JP5693919B2 - Multi-layer coating formation method - Google Patents
Multi-layer coating formation method Download PDFInfo
- Publication number
- JP5693919B2 JP5693919B2 JP2010248767A JP2010248767A JP5693919B2 JP 5693919 B2 JP5693919 B2 JP 5693919B2 JP 2010248767 A JP2010248767 A JP 2010248767A JP 2010248767 A JP2010248767 A JP 2010248767A JP 5693919 B2 JP5693919 B2 JP 5693919B2
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- acid
- hydroxyl group
- resin
- paint
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000576 coating method Methods 0.000 title claims description 159
- 239000011248 coating agent Substances 0.000 title claims description 158
- 238000000034 method Methods 0.000 title claims description 31
- 230000015572 biosynthetic process Effects 0.000 title 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 47
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- 239000011347 resin Substances 0.000 claims description 34
- -1 isocyanate compound Chemical class 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 24
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- 239000012948 isocyanate Substances 0.000 claims description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
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- 239000001055 blue pigment Substances 0.000 description 1
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- 125000005372 silanol group Chemical group 0.000 description 1
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Description
本発明は、白色度が高く、耐水性及び耐候性に優れた塗膜を形成し得る複層塗膜形成方法に関する。 The present invention relates to a multilayer coating film forming method capable of forming a coating film having high whiteness and excellent water resistance and weather resistance.
自動車等の工業製品の外装色においては、高級感及び清潔感を併せ持つ白色系の塗色は、従来から継続して人気が高い塗色となっている。白色系の塗色は、着色顔料として白色酸化チタン顔料を含む塗料を基材に塗装することによって得られるが、着色顔料として白色酸化チタン顔料のみを含む塗料による塗色は、黄味や赤味が感じられることがあり、高級感が十分でないという問題点がある。 In the exterior colors of industrial products such as automobiles, white paint colors that have both a high-class feeling and a clean feeling have been continuously popular. A white paint color can be obtained by coating a base material with a paint containing a white titanium oxide pigment as a color pigment. However, a paint color containing only a white titanium oxide pigment as a color pigment can be applied to a yellowish or reddish color. May be felt, and there is a problem that a sense of quality is not sufficient.
これまで、赤味や黄味を感じさせない塗色を得るために、着色顔料として、黒色顔料や青色顔料を少量併用する手法がとられてきた。この手法によれば、黄味や赤味を低減することができるが、白色酸化チタン顔料以外の着色顔料を併用することによって、明度が低下するという問題点がある。 Until now, in order to obtain a coating color that does not feel reddish or yellowish, a technique of using a small amount of a black pigment or a blue pigment as a coloring pigment has been used. According to this method, yellowishness and redness can be reduced, but there is a problem that the brightness is lowered by using a coloring pigment other than the white titanium oxide pigment.
また、白色度を高くする手法として、塗料中に蛍光増白剤を配合する方法がある。特許文献１には、黄色味のない純白を呈する白色塗膜を形成し得る塗料組成物として、熱硬化性樹脂及び／又は熱可塑性樹脂を塗膜形成成分とし、チタン白顔料及び蛍光増白剤を所定量含有する塗料組成物が開示されている。しかし、蛍光増白剤として、具体的には、スチルベン系、ベンズイミダゾール系等の有機系材料を１種又は複数種使用することができるという記載があるのみである。これら有機系の蛍光増白剤は耐候性が不十分であることは広く知られており、白色度を高める効果を長期間継続させることができないという問題点がある。 Further, as a technique for increasing the whiteness, there is a method of blending a fluorescent whitening agent in the paint. In Patent Document 1, as a coating composition capable of forming a white coating film exhibiting a pure white without yellowishness, a thermosetting resin and / or a thermoplastic resin is used as a coating film forming component, and a titanium white pigment and a fluorescent whitening agent are used. A coating composition containing a predetermined amount of is disclosed. However, specifically, there is only a description that one or more organic materials such as stilbene and benzimidazole can be used as the fluorescent brightening agent. These organic fluorescent whitening agents are widely known to have insufficient weather resistance, and there is a problem that the effect of increasing whiteness cannot be continued for a long period of time.
本発明の目的は、白色度が高く、耐水性及び耐候性に優れた塗膜を形成し得る複層塗膜形成方法を提供することである。 An object of the present invention is to provide a method for forming a multilayer coating film capable of forming a coating film having high whiteness and excellent water resistance and weather resistance.
本発明によれば、上記の目的は、基材に、白色ベース塗膜、蛍光顔料含有ベース塗膜及びクリヤー塗膜を順次積層せしめることからなる複層塗膜の形成方法であって、白色ベース塗膜及び蛍光顔料含有ベース塗膜がビヒクル形成成分として水酸基含有樹脂及びイソシアネート化合物を含有するウレタン化反応により架橋硬化し得る樹脂組成物を含んでなり且つ蛍光顔料含有ベース塗膜が化学式（Ｂａ１−ｘ―ｙＣａｘＥｕｙ）ＭｇＡｌ１０Ｏ１７（式中、ｘは０≦ｘ≦０．３３であり、ｙは０．０７≦ｙ≦０．３５であり、かつ０．１≦ｘ＋ｙ≦０．４である）で示される蛍光顔料を含有することを特徴とする複層塗膜形成方法を提供することにより達成される。 According to the present invention, the above object is a method for forming a multi-layer coating film comprising sequentially laminating a white base coating film, a fluorescent pigment-containing base coating film and a clear coating film on a base material. The coating film and the fluorescent pigment-containing base coating film comprise a resin composition that can be crosslinked and cured by a urethanization reaction containing a hydroxyl group-containing resin and an isocyanate compound as vehicle-forming components, and the fluorescent pigment-containing base coating film has a chemical formula (Ba 1 −xy Ca x Eu y ) MgAl 10 O 17 (wherein x is 0 ≦ x ≦ 0.33, y is 0.07 ≦ y ≦ 0.35, and 0.1 ≦ x + y ≦ It is achieved by providing a method for forming a multilayer coating film characterized by containing a fluorescent pigment represented by formula (4).
本発明の方法によれば、白色度が高く、耐水性及び耐候性に優れた、高級感及び清潔感を併せ持つ白色系の塗色を有する複層塗膜を簡単に形成せしめることができる。 According to the method of the present invention, it is possible to easily form a multi-layer coating film having a white coating color having high whiteness, excellent water resistance and weather resistance, and having both a high-class feeling and a clean feeling.
基材：
本発明の方法に従い複層塗膜を形成せしめることができる基材としては、例えば、鉄、亜鉛、アルミニウム等の金属やこれらの金属を含む合金、これらの金属や合金によるメッキまたは蒸着が施された成型物；ガラス、さらにはポリプロピレン樹脂、ＡＢＳ樹脂、ポリフェニレンオキサイド樹脂等のプラスチック素材やプラスチック素材の発泡体、プラスチック素材にガラス繊維やカーボン繊維を混入せしめた繊維強化プラスチック等からなる成型物等を挙げることができる。これら基材には、その種類に応じて適宜、脱脂処理や表面処理を施すことができ、また、上記基材には、予め下塗り塗膜や中塗り塗膜を設けることもでき、これらのものが特に好ましい。
Base material :
Examples of a substrate on which a multilayer coating film can be formed according to the method of the present invention include metals such as iron, zinc and aluminum, alloys containing these metals, and plating or vapor deposition using these metals and alloys. Molded products made of glass, plastic materials such as polypropylene resin, ABS resin, polyphenylene oxide resin, foams of plastic materials, and fiber reinforced plastics in which glass fibers or carbon fibers are mixed into plastic materials, etc. Can be mentioned. These base materials can be appropriately subjected to a degreasing treatment or a surface treatment according to the kind thereof, and the base material can be provided with an undercoat film or an intermediate coat film in advance. Is particularly preferred.
上記下塗り塗膜は、素材表面を隠蔽したり、素材に防食性、防錆性等を付与することを目的として形成されるものであり、下塗り塗料を塗装し、乾燥、硬化することによって形成することができる。該下塗り塗料としては、特に限定されるものではなく、例えば、電着塗料、溶剤型プライマー等を挙げることができる。 The undercoat coating film is formed for the purpose of concealing the surface of the material or imparting anticorrosion properties, rust prevention properties, etc. to the material, and is formed by applying an undercoat paint, drying and curing. be able to. The undercoat paint is not particularly limited, and examples thereof include an electrodeposition paint and a solvent-type primer.
また、上記中塗り塗膜は、下塗り塗膜を隠蔽したり、付着性、耐チッピング性等を付与することを目的として形成されるものであり、乾燥硬化した下塗り塗膜又は未硬化の下塗り塗膜上に、中塗り塗料を塗装し、乾燥、硬化することによって形成することができる。中塗り塗料としては、特に限定されるものではなく、それ自体既知のものを使用することができ、例えば、熱硬化性樹脂組成物及び着色顔料を含有する有機溶剤系又は水系の中塗り塗料を好ましく使用することができる。 The intermediate coating film is formed for the purpose of concealing the undercoating film or imparting adhesion, chipping resistance, etc., and is a dry-cured undercoating film or an uncured undercoating film. It can be formed by applying an intermediate coating on the film, drying and curing. The intermediate coating is not particularly limited, and those known per se can be used. For example, an organic solvent-based or water-based intermediate coating containing a thermosetting resin composition and a color pigment is used. It can be preferably used.
また、基材に予め下塗り塗膜あるいは中塗り塗膜を設ける場合、これらの下塗り塗膜及び／又は中塗り塗膜を加熱し、架橋硬化後に本発明に従い複層塗膜を形成せしめることができ、あるいは、下塗り塗膜及び／又は中塗り塗膜が未硬化の状態で本発明の方法に従い複層塗膜を形成せしめることもできる。 In addition, when an undercoat film or an intermediate coat film is provided on the substrate in advance, the undercoat film and / or the intermediate coat film can be heated to form a multilayer coating film according to the present invention after crosslinking and curing. Alternatively, a multilayer coating film can be formed according to the method of the present invention in a state where the undercoat film and / or the intermediate coat film is uncured.
