JP4859087B2 - Water-based paint and painting method - Google Patents
Water-based paint and painting method Download PDFInfo
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- JP4859087B2 JP4859087B2 JP2004216855A JP2004216855A JP4859087B2 JP 4859087 B2 JP4859087 B2 JP 4859087B2 JP 2004216855 A JP2004216855 A JP 2004216855A JP 2004216855 A JP2004216855 A JP 2004216855A JP 4859087 B2 JP4859087 B2 JP 4859087B2
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- water
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- paint
- modifier
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- 238000010298 pulverizing process Methods 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
本発明は、新規な水性メタリック塗料、及び該水性メタリック塗料を用いた塗装方法に関するものである。 The present invention relates to a novel water-based metallic paint and a coating method using the water-based metallic paint.
一般にメタリック塗料は、顔料としてアルミニウム粉等の金属粉顔料を含んでおり、この金属粉顔料の作用によって独特の美観性を表出することができ、また熱線反射等の性能を発揮することもできる。
メタリック塗料におけるこのような特徴は、金属粉顔料のリーフィング現象によるところが大きい。リーフィング現象とは、塗膜形成時に生じる表面張力等によって、金属粉顔料が塗膜上層に浮上し、被塗面と平行に配向する現象のことである。
しかし、メタリック塗料を塗装後、クリヤー塗料を塗り重ねた場合には、上述の如き金属粉顔料のリーフィング現象によって、メタリック塗膜とクリヤー塗膜の層間密着性が低下し、界面剥離等の問題が引き起こされるおそれがある。
In general, a metallic paint contains a metal powder pigment such as aluminum powder as a pigment, and can exhibit a unique aesthetic appearance by the action of the metal powder pigment, and can also exhibit performance such as heat ray reflection. .
Such characteristics in metallic paints are largely due to the leafing phenomenon of metal powder pigments. The leafing phenomenon is a phenomenon in which the metal powder pigment floats on the upper layer of the coating film and is oriented parallel to the surface to be coated due to surface tension generated during the coating film formation.
However, when the clear paint is applied repeatedly after applying the metallic paint, the interlaminar adhesion between the metallic paint and the clear paint is reduced due to the leafing phenomenon of the metal powder pigment as described above, which causes problems such as interfacial peeling. May be caused.
このような問題を改善する手法として、メタリック塗料にシランカップリング剤を配合する処方が提案されている。例えば、特公平6-19080号公報(特許文献1)には、金属粉、樹脂、溶剤ならびに塗料用添加剤からなるメタリック塗料組成物において、シランカップリング剤を全固形分に対し0.1〜5重量%配合せしめることが記載されている。特開2000-178478号公報(特許文献2)には、蒸着金属膜を粉砕して金属片とした光輝性顔料及びリン酸基含有化合物を含有するメタリック塗料に、さらにシランカップリング剤を混合することが記載されている。また、特開2000-186234号公報(特許文献3)には、含フッ素共重合体、シランカップリング剤、及びメタリック顔料を含有してなるメタリック塗料組成物が記載されている。 As a technique for improving such a problem, a formulation in which a silane coupling agent is blended with a metallic paint has been proposed. For example, in Japanese Patent Publication No. 6-19080 (Patent Document 1), in a metallic coating composition comprising a metal powder, a resin, a solvent and a coating additive, a silane coupling agent is added in an amount of 0.1 to the total solid content. It is described that 5% by weight is incorporated. In Japanese Patent Laid-Open No. 2000-178478 (Patent Document 2), a silane coupling agent is further mixed into a metallic paint containing a bright pigment and a phosphoric acid group-containing compound obtained by pulverizing a deposited metal film into a metal piece. It is described. Japanese Patent Application Laid-Open No. 2000-186234 (Patent Document 3) describes a metallic coating composition containing a fluorine-containing copolymer, a silane coupling agent, and a metallic pigment.
ただし、上記特許文献に記載のメタリック塗料は、いずれもトルエン、キシレン、酢酸ブチル等の強溶剤を媒体とする溶剤系塗料である。環境問題、省資源、労働安全衛生等の見地からすると、このような強溶剤の使用は差し控えたほうが良く、水を媒体とする水性塗料への転換が望まれる。
ところが、水を媒体とするメタリック塗料に、単にシランカップリング剤を配合するだけでは、水とシランカップリング剤との反応性を制御することが困難であるため、密着性等において所望の効果を十分に得ることができない。すなわち、上記特許文献の技術は、いずれも溶剤系塗料のみを対象とするものであり、水性塗料にそのまま適用できるものではない。
However, all of the metallic paints described in the above patent documents are solvent-based paints using a strong solvent such as toluene, xylene, butyl acetate or the like as a medium. From the viewpoint of environmental problems, resource saving, occupational safety and health, etc., it is better to refrain from using such strong solvents, and it is desirable to switch to water-based paints using water as a medium.
However, it is difficult to control the reactivity between water and the silane coupling agent by simply adding a silane coupling agent to the metallic paint using water as a medium. I can't get enough. That is, all of the techniques of the above-mentioned patent documents are directed only to solvent-based paints and cannot be applied to water-based paints as they are.
本発明は、以上のような問題点に鑑みなされたものであり、水性メタリック塗料における密着性不良や界面剥離の問題を十分に改善すること目的とするものである。 The present invention has been made in view of the above problems, and an object thereof is to sufficiently improve the problem of poor adhesion and interfacial peeling in a water-based metallic paint.
