposition coated plate was spray coated so as to have a dry film thickness of 15 μm, and baked and dried at 150 ° C. for 25 minutes to obtain a test specimen. The following tests were conducted on this test body, and the results are shown in Table 1.
スノーテックＯ（コロイダルシリカ、固形分２０％：日産化学（株）製）２０部、ＮＺＳ−３０Ａ（ジルコニアゾル、固形分３０％：日産化学（株）製）１００部、イソプロピルアルコール３５部、水１４部、メチルトリメトキシシラン７６部、アクリル樹脂Ａ−２（合成例２） ５４部、ジブチル錫ジラウレート１部を２５℃で２時間ディスパーで撹拌混合した。その後、上記電着塗装板の製造例２で示した塗装鋼板に乾燥膜厚１５μｍになる様にスプレー塗装し、１５０℃にて２５分間焼付乾燥して試験体を得た。この試験体に下記試験を行い、結果を表１に示した。 Snowtec O (colloidal silica, solid content 20%: manufactured by Nissan Chemical Co., Ltd.) 20 parts, NZS-30A (zirconia sol, solid content 30%: manufactured by Nissan Chemical Co., Ltd.) 100 parts, isopropyl alcohol 35 parts, water 14 parts, 76 parts of methyltrimethoxysilane, 54 parts of acrylic resin A-2 (Synthesis Example 2), and 1 part of dibutyltin dilaurate were stirred and mixed at 25 ° C. for 2 hours with a disper. Thereafter, the coated steel plate shown in Production Example 2 of the electrodeposition coated plate was spray coated so as to have a dry film thickness of 15 μm, and baked and dried at 150 ° C. for 25 minutes to obtain a test specimen. The following tests were conducted on this test body, and the results are shown in Table 1.
［比較例１］
上記電着塗装板の製造例１で示した塗装アルミニウム板を実施例と同様の試験に供した。
[Comparative Example 1]
The coated aluminum plate shown in Production Example 1 of the electrodeposition coated plate was subjected to the same test as in the example.
［比較例２］
イソプロピルアルコール２６部、水１４５部、メチルトリメトキシシラン１００部、ジメチルジメトキシシラン２６部、γ―グリシドキシプロピルトリメトキシシラン２６部、アクリル樹脂Ａ−１（合成例１） ２６部、ジブチル錫ジラウレート１部を２５℃で２時間ディスパーで撹拌混合した。その後、上記電着塗装板の製造例１で示した塗装アルミニウム板に乾燥膜厚１５μｍになる様にスプレー塗装し、１５０℃にて３０分間焼付乾燥して試験体を得た。この試験体に下記試験を行い、結果を表１に示した。
[Comparative Example 2]
26 parts isopropyl alcohol, 145 parts water, 100 parts methyltrimethoxysilane, 26 parts dimethyldimethoxysilane, 26 parts γ-glycidoxypropyltrimethoxysilane, 26 parts acrylic resin A-1 (Synthesis Example 1), dibutyltin dilaurate One part was stirred and mixed with a disper at 25 ° C. for 2 hours. Thereafter, the coated aluminum plate shown in Production Example 1 of the above electrodeposition coated plate was spray coated so as to have a dry film thickness of 15 μm, and baked and dried at 150 ° C. for 30 minutes to obtain a test specimen. The following tests were conducted on this test body, and the results are shown in Table 1.
［比較例３］
スノーテックＯ（コロイダルシリカ、固形分２０％：日産化学（株）製）２５部、ＡＳ５２０（アルミナゾル、固形分２０％：日産化学（株）製）１８０部、イソプロピルアルコール２５部、水９部、メチルトリメトキシシラン９２部、ジメチルジメトキシシラン１８部、ジブチル錫ジラウレート１部を２５℃で２時間ディスパーで撹拌混合した。その後、上記電着塗装板の製造例１で示した塗装アルミニウム板に乾燥膜厚１５μｍになる様にスプレー塗装し、１５０℃にて３０分間焼付乾燥して試験体を得た。この試験体に下記試験を行い、結果を表１に示した。
[Comparative Example 3]
Snowtec O (colloidal silica, solid content 20%: manufactured by Nissan Chemical Co., Ltd.) 25 parts, AS520 (alumina sol, solid content 20%: manufactured by Nissan Chemical Co., Ltd.) 180 parts, isopropyl alcohol 25 parts, water 9 parts, 92 parts of methyltrimethoxysilane, 18 parts of dimethyldimethoxysilane, and 1 part of dibutyltin dilaurate were stirred and mixed with a disper at 25 ° C. for 2 hours. Thereafter, the coated aluminum plate shown in Production Example 1 of the above electrodeposition coated plate was spray coated so as to have a dry film thickness of 15 μm, and baked and dried at 150 ° C. for 30 minutes to obtain a test specimen. The following tests were conducted on this test body, and the results are shown in Table 1.