白色ベース塗膜：
本発明の複層塗膜形成方法においては、上記の如き基材上に、まず、白色ベース塗膜が形成せしめられる。
White base coating :
In the multilayer coating film forming method of the present invention, a white base coating film is first formed on the substrate as described above.
白色ベース塗膜は、最終的に形成される複層塗膜の白さの観点から、明度、例えば、Ｌ＊ａ＊ｂ＊表色系における明度Ｌ＊が８０以上、特に８５以上となるように、後述する白色ベース塗料における着色剤の量や組成を決定することが好ましい。Ｌ＊ａ＊ｂ＊表色系とは、１９７６年に国際照明委員会で規定され、ＪＩＳ Ｚ ８７２９にも採用されている表色系であり、Ｌ＊は明度を表わす数値である。本明細書において、白色ベース塗膜のＬ＊ａ＊ｂ＊表色系における明度Ｌ＊は、乾燥硬化した白色ベース塗膜をＭＡ−６８ＩＩ（商品名、多角度分光光度計、ｘ−ｒｉｔｅ社製）を使用して、塗膜に対して４５度の角度から照射した光を正反射光から４５度の角度で受光したときの分光反射率から計算して得られる数値である。 From the viewpoint of the whiteness of the finally formed multilayer coating film, the white base coating film has a lightness, for example, a lightness L * in the L * a * b * color system of 80 or more, particularly 85 or more. In addition, it is preferable to determine the amount and composition of the colorant in the white base paint described later. The L * a * b * color system is a color system defined by the International Lighting Commission in 1976 and adopted in JIS Z 8729, and L * is a numerical value representing lightness. In this specification, the lightness L * of the white base coating film in the L * a * b * color system is the MA-68II (trade name, multi-angle spectrophotometer, x-rite) This is a numerical value obtained by calculating from the spectral reflectance when the light irradiated from the angle of 45 degrees to the coating film is received at an angle of 45 degrees from the regular reflection light.
白色ベース塗膜は、白色ベース塗料を塗装し、乾燥、硬化することによって得ることができる。 The white base coating film can be obtained by applying a white base paint, drying and curing.
該白色ベース塗料としては、着色顔料として酸化チタン顔料を含むものが好適に使用される。酸化チタン顔料は、屈折率が高いことから白色顔料として広く使用されているものであり、結晶形によってルチル型とアナターゼ型があり、本発明においてはこれらのいずれを使用してもよいが、耐候性等の観点から、ルチル型を使用することが好ましい。また
、分散性や耐候性を向上させることを目的として、表面をシリカ、ジルコニウム、アルミニウム等の無機化合物で処理したものを使用することもできる。酸化チタン顔料は、白色ベース塗膜の隠蔽力の観点から、一般に１００〜４００ｎｍ、特に２００〜３００ｎｍの範囲内の一次粒子径を有するものが好適である。なお、本明細書において、一次粒子径は、粒度分布測定装置（島津製作所社製、粒度分布測定装置「ＳＡＬＤ−２１００」）にて体積粒度分布を測定した際の、累積体積５０％通過径（Ｄ５０）を用いた値である。
As the white base paint, those containing a titanium oxide pigment as a color pigment are preferably used. Titanium oxide pigments are widely used as white pigments because of their high refractive index, and there are rutile and anatase types depending on the crystal form, and any of these may be used in the present invention. From the viewpoint of properties and the like, it is preferable to use a rutile type. Moreover, what processed the surface with inorganic compounds, such as a silica, a zirconium, and aluminum, for the purpose of improving a dispersibility and a weather resistance can also be used. In view of the hiding power of the white base coating film, titanium oxide pigments having a primary particle diameter in the range of 100 to 400 nm, particularly 200 to 300 nm are suitable. In the present specification, the primary particle size is the particle size distribution measuring device (manufactured by Shimadzu Corporation, particle size distribution measuring device “SALD-2100”), when the volume particle size distribution is measured, D50).
白色ベース塗料における酸化チタン顔料の含有量は、隠蔽性や仕上がり性等の観点から、後述するビヒクル形成成分である樹脂組成物（固形分）１００質量部に対して、一般に３０〜２００質量部、特に５０〜１５０質量部、さらに特に８０〜１２０質量部の範囲内が好適である。 The content of the titanium oxide pigment in the white base paint is generally 30 to 200 parts by mass with respect to 100 parts by mass of a resin composition (solid content) which is a vehicle-forming component described later, from the viewpoints of concealment and finish. Particularly preferred is a range of 50 to 150 parts by mass, more particularly 80 to 120 parts by mass.
白色ベース塗料には、酸化チタン顔料の他に、複層塗膜の色相や明度を微調整することを目的として、他の着色顔料を配合することができる。該他の着色顔料としては、特に制限されるものではないが、具体的には、例えば、透明性酸化鉄顔料、チタンイエロー等の複合酸化物顔料等の無機顔料；アゾ系顔料、キナクリドン系顔料、ジケトピロロピロール系顔料、ペリレン系顔料、ペリノン系顔料、ベンズイミダゾロン系顔料、イソインドリン系顔料、イソインドリノン系顔料、金属キレートアゾ系顔料、フタロシアニン系顔料、インダンスロン系顔料、ジオキサジン系顔料、スレン系顔料、インジゴ系顔料等の有機顔料；カーボンブラック顔料等が挙げられ、これらはそれぞれ単独で又は２種もしくはそれ以上を組み合わせて使用することができる。 In addition to the titanium oxide pigment, other color pigments can be blended with the white base paint for the purpose of finely adjusting the hue and brightness of the multilayer coating film. The other colored pigments are not particularly limited, but specific examples include inorganic pigments such as transparent iron oxide pigments and composite oxide pigments such as titanium yellow; azo pigments and quinacridone pigments. , Diketopyrrolopyrrole pigment, perylene pigment, perinone pigment, benzimidazolone pigment, isoindoline pigment, isoindolinone pigment, metal chelate azo pigment, phthalocyanine pigment, indanthrone pigment, dioxazine Examples thereof include organic pigments such as pigments, selenium pigments, and indigo pigments; carbon black pigments and the like, and these can be used alone or in combination of two or more.
該着色顔料は、粉体として配合することができるが、後述する樹脂組成物の一部を使用して顔料分散体を調製し、これを残りの樹脂成分に他の成分と共に添加することにより塗料化することもできる。顔料分散体の調製にあたっては、必要に応じて、消泡剤、分散剤、表面調整剤等の慣用の塗料添加剤を使用することができる。 The colored pigment can be blended as a powder, but a paint dispersion is prepared by using a part of the resin composition described later, and this is added to the remaining resin components together with other components. It can also be converted. In preparing the pigment dispersion, conventional paint additives such as an antifoaming agent, a dispersing agent, and a surface conditioner can be used as necessary.
本発明において、白色ベース塗料に酸化チタン顔料以外の着色顔料を配合せしめる場合、その配合量は、複層塗膜の明度等の観点から、有機顔料やカーボンブラック顔料の場合には、樹脂組成物（固形分）１００質量部に対し通常０．１質量部以下とすることが好ましく、無機顔料の場合には、通常０．０１〜５質量部、特に０．０５〜３質量部の範囲内であることが好ましい。 In the present invention, when a color pigment other than the titanium oxide pigment is blended in the white base paint, the blending amount is a resin composition in the case of an organic pigment or a carbon black pigment from the viewpoint of the brightness of the multilayer coating film. (Solid content) It is preferably 0.1 parts by mass or less with respect to 100 parts by mass, and in the case of inorganic pigments, usually 0.01 to 5 parts by mass, particularly 0.05 to 3 parts by mass. Preferably there is.
白色ベース塗料は、ビヒクル形成成分として、水酸基含有樹脂及びイソシアネート基を有する化合物を含んでなるウレタン化反応により架橋硬化し得る樹脂組成物を含有することができる。 The white base coating material can contain a resin composition that can be crosslinked and cured by a urethanization reaction comprising a hydroxyl group-containing resin and a compound having an isocyanate group as a vehicle-forming component.
上記水酸基含有樹脂としては、例えば、水酸基含有アクリル樹脂、水酸基含有ポリエステル樹脂等が挙げられ、これらはそれぞれ単独で又は２種以上を組み合わせて使用することができる。これらの水酸基含有樹脂は、通常、有機溶剤及び／又は水等の溶媒に溶解または分散して使用される。 As said hydroxyl-containing resin, a hydroxyl-containing acrylic resin, a hydroxyl-containing polyester resin, etc. are mentioned, for example, These can be used individually or in combination of 2 or more types, respectively. These hydroxyl group-containing resins are usually used by being dissolved or dispersed in a solvent such as an organic solvent and / or water.
上記水酸基含有アクリル樹脂は、水酸基含有重合性単量体を必須成分とし、さらに必要に応じてカルボキシル基含有重合性単量体及びアクリル系単量体を含んでなる重合性単量体成分を常法により（共）重合することによって製造されるものを使用することができる。水酸基含有アクリル樹脂としては、一般に１０００〜１０００００、特に５０００〜８００００の範囲内の数平均分子量、一般に２０〜２００ｍｇＫＯＨ／ｇ、特に５０〜１５０ｍｇＫＯＨ／ｇの範囲内の水酸基価、及び一般に０〜１００ｍｇＫＯＨ／ｇ、特に０〜７０ｍｇＫＯＨ／ｇの範囲内の酸価を有するものが好適である。 The above hydroxyl group-containing acrylic resin has a hydroxyl group-containing polymerizable monomer as an essential component, and further contains a polymerizable monomer component containing a carboxyl group-containing polymerizable monomer and an acrylic monomer as required. Those produced by (co) polymerization by the method can be used. The hydroxyl group-containing acrylic resin is generally a number average molecular weight in the range of 1000 to 100000, particularly 5000 to 80000, generally 20 to 200 mg KOH / g, particularly 50 to 150 mg KOH / g, and generally 0 to 100 mg KOH / g. g, in particular those having an acid number in the range of 0 to 70 mg KOH / g are preferred.
