JP2005240013A - Metallic coating composition for automobile excellent in orientation properties - Google Patents
Metallic coating composition for automobile excellent in orientation properties Download PDFInfo
- Publication number
- JP2005240013A JP2005240013A JP2004315137A JP2004315137A JP2005240013A JP 2005240013 A JP2005240013 A JP 2005240013A JP 2004315137 A JP2004315137 A JP 2004315137A JP 2004315137 A JP2004315137 A JP 2004315137A JP 2005240013 A JP2005240013 A JP 2005240013A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum pigment
- aluminum
- radical polymerizable
- aluminum powder
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000008199 coating composition Substances 0.000 title abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 161
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 96
- 239000000049 pigment Substances 0.000 claims abstract description 90
- 239000002245 particle Substances 0.000 claims abstract description 58
- 238000000576 coating method Methods 0.000 claims abstract description 55
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 8
- 150000005690 diesters Chemical class 0.000 claims abstract description 8
- 239000003973 paint Substances 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 18
- 230000003746 surface roughness Effects 0.000 claims description 16
- 238000009503 electrostatic coating Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000003505 polymerization initiator Substances 0.000 claims description 7
- 230000008439 repair process Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
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Landscapes
- Polymerisation Methods In General (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、自動車ボディや部品の高級メタリックベースコート静電塗装用塗料、自動車補修用メタリックベースコート塗料分野に使用されるアルミニウム顔料を用いた塗料に関するものである。更に詳しくは、上記用途において形成した塗膜において、塗膜中のアルミニウム顔料粒子の配向性に特に優れており、それゆえ極めて高い光輝度、かつ極めて滑らかな外観を有する塗膜を与えるメタリック塗料組成物に関するものである。 TECHNICAL FIELD The present invention relates to a paint using an aluminum pigment used in the field of high-grade metallic base coat electrostatic coating paint for automobile bodies and parts and metallic base coat paint for automobile repair. More specifically, in the coating film formed in the above application, the metallic paint composition is particularly excellent in the orientation of the aluminum pigment particles in the coating film, and therefore provides a coating film having an extremely high light brightness and an extremely smooth appearance. It is about things.
一般にアルミニウム顔料は、他の顔料にない独特のメタリック感と、下地に対する優れた隠蔽力を併せ持つ顔料として、前述した分野に多用されている。 特に、近年、自動車ボディ塗装におけるファッション性は、自動車の本来持っている機能と同等以上の価値観で評価されるようになってきた。
特にここ数年における自動車ボディ塗装のファッション性の傾向を見ると、従来から根強かった高白度タイプやギラギラとした単調なシルバーメタリック調は減少し、光輝度、フロップ性が強く、かつ滑らかで緻密な粒子感の小さい塗膜の要求が高まってきている。
In general, aluminum pigments are frequently used in the above-mentioned fields as pigments having both a unique metallic feeling not found in other pigments and an excellent hiding power with respect to the base. In particular, in recent years, the fashionability of automobile body painting has been evaluated with values that are equal to or better than the functions inherent in automobiles.
Looking at the trend of fashionability of automobile body painting in the past few years in particular, the monotonous silver metallic tone, which has been a strong whiteness type and glaring, has been decreasing, and the brightness and flop properties are strong, smooth and precise. The demand for a coating film with a small particle feeling is increasing.
これまでに、高い光の反射率を得ることを目的としたアルミニウム顔料として、特許文献１（特許第２５７５５１６号公報）には、高い光の反射率と高い隠蔽力を兼備したアルミニウム顔料が、また、特許文献２（特開昭４９−１４３５８号公報）には湿式ボールミル法にてアルミニウム粉の表面を磨き、高い反射率を備えたアルミニウム顔料を得る方法、さらには特許文献３（特公昭５４−３６６０７号公報）にはスパークリング効果のすぐれたメタリック塗膜の形成方法などが開示されている。また、特許文献４（特開平８−１７００３４号公報）には、塗膜に強い光輝感および優れた外観の塗膜を与えるアルミニウム顔料が記載されている。しかしながら上記文献１〜４のいずれのアルミニウム顔料においても、現在望まれる高い光輝度と高いフロップ性を満足するレベルには達していない。 So far, as an aluminum pigment for the purpose of obtaining a high light reflectance, Patent Document 1 (Japanese Patent No. 2575516) discloses an aluminum pigment having both a high light reflectance and a high hiding power. Patent Document 2 (Japanese Patent Laid-Open No. 49-14358) discloses a method of polishing the surface of an aluminum powder by a wet ball mill method to obtain an aluminum pigment having a high reflectance. No. 36607) discloses a method for forming a metallic coating film having an excellent sparkling effect. Patent Document 4 (Japanese Patent Laid-Open No. 8-170034) describes an aluminum pigment that gives a coating film with a strong glitter and excellent appearance to the coating film. However, none of the aluminum pigments of the above-mentioned documents 1 to 4 has reached a level that satisfies the currently desired high light luminance and high flop property.
さらには、特許文献５（特開2003-147270号公報）には、反射ムラを抑制するアルミニウム顔料が記載されている。しかしながら、特に高い光輝度を有する塗膜のムラについては、必ずしも抑制できているとは言えない。一方、特許文献６（特開2002-226733号公報）には、本発明のメタリック塗料に用いられるアルミニウム顔料が開示されており、光沢度を維持しつつ密着性に優れると言う効果をうたっている。しかしながら、特に水性塗料系において現在望まれる高い光輝度と高いフロップ性を満足するレベルには達していない。
本発明は、先行技術では得られなかった高度な光学的特性、特に、高い光輝性と粒子感の小さい緻密で滑らかな塗膜外観を実現する、アルミニウム顔料粒子の配向性に優れた自動車ベースコート用メタリック塗料を提供する。 The present invention provides high optical properties not obtained by the prior art, particularly for automobile base coats that achieve a fine and smooth coating appearance with high brightness and small particle feeling and excellent orientation of aluminum pigment particles. Provide metallic paint.
上記課題を解決するために、本発明者らは、アルミニウム顔料の基本的物性と光学的特性、並びに、製造条件の関係について鋭意検討を重ねた結果、フレーク状アルミニウム粉末の表面に、制御された特定量の樹脂をコーティングすることにより、自動車のボディ用やバンパー用さらには部品用、補修用等のメタリック塗装において、上記の樹脂コートアルミニウム顔料粒子が極めて優れた配向性を示し、それゆえ高い光輝度並びに粒子感の小さい塗膜を与えうることを見い出し、本発明を完成した。 In order to solve the above-mentioned problems, the present inventors have made extensive studies on the relationship between basic physical properties and optical properties of aluminum pigments and production conditions, and as a result, the surface of the flaky aluminum powder was controlled. By coating a specific amount of resin, the above resin-coated aluminum pigment particles exhibit extremely excellent orientation in metallic coatings for automobile bodies, bumpers, parts, and repairs. The inventors have found that a coating film with low brightness and particle feeling can be provided, thereby completing the present invention.
すなわち、本発明は、下記の通りである。
１．フレーク状アルミニウム粉末１００質量部に対して０．１〜２．１重量部の樹脂をフレーク状アルミニウム粉末表面に形成したアルミニウム顔料であって、該樹脂が、（Ａ）ラジカル重合性不飽和カルボン酸、ラジカル重合性二重結合を有するリン酸またはホスホン酸のモノまたはジエステル、及び、ラジカル重合性二重結合を有するカップリング剤から選ばれた少なくとも１種と、（Ｂ）ラジカル重合性二重結合を２個以上有する単量体を少なくとも１種以上含有するラジカル重合性単量体の１種もしくは２種以上の重合物よりなり、かつ、その質量比Ａ／Ｂが０．１〜４であるアルミニウム顔料を含有することを特徴とする、塗装後のアルミニウム顔料粒子の配向性に優れた自動車ベースコート用メタリック塗料組成物。
That is, the present invention is as follows.
1. An aluminum pigment in which 0.1 to 2.1 parts by weight of resin is formed on the surface of flaky aluminum powder with respect to 100 parts by mass of flaky aluminum powder, and the resin is (A) a radical polymerizable unsaturated carboxylic acid At least one selected from mono- or diesters of phosphoric acid or phosphonic acid having a radical polymerizable double bond, and a coupling agent having a radical polymerizable double bond, and (B) a radical polymerizable double bond 1 or 2 or more of radically polymerizable monomers containing at least one monomer having at least one monomer, and the mass ratio A / B is 0.1-4. A metallic paint composition for automobile base coats, which contains an aluminum pigment and has excellent orientation of aluminum pigment particles after coating.
２．フレーク状アルミニウム粉末の平均厚みｔ（μｍ）に対する平均粒径ｄ５０（μｍ）の比が３０〜９０、平均表面粗さＲａが２０ｎｍ以下であり、かつ、表面粗さ曲線の凹凸の平均高さＲｃが８０ｎｍ以下である前記１．に記載のアルミニウム顔料を含有する自動車ベースコート用メタリック塗料組成物。
３．フレーク状アルミニウム粉末の平均粒径ｄ５０が５〜１５μｍである１．、または２．に記載のアルミニウム顔料を含有する自動車ベースコート用メタリック塗料組成物。 ４．フレーク状アルミニウム粉末の平均粗さＲａが１５ｎｍ以下である２．に記載のアルミニウム顔料を含有する自動車ベースコート用メタリック塗料組成物。
2. The ratio of the average particle diameter d50 (μm) to the average thickness t (μm) of the flaky aluminum powder is 30 to 90, the average surface roughness Ra is 20 nm or less, and the average height Rc of the unevenness of the surface roughness curve 1 is 80 nm or less. A metallic paint composition for automobile base coats containing the aluminum pigment described in 1.