本発明者は、上記目的を達成するため鋭意検討を行なった結果、シランカップリング剤を特定の処方で混合してなる水性メタリック塗料に想到し、本発明を完成させるに到った。 As a result of intensive studies to achieve the above object, the present inventor has conceived an aqueous metallic paint obtained by mixing a silane coupling agent with a specific formulation, and has completed the present invention.
すなわち、本発明は以下の特徴を有するものである。
1.合成樹脂エマルション(I)、金属粉顔料(II)、及び改質剤(III)を必須成分とし、前記金属粉顔料(II)が前記合成樹脂エマルション(I)の固形分100重量部に対し1〜100重量部混合され、前記改質剤(III)が下記(ア)〜(ウ)の条件を満たして混合されることを特徴とする水性塗料の製造方法。
(ア)前記改質剤(III)は、シランカップリング剤(p)と水への溶解度10g/100g以下の溶剤(q)とを2成分のみで混合して得られるものである。
(イ)前記改質剤(III)における前記シランカップリング剤(p)と前記溶剤(q)の重量比率は1:99〜95:5である。
(ウ)前記改質剤(III)は、前記合成樹脂エマルション(I)の固形分100重量部に対し0.1〜30重量部混合する。
2.さらに、着色顔料(IV)を必須成分とし、前記着色顔料(IV)が前記合成樹脂エマルション(I)の固形分100重量部に対し0.1〜200重量部混合されることを特徴とする1.記載の水性塗料の製造方法。
3.1.または2.記載の製造方法によって得られた水性塗料を塗装した後、水性クリヤー塗料を塗装することを特徴とする塗装方法。
That is, the present invention has the following characteristics.
1. The synthetic resin emulsion (I), the metal powder pigment (II), and the modifier (III) are essential components, and the metal powder pigment (II) is 1 per 100 parts by weight of the solid content of the synthetic resin emulsion (I). A method for producing a water-based paint, wherein 100 parts by weight is mixed and the modifier (III) is mixed while satisfying the following conditions (a) to (c).
(A) The modifier (III) is obtained by mixing the silane coupling agent (p) and the solvent (q) having a solubility in water of 10 g / 100 g or less with only two components.
(A) The weight ratio of the silane coupling agent (p) and the solvent (q) in the modifier (III) is 1:99 to 95: 5.
(C) The modifier (III) is mixed in an amount of 0.1 to 30 parts by weight with respect to 100 parts by weight of the solid content of the synthetic resin emulsion (I).
2. Further, the coloring pigment (IV) is an essential component, and the coloring pigment (IV) is mixed in an amount of 0.1 to 200 parts by weight with respect to 100 parts by weight of the solid content of the synthetic resin emulsion (I). . A method for producing the water-based paint as described.
3.1. Or 2. A coating method comprising: coating a water-based paint obtained by the production method described above, and then coating a water-based clear paint.
本発明の塗料は、水を媒体とする水性塗料であり、環境問題、省資源、労働安全衛生等の点において好ましいものである。
本発明の塗料を使用すれば、メタリック塗膜とその上のクリヤー塗膜との層間密着性が改善され、界面剥離等の塗膜異常の発生を抑制することができる。
The paint of the present invention is a water-based paint using water as a medium, which is preferable in terms of environmental problems, resource saving, occupational safety and health, and the like.
If the coating material of this invention is used, the interlayer adhesiveness of a metallic coating film and the clear coating film on it will be improved, and generation | occurrence | production of coating film abnormalities, such as interface peeling, can be suppressed.
以下、本発明を実施するための最良の形態について説明する。 Hereinafter, the best mode for carrying out the present invention will be described.
本発明の水性メタリック塗料では、バインダーとして合成樹脂エマルション(I)を使用する。
具体的に合成樹脂エマルション(I)としては、例えば、酢酸ビニル樹脂エマルション、塩化ビニル樹脂エマルション、エポキシ樹脂エマルション、アクリル樹脂エマルション、ウレタン樹脂エマルション、アクリルシリコン樹脂エマルション、フッ素樹脂エマルション等、あるいはこれらの複合系等を挙げることができる。これらは1種または2種以上で使用することができる。
In the aqueous metallic paint of the present invention, the synthetic resin emulsion (I) is used as a binder.
Specifically, as the synthetic resin emulsion (I), for example, a vinyl acetate resin emulsion, a vinyl chloride resin emulsion, an epoxy resin emulsion, an acrylic resin emulsion, a urethane resin emulsion, an acrylic silicon resin emulsion, a fluororesin emulsion, or a composite thereof And the like. These can be used alone or in combination of two or more.