上記水酸基含有重合性単量体は、１分子中に水酸基及び重合性不飽和結合をそれぞれ少なくとも１個有する化合物であり、例えば、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）アクリレート等の炭素数２〜２０のグリコールと（メタ）アクリル酸とのモノエステル化物等を挙げることができる。 The hydroxyl group-containing polymerizable monomer is a compound having at least one hydroxyl group and polymerizable unsaturated bond in one molecule. For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl ( Examples thereof include monoesterified products of a glycol having 2 to 20 carbon atoms such as (meth) acrylate and (meth) acrylic acid.
上記カルボキシル基含有重合性単量体は、１分子中にカルボキシル基及び重合性不飽和結合をそれぞれ少なくとも１個有する化合物であり、例えば、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、フマル酸、メサコン酸等及びこれらの酸の無水物やハーフエステル化物等を挙げることができる。 The carboxyl group-containing polymerizable monomer is a compound having at least one carboxyl group and polymerizable unsaturated bond in one molecule, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, Examples thereof include mesaconic acid and the like, and anhydrides and half-esterified products of these acids.
上記アクリル系単量体には、（メタ）アクリル酸と炭素数１〜２２の１価アルコールとのモノエステル化物が包含され、具体的には、例えば、メチル（メタ）アクリレート、エチル（メタ）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、オクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート等を挙げることができる。 The acrylic monomer includes a monoesterified product of (meth) acrylic acid and a monohydric alcohol having 1 to 22 carbon atoms. Specifically, for example, methyl (meth) acrylate, ethyl (meth) Examples include acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
なお、本明細書において、「（メタ）アクリレート」はアクリレート又はメタアクリレートを、そして「（メタ）アクリル酸」は、アクリル酸又はメタクリル酸を意味する。 In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylic acid” means acrylic acid or methacrylic acid.
水酸基含有アクリル樹脂の製造にあたり、上記の水酸基含有重合性単量体、カルボキシル基含有重合性単量体及びアクリル系単量体に加えて、その他の重合性単量体を併用することもできる。 In production of the hydroxyl group-containing acrylic resin, in addition to the hydroxyl group-containing polymerizable monomer, the carboxyl group-containing polymerizable monomer, and the acrylic monomer, other polymerizable monomers can be used in combination.
その他の重合性単量体としては、例えば、メトキシブチル（メタ）アクリレート、メトキシエチル（メタ）アクリレート等の（メタ）アクリル酸と炭素数２〜１８のアルコキシエステル；Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ−ｔ−ブチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート等のアミノアクリル系単量体；（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−ブチル（メタ）アクリルアミド、Ｎ−ジメチル（メタ）アクリルアミド等のアクリルアミド系単量体；グリシジル（メタ）アクリレート等のグリシジル基含有単量体；スチレン、α−メチルスチレン、ビニルトルエン、アクリロニトリル、酢酸ビニル、塩化ビニル等を挙げることができる。 Other polymerizable monomers include, for example, (meth) acrylic acid such as methoxybutyl (meth) acrylate and methoxyethyl (meth) acrylate and an alkoxy ester having 2 to 18 carbon atoms; N, N-dimethylaminoethyl ( Amino acrylic monomers such as (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate; Acrylamide monomers such as acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-butyl (meth) acrylamide, and N-dimethyl (meth) acrylamide; glycidyl groups such as glycidyl (meth) acrylate Containing monomer: Styrene, α-methylstyrene , Vinyl toluene, acrylonitrile, vinyl acetate, vinyl chloride and the like.
上記水酸基含有ポリエステル樹脂としては、通常、多塩基酸と多価アルコールとをエステル化反応させることによって製造されるものを使用することができる。 As said hydroxyl-containing polyester resin, what is normally manufactured by esterifying a polybasic acid and a polyhydric alcohol can be used.
上記多塩基酸は、１分子中に２個以上のカルボキシル基を有する化合物であり、例えば、フタル酸、イソフタル酸、テレフタル酸、コハク酸、アジピン酸、アゼライン酸、セバシン酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ヘット酸、マレイン酸、フマル酸、イタコン酸、トリメリット酸、ピロメリット酸及びこれらの無水物等を挙げることができ、また、上記多価アルコールは、１分子中に２個以上の水酸基を有する化合物であり、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、ブチレングリコール、ヘキサンジオール、ジエチレングリコール、ジプロピレングリコール、ネオペンチルグリコール、水素化ビスフェノールＡ、トリエチレングリコール、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール等を挙げることができる。 The polybasic acid is a compound having two or more carboxyl groups in one molecule. For example, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic acid, hexa Hydrophthalic acid, hetic acid, maleic acid, fumaric acid, itaconic acid, trimellitic acid, pyromellitic acid and their anhydrides can be mentioned. The polyhydric alcohol is two or more in one molecule. For example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, hydrogenated bisphenol A, triethylene glycol, glycerin, trimethylolethane, tri Ji trimethylolpropane, and pentaerythritol and the like.
また、ポリエステル樹脂として、あまに油脂肪酸、やし油脂肪酸、サフラワー油脂肪酸
、大豆油脂肪酸、ゴマ油脂肪酸、エノ油脂肪酸、麻油脂肪酸、トール油脂肪酸、脱水ヒマシ油脂肪酸等の（半）乾性油脂肪酸等で変性した脂肪酸変性ポリエステル樹脂を使用することもできる。これらの脂肪酸による変性量は、油長で一般に３０質量％以下であることが好ましい。また、安息香酸等の一塩基酸を一部反応させたものであってもよい。
In addition, as the polyester resin, (semi) drying oil such as oil fatty acid, coconut oil fatty acid, safflower oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, eno oil fatty acid, hemp oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, etc. A fatty acid-modified polyester resin modified with a fatty acid or the like can also be used. The amount of modification with these fatty acids is preferably 30% by mass or less in terms of oil length. Further, it may be a partially reacted monobasic acid such as benzoic acid.
ポリエステル樹脂としては、一般に１０００〜５００００、特に２０００〜２００００の範囲内の数平均分子量、一般に２０〜２００ｍｇＫＯＨ／ｇ、特に５０〜１５０ｍｇＫＯＨ／ｇの範囲内の水酸基価、及び一般に０〜１００ｍｇＫＯＨ／ｇ、特に０〜７０ｍｇＫＯＨ／ｇの範囲内の酸価を有するものが好適である。 Polyester resins generally have a number average molecular weight in the range of 1000 to 50000, especially 2000 to 20000, generally 20 to 200 mg KOH / g, in particular 50 to 150 mg KOH / g, and generally 0 to 100 mg KOH / g, Particularly preferred are those having an acid value within the range of 0 to 70 mg KOH / g.
上記イソシアネート化合物には、１分子中に少なくとも２個の遊離のイソシアネート基を有するポリイソシアネート化合物が包含され、該ポリイソシアネート化合物としては、例えば、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート、リジンジイソシアネート等の脂肪族ポリイソシアネート類、これらのポリイソシアネートのビューレットタイプ付加物及びイソシアヌレート環付加物；イソホロンジイソシアネート、４，４’−メチレンビス（シクロヘキシルイソシアネート）、メチルシクロヘキサン−２，４−（もしくは−２，６−）ジイソシアネート、１，３−（もしくは１，４−）ジ（イソシアナトメチル）シクロヘキサン、１，４−シクロヘキサンジイソシアネ−ト、１，３−シクロペンタンジイソシアネ−ト、１，２−シクロヘキサンジイソシアネ−ト等の脂環族ジイソシアネート類、これらのポリイソシアネートのビューレットタイプ付加物及びイソシアヌレ−ト環付加物；キシリレンジイソシアネ−ト、テトラメチルキシリレンジイソシアネ−ト、トリレンジイソシアネ−ト、４，４’−ジフェニルメタンジイソシアネート（ＭＤＩ）、１，５−ナフタレンジイソシアネート、１，４−ナフタレンジイソシアネート、４，４’−トルイジンジイソシアネート、４，４’−ジフェニルエーテルジイソシアネート、（ｍ−もしくはｐ−）フェニレンジイソシアネート、４，４’−ビフェニレンジイソシアネート、３，３’−ジメチル−４，４’−ビフェニレンジイソシアネート、ビス（４−イソシアナトフェニル）スルホン、イソプロピリデンビス（４−フェニルイソシアネート）等の芳香族ジイソシアネート化合物、これらのポリイソシアネートのビューレットタイプ付加物及びイソシアヌレート環付加物；水添ＭＤＩ及び水添ＭＤＩの誘導体；トリフェニルメタン−４，４’，４’’−トリイソシアネート、１，３，５−トリイソシアナトベンゼン、２，４，６−トリイソシアナトトルエン、４，４’−ジメチルジフェニルメタン−２，２’，５，５’−テトライソシアネート等の１分子中に少なくとも３個のイソシアネート基を有するポリイソシアネート類、これらのポリイソシアネートのビューレットタイプ付加物及びイソシアヌレート環付加物；エチレングリコール、プロピレングリコール、１，４−ブチレングリコール、ジメチロールプロピオン酸、ポリアルキレングリコール、トリメチロールプロパン 、ヘキサントリオール等のポリオールの水酸基にイソシアネート基が過剰量となる比率でポリイソシアネート化合物を反応させてなるウレタン化付加物、これらのポリイソシアネートのビューレットタイプ付加物及びソシアヌレート環付加物等を挙げることができる。 The isocyanate compound includes a polyisocyanate compound having at least two free isocyanate groups in one molecule. Examples of the polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and lysine. Aliphatic polyisocyanates such as diisocyanates, burette type adducts and isocyanurate cycloadducts of these polyisocyanates; isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or − 2,6-) diisocyanate, 1,3- (or 1,4-) di (isocyanatomethyl) cyclohexane, 1,4-cyclohexane diisocyanate, Alicyclic diisocyanates such as 1,3-cyclopentane diisocyanate, 1,2-cyclohexane diisocyanate, burette type adducts and isocyanurate ring adducts of these polyisocyanates; xylylene diisocyanate Net, tetramethylxylylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 4,4'- Toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, (m- or p-) phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, bis (4-isocyanatof Nyl) sulfone, aromatic diisocyanate compounds such as isopropylidenebis (4-phenylisocyanate), burette type adducts and isocyanurate cycloadducts of these polyisocyanates; hydrogenated MDI and hydrogenated MDI derivatives; triphenylmethane -4,4 ', 4 "-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 4,4'-dimethyldiphenylmethane-2,2', 5 Polyisocyanates having at least three isocyanate groups in one molecule such as 5′-tetraisocyanate, burette-type adducts and isocyanurate cycloadducts of these polyisocyanates; ethylene glycol, propylene glycol, 1,4- Butylene glycol, dimethylol Urethane adducts obtained by reacting a polyisocyanate compound in an excess ratio of isocyanate groups to the hydroxyl groups of polyols such as propionic acid, polyalkylene glycol, trimethylolpropane and hexanetriol, and burette type addition of these polyisocyanates Products and socyanurate cycloadducts.