3. 1. The average particle diameter d50 of the flaky aluminum powder is 5 to 15 μm. Or 2. A metallic paint composition for automobile base coats containing the aluminum pigment described in 1. 4). 1. The average roughness Ra of the flaky aluminum powder is 15 nm or less. A metallic paint composition for automobile base coats containing the aluminum pigment described in 1.
５．前記１．〜４．のいずれかに記載のアルミニウム顔料を含有する、塗装後のアルミニウム顔料粒子の配向性に優れた新車ボディベースコート静電塗装用メタリック塗料組成物。
６．前記１．〜４．のいずれかに記載のアルミニウム顔料を含有する、塗装後のアルミニウム顔料粒子の配向性に優れた新車バンパーベースコート静電塗装用または新車部品ベースコート静電塗装用メタリック塗料組成物。
７．前記１．〜３．のいずれかに記載のアルミニウム顔料を含有する、塗装後のアルミニウム顔料粒子の配向性に優れた自動車補修ベースコート用メタリック塗料組成物。
5). 1 above. ~ 4. A metallic paint composition for new vehicle body base coat electrostatic coating, which contains the aluminum pigment according to any one of the above, and is excellent in the orientation of aluminum pigment particles after coating.
6). 1 above. ~ 4. A metallic paint composition for new car bumper base coat electrostatic coating or new car part base coat electrostatic coating, which contains the aluminum pigment according to any one of the above, and has excellent orientation of the painted aluminum pigment particles.
7). 1 above. ~ 3. A metallic paint composition for automobile repair base coat, which contains the aluminum pigment according to any one of the above, and is excellent in the orientation of aluminum pigment particles after coating.
本発明によれば塗装後のアルミニウム顔料粒子の配向性に優れ、それゆえこれまでにない高い光輝度とフロップ感が得られるメタリック塗料、特に自動車用途向けに優れたメタリック塗料組成物を提供することができる。 According to the present invention, there is provided a metallic paint excellent in the orientation of the aluminum pigment particles after coating, and thus obtaining an unprecedented high light brightness and flop feeling, and particularly excellent in automotive applications. Can do.
以下、本発明について、特にその好ましい形態を中心に、具体的に説明する。
本発明において、フレーク状アルミニウム粉末の平均粒径ｄ５０（μｍ）、平均厚みｔ（μｍ）、平均表面粗さＲａ（ｎｍ）、表面粗さ曲線の凹凸の平均高さＲｃ（ｎｍ）は、次の様に定義される。
平均粒径ｄ５０（μｍ）は、レーザーミクロンサイザーＬＭＳ−２４（セイシン企業株式会社製）を用いて測定した値である。
この平均粒径ｄ５０は、意図する意匠性に合わせて極細目、細目、中目、粗目、極粗目を選択するが、平均粒径ｄ５０は５〜１５μｍが好ましい。平均粒径が５μｍより小さいものは、塗膜中でアルミニウム粒子の配向が乱れやすく、その結果、光の散乱が発生しやすくなるので目的とする光輝度感が得られない。一方、１５μｍより大きいものは、現状の塗装技術の範囲でも配向性の良いものを得ることが可能である。
Hereinafter, the present invention will be specifically described focusing on its preferred form.
In the present invention, the average particle diameter d50 (μm), the average thickness t (μm), the average surface roughness Ra (nm), and the average height Rc (nm) of the unevenness of the surface roughness curve are as follows: It is defined as
The average particle diameter d50 (μm) is a value measured using a laser micron sizer LMS-24 (manufactured by Seishin Enterprise Co., Ltd.).
The average particle diameter d50 is selected to be very fine, fine, medium, coarse, or extremely coarse in accordance with the intended design, and the average particle diameter d50 is preferably 5 to 15 μm. When the average particle size is less than 5 μm, the orientation of the aluminum particles is likely to be disturbed in the coating film, and as a result, light scattering is likely to occur, so that the desired light brightness cannot be obtained. On the other hand, if the size is larger than 15 μm, it is possible to obtain a product having good orientation even within the range of the current coating technology.
平均厚みｔ（μｍ）は、金属成分１ｇ当たりの水面拡散面積ＷＣＡ（ｍ2／ｇ）を測定し、下式により算出した値である。
ｔ（μｍ）＝０．４／［ＷＣＡ（ｍ2／ｇ）］
本発明でいう平均厚みｔに対する平均粒径ｄ５０の比は、ｄ５０／ｔで与えられ、フレーク状アルミニウム粉末のいわゆる扁平度として表される。扁平度は、アルミニウム粉を媒体攪拌ミルまたはボールミルで摩砕を行うと、徐々に大きくなり、ある程度まで展延されると粒子は折れ曲がり易くなる。概して、２００を越えると粒子にクラックが入りやすくなり折れ曲がり易くなる。本発明における扁平度ｄ５０／ｔは３０〜９０が好ましく、４０〜８０であればより好ましい。扁平度が３０以上で、粒子の展延が十分行われ、アルミニウム顔料に求められる隠蔽性が得られる。一方、扁平度が９０以下で、粒子の展延が過度でなく、粒子表面の平滑性が得られ、必要とする高い光輝度が得られる。
The average thickness t (μm) is a value obtained by measuring the water surface diffusion area WCA (g 2 / g) per 1 g of the metal component and calculating by the following equation.
t (μm) = 0.4 / [WCA (m 2 / g)]
The ratio of the average particle diameter d50 to the average thickness t in the present invention is given by d50 / t and is expressed as so-called flatness of the flaky aluminum powder. The flatness gradually increases when the aluminum powder is ground with a medium stirring mill or a ball mill, and when the aluminum powder is spread to a certain extent, the particles are easily bent. In general, if it exceeds 200, the particles are likely to crack and bend easily. The flatness d50 / t in the present invention is preferably 30 to 90, more preferably 40 to 80. The flatness is 30 or more, the particles are sufficiently spread, and the concealability required for the aluminum pigment is obtained. On the other hand, the flatness is 90 or less, the spread of the particles is not excessive, the smoothness of the particle surface is obtained, and the required high light luminance is obtained.
本発明で言う平均表面粗さＲａは、原子間力顕微鏡（以下ＡＦＭと略記する）により測定される。本発明のアルミニウム顔料の平均表面粗さＲａは２０ｎｍ以下であり、１５ｎｍ以下であればより好ましい。Ｒａが２０ｎｍ以下の時、表面での光の正反射率が大きいため極めて優れた光輝度を示すと共にフロップ性も良好である。
また、表面粗さ曲線の凹凸の平均高さＲｃが、８０ｎｍ以下であること好ましい。Ｒｃは、表面凹凸の大小を表すもので、表面粗さ曲線の山頂の高さの絶対値の平均値と表面粗さ曲線の谷底の深さの絶対値の平均値の和で表されるが、Ｒｃが８０ｎｍ以下であると、極めて高い光輝度を示すと共にフロップ性も良好である。
The average surface roughness Ra referred to in the present invention is measured by an atomic force microscope (hereinafter abbreviated as AFM). The average surface roughness Ra of the aluminum pigment of the present invention is 20 nm or less, and more preferably 15 nm or less. When Ra is 20 nm or less, since the regular reflectance of light on the surface is large, it exhibits extremely excellent light luminance and good flop.
Moreover, it is preferable that the average height Rc of the unevenness | corrugation of a surface roughness curve is 80 nm or less. Rc represents the size of the surface roughness, and is represented by the sum of the average absolute value of the peak height of the surface roughness curve and the average absolute value of the depth of the valley bottom of the surface roughness curve. When Rc is 80 nm or less, extremely high light luminance is exhibited and flop property is also good.
上記の条件を満足するフレーク状アルミニウム粉末の表面は、走査型電子顕微鏡（ＳＥＭ）観察でも、表面の凹凸が少なく、また、表面に極微粉等の付着も少なく、また、粒子の中央から端部に至るまで均一な厚みを有するフレーク状アルミニウム粉末をかなり多く含むのが認められた。
本発明に用いるフレーク状アルミニウム粉末は、例えば媒体攪拌ミル、またはボールミルによって、原料となるアトマイズドアルミニウム粉を摩砕して製造される。摩砕時において、アルミニウム粉の質量に対する摩砕ボールの質量の比が、２〜１００が好ましい。
アルミニウム粉の質量に対する摩砕ボールの質量の比が、２以上であると、表面粗さの
小さいフレーク状アルミニウム粉末が得られ、光輝度並びにフロップ性も高いものが得ら
れ好ましい。また、１００以下であると、摩砕時間が著しく長くなりことで生産性が低く
なるのを抑制し、実用的である。アルミニウム粉の質量に対する摩砕ボールの質量の比は
１０〜１００がより好ましく、１４〜６５が更に好ましい。
The surface of the flaky aluminum powder that satisfies the above conditions has little surface irregularity even with scanning electron microscope (SEM) observation, and there is little adhesion of ultrafine powder to the surface. It was found that a considerable amount of flaky aluminum powder having a uniform thickness was obtained.