また、合成樹脂エマルション(I)は架橋反応性を有するものであってもよい。合成樹脂エマルション(I)が架橋反応型合成樹脂エマルションである場合は、塗膜の耐水性、耐候性、密着性等を高めることができる。架橋反応型合成樹脂エマルションは、それ自体で架橋反応を生じるもの、あるいは別途混合する架橋剤によって架橋反応を生じるもののいずれであってもよい。このような架橋反応性は、例えば、カルボキシル基と金属イオン、カルボキシル基とカルボジイミド基、カルボキシル基とエポキシ基、カルボキシル基とアジリジン基、カルボキシル基とオキサゾリン基、水酸基とイソシアネート基、カルボニル基とヒドラジド基、エポキシ基とアミノ基、アルド基とセミカルバジド基、ケト基とセミカルバジド基、アルコキシル基どうし等の反応性官能基を組み合わせることによって付与することができる。 Further, the synthetic resin emulsion (I) may have crosslinking reactivity. When the synthetic resin emulsion (I) is a crosslinking reaction type synthetic resin emulsion, the water resistance, weather resistance, adhesion and the like of the coating film can be improved. The crosslinking reaction type synthetic resin emulsion may be either one that causes a crosslinking reaction by itself or one that causes a crosslinking reaction by a separately mixed crosslinking agent. Such crosslinking reactivity includes, for example, carboxyl group and metal ion, carboxyl group and carbodiimide group, carboxyl group and epoxy group, carboxyl group and aziridine group, carboxyl group and oxazoline group, hydroxyl group and isocyanate group, carbonyl group and hydrazide group. It can be imparted by combining reactive functional groups such as epoxy groups and amino groups, aldo groups and semicarbazide groups, keto groups and semicarbazide groups, and alkoxyl groups.
合成樹脂エマルション(I)の製造方法は特に限定されず、例えば、乳化重合、ソープフリー乳化重合、分散重合、フィード乳化重合、フィード分散重合、シード乳化重合、シード分散重合等を採用することができる。
合成樹脂エマルション(I)のガラス転移温度は通常−60〜80℃(好ましくは−40〜60℃)程度である。また、合成樹脂エマルション(I)の平均粒子径は、通常0.05〜0.4μm程度である。
The production method of the synthetic resin emulsion (I) is not particularly limited, and for example, emulsion polymerization, soap-free emulsion polymerization, dispersion polymerization, feed emulsion polymerization, feed dispersion polymerization, seed emulsion polymerization, seed dispersion polymerization and the like can be employed. .
The glass transition temperature of the synthetic resin emulsion (I) is usually about −60 to 80 ° C. (preferably −40 to 60 ° C.). Moreover, the average particle diameter of synthetic resin emulsion (I) is about 0.05-0.4 micrometer normally.
本発明における金属粉顔料(II)は、本発明塗料の形成塗膜にメタリック感を付与する成分である。金属粉顔料(II)としては、例えばアルミニウム、銅、ニッケル、マグネシウム、亜鉛、真鍮等、及びそれらの合金等が使用できる。この中でも、本発明ではアルミニウム顔料が好適である。アルミニウム顔料としては、種々の表面処理を施したものも使用できる。例えば、アトマイズドアルミニウム粉及び/またはアルミニウム箔を、脂肪酸、脂肪族アミン、脂肪族アミド、脂肪族アルコール等の粉砕助剤を用いて粉砕した後、さらにクロム酸、リン酸、リン酸塩、リン酸エステル、バナジン酸塩、酸化バナジウム、モリブデン酸塩、シリカ等によって処理を施したもの等が使用できる。このような処理を施したアルミニウム顔料を使用すれば、水との接触による水素ガスの発生を抑制することができる。 The metal powder pigment (II) in the present invention is a component that imparts a metallic feeling to the formed coating film of the present paint. Examples of the metal powder pigment (II) that can be used include aluminum, copper, nickel, magnesium, zinc, brass, and alloys thereof. Among these, an aluminum pigment is suitable in the present invention. As the aluminum pigment, those subjected to various surface treatments can also be used. For example, after atomized aluminum powder and / or aluminum foil is pulverized using a grinding aid such as fatty acid, aliphatic amine, aliphatic amide, aliphatic alcohol, etc., chromic acid, phosphoric acid, phosphate, phosphorus Those treated with acid ester, vanadate, vanadium oxide, molybdate, silica or the like can be used. If the aluminum pigment which gave such a process is used, generation | occurrence | production of hydrogen gas by contact with water can be suppressed.
金属粉顔料(II)の形状は、通常リン片状であり、その平均粒径は通常1〜50μm(好ましくは5〜30μm)程度である。 The shape of the metal powder pigment (II) is usually scaly, and the average particle size is usually about 1 to 50 μm (preferably 5 to 30 μm).
金属粉顔料(II)の混合比率は、前記合成樹脂エマルション(I)の固形分100重量部に対し、通常1〜100重量部、好ましくは2〜80重量部である。金属粉顔料(II)が1重量部より少ない場合は、形成塗膜において十分なメタリック感を得ることができず、100重量部より多い場合は、塗料の流動性が低下し、塗装作業に支障をきたすおそれがある。 The mixing ratio of the metal powder pigment (II) is usually 1 to 100 parts by weight, preferably 2 to 80 parts by weight with respect to 100 parts by weight of the solid content of the synthetic resin emulsion (I). When the amount of the metal powder pigment (II) is less than 1 part by weight, a sufficient metallic feeling cannot be obtained in the formed coating film. When the amount of the metal powder pigment (II) is more than 100 parts by weight, the fluidity of the paint is lowered, which hinders the painting operation. There is a risk of causing.
本発明の水性メタリック塗料は、上述の成分に加え改質剤(III)を必須成分とするものである。本発明において、この改質剤(III)は下記(ア)〜(ウ)の条件を満たして混合されている。
(ア)改質剤(III)は、シランカップリング剤(p)と水への溶解度10g/100g以下の溶剤(q)との混合物である。
(イ)改質剤(III)におけるシランカップリング剤(p)と溶剤(q)の重量比率は1:99〜95:5である。
(ウ)改質剤(III)は、合成樹脂エマルション(I)の固形分100重量部に対し0.1〜30重量部混合されている。
The water-based metallic paint of the present invention contains the modifier (III) as an essential component in addition to the above-described components. In the present invention, the modifier (III) is mixed while satisfying the following conditions (a) to (c).