本発明の白色ベース塗料における上記水酸基含有樹脂及びイソシアネート化合物の配合割合は、水酸基含有樹脂中の水酸基１当量に対し、イソシアネート化合物中のイソシアネート基が一般に０．５〜２当量、特に０．８〜１．２当量の範囲内となるようにすることが好ましい。イソシアネート化合物中のイソシアネート基の割合が０．５当量未満であると、形成される塗膜の架橋密度が低く塗膜物性が不十分となり、反対に２当量を越えると、形成される塗膜の性能は良好であるが、塗膜の乾燥性が低下し、実用性に問題がある。 The mixing ratio of the hydroxyl group-containing resin and the isocyanate compound in the white base paint of the present invention is generally 0.5 to 2 equivalents, particularly 0.8 to 1,2 in terms of the isocyanate group in the isocyanate compound with respect to 1 equivalent of the hydroxyl group in the hydroxyl group-containing resin. It is preferable to be within the range of 1.2 equivalents. When the ratio of isocyanate groups in the isocyanate compound is less than 0.5 equivalent, the cross-linking density of the formed coating film is low and the physical properties of the coating film are insufficient. Although the performance is good, the drying property of the coating film is lowered and there is a problem in practicality.
さらに、白色ベース塗料には、必要に応じて、水あるいは有機溶剤等の溶媒、顔料分散剤、沈降防止剤、硬化触媒、消泡剤、酸化防止剤、紫外線吸収剤等の各種塗料添加剤、体質顔料等を適宜配合することができる。上記体質顔料は、前記着色顔料と同様に、粉体と
して配合することができるが、前記樹脂成分の一部を使用して顔料分散体を調製し、これを残りの樹脂成分に他の成分と共に添加することにより塗料化を行なうこともできる。
Furthermore, for white base paints, various paint additives such as solvents such as water or organic solvents, pigment dispersants, antisettling agents, curing catalysts, antifoaming agents, antioxidants, UV absorbers, etc. An extender pigment etc. can be mix | blended suitably. The extender pigment can be blended as a powder in the same manner as the colored pigment, but a pigment dispersion is prepared using a part of the resin component, and this is combined with other components in the remaining resin component. It can also be made into a paint by adding.
本発明の白色ベース塗料は、以上に述べた酸化チタン顔料やその他の着色顔料、ビヒクル形成成分である樹脂組成物や水又は有機溶剤等の溶媒、顔料分散剤、沈降防止剤、硬化触媒、消泡剤、酸化防止剤、紫外線吸収剤等の各種添加剤、体質顔料等を同一容器に梱包せしめた１液型塗料であってもよいが、イソシアネート化合物及び必要に応じて配合される水や有機溶媒等を別の容器に梱包し、塗装前に混合する２液型塗料であってもよい。 The white base paint of the present invention comprises the above-described titanium oxide pigment and other colored pigments, a resin composition as a vehicle forming component, a solvent such as water or an organic solvent, a pigment dispersant, an antisettling agent, a curing catalyst, It may be a one-component paint in which various additives such as foaming agents, antioxidants, UV absorbers, extender pigments, etc. are packed in the same container, but the isocyanate compound and water or organic compounded as necessary It may be a two-component paint in which a solvent or the like is packed in another container and mixed before painting.
白色ベース塗料は、水や有機溶媒等を加えて、塗装に適正な粘度に調整した後に、回転霧化塗装、エアスプレー、エアレススプレー等の公知の方法で塗装することができ、その膜厚は、基材の隠蔽性、塗膜の平滑性等の観点から、硬化塗膜に基づいて通常１０〜１５０μｍ、好ましくは２０〜１００μｍの範囲内とすることができる。本発明の白色ベース塗料による塗膜は、用いるイソシアネート化合物の種類等に応じて、通常、常温〜約１５０℃の範囲内の温度で架橋硬化させることができ、それによって白色ベース塗膜を形成せしめることができる。 The white base paint can be applied by a known method such as rotary atomization, air spray, airless spray, etc. after adjusting the viscosity to an appropriate level by adding water or an organic solvent. From the viewpoint of the concealing property of the base material, the smoothness of the coating film, etc., it can be usually in the range of 10 to 150 μm, preferably 20 to 100 μm, based on the cured coating film. The coating film with the white base paint of the present invention can be crosslinked and cured at a temperature in the range of room temperature to about 150 ° C., depending on the type of isocyanate compound to be used, thereby forming a white base coating film. be able to.
蛍光顔料含有ベース塗膜：
本発明の複層塗膜形成方法においては、前述の如くして形成される白色ベース塗膜上に、蛍光顔料含有ベース塗膜が形成される。蛍光顔料含有ベース塗膜は、蛍光顔料を含有するベース塗料を塗装し、硬化せしめることによって形成せしめることができる。
Fluorescent pigment-containing base coating :
In the multilayer coating film forming method of the present invention, the fluorescent pigment-containing base coating film is formed on the white base coating film formed as described above. The fluorescent pigment-containing base coating film can be formed by applying and curing a base paint containing a fluorescent pigment.
蛍光顔料は、紫外線（波長３８０ｎｍ付近）を吸収し、それを青色の可視光（波長４２０ｎｍ付近；蛍光という）に変換して放出する蛍光増白効果を奏する顔料である。この効果により、得られる塗膜は色相が青みを帯びて白色度が高くなり、赤味や黄味を感じさせない塗膜が得られる。 The fluorescent pigment is a pigment that exhibits a fluorescent whitening effect that absorbs ultraviolet rays (wavelength around 380 nm), converts it into blue visible light (wavelength around 420 nm; referred to as fluorescence) and emits it. Due to this effect, the obtained coating film has a bluish hue and high whiteness, and a coating film that does not feel reddish or yellowish is obtained.
蛍光顔料としては、化学的に安定で耐水性や耐候性に優れる無機系の蛍光体であるアルミン酸塩バリウムマグネシウム蛍光体が好適であり、具体的には、特開２００６−１４３８９４号公報に開示されている化学式（Ｂａ１−ｘ−ｙＣａｘＥｕｙ）ＭｇＡｌ１０Ｏ１７（式中、ｘは０≦ｘ≦０．３３、好ましくは０．０１≦ｘ≦０．１５、ｙは０．０７≦ｙ≦０．３５、好ましくは０．１０≦ｙ≦０．３０且つ０．１≦ｘ＋ｙ≦０．４、好ましくは０．１≦ｘ＋ｙ≦０．３）で示される蛍光増白体を使用することができる。 As the fluorescent pigment, a barium magnesium aluminate phosphor, which is an inorganic phosphor that is chemically stable and excellent in water resistance and weather resistance, is preferable, and specifically disclosed in JP-A-2006-143894. Chemical formula (Ba 1-xy Ca x Eu y ) MgAl 10 O 17 (wherein x is 0 ≦ x ≦ 0.33, preferably 0.01 ≦ x ≦ 0.15, and y is 0.8. 07 ≦ y ≦ 0.35, preferably 0.10 ≦ y ≦ 0.30 and 0.1 ≦ x + y ≦ 0.4, preferably 0.1 ≦ x + y ≦ 0.3). Can be used.
上記蛍光顔料としては、一次平均粒子径が、Ｄ５０で一般に２μｍ〜４．５μｍ、特に３μｍ〜４μｍの範囲内にあり、且つ９０％メジアン径で一般に１０μｍ以下、特に５μｍ〜７μｍの範囲内にあるものが好ましい。また、分散性や耐候性を向上させることを目的として、表面をシリカ、ジルコニウム、アルミニウム等の無機化合物で処理したものを使用することもできる。 The above-mentioned fluorescent pigment has a primary average particle diameter of generally 2 μm to 4.5 μm, particularly 3 μm to 4 μm, and a 90% median diameter of generally 10 μm or less, particularly 5 μm to 7 μm, as D50. Those are preferred. Moreover, what processed the surface with inorganic compounds, such as a silica, a zirconium, and aluminum, for the purpose of improving a dispersibility and a weather resistance can also be used.
蛍光顔料含有ベース塗料における蛍光顔料の含有量は、塗膜の仕上がり性や複層塗膜において黄味を消す効果がある等の観点から、後述する樹脂組成物（固形分）１００質量部に対して一般に１０〜２００質量部、特に２０〜１００質量部、さらに特に３０〜８０質量部の範囲内であることが好ましい。 The content of the fluorescent pigment in the fluorescent pigment-containing base paint is based on 100 parts by mass of the resin composition (solid content) to be described later from the viewpoint of the finish of the coating film and the effect of eliminating yellowing in the multilayer coating film. In general, it is preferable to be within the range of 10 to 200 parts by mass, particularly 20 to 100 parts by mass, and more particularly 30 to 80 parts by mass.
蛍光顔料含有ベース塗料には、ビヒクル形成成分として、上記白色ベース塗料と同様に、水酸基含有樹脂及びイソシアネート基を有する化合物を含んでなるウレタン化反応により架橋硬化し得る樹脂組成物を含有することができる。具体的には、上記白色ベース塗料の説明において樹脂成分として記載したものを同様に用いることができる。 As in the case of the white base paint, the fluorescent pigment-containing base paint may contain a resin composition that can be crosslinked and cured by a urethanization reaction comprising a hydroxyl group-containing resin and a compound having an isocyanate group. it can. Specifically, those described as the resin component in the description of the white base paint can be used similarly.