The flaky aluminum powder used in the present invention is produced by grinding atomized aluminum powder as a raw material, for example, with a medium stirring mill or a ball mill. At the time of grinding, the ratio of the mass of the grinding ball to the mass of the aluminum powder is preferably 2 to 100.
When the ratio of the mass of the grinding balls to the mass of the aluminum powder is 2 or more, a flaky aluminum powder having a small surface roughness can be obtained, and a product having high light luminance and flop properties can be obtained. On the other hand, if it is 100 or less, it is practical because the grinding time is remarkably increased to prevent the productivity from being lowered. As for the ratio of the mass of the grinding ball with respect to the mass of aluminum powder, 10-100 are more preferable, and 14-65 are still more preferable.
また、アルミニウム粉の質量に対する摩砕溶剤の質量の比が、１．８〜３０であること
が好ましい。より好ましくは、２．６〜１８である。
アルミニウム粉の質量に対する摩砕溶剤の質量の比が１．８以上で、摩砕時アルミニウム粒子同士の接触が少なく、粒子表面の傷が抑制され、反射率の低下が少なく、３０以下で、アルミニウム粒子濃度が低い事が原因で摩砕が急激に進行するような事は無く、摩砕のコントロールが容易である。
原料となるアトマイズドアルミニウム粉としては、アルミニウム以外の不純物の少ない物が好ましい。一般的には、９９．５％以上のものが使用されるが、好ましくは、９９．７％以上で、更に好ましくは、９９．８％以上である。
アトマイズドアルミニウム粉の平均粒径としては、２〜２０μｍのものが好ましい。更には、３〜１２μｍのものがより好ましい。２μｍ以上では、摩砕してもアルミニウム顔料表面ならびに粒子が崩れ難いので好ましい。また、２０μｍ以下であると、摩砕によるアルミニウム顔料表面の展延時間も短くてすみ、一方で摩砕ボールによるずり応力の履歴も少なく、展延時間とともに増大する表面の起伏も顕著にならずに好ましい。
アトマイズドアルミニウム粉の形状としては、球状粉、涙滴状粉のようなものが好ましい。
Moreover, it is preferable that ratio of the mass of the grinding solvent with respect to the mass of aluminum powder is 1.8-30. More preferably, it is 2.6-18.
The ratio of the mass of the grinding solvent to the mass of the aluminum powder is 1.8 or more, there is little contact between the aluminum particles at the time of grinding, scratches on the particle surface are suppressed, there is little decrease in reflectance, and aluminum is 30 or less. Grinding does not proceed rapidly due to the low particle concentration, and grinding control is easy.
As the atomized aluminum powder used as a raw material, a material having few impurities other than aluminum is preferable. Generally, 99.5% or more is used, but preferably 99.7% or more, and more preferably 99.8% or more.
The average particle size of the atomized aluminum powder is preferably 2 to 20 μm. Furthermore, the thing of 3-12 micrometers is more preferable. A thickness of 2 μm or more is preferable because the surface and particles of the aluminum pigment are not easily broken even when ground. Further, when the thickness is 20 μm or less, the spreading time of the aluminum pigment surface by grinding can be shortened, and on the other hand, the history of shear stress due to the grinding ball is small, and the surface undulation that increases with the spreading time does not become remarkable. Is preferable.
The shape of the atomized aluminum powder is preferably a spherical powder or a teardrop-shaped powder.
摩砕溶剤は、従来より使用されているミネラルスピリット、ソルベントナフサ等の炭化
水素系溶剤やアルコール系、エーテル系、ケトン系、エステル系等の溶剤が使用できる。またこれらの溶剤類は、アルミニウム顔料のペースト化溶剤としても用いられる。添加量は、好ましくはペーストの加熱残分が５０〜８０％になるように調整する。
摩砕助剤はノンリーフィングタイプにおいてはオレイン酸を代表とする高級不飽和脂肪酸が使用される。またリーフィングタイプにおいてはステアリン酸を代表とする高級飽和脂肪酸が使用される。摩砕助剤の量はアルミニウムの質量に対し１〜５０質量％使用されることが望ましい。
As the grinding solvent, conventionally used hydrocarbon solvents such as mineral spirit and solvent naphtha, and alcohol, ether, ketone and ester solvents can be used. These solvents are also used as pasting solvents for aluminum pigments. The addition amount is preferably adjusted so that the heating residue of the paste is 50 to 80%.
As the grinding aid, in the non-leafing type, a higher unsaturated fatty acid typified by oleic acid is used. In the leafing type, higher saturated fatty acids such as stearic acid are used. The amount of grinding aid is preferably 1 to 50% by weight based on the weight of aluminum.
本発明のアルミニウム顔料を得るには、例えば先ず未処理の上記のフレーク状アルミニウム粉末を有機溶剤中に分散後、加温し、攪拌しながら第一工程として（Ａ）ラジカル重合性不飽和カルボン酸、ラジカル重合性二重結合を有するリン酸またはホスホン酸モノまたはジエステル、及び、ラジカル重合性二重結合を有するカップリング剤から選ばれた少なくとも１種を添加し金属顔料の表面を処理する。次に第二工程として（Ｂ）ラジカル重合性二重結合を２個以上有する単量体と重合開始剤を添加する。それにより、第一工程でフレーク状アルミニウム粉末表面に吸着した（Ａ）成分へラジカル重合性二重結合を２個以上有する単量体を重合させ、樹脂層を形成させることで得られる。 In order to obtain the aluminum pigment of the present invention, for example, first, the untreated flaky aluminum powder is dispersed in an organic solvent, heated, and stirred as a first step (A) radical polymerizable unsaturated carboxylic acid. The surface of the metal pigment is treated by adding at least one selected from phosphoric acid or phosphonic acid mono- or diester having a radical polymerizable double bond and a coupling agent having a radical polymerizable double bond. Next, as a second step, (B) a monomer having two or more radical polymerizable double bonds and a polymerization initiator are added. Thereby, it is obtained by polymerizing a monomer having two or more radical polymerizable double bonds to the component (A) adsorbed on the surface of the flaky aluminum powder in the first step to form a resin layer.
まず、未処理の上記のフレーク状アルミニウム粉末を有機溶剤中に分散する。
有機溶剤は、フレーク状アルミニウム粉末に対し不活性であればよく、例えばヘキサン、ヘプタン、オクタン、ミネラルスピリット等の脂肪族炭化水素、ベンゼン、トルエン、キシレン、ソルベントナフサ等の芳香族炭化水素、テトラヒドロフラン、ジエチルエーテル等のエーテル類、エタノール、２−プロパノール、ブタノール等のアルコール類、酢酸エチル、酢酸ブチル等のエステル類、エチレングリコールモノエチルエーテル等のセロソルブ類が挙げられる。
有機溶剤中のフレーク状アルミニウム粉末の質量濃度は０．１〜４０％が好ましく、更に好ましくは１％〜３５％である。
溶剤除去の労力の点で０．１％以上、フレーク状アルミニウム粉末の分散性の点で４０％以下が好ましい。
First, the untreated flaky aluminum powder is dispersed in an organic solvent.
The organic solvent may be inert to the flaky aluminum powder, for example, aliphatic hydrocarbons such as hexane, heptane, octane, mineral spirit, aromatic hydrocarbons such as benzene, toluene, xylene, solvent naphtha, tetrahydrofuran, Examples include ethers such as diethyl ether, alcohols such as ethanol, 2-propanol and butanol, esters such as ethyl acetate and butyl acetate, and cellosolves such as ethylene glycol monoethyl ether.
The mass concentration of the flaky aluminum powder in the organic solvent is preferably 0.1 to 40%, more preferably 1% to 35%.
It is preferably 0.1% or more in terms of solvent removal labor and 40% or less in terms of dispersibility of the flaky aluminum powder.
次に、第一工程である（Ａ）ラジカル重合性不飽和カルボン酸、ラジカル重合性二重結合を有するリン酸またはホスホン酸のモノまたはジエステル、及び、ラジカル重合性二重結合を有するカップリング剤から選ばれた少なくとも１種を添加する。（Ａ）成分の中では特にラジカル重合性不飽和カルボン酸が好ましい。
ラジカル重合性不飽和カルボン酸としては、例えば、アクリル酸、メタクリル酸、イタコン酸、フマル酸等が例示され、その一種または二種以上を混合して使用することができる。使用される量は該フレーク状アルミニウム粉末の種類と特性、特にその表面積によって異なるが、本発明ではフレーク状アルミニウム粉末１００質量部に対して０．１〜２．０質量部が好ましく、更に好ましくは０．２質量部〜１．５質量部である。
フレーク状アルミニウム粉末表面への樹脂層の形成性の点で、０．１質量部以上、意匠性の点で２質量部以下が好ましい。
Next, the first step (A) radical polymerizable unsaturated carboxylic acid, mono- or diester of phosphoric acid or phosphonic acid having a radical polymerizable double bond, and a coupling agent having a radical polymerizable double bond At least one selected from the above is added. Among the components (A), radically polymerizable unsaturated carboxylic acids are particularly preferable.
Examples of the radical polymerizable unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and the like, and one or more of them can be used in combination. The amount used varies depending on the type and characteristics of the flaky aluminum powder, particularly the surface area thereof, but in the present invention, 0.1 to 2.0 parts by mass is preferable, more preferably 100 parts by mass of flaky aluminum powder. 0.2 parts by mass to 1.5 parts by mass.