(A) The modifier (III) is a mixture of a silane coupling agent (p) and a solvent (q) having a solubility in water of 10 g / 100 g or less.
(A) The weight ratio of the silane coupling agent (p) to the solvent (q) in the modifier (III) is 1:99 to 95: 5.
(C) The modifier (III) is mixed in an amount of 0.1 to 30 parts by weight with respect to 100 parts by weight of the solid content of the synthetic resin emulsion (I).
本発明では、改質剤(III)を上記条件で混合することにより、水性メタリック塗料における密着性不良や界面剥離の問題を十分に改善することができる。具体的には、本発明の水性メタリック塗料によって形成されたメタリック塗膜と、その上に形成されたクリヤー塗膜との密着性や界面剥離を防止することができる。その作用機構は明らかではないが、概ね以下の点によるものと推測される。
第1に、シランカップリング剤(p)は、溶剤(q)に溶解した状態で合成樹脂エマルション(I)の粒子中に分配される。すなわち、本発明では、シランカップリング剤(p)が水との接触によって失活するのを抑制することができる。
第2に、シランカップリング剤(p)は、塗膜形成時に、金属粉顔料(II)表面の官能基(水酸基等)と反応する。この際、溶剤(q)は、金属粉顔料(II)の表面に残存した粉砕助剤(脂肪酸等)を溶出させ、シランカップリング剤(p)の反応を補助する。
以上の作用により、本発明の水性メタリック塗料では、シランカップリング剤(p)による密着性改善効果が最大限に発揮されるものと考えられる。
In the present invention, by mixing the modifier (III) under the above conditions, the problem of poor adhesion and interfacial peeling in the aqueous metallic paint can be sufficiently improved. Specifically, it is possible to prevent adhesion and interfacial peeling between the metallic coating film formed by the aqueous metallic paint of the present invention and the clear coating film formed thereon. The mechanism of action is not clear, but is presumably due to the following points.
First, the silane coupling agent (p) is distributed in the particles of the synthetic resin emulsion (I) in a state dissolved in the solvent (q). That is, in this invention, it can suppress that a silane coupling agent (p) deactivates by contact with water.
Secondly, the silane coupling agent (p) reacts with a functional group (such as a hydroxyl group) on the surface of the metal powder pigment (II) at the time of coating film formation. At this time, the solvent (q) elutes the grinding aid (such as fatty acid) remaining on the surface of the metal powder pigment (II) and assists the reaction of the silane coupling agent (p).
Due to the above action, it is considered that the adhesion improving effect by the silane coupling agent (p) is maximized in the aqueous metallic paint of the present invention.
シランカップリング剤(q)としては、例えば、β−(3、4エポキシシクロヘキシル)エチルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルシラン、N−β(アミノエチル)γ−アミノプロピルメチルジメトキシシラン、N−β(アミノエチル)γ−アミノプロピルメチルトリメトキシシラン、イソシアネート官能性シラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロオピルメチルジエトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−メルカプトプロピルトリメトキシシラン、N−[2−(ビニルベンジルアミノ)エチル]−3−アミノプロピルトリメトキシシラン等が挙げられ、これらの1種または2種以上を用いることができる。 Examples of the silane coupling agent (q) include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylethoxysilane, γ -Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylsilane, N -Β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyltrimethoxysilane, isocyanate functional silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxyproo Pyrmethyl Diet Examples include silane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane, and one or two of these. More than seeds can be used.
水への溶解度10g/100g以下の溶剤(q)としては、例えば、エチレングリコールモノヘキシルエーテル、エチレングリコール−2−エチルヘキシルエーテル、エチレングリコールモノブチルエーテルアセテート、エチレングリコールジブチルエーテル、ジエチレングリコールモノヘキシルエーテル、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールジブチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールフェニルエーテル、プロピレングリコールジアセテート、ジプロピレングリコールモノブチルエーテル、ジプロピレングリコールターシャリーブチルエーテル、トリプロピレングリコールモノブチルエーテル、オクチレングリコール、2−エチルヘキシレングリコール、2,2,4−トリメチル−1,3−ペンタンジオールモノイソブチレート、ベンジルアルコール等が挙げられ、これらの1種または2種以上を用いることができる。
溶剤(q)の水への溶解度は10g/100g未満であるが、好ましくは5g/100g未満である。
Examples of the solvent (q) having a solubility in water of 10 g / 100 g or less include ethylene glycol monohexyl ether, ethylene glycol-2-ethylhexyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol dibutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono Butyl ether acetate, diethylene glycol dibutyl ether, propylene glycol monobutyl ether, propylene glycol phenyl ether, propylene glycol diacetate, dipropylene glycol monobutyl ether, dipropylene glycol tertiary butyl ether, tripropylene glycol monobutyl ether, octylene glycol, 2-ethylhexylene Glycol, , 2,4-trimethyl-1,3-pentanediol mono-isobutyrate, benzyl alcohol and the like, may be used alone or two or more thereof.
The solubility of the solvent (q) in water is less than 10 g / 100 g, but preferably less than 5 g / 100 g.