さらに、蛍光顔料含有ベース塗料には、必要に応じて、水あるいは有機溶剤等の溶媒、顔料分散剤、沈降防止剤、硬化触媒、消泡剤、酸化防止剤、紫外線吸収剤等の各種塗料添加剤、体質顔料等を適宜配合することができる。 Furthermore, various paints such as solvents such as water or organic solvents, pigment dispersants, anti-settling agents, curing catalysts, antifoaming agents, antioxidants, and UV absorbers are added to the fluorescent pigment-containing base paint as necessary. An agent, extender, etc. can be appropriately blended.
蛍光顔料含有ベース塗料は、白色ベース塗料と同様に、１液型であってもよいし、２液型であってもよい。 As with the white base paint, the fluorescent pigment-containing base paint may be a one-pack type or a two-pack type.
蛍光顔料含有ベース塗料は、水や有機溶媒等を加えて、塗装に適正な粘度に調整した後に、回転霧化塗装、エアスプレー、エアレススプレー等公知の方法で塗装することができ、その膜厚は、塗膜の平滑性等の観点から、硬化塗膜に基づいて通常５〜１００μｍ、好ましくは１５〜５０μｍの範囲内であることができる。蛍光顔料含有ベース塗膜は、用いるイソシアネート化合物の種類等に応じて、通常、常温〜約１５０℃の範囲内の温度で架橋硬化させることができ、それによって蛍光顔料含有ベース塗膜を形成せしめることができる。 The fluorescent pigment-containing base paint can be applied by a known method such as rotary atomization painting, air spraying, airless spraying, etc. after adjusting the viscosity to an appropriate level by adding water or an organic solvent. From the viewpoint of the smoothness of the coating film, etc., it can usually be in the range of 5 to 100 μm, preferably 15 to 50 μm, based on the cured coating film. Depending on the type of isocyanate compound used, the fluorescent pigment-containing base coating can usually be crosslinked and cured at a temperature in the range of room temperature to about 150 ° C., thereby forming the fluorescent pigment-containing base coating. Can do.
クリヤー塗膜：
本発明の複層塗膜形成方法においては、以上に述べた硬化又は未硬化の蛍光顔料含有ベース塗膜上に、クリヤー塗料を塗装して、クリヤー塗膜が形成せしめられる。
Clear coating :
In the multilayer coating film forming method of the present invention, a clear coating film is formed by applying a clear coating onto the above-described cured or uncured fluorescent pigment-containing base coating film.
クリヤー塗膜は、クリヤー塗料を１回塗装して乾燥、硬化してなる１層の塗膜であることができ、あるいはクリヤー塗料の塗装から乾燥、硬化の工程を複数回繰り返すことによって形成される２層以上の塗膜であってもよい。クリヤー塗膜を２層以上の塗膜として形成せしめることによって、複層塗膜の仕上がり性や鮮映性を向上させることができる。 The clear coating can be a single-layer coating formed by applying the clear coating once and then drying and curing, or can be formed by repeating the steps of coating, drying and curing a plurality of times. Two or more coating films may be used. By forming the clear coating film as a coating film of two or more layers, it is possible to improve the finish property and sharpness of the multilayer coating film.
クリヤー塗膜を２層以上の塗膜とする場合、１層目のクリヤー塗膜と、２層目以降のクリヤー塗膜とは、同一の材質のものであってもよく、あるいは異なる材質であってもよい。 When the clear coating is composed of two or more layers, the first clear coating and the second and subsequent clear coatings may be the same material or different materials. May be.
本発明の複層塗膜形成方法において使用されるクリヤー塗料は、樹脂成分および溶剤を含有し、さらにその他の塗料用添加剤等を適宜配合してなる無色もしくは有色の透明塗膜を形成する液状塗料であることができ、該クリヤー塗料としては、それ自体既知のものを制限なく使用することができ、例えば、基体樹脂及び架橋剤を含有する液状もしくは粉体状の塗料組成物が挙げられる。該基体樹脂の例としては、例えば、水酸基、カルボキシル基、シラノール基、エポキシ基等の架橋性官能基を含有する、アクリル樹脂、ポリエステル樹脂、アルキド樹脂、フッ素樹脂、ウレタン樹脂、シリコン含有樹脂等が挙げられる。上記架橋剤としては、上記基体樹脂の官能基と反応しうるメラミン樹脂、尿素樹脂、ポリイソシアネート化合物、ブロックポリイソシアネート化合物、エポキシ化合物又は樹脂、カルボキシル基含有化合物又は樹脂、酸無水物、アルコキシシラン基含有化合物又は樹脂等が挙げられる。また、必要に応じて、水や有機溶剤等の溶媒、硬化触媒、消泡剤、レオロジーコントロール剤、酸化防止剤、表面調整剤等の塗料添加剤を適宜配合することができる。 The clear paint used in the method for forming a multilayer coating film of the present invention contains a resin component and a solvent, and further forms a colorless or colored transparent coating film by appropriately blending other paint additives and the like. As the clear paint, those known per se can be used without limitation, and examples thereof include a liquid or powder paint composition containing a base resin and a crosslinking agent. Examples of the base resin include, for example, an acrylic resin, a polyester resin, an alkyd resin, a fluororesin, a urethane resin, and a silicon-containing resin containing a crosslinkable functional group such as a hydroxyl group, a carboxyl group, a silanol group, and an epoxy group. Can be mentioned. Examples of the crosslinking agent include melamine resin, urea resin, polyisocyanate compound, block polyisocyanate compound, epoxy compound or resin, carboxyl group-containing compound or resin, acid anhydride, alkoxysilane group that can react with the functional group of the base resin. Examples thereof include a containing compound or a resin. In addition, if necessary, paint additives such as a solvent such as water and an organic solvent, a curing catalyst, an antifoaming agent, a rheology control agent, an antioxidant, and a surface conditioner can be appropriately blended.
上記クリヤー塗料には、透明性を損なわない範囲内において、着色顔料を適宜配合することができる。着色顔料としては、インク用、塗料用としてそれ自体既知の顔料をそれぞれ単独で又は２種以上組み合わせて配合することができる。その添加量は、塗膜の透明性を実質的に害さない範囲において適宜決定することができ、具体的には、クリヤー塗料中の基体樹脂と架橋剤の合計固形分１００質量部に対して、通常３０質量部以下、好ましくは０.０１〜５質量部の範囲内とすることができる。 The clear paint can be appropriately blended with a color pigment within a range not impairing transparency. As the color pigment, pigments known per se for ink and paint can be used alone or in combination of two or more. The addition amount can be appropriately determined within a range that does not substantially impair the transparency of the coating film. Specifically, with respect to 100 parts by mass of the total solid content of the base resin and the crosslinking agent in the clear coating, Usually, it is 30 mass parts or less, Preferably it can be in the range of 0.01-5 mass parts.
本発明の複層塗膜形成方法において、クリヤー塗膜を２層以上の複層塗膜とする場合に
は、１層目のクリヤー塗膜を形成せしめるためのクリヤー塗料として、ビヒクル形成成分が、上記白色ベース塗料においてビヒクル形成成分として用いられる樹脂組成物と同様に、水酸基含有樹脂及びイソシアネート基を有する化合物を含んでなるウレタン化反応により架橋硬化し得る樹脂組成物を含有するものを使用することができる。具体的には、白色ベース塗料におけるビヒクル形成成分として前記で説明した樹脂組成物を同様に用いることができる。
In the method for forming a multilayer coating film of the present invention, when the clear coating film is a multilayer coating film having two or more layers, as a clear coating for forming the first clear coating film, a vehicle forming component, Similar to the resin composition used as the vehicle-forming component in the white base paint, a resin composition containing a resin composition that can be crosslinked and cured by a urethanization reaction comprising a hydroxyl group-containing resin and a compound having an isocyanate group is used. Can do. Specifically, the resin composition described above can be similarly used as a vehicle forming component in the white base paint.
上記クリヤー塗料は、水や有機溶媒等を加えて、塗装に適した粘度に調整した後、回転霧化塗装、エアスプレー、エアレススプレー等の公知の方法で塗装することができ、その膜厚は、硬化塗膜に基づいて通常５〜４０μｍ、特に２０〜３５μｍの範囲内とするのが好ましい。クリヤー塗料の塗膜それ自体は常温〜約１５０℃の範囲内の温度で架橋硬化させることができる。 The above clear paint can be applied by a known method such as rotary atomization coating, air spray, airless spray, etc. after adjusting the viscosity to be suitable for coating by adding water or an organic solvent. Based on the cured coating film, it is usually preferably in the range of 5 to 40 μm, particularly 20 to 35 μm. The clear coating film itself can be crosslinked and cured at a temperature in the range from room temperature to about 150 ° C.
クリヤー塗膜を２層以上の塗膜として形成せしめる場合、１層目のクリヤー塗膜を乾燥、硬化せしめた塗膜上に２層目以降のクリヤー塗膜を形成せしめることができるが、１層目のクリヤー塗料を塗装後、その未硬化の塗膜上に２層目のクリヤー塗膜を形成せしめてもよい。 When a clear coating film is formed as two or more coating films, the second and subsequent clear coating films can be formed on the coating film obtained by drying and curing the first clear coating film. After applying the clear paint for the eyes, a second clear paint film may be formed on the uncured paint film.
本発明の複層塗膜形成方法において、白色ベース塗膜、蛍光顔料含有ベース塗膜及びクリヤー塗膜の各塗膜は、各々加熱して乾燥硬化後に、順次塗り重ねて複層塗膜を形成する、３Ｃ３Ｂ方式により形成することができ、あるいは少なくとも一部の塗膜が未硬化の状態で塗り重ね、形成される複層塗膜を加熱して同時に硬化せしめる３Ｃ２Ｂ方式又は３Ｃ１Ｂ方式により形成せしめることもできる。 In the multilayer coating film forming method of the present invention, each of the white base coating film, the fluorescent pigment-containing base coating film, and the clear coating film is heated, dried and cured, and then sequentially coated to form a multilayer coating film. Can be formed by 3C3B method, or can be formed by 3C2B method or 3C1B method in which at least a part of the coating film is applied in an uncured state and the formed multilayer coating film is heated and cured at the same time. You can also.