In terms of the formability of the resin layer on the surface of the flaky aluminum powder, it is preferably 0.1 parts by mass or more and 2 parts by mass or less in terms of design.
ラジカル重合性二重結合を有するリン酸またはホスホン酸のモノまたはジエステルと
しては、２−メタクリロイロキシエチルホスフェート、ジ−２−メタクリロイロキシエチルホスフェート、トリ−２−メタクリロイロキシエチルホスフェート、２−アクリロイロキシエチルホスフェート、ジ−２−アクリロイロキシエチルホスフェート、トリ−２−アクリロイロキシエチルホスフェート、ジフェニル−２−アクリロイロキシエチルホスフェート、ジブチル−２−メタクリロイロキシエチルホスフェート、ジオクチル−２−アクリロイロキシエチルホスフェート、２−メタクリロイロキシプロピルホスフェート、ビス（２−クロロエチル）ビニルホスホネート、ジアリルジブチルホスホノサクシネート等が挙げられ、その一種または二種以上を混合して使用することができる。
Examples of mono- or diesters of phosphoric acid or phosphonic acid having a radical polymerizable double bond include 2-methacryloyloxyethyl phosphate, di-2-methacryloyloxyethyl phosphate, tri-2-methacryloyloxyethyl phosphate, 2- Acryloyloxyethyl phosphate, di-2-acryloyloxyethyl phosphate, tri-2-acryloyloxyethyl phosphate, diphenyl-2-acryloyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate, dioctyl-2- Examples include acryloyloxyethyl phosphate, 2-methacryloyloxypropyl phosphate, bis (2-chloroethyl) vinylphosphonate, diallyldibutylphosphonosuccinate, and the like. Mixed and can be used.
好ましいものとしてはリン酸モノエステルを挙げることができる。これはリン酸基の持つＯＨ基が２個あることにより、より強固にフレーク状アルミニウム粉末表面に固定されることに起因すると推定される。より好ましいリン酸モノエステルとして、メタクリロイロキシ基およびアクロイロキシ基を有したモノエステルが挙げられ、例えば、２−メタクリロイロキシエチルホスフェート、２−アクロイロキシエチルホスフェートが挙げられる。 その使用量は、該フレーク状アルミニウム粉末の種類と特性、特にその表面積によって異なるが、本発明ではフレーク状アルミニウム粉末１００質量部に対して０．１〜２．０質量部が好ましく、更に好ましくは０．２質量部〜１．５質量部である。フレーク状アルミニウム粉末表面への樹脂層の形成性の点で０．１質量部以上、意匠性の点で２質量部以下が好ましい。 Preferable examples include phosphoric acid monoesters. This is presumed to be due to the fact that the phosphoric acid group has two OH groups and is more firmly fixed to the surface of the flaky aluminum powder. More preferable phosphoric acid monoesters include monoesters having a methacryloyloxy group and an acryloyloxy group, and examples include 2-methacryloyloxyethyl phosphate and 2-acryloyloxyethyl phosphate. The amount used varies depending on the type and characteristics of the flaky aluminum powder, particularly the surface area thereof, but in the present invention, it is preferably 0.1 to 2.0 parts by weight, more preferably 100 parts by weight of flaky aluminum powder. 0.2 parts by mass to 1.5 parts by mass. In terms of the formability of the resin layer on the surface of the flaky aluminum powder, it is preferably 0.1 parts by mass or more and 2 parts by mass or less in terms of design.
ラジカル重合性二重結合を有するカップリング剤としては、シランカップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤等が挙げられる。
シランカップリング剤の例としては、γ−メタクリロキシプロピルトリメトキシシラン、ビニルトリクロルシラン、ビニ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・トリス（β−メトキシエトキシ）シラン等が挙げられる。
チタネート系カップリング剤の例としては、イソプロピルイソステアロイルジアクリルチタネート等が挙げられる。
アルミニウム系カップリング剤の例としては、アセトアルコキシアルミニウムジイソプロピレート、ジルコアルミネート等が挙げられる。
Examples of the coupling agent having a radical polymerizable double bond include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent.
Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl tris (β-methoxyethoxy) silane, and the like.
Examples of titanate coupling agents include isopropyl isostearoyl diacryl titanate.
Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate and zircoaluminate.
使用されるラジカル重合性二重結合を有するカップリング剤の量は、該フレーク状アルミニウム粉末の種類と特性、特にその表面積によって異なるが、本発明ではフレーク状アルミニウム粉末１００質量部に対して０．１〜２．０質量部が好ましく、更に好ましくは０．２質量部〜１．５質量部である。フレーク状アルミニウム粉末表面への樹脂層の形成性の点で０．１質量部以上、意匠性の点で２質量部以下が好ましい。
（Ａ）成分の添加は４０℃〜１５０℃の温度で加温、攪拌しながら行うことが望ましい。４０℃未満では（Ｂ）の重合温度まで昇温するのに時間を要し、１５０℃を越えると有機溶剤の蒸気の発火等に対する配慮を充分にしなければならない。（Ａ）成分の添加終了後、４０℃〜１５０℃の温度で引き続き５分〜１０時間程度攪拌を続けることが好ましい。この時間が５分未満では（Ａ）の有機溶剤中の拡散およびフレーク状アルミニウム粉末表面への吸着が不十分となりやすく、１０時間を越えても効果の増大はない。
The amount of the coupling agent having a radically polymerizable double bond to be used varies depending on the kind and characteristics of the flaky aluminum powder, particularly the surface area thereof. 1-2.0 mass parts is preferable, More preferably, it is 0.2-1.5 mass parts. In terms of the formability of the resin layer on the surface of the flaky aluminum powder, it is preferably 0.1 parts by mass or more and 2 parts by mass or less in terms of design.
It is desirable to add the component (A) while heating and stirring at a temperature of 40 ° C to 150 ° C. If it is less than 40 ° C., it takes time to raise the temperature to the polymerization temperature (B). If it exceeds 150 ° C., consideration must be given to the ignition of organic solvent vapor. (A) After completion | finish of addition of component, it is preferable to continue stirring at the temperature of 40 to 150 degreeC continuously for about 5 minutes-10 hours. If this time is less than 5 minutes, the diffusion of (A) in the organic solvent and the adsorption onto the surface of the flaky aluminum powder tend to be insufficient, and the effect is not increased even if it exceeds 10 hours.
次に第二工程である（Ｂ）ラジカル重合性二重結合を２個以上有する単量体を含有するラジカル重合性単量体と重合開始剤を添加する。
ラジカル重合性二重結合を１個有する単量体とは、下記式（１）の一般式で示される
単量体をいう。
Next, a radically polymerizable monomer containing a monomer having two or more radically polymerizable double bonds (B), which is the second step, and a polymerization initiator are added.
The monomer having one radical polymerizable double bond refers to a monomer represented by the following general formula (1).
Ｘ1，Ｘ2，Ｘ3，Ｘ4はＨまたはＣ1〜18のアルキル、ヒドロキシアルキル、アミノアルキルフェニル、トリル、シアノ、カルボキシル、アルキルカルボキシル、シクロヘキシル、フルオロアルキル等の中から適宜選ぶことができる。
その具体的単量体には例えば、スチレン、ビニルトルエン、アクリロニトリル、メタクリロニトリル、酢酸ビニル、プロピオン酸ビニル、アクリル酸、イソアミルアクリレート、ラウリルアクリレート、ステアリルアクリレート、フェノキシエチルアクリレート、２−ヒドロキシエチルアクリレート等のアクリル酸エステル類、メタクリル酸、メチルメタクリレート、イソブチルメタクリレート、ラウリルメタクリレート、ステアリルメタクリレート、シクロヘキシルメチクリレート、２−ヒドロキシプロピルメタクリレート、メトキシポリエチレングリコールメタクリレート、ジメチルアミノエチルメタクリレート、グリシジルメタクリレート等のメタクリル酸エステル類、クロトン酸、イタコン酸、オレイン酸、マレイン酸、無水マレイン酸、トリフルオロエチルアクリート、トリフルオロエチルメタクリート、パーフルオロオクチルエチルアクリレート、パーフルオロオクチルエチルメタクリレート、２，２，３，３，テトラフルオロプロピルアクリレ―ト、２，２，３，３，テトラフルオロプロピルメタクリレート、パーフルオロプロピルビニルエーテル等のフッ素系モノマーが挙げられる。
X1, X2, X3, and X4 can be appropriately selected from H or C1-18 alkyl, hydroxyalkyl, aminoalkylphenyl, tolyl, cyano, carboxyl, alkylcarboxyl, cyclohexyl, fluoroalkyl, and the like.
Specific monomers include, for example, styrene, vinyl toluene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, acrylic acid, isoamyl acrylate, lauryl acrylate, stearyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, etc. Acrylic acid esters, methacrylic acid, methyl methacrylate, isobutyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, 2-hydroxypropyl methacrylate, methoxypolyethylene glycol methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, etc. , Crotonic acid, itaconic acid, oleic acid, maleic acid, maleic anhydride Acid, trifluoroethyl acrylate, trifluoroethyl methacrylate, perfluorooctylethyl acrylate, perfluorooctylethyl methacrylate, 2,2,3,3, tetrafluoropropyl acrylate, 2,2,3,3, tetra Examples thereof include fluorine monomers such as fluoropropyl methacrylate and perfluoropropyl vinyl ether.