シランカップリング剤(p)と溶剤(q)との重量比率は、通常1:99〜95:5であり、好ましくは5:95〜80:20である。本発明では、かかる比率で両成分を併用することによって、形成塗膜の密着性を十分に改善することができる。 The weight ratio of the silane coupling agent (p) and the solvent (q) is usually 1:99 to 95: 5, preferably 5:95 to 80:20. In this invention, the adhesiveness of a formed coating film can fully be improved by using both components together in this ratio.
水性メタリック塗料中における改質剤(III)の混合比率は、合成樹脂エマルション(I)の固形分100重量部に対し、通常0.1〜30重量部、好ましくは0.2〜20重量部である。改質剤(III)の混合比率がかかる範囲内であれば、形成塗膜の密着性を十分に改善することができる。改質剤(III)の混合比率が小さすぎる場合は、密着性改善効果を得ることが困難となる。混合比率が大きすぎる場合は、塗膜の乾燥に必要以上に時間を要したり、塗膜表面に粘着性が出てくる等の不具合が生じるおそれがある。 The mixing ratio of the modifier (III) in the aqueous metallic paint is usually 0.1 to 30 parts by weight, preferably 0.2 to 20 parts by weight, based on 100 parts by weight of the solid content of the synthetic resin emulsion (I). is there. If the mixing ratio of the modifier (III) is within such a range, the adhesion of the formed coating film can be sufficiently improved. When the mixing ratio of the modifier (III) is too small, it becomes difficult to obtain an adhesion improving effect. When the mixing ratio is too large, there is a possibility that problems such as taking more time than necessary for drying the coating film and causing stickiness on the surface of the coating film may occur.
本発明では、上記金属粉顔料以外の着色顔料(IV)を使用することもできる。かかる着色顔料(IV)を水性メタリック塗料に混合することで、塗料の色相を調整することができ、様々な色彩を有するメタリック塗膜が得られる。
着色顔料(IV)としては、通常塗料に使用可能なものであれば特に制限されず、例えば酸化チタン、カーボンブラック、酸化第二鉄(ベンガラ)、黄色酸化鉄、オーカー、群青、コバルトグリーン等の無機系顔料、アゾ系、ナフトール系、ピラゾロン系、アントラキノン系、ペリレン系、キナクリドン系、ジスアゾ系、イソインドリノン系、ベンゾイミダゾール系、フタロシアニン系、キノフタロン系等の有機顔料等が使用できる。これら着色顔料(IV)は、所望の色彩に応じて1種または2種以上を適宜使用することができる。
In the present invention, a color pigment (IV) other than the metal powder pigment can also be used. By mixing the colored pigment (IV) with the aqueous metallic paint, the hue of the paint can be adjusted, and metallic coatings having various colors can be obtained.
The coloring pigment (IV) is not particularly limited as long as it can be used in a normal paint, and examples thereof include titanium oxide, carbon black, ferric oxide (bengala), yellow iron oxide, ocher, ultramarine, and cobalt green. Inorganic pigments, organic pigments such as azo, naphthol, pyrazolone, anthraquinone, perylene, quinacridone, disazo, isoindolinone, benzimidazole, phthalocyanine, and quinophthalone can be used. These color pigments (IV) can be appropriately used alone or in combination of two or more depending on the desired color.
本発明の水性メタリック塗料には、上述の成分の他に通常塗料に使用可能な成分を混合することもできる。かかる成分としては、例えば、増粘剤、造膜助剤、体質顔料、レベリング剤、湿潤剤、可塑剤、凍結防止剤、防腐剤、防黴剤、防藻剤、抗菌剤、分散剤、吸着剤、紫外線吸収剤、酸化防止剤、光安定剤、触媒、架橋剤等が挙げられる。 In addition to the above-mentioned components, the water-based metallic paint of the present invention can be mixed with components that can be used in ordinary paints. Examples of such components include thickeners, film-forming aids, extender pigments, leveling agents, wetting agents, plasticizers, antifreezing agents, antiseptics, antifungal agents, anti-algae agents, antibacterial agents, dispersants, and adsorption agents. Agents, ultraviolet absorbers, antioxidants, light stabilizers, catalysts, crosslinking agents and the like.
本発明の水性メタリック塗料は、上述の各成分を常法により混合・攪拌することで製造することができる。この際、改質剤(III)は、少なくとも合成樹脂エマルション(I)の存在下に混合することが望ましい。かかる方法によれば、本発明の効果が十分に発揮される。金属粉顔料(II)、着色顔料(IV)等の混合順序は特に制限されない。 The water-based metallic paint of the present invention can be produced by mixing and stirring the above-mentioned components by a conventional method. At this time, the modifier (III) is desirably mixed in the presence of at least the synthetic resin emulsion (I). According to this method, the effects of the present invention are sufficiently exhibited. The mixing order of the metal powder pigment (II), the color pigment (IV), etc. is not particularly limited.