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。ただし、本発明はこれらの実施例のみに限定されるものではない。なお、「部」及び「％」はいずれも質量基準によるものである。また、水酸基含有アクリル樹脂の数平均分子量は、ゲル浸透クロマトグラフィー（ＧＰＣ）によって標準ポリスチレンの検量線を用いて測定したものである。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to only these examples. “Part” and “%” are based on mass. The number average molecular weight of the hydroxyl group-containing acrylic resin is measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.
実施例１〜７、比較例１〜５
製造例１：水酸基含有アクリル樹脂（１）の製造
温度計、サーモスタット、撹拌器、還流冷却器及び滴下装置を備えた反応容器にキシレン５０部及び酢酸ブチル２２部を仕込み、撹拌混合し、１２０℃に昇温した。次いで同温度に保持した反応容器内に、下記のモノマー／重合開始剤の混合物（１）を３時間かけて滴下し、滴下終了後１時間熟成を行なった。その後、キシレン１０部及び２，２’−アゾビス（２−メチルプロピオニトリル）０．６部からなる混合物を同温度に保持しつつ１時間３０分かけて滴下し、さらに２時間熟成して、水酸基価８２ｍｇＫＯＨ／ｇ、数平均分子量２０，０００、樹脂固形分５５％の水酸基含有アクリル樹脂（１）を得た。
モノマー／重合開始剤の混合物（１）：
メチルメタクリレ−ト２７部、ｎ−ブチルアクリレート２３部、ヒドロキシエチルメタクリレート１９部、スチレン３０部、アクリル酸１部及び２，２'−アゾビス（２−メチルプロピオニトリル）２.５部からなる混合物。
Examples 1-7, Comparative Examples 1-5
Production Example 1: Production of hydroxyl group-containing acrylic resin (1) A reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping device was charged with 50 parts of xylene and 22 parts of butyl acetate, stirred and mixed at 120 ° C. The temperature was raised to. Next, the following monomer / polymerization initiator mixture (1) was added dropwise to the reaction vessel maintained at the same temperature over 3 hours, and aging was performed for 1 hour after the completion of the addition. Thereafter, a mixture of 10 parts of xylene and 0.6 part of 2,2′-azobis (2-methylpropionitrile) was added dropwise over 1 hour and 30 minutes while maintaining the same temperature, and further aged for 2 hours, A hydroxyl group-containing acrylic resin (1) having a hydroxyl value of 82 mgKOH / g, a number average molecular weight of 20,000, and a resin solid content of 55% was obtained.
Monomer / polymerization initiator mixture (1):
Consists of 27 parts of methyl methacrylate, 23 parts of n-butyl acrylate, 19 parts of hydroxyethyl methacrylate, 30 parts of styrene, 1 part of acrylic acid and 2.5 parts of 2,2′-azobis (2-methylpropionitrile). blend.
製造例２：水酸基含有アクリル樹脂（２）の製造
温度計、サーモスタット、撹拌器、還流冷却器及び滴下装置を備えた反応容器にキシレン５０部及び酢酸ブチル２２部を仕込み、撹拌混合し、１２０℃に昇温した。次いで同温度に保持した反応容器内に、下記のモノマー／重合開始剤の混合物（２）を３時間かけて滴下し、滴下終了後１時間熟成を行なった。その後、キシレン１０部及び２，２’−アゾ
ビス（２−メチルプロピオニトリル）０．６部からなる混合物を同温度に保持しつつ１時間３０分かけて滴下し、さらに２時間熟成して、水酸基価８２ｍｇＫＯＨ／ｇ、数平均分子量２０，０００、樹脂固形分５５％の水酸基含有アクリル樹脂（２）を得た。
モノマー／重合開始剤の混合物（２）：
スチレン３５部、メチルメタクリレ−ト５部、ｉ−ブチルメタクリレート３２部、２−エチルヘキシルアクリレート１０部、ヒドロキシエチルアクリレート１７部、アクリル酸１部及び２，２'−アゾビス（２−メチルプロピオニトリル）２.５部からなる混合物。
Production Example 2: Production of hydroxyl group-containing acrylic resin (2) 50 parts of xylene and 22 parts of butyl acetate were charged in a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping device, and stirred and mixed at 120 ° C. The temperature was raised to. Next, the following monomer / polymerization initiator mixture (2) was added dropwise to the reaction vessel maintained at the same temperature over 3 hours, and aging was performed for 1 hour after the completion of the addition. Thereafter, a mixture of 10 parts of xylene and 0.6 part of 2,2′-azobis (2-methylpropionitrile) was added dropwise over 1 hour and 30 minutes while maintaining the same temperature, and further aged for 2 hours, A hydroxyl group-containing acrylic resin (2) having a hydroxyl value of 82 mgKOH / g, a number average molecular weight of 20,000, and a resin solid content of 55% was obtained.
Monomer / polymerization initiator mixture (2):
35 parts of styrene, 5 parts of methyl methacrylate, 32 parts of i-butyl methacrylate, 10 parts of 2-ethylhexyl acrylate, 17 parts of hydroxyethyl acrylate, 1 part of acrylic acid and 2,2′-azobis (2-methylpropionitrile ) A mixture consisting of 2.5 parts.
ベース塗料１〜４、１０の調製
製造例１で得られた水酸基含有アクリル樹脂（１）１００部（固形分）あたり、着色顔料及び蛍光顔料を下記表１に示す比率で配合して攪拌混合し、スミジュールＮ３３００（商品名、ヘキサメチレンジイソシアネート、住化バイエルウレタン社製）２８部を加え、塗装に適正な粘度に希釈して、固形分約５０％の有機溶剤型塗料を調製し、実施例及び比較例に使用するベース塗料１〜４及び１０を調製した（水酸基含有アクリル樹脂中の水酸基１当量に対するイソシアネート化合物中のイソシアネート基の割合は１当量である）。
Preparation of base paints 1 to 4 and 10 Per 100 parts (solid content) of the hydroxyl group-containing acrylic resin (1) obtained in Production Example 1, the color pigment and the fluorescent pigment were blended in the ratios shown in Table 1 below and mixed by stirring. , Sumijoule N3300 (trade name, hexamethylene diisocyanate, manufactured by Sumika Bayer Urethane Co., Ltd.), 28 parts, diluted to an appropriate viscosity for coating, an organic solvent-type paint having a solid content of about 50% was prepared. And base paints 1 to 4 and 10 used in Comparative Examples were prepared (the ratio of the isocyanate group in the isocyanate compound to 1 equivalent of the hydroxyl group in the hydroxyl group-containing acrylic resin was 1 equivalent).
ベース塗料５、６の調製
製造例１で得られた水酸基含有アクリル樹脂（１）１３６部及びユーバン２８−６０（商品名、ブチルエーテル化メラミン樹脂、三井化学社製）４２部からなる樹脂成分１００部（固形分）あたり、着色顔料及び蛍光顔料を下記表１に示す比率で配合して攪拌混合し、塗装に適正な粘度に希釈して、固形分約５０％の有機溶剤型塗料を調製し、比較例として使用するベース塗料５、６を調製した。
Preparation of Base Paints 5 and 6 100 parts of a resin component consisting of 136 parts of the hydroxyl group-containing acrylic resin (1) obtained in Production Example 1 and 42 parts of Uban 28-60 (trade name, butyl etherified melamine resin, manufactured by Mitsui Chemicals) (Solid content) per color pigment and fluorescent pigment blended in the ratio shown in Table 1 below, and mixed by stirring, diluted to a viscosity suitable for coating, to prepare an organic solvent-type paint with a solid content of about 50%, Base paints 5 and 6 used as comparative examples were prepared.
ベース塗料７の調製
製造例１で得られた水酸基含有アクリル樹脂（１）１００部（固形分）あたり、着色顔料及び蛍光顔料を下記表１に示す比率で配合して攪拌混合し、スミジュールＮ３３００（商品名、ヘキサメチレンジイソシアネート、住化バイエルウレタン社製）２２．４部を加え、塗装に適正な粘度に希釈して、固形分約５０％の有機溶剤型塗料を調製し、実施例に使用するベース塗料７を調製した（水酸基含有アクリル樹脂中の水酸基１当量に対するイソシアネート化合物中のイソシアネート基の割合は０．８当量である）。
Preparation of Base Paint 7 For 100 parts (solid content) of the hydroxyl group-containing acrylic resin (1) obtained in Production Example 1, the color pigment and the fluorescent pigment were blended in the ratios shown in Table 1 below and mixed with stirring to obtain Sumijour N3300. (Trade name, hexamethylene diisocyanate, manufactured by Sumika Bayer Urethane Co., Ltd.) 22.4 parts is added, diluted to an appropriate viscosity for coating, and an organic solvent-type paint having a solid content of about 50% is prepared and used in the examples. The base coating material 7 was prepared (the ratio of isocyanate groups in the isocyanate compound to 1 equivalent of hydroxyl groups in the hydroxyl group-containing acrylic resin was 0.8 equivalents).
ベース塗料８の調製
製造例２で得られた水酸基含有アクリル樹脂（２）１００部（固形分）あたり、着色顔料及び蛍光顔料を下記表１に示す比率で配合して攪拌混合し、スミジュールＮ３３００（商品名、ヘキサメチレンジイソシアネート、住化バイエルウレタン社製）２８部を加え、塗装に適正な粘度に希釈して、固形分約５０％の有機溶剤型塗料を調製し、実施例に使用するベース塗料８を調製した。
Preparation of base paint 8 For 100 parts (solid content) of the hydroxyl group-containing acrylic resin (2) obtained in Production Example 2, color pigments and fluorescent pigments were blended in the ratios shown in Table 1 below, and mixed by stirring. (Product name, hexamethylene diisocyanate, manufactured by Sumika Bayer Urethane Co., Ltd.) 28 parts are added, diluted to an appropriate viscosity for coating, and an organic solvent-type paint having a solid content of about 50% is prepared and used in the examples. Paint 8 was prepared.