またラジカル重合性二重結合を２個以上有する単量体とは、「２個の例」の下記式（２），「３個の例」の式（３）の一般式で示される単量体をいう。 The monomer having two or more radical polymerizable double bonds is a monomer represented by the following formula (2) of “two examples” and the general formula of formula (3) of “three examples”. Refers to the body.
Ｘ8，Ｘ9,Ｘ10はＨまたはＣ1〜Ｃ3のアルキル、Ｘ11はＣ1〜Ｃ6のヒドロキシアルキルの中から選ばれる。
その具体的単量体には例えば、トリエチレングリコールジアクリレート、エチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、テトラメチロールプロパンテトラアクリレート、ジ−トリメチロールプロパンテトラアクリレート、ペンタエリスリトールテトラアクリレート、ジ−ペンタエリスリトールヘキサアクリレート、ジ−ペンタエリスリトールペンタアクリレート、ジ−ペンタエリスリトールペンタアクリレートモノプロピオネート等を挙げることができ、これらの１種以上を混合して用いても、またこれらの１種以上と前記のラジカル重合性二重結合を１個有する単量体を混合して使用してもよい。
X8, X9 and X10 are selected from H or C1 to C3 alkyl, and X11 is selected from C1 to C6 hydroxyalkyl.
Specific monomers include, for example, triethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, di-trimethylolpropane. Examples include tetraacrylate, pentaerythritol tetraacrylate, di-pentaerythritol hexaacrylate, di-pentaerythritol pentaacrylate, di-pentaerythritol pentaacrylate monopropionate, and the like. Alternatively, one or more of these may be mixed with a monomer having one radical polymerizable double bond.
ラジカル重合性二重結合を２個以上有する単量体の使用量は、フレーク状アルミニウム粉末１００質量部に対して０．１〜２．１質量部が好ましく、更に好ましくは、０．２〜１．５質量部である。フレーク状アルミニウム粉末表面への樹脂層の形成性の点で０．１質量部以上、意匠性の点で２質量部以下が好ましい。第一工程で処理する（Ａ）成分のラジカル重合性不飽和カルボン酸、ラジカル重合性二重結合を有するリン酸またはホスホン酸モノまたはジエステル、及び、ラジカル重合性二重結合を有するカップリング剤から選ばれた少なくとも１種と、第二工程で処理する（Ｂ）成分の、少なくともラジカル重合性二重結合を２個以上有する単量体を含有するラジカル重合性単量体の比Ａ／Ｂは、塗膜中におけるアルミニウム顔料粒子の配向性を良くするという本発明の効果を得るために重要である。そのＡ／Ｂの範囲は、０．１〜４であるが、更に好ましくは、０．５〜３である。０．１以下ではＡ成分の量が少なくＢ成分の量が多いため、第一工程が不十分となり、フレーク状アルミニウム粉末表面に強固な樹脂層を形成できないので好ましくない。４以上ではＡ成分の方が多くなるので、Ａ成分の遊離物や処理後のアルミニウム顔料に残存する重合基により貯蔵安定性が悪くなるので好ましくない。 As for the usage-amount of the monomer which has 2 or more of radically polymerizable double bonds, 0.1-2.1 mass parts is preferable with respect to 100 mass parts of flaky aluminum powder, More preferably, it is 0.2-1 .5 parts by mass. In terms of the formability of the resin layer on the surface of the flaky aluminum powder, it is preferably 0.1 parts by mass or more and 2 parts by mass or less in terms of design. From the radically polymerizable unsaturated carboxylic acid of component (A) to be treated in the first step, phosphoric acid or phosphonic acid mono- or diester having a radically polymerizable double bond, and a coupling agent having a radically polymerizable double bond The ratio A / B of at least one selected and a radical polymerizable monomer containing a monomer having at least two radical polymerizable double bonds of the component (B) to be treated in the second step is: It is important for obtaining the effect of the present invention to improve the orientation of the aluminum pigment particles in the coating film. The range of A / B is 0.1 to 4, more preferably 0.5 to 3. If it is 0.1 or less, the amount of the A component is small and the amount of the B component is large, so that the first step becomes insufficient, and a strong resin layer cannot be formed on the surface of the flaky aluminum powder. When the number is 4 or more, the A component increases, which is not preferable because storage stability is deteriorated due to the free component of the A component or the polymer group remaining in the treated aluminum pigment.
重合開始剤は、一般にラジカル発生剤として知られるものであり、特に制限されない。たとえば、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、ビス−（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート等のパーオキサイド類、および２、２’−アゾビス−イソブチロニトリル、２、２’−アゾビス−２、４−ジメチルバレロニトリル等のアゾ化合物が挙げられる。使用される量は、重合性モノマーの反応速度によってそれぞれ調整されるため特に限定されないが、フレーク状アルミニウム粉末１００質量部に対して、０．１質量部〜２５質量部が好ましい。
（Ｂ）成分である、少なくともラジカル重合性二重結合を２個以上有する単量体を含有するラジカル重合性単量体と、重合開始剤の添加の態様としては、両方を同時に一括で添加する態様、両方を同時に徐々に添加する態様、ラジカル重合性二重結合を有する単量体を先に添加後重合開始剤のみを徐々に添加する態様、などの種々の態様をとることができる。（Ｂ）成分の添加は、攪拌しながら、加温された状態で添加するのが望ましい。
The polymerization initiator is generally known as a radical generator and is not particularly limited. For example, peroxides such as benzoyl peroxide, lauroyl peroxide, bis- (4-t-butylcyclohexyl) peroxydicarbonate, and 2,2′-azobis-isobutyronitrile, 2,2′-azobis- Examples include azo compounds such as 2,4-dimethylvaleronitrile. The amount to be used is not particularly limited because it is adjusted depending on the reaction rate of the polymerizable monomer, but it is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the flaky aluminum powder.
(B) As a mode of addition of a radical polymerizable monomer containing a monomer having at least two radical polymerizable double bonds as a component and a polymerization initiator, both are added simultaneously. Various modes such as a mode, a mode in which both are gradually added simultaneously, a mode in which only a polymerization initiator is gradually added after a monomer having a radical polymerizable double bond is added first can be taken. It is desirable to add the component (B) in a heated state while stirring.
添加する際の温度は、重合が生ずればよく特に限定されないが６０℃〜１５０℃が好ましい。また、重合効率を高めるために窒素、ヘリウム等の不活性ガス雰囲気下で添加、重合することが望ましい。
（Ｂ）成分の添加後の重合は、攪拌を連続、もしくは断続的に行い、分散を維持した状態で、６０℃〜１５０℃の温度で引き続き５分〜１０時間の間で行うのが望ましい。この時間が５分未満ではラジカル重合性二重結合を２個以上有する単量体同士の重合および第一工程でフレーク状アルミニウム粉末表面に吸着した（Ａ）成分への重合が不十分となりやすく、１０時間を越えても効果の増大はあまりない。 ここにいう重合時間とは、（Ｂ）成分の、少なくともラジカル重合性二重結合を２個以上有する単量体を含有するラジカル重合性単量体と重合開始剤が反応系中に同時に存在した時点から、少なくともラジカル重合性二重結合を２個以上有する単量体を含有するラジカル重合性単量体の未反応物が１％未満になるまでの時間をいう。
The temperature at the time of addition is not particularly limited as long as polymerization occurs, but is preferably 60 ° C to 150 ° C. In order to increase the polymerization efficiency, it is desirable to add and polymerize in an inert gas atmosphere such as nitrogen or helium.
The polymerization after the addition of the component (B) is desirably carried out continuously or intermittently at a temperature of 60 ° C. to 150 ° C. for 5 minutes to 10 hours with continuous stirring. When this time is less than 5 minutes, polymerization of monomers having two or more radical polymerizable double bonds and polymerization to the component (A) adsorbed on the surface of the flaky aluminum powder in the first step tend to be insufficient. Even if it exceeds 10 hours, the effect does not increase much. The polymerization time here means that the radically polymerizable monomer containing the monomer having at least two radically polymerizable double bonds of component (B) and the polymerization initiator were simultaneously present in the reaction system. The time from the time point until the unreacted product of the radical polymerizable monomer containing the monomer having at least two radical polymerizable double bonds becomes less than 1%.
本発明のメタリック塗料は、溶剤型塗料、水性塗料等として使用可能であり、主として３つの基本成分、即ち(ａ)塗料用樹脂、(ｂ)塗料用樹脂 １００質量部に対し０．１質量部〜１００質量部の本発明のアルミニウム顔料、及び(ｃ)稀釈剤からなることが好ましい。
溶剤型塗料の塗料用樹脂としては、従来のメタリック塗料で用いられている塗料用樹脂の中の任意のものを用いることができる。その樹脂としては、アクリル樹脂、アルキッド樹脂、オイルフリーアルキッド樹脂、塩化ビニル樹脂、ウレタン樹脂、メラミン樹脂、不飽和ポリエステル樹脂、尿素樹脂、セルロース系樹脂、エポキシ樹脂、フッ素樹脂等が挙げられ、これらは単独で用いてもよいし混合して用いてもよい。
The metallic paint of the present invention can be used as a solvent-type paint, a water-based paint, etc., and is mainly composed of three basic components, namely (a) a resin for paint and (b) a resin for paint in an amount of 0.1 parts by weight. It is preferably composed of ˜100 parts by mass of the aluminum pigment of the present invention and (c) a diluent.