本発明の水性メタリック塗料は、金属、コンクリート、プラスチック等の各種素材に直接塗装することもできるし、何らかの表面処理(シーラー、フィラー、サーフェーサ、パテ等による下地処理等)を施した上に塗装することも可能である。塗装方法としては、ハケ塗り、スプレー塗装、ローラー塗装等の種々の方法を採用することができる。塗装を行う際の塗付量は、通常0.1〜0.5kg/m2程度である。塗付時には水等で希釈することによって、塗料の粘性を適宜調製することもできる。希釈割合は、通常0〜20重量%程度である。塗装後の乾燥は通常、常温で行えばよいが、必要に応じ加熱することもできる。 The water-based metallic paint of the present invention can be applied directly to various materials such as metal, concrete, plastic, etc., or after applying some surface treatment (such as a surface treatment with a sealer, filler, surfacer, putty, etc.). It is also possible. As a coating method, various methods such as brush coating, spray coating, and roller coating can be employed. The coating amount at the time of coating is usually about 0.1 to 0.5 kg / m 2 . At the time of application, the viscosity of the paint can be appropriately adjusted by diluting with water or the like. The dilution ratio is usually about 0 to 20% by weight. Drying after coating is usually performed at room temperature, but can be heated as necessary.
水性メタリック塗料を塗装した後には、通常、水性クリヤー塗料を塗装する。かかる水性クリヤー塗料の塗装により、耐久性、耐汚染性、美観性(光沢感)等を高めることができる。さらに、本発明では、メタリック塗膜とクリヤー塗膜との層間密着性が十分に確保されるため、界面剥離等の塗膜異常の発生を抑制することもできる。 After applying the water-based metallic paint, the water-based clear paint is usually applied. By applying such a water-based clear paint, durability, stain resistance, aesthetics (glossiness), and the like can be enhanced. Furthermore, in the present invention, since the interlayer adhesion between the metallic coating and the clear coating is sufficiently ensured, the occurrence of coating film abnormalities such as interfacial peeling can be suppressed.
水性クリヤー塗料の組成は特に限定されず、例えば、アクリル樹脂系、ウレタン樹脂系、エポキシ樹脂系、アクリルシリコン樹脂系、フッ素樹脂系等の塗料が使用できる。また、下層のメタリック塗膜の美観性が著しく損なわれない範囲内であれば、着色タイプのものも使用できる。
水性クリヤー塗料の塗装方法は、公知の方法に従えばよく、ハケ塗り、スプレー塗装、ローラー塗装等の種々の方法を採用することができる。塗装を行う際の塗付量は、通常0.1〜0.5kg/m2程度である。塗付時には水等で希釈することによって、塗料の粘性を適宜調製することもできる。希釈割合は、通常0〜20重量%程度である。水性クリヤー塗料を塗装した後の乾燥は通常、常温で行えばよいが、必要に応じ加熱することもできる。
The composition of the water-based clear coating is not particularly limited, and for example, acrylic resin-based, urethane resin-based, epoxy resin-based, acrylic silicon resin-based, fluorine resin-based coatings, and the like can be used. Moreover, a colored type can be used as long as the aesthetics of the lower metallic coating are not significantly impaired.
The method for applying the water-based clear coating may be a known method, and various methods such as brush coating, spray coating, and roller coating can be employed. The coating amount at the time of coating is usually about 0.1 to 0.5 kg / m 2 . At the time of application, the viscosity of the paint can be appropriately adjusted by diluting with water or the like. The dilution ratio is usually about 0 to 20% by weight. Drying after applying the water-based clear coating is usually performed at room temperature, but may be heated as necessary.
以下に実施例を示し、本発明の特徴をより明確にする。 Examples are given below to clarify the features of the present invention.
(改質剤A)
γ−アミノプロピルトリエトキシシランとジエチレングリコールジブチルエーテル(水への溶解度0.3g/100g)を重量比率20:80で混合して、改質剤Aを得た。
(Modifier A)
γ-aminopropyltriethoxysilane and diethylene glycol dibutyl ether (water solubility 0.3 g / 100 g) were mixed at a weight ratio of 20:80 to obtain modifier A.
(改質剤B)
γ−アミノプロピルトリエトキシシランと2,2,4−トリメチル−1,3−ペンタンジオールモノイソブチレート(水への溶解度0.9g/100g)を重量比率20:80で混合して、改質剤Bを得た。
(Modifier B)
γ-aminopropyltriethoxysilane and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (solubility in water 0.9 g / 100 g) were mixed at a weight ratio of 20:80 for modification. Agent B was obtained.
(改質剤C)
γ−アミノプロピルトリエトキシシランとプロピレングリコールモノプロピルエーテル(水への溶解度∞)を重量比率20:80で混合して、改質剤Cを得た。
(Modifier C)
γ-aminopropyltriethoxysilane and propylene glycol monopropyl ether (water solubility ∞) were mixed at a weight ratio of 20:80 to obtain modifier C.
(実施例1)
合成樹脂エマルション200重量部に対し、金属粉顔料18重量部、改質剤A20重量部、増粘剤2重量部、消泡剤1重量部を常法にて順次混合・攪拌することによって水性塗料Aを製造した。なお、改質剤以外の原料としては下記のものを使用した。
・合成樹脂エマルション:アクリル樹脂エマルション(メチルメタクリレート−スチレン−2−エチルヘキシルアクリレート−アクリル酸共重合体、固形分50重量%、ガラス転移温度20℃)
・金属粉顔料:アルミニウム顔料(平均粒子径15μm)
・増粘剤:ウレタン系会合性増粘剤
・消泡剤:鉱物油系消泡剤
Example 1
Water-based paint by mixing and stirring 18 parts by weight of metal powder pigment, 20 parts by weight of modifier A, 2 parts by weight of thickener, and 1 part by weight of antifoaming agent in order in a usual manner with respect to 200 parts by weight of synthetic resin emulsion. A was produced. In addition, the following were used as raw materials other than the modifier.