ベース塗料９の調製
製造例１で得られた水酸基含有アクリル樹脂（１）１００部（固形分）あたり、着色顔料及び蛍光顔料を下記表１に示す比率で配合して攪拌混合し、デスモジュールＺ４４７０（商品名、イソホロンジイソシアネート、住化バイエルウレタン社製）３６部を加え、塗装に適正な粘度に希釈して、固形分約５０％の有機溶剤型塗料を調製し、実施例に使用するベース塗料９を調製した。
Preparation of base paint 9 For 100 parts (solid content) of the hydroxyl group-containing acrylic resin (1) obtained in Production Example 1, color pigments and fluorescent pigments were blended in the ratios shown in Table 1 below, and stirred and mixed. (Product name, isophorone diisocyanate, manufactured by Sumika Bayer Urethane Co., Ltd.) 36 parts are added, diluted to an appropriate viscosity for coating, an organic solvent-type paint having a solid content of about 50% is prepared, and the base paint used in the examples 9 was prepared.
クリヤー塗料１の調製
ステンレス製ビーカーにカルボキシル基含有アクリル樹脂（注１）５０部、エポキシ基含有アクリル樹脂（注２）５０部、Ｔｉｎｕｖｉｎ４００（商品名、ヒドロキシフェニルトリアジン系紫外線吸収剤、チバスペシャリティケミカルズ社製）３部、テトラブチルアンモニウムブロマイドとモノブチルりん酸との当量配合物２部及びＢＹＫ３００（商品名、表面調整剤、ビッグケミー社製）０．１部を配合して攪拌混合し、塗装に適した粘度に希釈してクリヤー塗料１を調製した。
（注１）カルボキシル基含有アクリル樹脂： 無水マレイン酸のメタノールハーフエステル化物２０部、アクリル酸４ーヒドロキシｎーブチル２０部、ｎーブチルアクリレート４０部及びスチレン２０部からなる単量体成分の共重合体。数平均分子量３５００、水酸基価７８ｍｇＫＯＨ／ｇ、酸価８６ｍｇＫＯＨ／ｇ。
（注２）エポキシ基含有アクリル樹脂： グリシジルメタクリレート３０部、アクリル酸４ーヒドロキシｎーブチル２０部、ｎーブチルアクリレート３０部及びスチレン２０部からなる単量体成分の共重合体。数平均分子量３０００、エポキシ基含有量２．１２ミリモル／ｇ、水酸基価７８ｍｇＫＯＨ／ｇ。
Preparation of Clear Paint 1 In a stainless steel beaker, 50 parts of a carboxyl group-containing acrylic resin (Note 1), 50 parts of an epoxy group-containing acrylic resin (Note 2), Tinuvin 400 (trade name, hydroxyphenyltriazine UV absorber, Ciba Specialty Chemicals 3 parts), 2 parts of an equivalent compound of tetrabutylammonium bromide and monobutyl phosphoric acid and 0.1 part of BYK300 (trade name, surface conditioner, manufactured by Big Chemie) were mixed with stirring and mixed, suitable for coating. The clear coating material 1 was prepared by diluting to a viscosity.
(Note 1) Carboxyl group-containing acrylic resin: Copolymer of monomer components comprising 20 parts of methanol half esterified maleic anhydride, 20 parts of 4-hydroxy n-butyl acrylate, 40 parts of n-butyl acrylate and 20 parts of styrene . Number average molecular weight 3,500, hydroxyl value 78 mgKOH / g, acid value 86 mgKOH / g.
(Note 2) Epoxy group-containing acrylic resin: a copolymer of monomer components consisting of 30 parts of glycidyl methacrylate, 20 parts of 4-hydroxy n-butyl acrylate, 30 parts of n-butyl acrylate and 20 parts of styrene. Number average molecular weight 3000, epoxy group content 2.12 mmol / g, hydroxyl value 78 mgKOH / g.
クリヤー塗料２の調製
製造例１で得られた水酸基含有アクリル樹脂（１）１００部（固形分）、Ｔｉｎｕｖｉｎ４００（商品名、ヒドロキシフェニルトリアジン系紫外線吸収剤、チバスペシャリティケミカルズ社製）３部、Ｔｉｎｕｖｉｎ２９２（商品名、光安定剤吸収剤、チバスペシャリティケミカルズ社製）１部及びモダフロー（商品名、表面調整剤、モンサント社製）０．１部を攪拌混合した後、スミジュールＮ３３００（商品名、ＨＤＩイソシアヌレート３量体、住化バイエルウレタン社製）２７部を配合して攪拌混合し、塗装に適した粘度に希釈してクリヤー塗料２を調製した。
Preparation of Clear Paint 2 Hydroxyl-containing acrylic resin obtained in Production Example 1 (1) 100 parts (solid content), Tinuvin 400 (trade name, hydroxyphenyltriazine UV absorber, manufactured by Ciba Specialty Chemicals), Tinuvin 292 ( The product name, light stabilizer absorber, 1 part of Ciba Specialty Chemicals Co., Ltd. and Modaflow (trade name, surface conditioner, Monsanto Co., Ltd.) 0.1 part were mixed with stirring, and Sumijoule N3300 (trade name, HDI isocyania). 27 parts of a nurate trimer (manufactured by Sumika Bayer Urethane Co., Ltd.) were blended, mixed with stirring, and diluted to a viscosity suitable for coating to prepare a clear paint 2.
試験板の作製
中塗り塗膜が形成された塗板
脱脂及びりん酸亜鉛処理した鋼板（ＪＩＳＧ３１４１、大きさ４００×３００×０．８ｍｍ）にカチオン電着塗料「エレクロン９４００ＨＢ」（商品名：関西ペイント株式会社製、エポキシ樹脂・ポリアミン系カチオン樹脂に硬化剤としてブロックポリイソシアネート化合物を使用したもの）を硬化塗膜に基づいて膜厚２０μｍになるように電着塗装し、１７０℃で２０分加熱して架橋硬化させて電着塗膜を得た。
Preparation of test plate
Cationic electrodeposition paint “Electron 9400HB” (trade name: manufactured by Kansai Paint Co., Ltd.) on steel plate (JISG 3141, size 400 × 300 × 0.8 mm) treated with degreasing and zinc phosphate treated with an intermediate coating film A resin / polyamine-based cationic resin using a block polyisocyanate compound as a curing agent) is electrodeposited to a film thickness of 20 μm based on the cured coating, and heated at 170 ° C. for 20 minutes to be crosslinked and cured. An electrodeposition coating was obtained.
得られた電着塗面に、中塗り塗料「ルーガベーク中塗りグレー」（商品名：関西ペイント株式会社製、ポリエステル樹脂・メラミン樹脂系、有機溶剤型）をエアスプレーにて硬化塗膜に基づいて膜厚３０μｍになるように塗装し、１４０℃で３０分加熱して架橋硬化させて、中塗り塗膜が形成された塗板を作製した。 Based on the cured coating film by air spraying on the resulting electrodeposition coated surface with an intermediate coating "Lugabake Intermediate Coating Gray" (trade name: manufactured by Kansai Paint Co., Ltd., polyester resin / melamine resin type, organic solvent type) The film was coated to a thickness of 30 μm, heated at 140 ° C. for 30 minutes to be crosslinked and cured, and a coated plate on which an intermediate coating film was formed was produced.
ベース塗料及びクリヤー塗料の塗装
実施例１
上記中塗り塗膜を形成した塗板にベース塗料１を、エアスプレーを用いて、硬化塗膜として４０μｍとなるように塗装し、塗装後、室温約２０℃の実験室に約１５分静置した後、ベース塗料２をエアスプレーを用いて、硬化塗膜として４０μｍとなるように塗装した。塗装後、室温約２０℃の実験室に約１５分静置し、熱風循環式乾燥炉を使用して、１４０℃で３０分間加熱して乾燥硬化せしめ、さらにクリヤ塗料１を硬化塗膜として３０μｍとなるように塗装し、塗装後、室温約２０℃の実験室に約１５分静置した後、１４０℃で３０分間加熱して試験板を得た。
Application of base paint and clear paint Example 1
The base coating 1 was applied to the coating plate on which the intermediate coating film was formed using an air spray so as to be 40 μm as a cured coating film, and after coating, it was left in a laboratory at a room temperature of about 20 ° C. for about 15 minutes. After that, the base paint 2 was applied using an air spray so as to be 40 μm as a cured coating film. After painting, leave it in a laboratory at room temperature of about 20 ° C for about 15 minutes, heat and dry at 140 ° C for 30 minutes using a hot air circulating drying oven, and then use clear paint 1 as a cured coating film at 30 µm After coating, it was allowed to stand in a laboratory at room temperature of about 20 ° C. for about 15 minutes, and then heated at 140 ° C. for 30 minutes to obtain a test plate.
実施例２
上記中塗り塗膜を形成した塗板にベース塗料１を、エアスプレーを用いて、硬化塗膜として４０μｍとなるように塗装し、塗装後、室温約２０℃の実験室に約１５分静置した。次いでベース塗料２をエアスプレーを用いて、硬化塗膜として４０μｍとなるように塗装し、塗装後、室温約２０℃の実験室に約１５分放置し、熱風循環式乾燥炉を使用して、１４０℃で３０分間加熱し、乾燥硬化せしめ、その後にクリヤー塗料２を硬化塗膜として３０μｍとなるように塗装した。塗装後、室温にて１５分間静置した後に、さらにクリヤ塗料１を硬化塗膜として３０μｍとなるように塗装し、塗装後、室温約２０℃の実験室に約１５分静置し、１４０℃で３０分間加熱して試験板を得た。
Example 2
The base coating 1 was applied to the coating plate on which the intermediate coating film was formed using an air spray so as to be 40 μm as a cured coating film, and after coating, it was left in a laboratory at a room temperature of about 20 ° C. for about 15 minutes. . Next, the base paint 2 was applied using an air spray so that the cured coating film had a thickness of 40 μm. After coating, the base paint 2 was left in a laboratory at a room temperature of about 20 ° C. for about 15 minutes, and a hot air circulation drying oven was used. It was heated at 140 ° C. for 30 minutes, dried and cured, and then the clear paint 2 was applied as a cured coating film to a thickness of 30 μm. After painting, the mixture was allowed to stand at room temperature for 15 minutes, and then the clear paint 1 was further applied as a cured coating film to a thickness of 30 μm. After painting, it was left in a laboratory at room temperature of about 20 ° C. for about 15 minutes, and 140 ° C. For 30 minutes to obtain a test plate.