As the paint resin for the solvent-type paint, any of the paint resins used in conventional metallic paints can be used. Examples of the resin include acrylic resin, alkyd resin, oil-free alkyd resin, vinyl chloride resin, urethane resin, melamine resin, unsaturated polyester resin, urea resin, cellulosic resin, epoxy resin, fluorine resin, etc. They may be used alone or in combination.
溶剤型塗料に使用される本発明のアルミニウム顔料は、塗料用樹脂１００質量部に対して０．１質量部〜１００質量部が好ましい。特に１質量部〜５０質量部用いることが好ましい。金属光沢発揮の点で、０．１質量部以上、塗装作業性の点で１００質量部以下が好ましい。
溶剤型塗料での希釈剤としては、トルエン、キシレン等の芳香族系化合物、ヘキサン、ヘプタン、オクタン等の脂肪族系化合物、エタノール、プタノール等のアルコール類、酢酸エチル、酢酸ブチル等のエスチル類、メチルエチルケトン等のケトン類、トリクロロエチレン等の塩素化合物、エチレングリコールモノエチルエーテル等のセロソルブ類が挙げられ、これらの希釈剤は単独または二種以上混合して使用される。その組成は塗料用樹脂に対する溶解性、塗膜形成特性、塗装作業性等を考慮して決定される。
As for the aluminum pigment of this invention used for a solvent-type coating material, 0.1 mass part-100 mass parts are preferable with respect to 100 mass parts of resin for coating materials. In particular, it is preferable to use 1 part by mass to 50 parts by mass. From the standpoint of exhibiting metallic luster, it is preferably 0.1 parts by mass or more and 100 parts by mass or less from the viewpoint of coating workability.
Diluents in solvent-based paints include aromatic compounds such as toluene and xylene, aliphatic compounds such as hexane, heptane, and octane, alcohols such as ethanol and ptanol, estiles such as ethyl acetate and butyl acetate, Examples include ketones such as methyl ethyl ketone, chlorine compounds such as trichloroethylene, and cellosolves such as ethylene glycol monoethyl ether. These diluents are used alone or in combination of two or more. The composition is determined in consideration of solubility in coating resin, coating film forming characteristics, coating workability, and the like.
なお、塗料業界で一般に使用されている顔料、染料、湿潤剤、分散剤、色分れ防止剤、レベリング剤、スリップ剤、皮張り防止剤、ゲル化防止剤、消泡剤等の添加剤を加えることができる。
本発明の塗料組成物は、水性塗料にも使用可能であるが、ここで水性塗料に用いられる樹脂は、水溶性樹脂または水分散性樹脂であってこれらの単独または混合物であってもよい。その種類は目的、用途により千差万別であり、特に限定するものではないが、一般にはアクリル系、アクリルーメラミン系、ポリエステル系、ポリウレタン系等の水性塗料用樹脂が挙げられ、これらは単独で用いてもよいし混合して用いてもよい。
Additives commonly used in the paint industry such as pigments, dyes, wetting agents, dispersants, anti-splitting agents, leveling agents, slip agents, anti-skinning agents, anti-gelling agents, antifoaming agents, etc. Can be added.
The coating composition of the present invention can also be used in water-based paints, but the resin used in the water-based paints here is a water-soluble resin or a water-dispersible resin, and these may be used alone or as a mixture thereof. The types vary depending on the purpose and application, and are not particularly limited, but in general, resins for water-based paints such as acrylic, acrylic-melamine, polyester, and polyurethane are used, and these are independent. It may be used in a mixed manner.
水性塗料に使用される本発明のアルミニウム顔料は、塗料用樹脂１００質量部に対して０．１質量部〜１００質量部が好ましい。特に１質量部〜５０質量部用いることが好ましい。金属光沢発揮の点で０．１質量部以上、塗装作業性の点で１００質量部以下が好ましい。
また、上記の各種添加剤としては、例えば、分散剤、増粘剤、タレ防止剤、防カビ剤、紫外線吸収剤、成膜助剤、界面活性剤、その他の有機溶剤、水等、当該分野に於いて通常使用され得るものであって、本発明に於ける効果を損なわないもの及び量であれば、添加しても差し支えない。
As for the aluminum pigment of this invention used for a water-based coating material, 0.1 mass part-100 mass parts are preferable with respect to 100 mass parts of resin for coating materials. In particular, it is preferable to use 1 part by mass to 50 parts by mass. It is preferably 0.1 parts by mass or more in terms of exhibiting metallic luster and 100 parts by mass or less in terms of coating workability.
Examples of the various additives include, for example, dispersants, thickeners, sagging inhibitors, antifungal agents, ultraviolet absorbers, film forming aids, surfactants, other organic solvents, water, and the like. In the present invention, it may be added as long as it can be usually used and does not impair the effects of the present invention.
本発明者らはフレーク状アルミニウム粉末に各種の表面処理を施したものを用い、各種の塗料系から得られた塗膜中におけるアルミニウム顔料粒子の配向性の関係を詳細に調べた結果、フレーク状アルミニウム粉末の表面に、制御された特定の量の樹脂をコーティングしたアルミニウム顔料粒子を自動車の新車ボディ用塗料やパンパー、部品用の塗料、自動車補修用の塗料に用いた場合に、いわゆる「メタリックベースコート層」と呼ばれるアルミニウム顔料を含有する塗膜中で該アルミニウム顔料粒子が極めて優れた配向性を示すことを見出した。 As a result of detailed investigations on the orientation relationship of aluminum pigment particles in coating films obtained from various coating systems, the present inventors used flaky aluminum powder subjected to various surface treatments. When aluminum pigment particles coated with a specific controlled amount of resin on the surface of aluminum powder are used in automotive body paints, bumpers, parts paints, and automotive repair paints, the so-called "metallic base coat" It has been found that the aluminum pigment particles exhibit an extremely excellent orientation in a coating film containing an aluminum pigment called “layer”.
従来、ＲＥＡ方式やベル方式などの静電塗装時に、比較的粒径の細かいアルミニウム顔料粒子は塗装後の塗膜内において、配向の乱れが顕著であったが、本発明によるアルミニウム顔料を含む自動車ベースコート用メタリック塗料組成物は、塗料化時における粒子の分散性が極めて良好であり、また塗装時に粒子にかかるシアーによりアルミニウム粒子が軟凝集を起こすことも無い。よって塗装後の塗膜内において、各アルミニウム粒子は濃淡差の無い均一な状態で分布し、鱗片状の粒子が塗膜に平行に配向することが可能である。この結果、極めて高い光輝度、かつ強いフロップ性を有し、さらには塗板のどの部位においても反射光の強度が一様になり、むらの発生を抑えることが可能になる。 Conventionally, during electrostatic coating such as the REA method and the bell method, aluminum pigment particles having a relatively small particle diameter have been noticeably disturbed in orientation in the coated film. The metallic coating composition for base coat has extremely good particle dispersibility during coating, and the aluminum particles do not cause soft aggregation due to the shear applied to the particles during coating. Therefore, in the coating film after coating, each aluminum particle is distributed in a uniform state with no difference in density, and scale-like particles can be oriented in parallel to the coating film. As a result, it has extremely high light brightness and strong flop, and the intensity of the reflected light is uniform in any part of the coated plate, so that the occurrence of unevenness can be suppressed.
以下、本発明の代表的な実施例を示す。なお、実施例、比較例中で用いた各種の測定方法は以下の通りである。
＜平均粒径ｄ５０＞ レーザーミクロンサイザーＬＭＳ-２４（商品名、セイシン企業株式会社製）により測定した。測定溶剤としては、ミネラルスピリットを使用し、フレーク状アルミニウム粉末の予備分散は、超音波分散（２分）を行った。
＜平均厚みｔ＞ 平均厚みｔは、水面拡散面積ＷＣＡを測定し、前述の式に従って算出した。ＷＣＡの測定は前処理として、フレーク状アルミニウム粉末約１ｇに、５％ステアリン酸のミネラルスピリット溶液を１〜２ｍｌ加え予備分散後、石油ベンジン５０ｍｌ加え混合し、４０〜４５℃で２時間加温後、フィルターで吸引濾過し、パウダー化した。前処理以外の測定はＪＩＳ Ｋ ５９０６に準じた方法で行った。
Hereinafter, typical examples of the present invention will be described. Various measurement methods used in Examples and Comparative Examples are as follows.
<Average particle diameter d50> It was measured with a laser micron sizer LMS-24 (trade name, manufactured by Seishin Enterprise Co., Ltd.). As the measurement solvent, mineral spirit was used, and the preliminary dispersion of the flaky aluminum powder was carried out by ultrasonic dispersion (2 minutes).
<Average thickness t> The average thickness t was calculated by measuring the water surface diffusion area WCA and according to the above formula. WCA was measured as a pretreatment by adding 1 to 2 ml of 5% stearic acid mineral spirit solution to about 1 g of flaky aluminum powder, pre-dispersed, mixed with 50 ml of petroleum benzine, and heated at 40 to 45 ° C. for 2 hours. The solution was suction filtered through a filter and powdered. Measurements other than pretreatment were carried out according to JIS K 5906.