Synthetic resin emulsion: acrylic resin emulsion (methyl methacrylate-styrene-2-ethylhexyl acrylate-acrylic acid copolymer, solid content 50% by weight, glass transition temperature 20 ° C.)
・ Metal powder pigment: Aluminum pigment (average particle size 15μm)
・ Thickener: Urethane-based associative thickener ・ Defoamer: Mineral oil-based defoamer
予めシーラー塗装が施されたスレート板に対し、上記方法で得られた水性塗料Aを塗付量300g/m2でスプレー塗装し、標準状態(温度23℃・相対湿度50%)にて24時間乾燥後、アクリルシリコン樹脂系水性クリヤー塗料を塗付量150g/m2でスプレー塗装して標準状態にて14日間養生した。以上の方法により、メタリックシルバー色の外観を有する試験板を得た。
この試験板について、水浸漬(23℃)18時間→−20℃3時間→50℃3時間を1サイクルとする温冷繰返し試験を合計10サイクル行った後、標準状態にて24時間放置後、JIS K 5600−5−6に準じた碁盤目テープ法にて、密着性を評価した。その結果、密着性は「○」となった。なお、密着性の評価基準は、剥れた面積が5%未満のものを「○」、剥れた面積が5%以上15%未満のものを「△」、剥れた欠損部の面積が15%以上のものを「×」とした。
Spray coating the aqueous paint A obtained by the above method to a slate plate that has been pre-sealed with a coating amount of 300 g / m2, and drying for 24 hours in standard conditions (temperature 23 ° C, relative humidity 50%) Thereafter, an acrylic silicone resin water-based clear paint was spray-coated at a coating amount of 150 g / m 2 and cured in a standard state for 14 days. By the above method, a test plate having a metallic silver appearance was obtained.
The test plate was subjected to a total of 10 cycles of water-cooling (23 ° C.) 18 hours → −20 ° C. 3 hours → 50 ° C. 3 hours, followed by a total of 10 cycles. The adhesion was evaluated by a cross-cut tape method according to JIS K 5600-5-6. As a result, the adhesion became “◯”. The evaluation criteria for adhesion are “◯” when the peeled area is less than 5%, “△” when the peeled area is 5% or more and less than 15%, and the area of the peeled defect is Those with 15% or more were evaluated as “x”.
(実施例2)
合成樹脂エマルション200重量部に対し、金属粉顔料18重量部、改質剤A20重量部、着色顔料(フタロシアニンブルー顔料)1重量部、増粘剤2重量部、消泡剤1重量部を常法にて順次混合・攪拌することによって水性塗料Bを製造した。
水性塗料Aに替えて水性塗料Bを使用した以外は、実施例1と同様の方法で試験板を作製したところ、ライトブルーメタリック色の外観を有する試験板が得られた。この試験板の密着性試験結果は「○」となった。
(Example 2)
For 200 parts by weight of synthetic resin emulsion, 18 parts by weight of metal powder pigment, 20 parts by weight of modifier A, 1 part by weight of coloring pigment (phthalocyanine blue pigment), 2 parts by weight of thickener, and 1 part by weight of antifoaming agent A water-based paint B was produced by mixing and stirring in order.
When a test plate was produced in the same manner as in Example 1 except that the water-based paint B was used in place of the water-based paint A, a test plate having a light blue metallic appearance was obtained. The adhesion test result of this test plate was “◯”.
(実施例3)
合成樹脂エマルション200重量部に対し、金属粉顔料18重量部、改質剤B20重量部、着色顔料(フタロシアニンブルー顔料)1重量部、増粘剤2重量部、消泡剤1重量部を常法にて順次混合・攪拌することによって水性塗料Cを製造した。
水性塗料Aに替えて水性塗料Cを使用した以外は、実施例1と同様の方法で試験板を作製したところ、ライトブルーメタリック色の外観を有する試験板が得られた。この試験板の密着性試験結果は「○」となった。
(Example 3)
For 200 parts by weight of the synthetic resin emulsion, 18 parts by weight of metal powder pigment, 20 parts by weight of modifier B, 1 part by weight of coloring pigment (phthalocyanine blue pigment), 2 parts by weight of thickener, and 1 part by weight of antifoaming agent are conventional methods. A water-based paint C was produced by mixing and stirring in order.
When a test plate was produced in the same manner as in Example 1 except that the water-based paint C was used in place of the water-based paint A, a test plate having a light blue metallic appearance was obtained. The adhesion test result of this test plate was “◯”.
(比較例1)
合成樹脂エマルション200重量部に対し、金属粉顔料18重量部、γ−アミノプロピルトリエトキシシラン4重量部、増粘剤2重量部、消泡剤1重量部を常法にて順次混合・攪拌することによって水性塗料Dを製造した。
水性塗料Aに替えて水性塗料Dを使用した以外は、実施例1と同様の方法で密着性試験を行ったところ、その結果は「×」となった。
(Comparative Example 1)
To 200 parts by weight of the synthetic resin emulsion, 18 parts by weight of a metal powder pigment, 4 parts by weight of γ-aminopropyltriethoxysilane, 2 parts by weight of a thickener, and 1 part by weight of an antifoaming agent are sequentially mixed and stirred in a conventional manner. Thus, water-based paint D was produced.