実施例３〜７及び比較例３，４
下記表２に示す塗膜構成となるようにして、ベース塗料及びクリヤー塗料を実施例１と同様にして塗装し試験板を得た。
Examples 3 to 7 and Comparative Examples 3 and 4
A base coating and a clear coating were applied in the same manner as in Example 1 so as to obtain the coating composition shown in Table 2 below to obtain a test plate.
比較例１
上記中塗り塗膜を形成した塗板にベース塗料１をエアスプレーを用いて、硬化塗膜として４０μｍとなるように塗装し、塗装後、室温約２０℃の実験室に約１５分静置した後、熱風循環式乾燥炉を使用して、１４０℃で３０分間加熱し、乾燥硬化せしめ、さらにクリヤ塗料１を硬化塗膜として３０μｍとなるように塗装し、塗装後、室温約２０℃の実験室に約１５分静置し、１４０℃で３０分間加熱して試験板を得た。
Comparative Example 1
After the base coating 1 is applied to the coated plate on which the intermediate coating film is formed using an air spray so as to be 40 μm as a cured coating film, after being applied and left in a laboratory at a room temperature of about 20 ° C. for about 15 minutes. Using a hot air circulation drying oven, heat at 140 ° C. for 30 minutes, dry and cure, and then apply clear paint 1 as a cured coating to a thickness of 30 μm. For about 15 minutes and heated at 140 ° C. for 30 minutes to obtain a test plate.
比較例２、５
表２に示す構成となるようにようにして、ベース塗料及びクリヤー塗料を比較例１と同様にして塗装し試験板を得た。
Comparative Examples 2 and 5
A base plate and a clear coating were applied in the same manner as in Comparative Example 1 so as to obtain the constitution shown in Table 2, to obtain a test plate.
評価
上記で得た試験板の意匠性を以下の要領にて評価し、その結果を下記表２に示す。
Evaluation The design properties of the test plate obtained above were evaluated in the following manner, and the results are shown in Table 2 below.
測色による白さ（明度Ｌ＊）と黄味（ｂ＊）の評価
試験板をＭＡ６８ＩＩ（商品名、多角度分光光度計、ｘ−ｒｉｔｅ社製）を使用して測定した正反射光に対して４５度の角度で受光した分光反射率から計算して得られた白さ（明度Ｌ＊）と黄味（ｂ＊）を表２に示す。
Evaluation test of whiteness (lightness L *) and yellowness (b *) by colorimetry with respect to specular reflection light measured using MA68II (trade name, multi-angle spectrophotometer, manufactured by x-rite) Table 2 shows the whiteness (lightness L *) and yellowness (b *) obtained from the spectral reflectance received at an angle of 45 degrees.
目視による白さの評価
晴れた日の午後に、直射日光が当たらない屋外において、自動車外板向け塗料の塗色設計に３年以上従事している熟練した技術者及びデザイナーが、塗板を観察して、白さを目視にて次の基準で評価する。
５：青味白さを非常に感じる。
４：青味白さを感じる。
３：青味白さを多少感じる。
２：青味を余り感じないが通常の黄味帯びた白さとは違うと感じる。
１：通常の黄味帯びた白さとして感じる。
Evaluation of visual whiteness On a sunny afternoon, outdoors, where there is no direct sunlight, skilled technicians and designers who have been engaged in paint color design for automotive exterior panels have observed the coated plates for more than three years. The whiteness is visually evaluated according to the following criteria.
5: I feel very blue and white.
4: Feels bluish white.
3: A little bluish white is felt.
2: I do not feel much blueness, but feel it is different from normal yellowish white.
1: Feels as normal yellowish white.
鮮映性
蛍光灯照明にて、作業可能な明るさに調整された実験室内で、試験板に蛍光灯を映し出して映り込みを次の基準で評価する。
３：蛍光灯の形状がはっきりと認識できる。
２：蛍光灯の形状が認識できる。
１：蛍光灯が認識できない。
A fluorescent lamp is projected on a test plate in a laboratory adjusted to a workable brightness with clear fluorescent lamp illumination, and the reflection is evaluated according to the following criteria.
3: The shape of the fluorescent lamp can be clearly recognized.
2: The shape of the fluorescent lamp can be recognized.
1: The fluorescent lamp cannot be recognized.
耐候性
Ｓｕｐｅｒｘｅｎｏｎウェザーメーター（商品名、促進耐候性試験機、スガ試験機社製）を使用して、ＪＩＳ Ｋ５６００−７−７（方法１）に記載された試験条件にて照射と降雨条件を組み合わせたサイクル試験を行った。サイクル試験時間の合計が１２００時間後に塗板の塗膜の劣化状態を目視で評価する。
Using weathering Superxenon weather meter (trade name, accelerated weathering tester, Suga Test Instruments Co., Ltd.), combining irradiation and rain conditions under the test conditions described in JIS K5600-7-7 (Method 1) Cycle tests were conducted. After the total cycle test time is 1200 hours, the deterioration state of the coating film on the coated plate is visually evaluated.
耐水性
試験板を４０℃の温水に７日間浸漬した後、室内にて試験板を観察して次の基準で評価する。
３：塗膜に異常がみられない。
２：引き上げ直後にチヂミが見られたが、乾燥後に回復した。
１：回復しないチヂミ、ふくれが見られた。
After immersing the water resistance test plate in warm water of 40 ° C. for 7 days, the test plate is observed indoors and evaluated according to the following criteria.
3: No abnormality is observed in the coating film.
2: Chijimi was observed immediately after pulling up, but recovered after drying.
1: Chijimi and blisters that did not recover were seen.
付着性
上記促進耐候性試験に供した試験板について、ＪＩＳ Ｋ５６００に準拠した碁盤目試験を行った。具体的には、塗膜上に縦横に２ｍｍの間隔で碁盤目状に素材に達する１００個の切れ目を入れ、密着力（１２０ｇｆ／１０ｍｍ）の接着テープを貼りつける。そしてこの接着テープを剥ぎ取り、剥離して接着テープに付着した塗膜片の数量を調べて下記の基準にて評価する。
４：剥離なし
３：剥離数１０％未満
２：剥離数１０％以上７０％未満
１：剥離数７０％以上
Adhesion A cross-cut test based on JIS K5600 was performed on the test plate subjected to the accelerated weathering test. Specifically, 100 cuts reaching the material in a grid pattern at intervals of 2 mm in the vertical and horizontal directions are put on the coating film, and an adhesive tape having an adhesion force (120 gf / 10 mm) is applied. Then, this adhesive tape is peeled off, and the number of coating film pieces peeled off and adhered to the adhesive tape is examined and evaluated according to the following criteria.
4: No peeling 3: Peeling number less than 10% 2: Peeling number of 10% or more and less than 70% 1: Peeling number of 70% or more
本発明の複層塗膜形成方法は、各種工業製品、特に自動車外板の塗装に適用することができる。 The multi-layer coating film forming method of the present invention can be applied to various industrial products, in particular, coating of automobile outer plates.
Claims (3)
白色ベース塗膜及び蛍光顔料含有ベース塗膜がビヒクル形成成分として水酸基含有樹脂及びイソシアネート化合物を含有するウレタン化反応により架橋硬化し得る樹脂組成物を含んでなり、
蛍光顔料含有ベース塗膜が化学式（Ｂａ1-x―yＣａxＥｕy）ＭｇＡｌ10Ｏ17（式中、ｘは０≦ｘ≦０．３３であり、ｙは０．０７≦ｙ≦０．３５であり、かつ０．１≦ｘ＋ｙ≦０．４である）で示される蛍光顔料を含有し、
該水酸基含有樹脂が、炭素数２〜２０のグリコールと（メタ）アクリル酸とのモノエステル化物から選ばれる水酸基含有重合性単量体、マレイン酸、イタコン酸、フマル酸、メサコン酸およびこれらの酸無水物またはハーフエステル、ならびにアクリル酸、メタクリル酸、マレイン酸、イタコン酸、フマル酸およびメサコン酸から選ばれるカルボキシル基含有重合性単量体、ならびに（メタ）アクリル酸と炭素数１〜２２の１価のアルコールとのモノエステル化物から選ばれるアクリル系単量体を重合することによって製造されるものであり、
該水酸基含有樹脂とイソシアネート化合物の配合割合が、水酸基含有樹脂中の水酸基１当量に対しイソシアネート化合物中のイソシアネート基が０．８〜１．２当量の範囲内にある、
ことを特徴とする複層塗膜形成方法。 A method for forming a multilayer coating film comprising sequentially laminating a white base coating film, a fluorescent pigment-containing base coating film and a clear coating film on a substrate,
The white base coating film and the fluorescent pigment-containing base coating film comprise a resin composition that can be crosslinked and cured by a urethanization reaction containing a hydroxyl group-containing resin and an isocyanate compound as a vehicle-forming component,
The fluorescent pigment-containing base coating film has the chemical formula (Ba 1-x -y Ca x Eu y ) MgAl 10 O 17 (wherein x is 0 ≦ x ≦ 0.33 and y is 0.07 ≦ y ≦ 0. 35, and 0.1 ≦ x + y ≦ 0.4),
The hydroxyl group-containing resin is a hydroxyl group-containing polymerizable monomer, maleic acid, itaconic acid, fumaric acid, mesaconic acid, and acids thereof selected from monoesterified products of glycols having 2 to 20 carbon atoms and (meth) acrylic acid An anhydride or half ester, a carboxyl group-containing polymerizable monomer selected from acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid and mesaconic acid , and (meth) acrylic acid and 1 to 22 carbon atoms It is produced by polymerizing an acrylic monomer selected from monoesterified products with a hydric alcohol ,
The mixing ratio of the hydroxyl group-containing resin and the isocyanate compound is such that the isocyanate group in the isocyanate compound is in the range of 0.8 to 1.2 equivalents relative to 1 equivalent of the hydroxyl group in the hydroxyl group-containing resin.
A method for forming a multilayer coating film.
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