＜平均表面粗さＲａ＞ 原子間力顕微鏡（ＡＦＭ）で測定した１視野５μｍ四方のラインプロファイル（３００スキャン）より算術平均表面粗さを求め、４視野以上についてその算術平均値を求め、Ｒａ(nm)とした。
＜光輝度と粒子感の評価＞
（塗料・塗膜の作製） ベースコート塗料は、アルミニウム顔料（加熱残分７５％）１０．０質量部、アクリディック４７−７１２（商品名、アクリル樹脂、大日本インキ（株）製）８０．０質量部、スーパーベッカミンＪ−８２０（商品名、メラミン樹脂、大日本インキ（株）製）２０質量部、シンナー（トルエン／酢酸エチル／ブチルセロソルブ＝７／２／１）１７８．５質量部を配合した。またトップコート塗料としてアクリディック４４−１７９（商品名、アクリル樹脂、大日本インキ（株）製）８０．０質量部、スーパーベッカミンＪ−８２０（商品名、メラミン樹脂、大日本インキ（株）製）２０質量部、シンナー（トルエン）１７８．５質量部を配合した。上記塗料を用いて、市販の鋼板の上に、ベースコート層は静電塗装機（ランズバーグ社製）により、霧化エアー圧１５７ｋＰａ、パターンエアー圧５８８ｋＰａ、レシプロ速度３２ｍｍ／分（水平）、２ｍｍ／分（垂直）、ガン距離３０ｃｍ、パターン幅３０ｃｍ、印加電圧マイナス６０ｋｖで、またトップコート層はエアースプレーガン（Wider77／商品名、岩田塗装機（株）製）により、エアー圧３９２ｋＰａで２Ｃ１Ｂ（２コート１ベーク）塗装を行い、焼き付け条件は１４０℃×３０分とした。ベースコートの膜厚は２０μｍになるように調整した。
<Average surface roughness Ra> The arithmetic average surface roughness is obtained from a line profile (300 scans) of 5 μm square per field measured with an atomic force microscope (AFM), and the arithmetic average value is obtained for four or more fields of view. nm).
<Evaluation of light intensity and particle feeling>
(Preparation of paint / coating film) Base coat paint is 10.0 parts by weight of aluminum pigment (75% of heating residue), ACRYDIC 47-712 (trade name, acrylic resin, manufactured by Dainippon Ink Co., Ltd.) 80.0 Part by mass, Superbecamine J-820 (trade name, melamine resin, manufactured by Dainippon Ink Co., Ltd.) 20 parts by mass, thinner (toluene / ethyl acetate / butyl cellosolve = 7/2/1) 178.5 parts by mass did. In addition, as a top coat paint, ACRIDIC 44-179 (trade name, acrylic resin, manufactured by Dainippon Ink Co., Ltd.) 80.0 parts by mass, Super Becamine J-820 (trade name, melamine resin, Dainippon Ink Co., Ltd.) 20 parts by mass) and 178.5 parts by mass of thinner (toluene) were blended. Using the above-mentioned paint, a base coat layer is formed on a commercially available steel plate by an electrostatic coating machine (manufactured by Landsburg), atomizing air pressure 157 kPa, pattern air pressure 588 kPa, reciprocating speed 32 mm / min (horizontal), 2 mm / Min (vertical), gun distance 30 cm, pattern width 30 cm, applied voltage minus 60 kv, and the top coat layer was air spray gun (Wider77 / trade name, manufactured by Iwata Coating Machine Co., Ltd.) with an air pressure of 392 kPa at 2C1B (2 (Coating 1 baking) Coating was performed, and baking conditions were set to 140 ° C. × 30 minutes. The film thickness of the base coat was adjusted to 20 μm.
（測色） 塗料の研究Ｎｏ.１１７、ページ６７〜７２（１９８９年関西ペイント（株）発行）の記載の方法に従って、レーザー式メタリック感測定装置アルコープ（商品名、関西ペイント（株）製）を用いて行った。光学的条件は、入射角４５度のレーザー光源と受光角０度と−３５度に受光器をもつ。測定値としては、レーザーの反射光のうち、塗膜表面で反射する鏡面反射領域の光を除いて最大光強度が得られる受光角−３５度で、アルミニウム顔料からの正反射光強度に比例するパラメーターとしてのＩＶ値を求めた。ＩＶ値は光輝度の大小を表わす。また、塗膜外観を目視観察することにより「粒子感」の大きさを判定した。 (Color measurement) In accordance with the method described in Paint Research No. 117, pages 67 to 72 (issued by Kansai Paint Co., Ltd. in 1989), a laser-type metallic feeling measuring device Alcorp (trade name, manufactured by Kansai Paint Co., Ltd.) was used. Used. The optical conditions include a laser light source with an incident angle of 45 degrees and a light receiver with light receiving angles of 0 and -35 degrees. The measured value is a light receiving angle of −35 degrees that can obtain the maximum light intensity except for the light in the specular reflection area reflected on the coating film surface among the reflected light of the laser, and is proportional to the intensity of the regular reflection light from the aluminum pigment. The IV value as a parameter was determined. The IV value represents the magnitude of light luminance. Moreover, the magnitude | size of the "particle feeling" was determined by visually observing the coating-film external appearance.
＜配向性＞ 超深度カラー３Ｄ形状測定顕微鏡（商品名、株式会社キーエンス製）を用い、上記塗膜中のアルミニウム粒子群のイメージ像（1,000倍観察）取得およびその三次元位置情報を測定した。次に上記情報の内、イメージ上の任意の水平方向についての位置情報を高さ×位置の形で取り出した。その後位置情報をグラフ化し、先に得られたイメージと照らし合わせ、アルミニウム顔料の末端部の位置情報として選別した。選別したアルミニウム顔料の末端部の位置情報から、各アルミニウム顔料の塗膜面に対する傾きを計算した。同様の操作を、４視野について行い、各アルミニウム顔料の塗膜面に対する傾きを計算した。その後、これらのアルミニウム顔料の塗膜面に対する傾きについて平均、及び、分散を計算した。 <Orientation> Using an ultra-deep color 3D shape measurement microscope (trade name, manufactured by Keyence Corporation), an image image (1,000 times observation) of an aluminum particle group in the coating film was obtained and its three-dimensional position information was measured. Next, of the above information, position information in an arbitrary horizontal direction on the image was extracted in the form of height × position. Thereafter, the positional information was graphed, compared with the previously obtained image, and selected as positional information on the end of the aluminum pigment. From the positional information of the terminal portion of the selected aluminum pigment, the inclination of each aluminum pigment with respect to the coating surface was calculated. The same operation was performed for four visual fields, and the inclination of each aluminum pigment with respect to the coating surface was calculated. Then, the average and dispersion | distribution were calculated about the inclination with respect to the coating-film surface of these aluminum pigments.
以下、本発明を実施例に基づいて説明する。
（実施例１）
内径１０ｃｍ、長さ３０ｃｍのボールミル内に、アトマイズドアルミニウム粉（平均粒径５μｍ）５０ｇ、ミネラルスピリット１Ｌ、及び、オレイン酸５ｇからなる配合物と、粉砕メディアとして直径２ｍｍのジルコニアボール２ｋｇを充填し、回転数４０ｒｐｍで３時間粉砕をおこなった。粉砕終了後、ミル内のスラリーをミネラルスピリットで洗い出し、４００メッシュの振動篩にかけ、通過したスラリーをフィルターで濾過、濃縮し、加熱残分８０％のケーキを得た。前記の平均粒径、平均厚み、平均表面粗さは、ここで得られたケーキ中に含まれるフレーク状アルミニウム粉末について測定したものである。上記の処理を複数回繰り返すことによって得られたケーキ１００ｇを、容積１リットルの四つ口フラスコに入れ、ミネラルスピリット５００ｇを加え、窒素ガスを導入しながら撹拌し、系内の温度を７０℃に昇温した。次いで、アクリル酸０．３７ｇを添加し７０℃で３０分撹拌を続けた。次にトリメチロールプロパントリメタクリレート０．３７ｇと２、２’−アゾビス−２、４−ジメチルバレロニトリル２．０ｇを一括添加し、系内の温度を７０℃に保ちながら合計６時間重合した。この時点でサンプリングしたろ液中のトリメチロールプロパントリメタクリレートの未反応量をガスクロマトグラフィで分析したところ、添加量の９９％以上が反応していた。重合終了後、自然冷却し、ペースト状のアルミニウム顔料を得た。このアルミニウム顔料の加熱残分（ＪＩＳ−Ｋ−５９１０による）は、７５．０質量％であった。成分（Ａ）のアクリル酸と成分（Ｂ）中のモノマー（トリメチロールプロパントリメタクリレート）の添加比Ａ／Ｂは１．０で、またアルミニウム金属分１００質量部に対する樹脂量は１．０質量部であった。これを用いて、上記試験方法および測定方法に基づいて性能評価を行った。その結果を表１に示す。
Hereinafter, the present invention will be described based on examples.