An adhesion test was conducted in the same manner as in Example 1 except that the water-based paint D was used in place of the water-based paint A, and the result was “x”.
(比較例2)
合成樹脂エマルション200重量部に対し、金属粉顔料18重量部、γ−アミノプロピルトリエトキシシラン4重量部、ジエチレングリコールジブチルエーテル16重量部、増粘剤2重量部、消泡剤1重量部を常法にて順次混合・攪拌することによって水性塗料Eを製造した。
水性塗料Aに替えて水性塗料Eを使用した以外は、実施例1と同様の方法で密着性試験を行ったところ、その結果は「×」となった。
(Comparative Example 2)
For 200 parts by weight of synthetic resin emulsion, 18 parts by weight of metal powder pigment, 4 parts by weight of γ-aminopropyltriethoxysilane, 16 parts by weight of diethylene glycol dibutyl ether, 2 parts by weight of thickener and 1 part by weight of antifoaming agent are used in a conventional manner. A water-based paint E was produced by sequentially mixing and stirring at.
An adhesion test was performed in the same manner as in Example 1 except that the water-based paint E was used in place of the water-based paint A. The result was “x”.
(比較例3)
合成樹脂エマルション200重量部に対し、金属粉顔料18重量部、改質剤C20重量部、増粘剤2重量部、消泡剤1重量部を常法にて順次混合・攪拌することによって水性塗料Fを製造した。
水性塗料Aに替えて水性塗料Fを使用した以外は、実施例1と同様の方法で密着性試験を行ったところ、その結果は「×」となった。
(Comparative Example 3)
Aqueous paint by mixing and stirring 18 parts by weight of metal powder pigment, 20 parts by weight of modifier C, 2 parts by weight of thickener, and 1 part by weight of defoaming agent in order in a conventional manner with respect to 200 parts by weight of synthetic resin emulsion. F was produced.
An adhesion test was performed in the same manner as in Example 1 except that the water-based paint F was used in place of the water-based paint A, and the result was “x”.
Claims (3)
(ア)前記改質剤(III)は、シランカップリング剤(p)と水への溶解度10g/100g以下の溶剤(q)とを2成分のみで混合して得られるものである。
(イ)前記改質剤(III)における前記シランカップリング剤(p)と前記溶剤(q)の重量比率は1:99〜95:5である。
(ウ)前記改質剤(III)は、前記合成樹脂エマルション(I)の固形分100重量部に対し0.1〜30重量部混合する。 The synthetic resin emulsion (I), the metal powder pigment (II), and the modifier (III) are essential components, and the metal powder pigment (II) is 1 per 100 parts by weight of the solid content of the synthetic resin emulsion (I). A method for producing a water-based paint, wherein 100 parts by weight is mixed and the modifier (III) is mixed while satisfying the following conditions (a) to (c).
(A) The modifier (III) is obtained by mixing the silane coupling agent (p) and the solvent (q) having a solubility in water of 10 g / 100 g or less with only two components.
(A) The weight ratio of the silane coupling agent (p) and the solvent (q) in the modifier (III) is 1:99 to 95: 5.
(C) The modifier (III) is mixed in an amount of 0.1 to 30 parts by weight with respect to 100 parts by weight of the solid content of the synthetic resin emulsion (I).
3. A coating method comprising applying a water-based clear paint after applying the water-based paint obtained by the production method according to claim 1 or 2.
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CN103756560A (en) * | 2013-12-31 | 2014-04-30 | 上海大通涂料化工有限公司 | Water-based high-temperature-resistant coating and preparation method thereof |
WO2020237419A1 (en) * | 2019-05-24 | 2020-12-03 | 河北比尔尼克新材料科技股份有限公司 | AQUEOUS ANTISEPTIC PAINT SPRAYABLE DIRECTLY AT 300ºC, AND PREPARATION METHOD THEREFOR AND USE THEREOF |
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JPH0619080B2 (en) * | 1985-07-30 | 1994-03-16 | 日本ペイント株式会社 | Metallic paint composition |
JP3408201B2 (en) * | 1999-07-01 | 2003-05-19 | エスケー化研株式会社 | Metallic water-based paint composition |
JP4633239B2 (en) * | 2000-09-12 | 2011-02-16 | 昭和アルミパウダー株式会社 | Silica-coated aluminum pigment and method for producing the same |
JP2002248413A (en) * | 2001-02-23 | 2002-09-03 | Nippon Paint Co Ltd | Coating film forming method and coating film |
JP2004124069A (en) * | 2002-07-31 | 2004-04-22 | Showa Denko Kk | Silica-coated aluminum pigment and its production method as well as application thereof |
JP4260454B2 (en) * | 2002-10-09 | 2009-04-30 | 旭化成ケミカルズ株式会社 | Aluminum pigment |
JP2004130237A (en) * | 2002-10-11 | 2004-04-30 | Kansai Paint Co Ltd | Coating method |
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CN103756560A (en) * | 2013-12-31 | 2014-04-30 | 上海大通涂料化工有限公司 | Water-based high-temperature-resistant coating and preparation method thereof |
WO2020237419A1 (en) * | 2019-05-24 | 2020-12-03 | 河北比尔尼克新材料科技股份有限公司 | AQUEOUS ANTISEPTIC PAINT SPRAYABLE DIRECTLY AT 300ºC, AND PREPARATION METHOD THEREFOR AND USE THEREOF |
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