［比較例４］
スノーテックＯ（コロイダルシリカ、固形分２０％：日産化学（株）製）１５部、ＡＳ５２０（アルミナゾル、固形分２０％：日産化学（株）製）８０部、イソプロピルアルコール７３部、水１７部、メチルトリメトキシシラン４０部、ジメチルジメトキシシラン１５部、アクリル樹脂Ａ−２（合成例２） １００部、ジブチル錫ジラウレート１部を２５℃で２時間ディスパーを用い撹拌混合した。その後、上記電着塗装板の製造例１で示した塗装アルミニウム板に乾燥膜厚１５μｍになる様にスプレー塗装し、１５０℃にて３０分間焼付乾燥して試験体を得た。この試験体に下記試験を行い、結果を表１に示した。
[Comparative Example 4]
Snowtec O (colloidal silica, solid content 20%: manufactured by Nissan Chemical Co., Ltd.) 15 parts, AS520 (alumina sol, solid content 20%: manufactured by Nissan Chemical Co., Ltd.) 80 parts, isopropyl alcohol 73 parts, water 17 parts, 40 parts of methyltrimethoxysilane, 15 parts of dimethyldimethoxysilane, 100 parts of acrylic resin A-2 (Synthesis Example 2) and 1 part of dibutyltin dilaurate were stirred and mixed at 25 ° C. for 2 hours using a disper. Thereafter, the coated aluminum plate shown in Production Example 1 of the above electrodeposition coated plate was spray coated so as to have a dry film thickness of 15 μm, and baked and dried at 150 ° C. for 30 minutes to obtain a test specimen. The following tests were conducted on this test body, and the results are shown in Table 1.
塗膜の試験方法
各塗膜の試験は以下の方法に従って実施し、またその評価方法も下記に記載する。
鉛筆硬度：ＪＩＳ Ｋ−５４００−８．４．２（鉛筆手かき法）に準拠。キズ判定。
碁盤目付着性：ＪＩＳ Ｋ−５４００−８．５．２（碁盤目テープ法）に準じた方法で判定。結果の数値は碁盤目数１００個中の、剥がれずに残存した碁盤目数を示した。
促進耐候性：スーパーＵＶテスター（岩崎電気社製メタルハライドランプ使用の促進耐候性試験機）を用い、２０００時間の試験を実施した後の光沢保持率を示した。この時の光沢値はグロスメーターで６０°鏡面反射率［％］を測定。
マジック汚染：赤及び黒色のマジックインキで線を引き、２５℃×７２時間乾燥後、石油ベンジンで拭き取って跡のつき方を評価。〇：跡が残らない △：やや跡が残る ×：くっきりと跡が残る
Coating Film Testing Method Each coating film test is performed according to the following method, and the evaluation method is also described below.
Pencil hardness: Conforms to JIS K-5400-8.4.2 (pencil scribing method). Scratch judgment.
Cross-cut adhesion: Determined by a method according to JIS K-5400-8.5.2 (cross cut tape method). The numerical value of the result showed the number of grids remaining without peeling out of 100 grids.
Accelerated weather resistance: Gloss retention after a 2000 hour test using a super UV tester (accelerated weather resistance tester using a metal halide lamp manufactured by Iwasaki Electric Co., Ltd.) was shown. The gloss value at this time is 60% specular reflectance [%] measured with a gloss meter.
Magic contamination: Draw a line with red and black magic inks, dry at 25 ° C for 72 hours, and then wipe off with petroleum benzine to evaluate how the marks are made. ◯: No trace left △: Some trace left ×: Clear trace left
耐候性と防錆性に優れた硬質の塗膜を金属製品表面に形成できる為、屋外で長期間使用しても塗装面が錆びたり傷ついたりせず、また光沢や色相等の外観変化も起こらない製品を提供できる。
A hard coating with excellent weather resistance and rust resistance can be formed on the surface of metal products, so that the painted surface will not rust or be damaged even when used outdoors for a long time, and appearance changes such as gloss and hue will not occur. Can provide no products.
Claims (5)
A metal product obtained by applying the coating film forming method according to claim 1, 2, 3 and 4 to form a coating film on the surface.
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