(Example 1)
A ball mill having an inner diameter of 10 cm and a length of 30 cm is filled with 50 g of atomized aluminum powder (average particle size 5 μm), 1 L of mineral spirit, and 5 g of oleic acid, and 2 kg of zirconia balls having a diameter of 2 mm as grinding media. Then, pulverization was performed at a rotation speed of 40 rpm for 3 hours. After completion of the pulverization, the slurry in the mill was washed out with mineral spirit, passed through a 400 mesh vibrating sieve, and the passed slurry was filtered and concentrated to obtain a cake having a heating residue of 80%. The average particle size, average thickness, and average surface roughness are measured for the flaky aluminum powder contained in the cake obtained here. Put 100 g of cake obtained by repeating the above treatment several times into a 1-liter four-necked flask, add 500 g of mineral spirits, stir while introducing nitrogen gas, and bring the temperature in the system to 70 ° C. The temperature rose. Next, 0.37 g of acrylic acid was added and stirring was continued at 70 ° C. for 30 minutes. Next, 0.37 g of trimethylolpropane trimethacrylate and 2.0 g of 2,2′-azobis-2,4-dimethylvaleronitrile were added all at once, and polymerization was performed for a total of 6 hours while maintaining the temperature in the system at 70 ° C. When the unreacted amount of trimethylolpropane trimethacrylate in the filtrate sampled at this time was analyzed by gas chromatography, 99% or more of the added amount had reacted. After completion of the polymerization, the mixture was naturally cooled to obtain a pasty aluminum pigment. The heating residue (according to JIS-K-5910) of this aluminum pigment was 75.0% by mass. The addition ratio A / B of the acrylic acid of the component (A) and the monomer (trimethylolpropane trimethacrylate) in the component (B) is 1.0, and the amount of resin relative to 100 parts by weight of the aluminum metal is 1.0 part by weight. Met. Using this, performance evaluation was performed based on the above test method and measurement method. The results are shown in Table 1.
（実施例２）
実施例１におけるアトマイズドアルミニウム粉の粒径を６ミクロンにし、粉砕時間を４時間とする以外は同一の条件でアルミニウム顔料を作製した。得られたアルミニウム顔料について、上記の測定を行った。結果を表１に示す。
(Example 2)
An aluminum pigment was produced under the same conditions except that the particle size of the atomized aluminum powder in Example 1 was 6 microns and the pulverization time was 4 hours. Said measurement was performed about the obtained aluminum pigment. The results are shown in Table 1.
（実施例３）
実施例１におけるアトマイズドアルミニウム粉の粒径を７ミクロンにし、粉砕間を５時間にする以外は同一の条件でアルミニウム顔料を作製した。得られたアルミニウム顔料について、上記の測定を行った。結果を表１に示す。
(Example 3)
An aluminum pigment was produced under the same conditions except that the particle size of the atomized aluminum powder in Example 1 was 7 microns and the grinding interval was 5 hours. Said measurement was performed about the obtained aluminum pigment. The results are shown in Table 1.
（実施例４）
実施例１における粉砕メディアを、直径４．８ｍｍのスチールボール２ｋｇ、粉砕時間を５時間に変更した以外は同一の条件でアルミニウム顔料を作製した。得られたアルミニウム顔料について、上記の測定を行った。結果を表１に示す。
Example 4
An aluminum pigment was produced under the same conditions except that the grinding media in Example 1 was changed to 2 kg of steel balls having a diameter of 4.8 mm and the grinding time was changed to 5 hours. Said measurement was performed about the obtained aluminum pigment. The results are shown in Table 1.
（実施例５）
実施例２における粉砕メディアを直径５ｍｍのジルコニアビーズ、回転数を３０ｒｐｍ、粉砕時間を４時間とする以外は同一の条件でアルミニウム顔料を作製した。得られたアルミニウム顔料について、上記の測定を行った。結果を表１に示す。
(Example 5)
An aluminum pigment was produced under the same conditions except that the grinding media in Example 2 were zirconia beads having a diameter of 5 mm, the rotation speed was 30 rpm, and the grinding time was 4 hours. Said measurement was performed about the obtained aluminum pigment. The results are shown in Table 1.
（実施例６）
実施例１におけるアトマイズドアルミニウム粉の粒径を８ミクロンにし、粉砕時間を４時間とする以外は同一の条件でアルミニウム顔料を作製した。得られたアルミニウム顔料について、上記の測定を行った。結果を表１に示す。
(Example 6)
An aluminum pigment was produced under the same conditions except that the particle size of the atomized aluminum powder in Example 1 was 8 microns and the pulverization time was 4 hours. Said measurement was performed about the obtained aluminum pigment. The results are shown in Table 1.
（実施例７）
実施例１におけるアトマイズドアルミニウム粉の粒径を３ミクロン、回転数を６０ｒｐｍ、粉砕時間を３時間とする以外は同一の条件でアルミニウム顔料を作製した。得られたアルミニウム顔料について、上記の測定を行った。結果を表１に示す。
(Example 7)
An aluminum pigment was produced under the same conditions except that the particle size of the atomized aluminum powder in Example 1 was 3 microns, the rotation speed was 60 rpm, and the pulverization time was 3 hours. Said measurement was performed about the obtained aluminum pigment. The results are shown in Table 1.
（比較例１）
実施例１において、ボールミルによって得られたケーキ原料のみを用い、その後の表面処理を全くおこなわずに塗料化して得た塗膜について、上記試験方法および測定方法に基づいて性能評価を行った。その結果を表１に示す。
(Comparative Example 1)
In Example 1, only the cake raw material obtained by the ball mill was used, and the coating film obtained by coating without any subsequent surface treatment was evaluated based on the above test method and measurement method. The results are shown in Table 1.
（比較例２）
実施例６と同一のボールミル条件によって得られたケーキのみを用い、その後の表面処理を全くおこなわずに塗料化して得た塗膜について、上記試験方法および測定方法に基づいて性能評価を行った。その結果を表１に示す。
(Comparative Example 2)
Using only the cake obtained under the same ball mill conditions as in Example 6, the coating film obtained by coating without any subsequent surface treatment was subjected to performance evaluation based on the above test method and measurement method. The results are shown in Table 1.
（比較例３）
実施例１におけるトリメチロールプロパントリメタクリレートを４．０ｇとした以外は同一の条件でアルミニウム顔料を作製した。得られたアルミニウム顔料について、上記の測定を行った。結果を表１に示す。
(Comparative Example 3)
An aluminum pigment was produced under the same conditions except that the amount of trimethylolpropane trimethacrylate in Example 1 was changed to 4.0 g. Said measurement was performed about the obtained aluminum pigment. The results are shown in Table 1.
（比較例４）
実施例１におけるアクリル酸を０．０５ｇ、トリメチロールプロパントリメタクリレートを１．２ｇ、とした以外は同一の条件でアルミニウム顔料を作製した。得られたアルミニウム顔料について、上記の測定を行った。結果を表１に示す。
(Comparative Example 4)
An aluminum pigment was produced under the same conditions except that 0.05 g of acrylic acid and 1.2 g of trimethylolpropane trimethacrylate were used in Example 1. Said measurement was performed about the obtained aluminum pigment. The results are shown in Table 1.
（比較例５）
実施例１におけるアクリル酸を１．０ｇ、トリメチロールプロパントリメタクリレートを０．２ｇ、とした以外は同一の条件でアルミニウム顔料を作製した。得られたアルミニウム顔料について、上記の測定を行った。結果を表１に示す。
(Comparative Example 5)
An aluminum pigment was produced under the same conditions except that 1.0 g of acrylic acid and 0.2 g of trimethylolpropane trimethacrylate were used in Example 1. Said measurement was performed about the obtained aluminum pigment. The results are shown in Table 1.
本発明の塗料組成物は、自動車用等の油性及び水性メタリック塗料用で特に効果が高いが、勿論他のプラスチック家電用塗料や一般の工業用塗料にも活用することができる。 The coating composition of the present invention is particularly effective for oil-based and water-based metallic coatings for automobiles and the like, but it can of course be used for other plastic household electrical appliance coatings and general industrial coatings.
Claims (8)
ーク状アルミニウム粉末表面に形成するアルミニウム顔料の製造方法が、フレーク状アル
ミニウム粉末を有機溶剤に分散せしめ、次に（Ａ）ラジカル重合性不飽和カルボン酸、ラ
ジカル重合性二重結合を有するリン酸またはホスホン酸のモノまたはジエステル、及び、
ラジカル重合性二重結合を有するカップリング剤から選ばれた少なくとも１種を添加する
第一工程を実施した後に、（Ｂ）ラジカル重合性二重結合を２個以上有する単量体と重合開始剤とを添加する第二工程を実施することを特徴とした、 Ａ／Ｂの重量比が０．１〜４であるアルミニウム顔料の製造方法。 An aluminum pigment manufacturing method for forming 0.1 to 2.1 parts by weight of resin on the surface of flaky aluminum powder with respect to 100 parts by mass of flaky aluminum powder disperses the flaky aluminum powder in an organic solvent, and then (A) a radical polymerizable unsaturated carboxylic acid, a mono- or diester of phosphoric acid or phosphonic acid having a radical polymerizable double bond, and
After carrying out the first step of adding at least one selected from coupling agents having a radically polymerizable double bond, (B) a monomer having two or more radically polymerizable double bonds and a polymerization initiator A method for producing an aluminum pigment having a weight ratio of A / B of 0.1 to 4, wherein the second step of adding is performed.
ミニウム顔料粒子の配向性に優れた新車ボディベースコート静電塗装用メタリック塗料組成物。 A metallic paint composition for new vehicle body base coat electrostatic coating, comprising the aluminum pigment according to any one of claims 1, 3, 4, and 5 and having excellent orientation of the painted aluminum pigment particles.
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