JP4771908B2 - Painting method - Google Patents
Painting method Download PDFInfo
- Publication number
- JP4771908B2 JP4771908B2 JP2006280576A JP2006280576A JP4771908B2 JP 4771908 B2 JP4771908 B2 JP 4771908B2 JP 2006280576 A JP2006280576 A JP 2006280576A JP 2006280576 A JP2006280576 A JP 2006280576A JP 4771908 B2 JP4771908 B2 JP 4771908B2
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- JP
- Japan
- Prior art keywords
- component
- resin
- weight
- primer
- group
- 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.)
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- 238000000034 method Methods 0.000 title description 14
- 238000010422 painting Methods 0.000 title description 9
- 239000000463 material Substances 0.000 claims description 78
- 238000000576 coating method Methods 0.000 claims description 57
- 239000011248 coating agent Substances 0.000 claims description 47
- 125000003700 epoxy group Chemical group 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000004925 Acrylic resin Substances 0.000 claims description 19
- 229920000178 Acrylic resin Polymers 0.000 claims description 19
- 239000003822 epoxy resin Substances 0.000 claims description 19
- 229920000647 polyepoxide Polymers 0.000 claims description 19
- -1 amine compound Chemical class 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 21
- 239000000194 fatty acid Substances 0.000 description 21
- 229930195729 fatty acid Natural products 0.000 description 21
- 150000004665 fatty acids Chemical class 0.000 description 21
- 239000000178 monomer Substances 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 15
- 229920002554 vinyl polymer Polymers 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000003973 paint Substances 0.000 description 11
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
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- 238000012360 testing method Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
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- 239000004606 Fillers/Extenders Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
Description
本発明は、建築物、土木構造物等において適用可能な塗装方法に関するものである。 The present invention relates to a coating method applicable to buildings, civil engineering structures, and the like.
従来、建築物、土木構造物等においては、その躯体の保護や美観性の向上等を目的として、各種の塗料によって塗装仕上げが行われており、トルエン、キシレン等の芳香族炭化水素系溶剤を媒体とする強溶剤形塗料が多く用いられてきた。これに対し、近年、環境や健康に対する意識が高まっており、塗装時の安全性や、作業衛生の点、あるいは大気汚染への影響等を考慮し、このような芳香族炭化水素系溶剤の使用を抑える動きが強まっている。 Conventionally, buildings, civil engineering structures, etc. have been painted with various paints for the purpose of protecting the enclosure and improving aesthetics, and using aromatic hydrocarbon solvents such as toluene and xylene. Many strong solvent-type paints have been used as media. On the other hand, in recent years, awareness of the environment and health has increased, and the use of such aromatic hydrocarbon solvents is considered in consideration of safety during painting, occupational hygiene, and air pollution. There is an increasing movement to control
このような動きに対応するため、塗料としては、脂肪族炭化水素系溶剤を用いる弱溶剤形塗料への転換が要望されるようになってきた。このような弱溶剤形塗料は、強溶剤形塗料に比べ、低毒性であり、作業上の安全性が高く、さらには大気汚染に対する影響も小さいという長所をもつため、環境対応型の塗料として好ましいものである。 In order to cope with such a movement, it has been demanded that the paint be changed to a weak solvent type paint using an aliphatic hydrocarbon solvent. Such weak solvent type paints are preferable as environmentally friendly paints because they have the advantages of low toxicity, high work safety and little influence on air pollution compared to strong solvent type paints. Is.
このような弱溶剤形塗料として、酸化硬化形樹脂を使用した上塗材が知られている（特許文献１等）。このような上塗材は、不飽和脂肪酸に含まれる反応性二重結合同士の酸化によって架橋反応を生じさせるものであり、その硬化触媒として、オクチル酸コバルト、ナフテン酸コバルト等の金属ドライヤーが使用されている。しかしながら、このような上塗材を用いて塗装を行う際、下塗材の種類によっては上塗材の硬化性、密着性等が不十分となり、所望の物性が発現されない場合がある。 As such a weak solvent-type paint, a top coating material using an oxidation-curing resin is known (Patent Document 1, etc.). Such a top coating material causes a crosslinking reaction by oxidation of reactive double bonds contained in unsaturated fatty acids, and a metal dryer such as cobalt octylate or cobalt naphthenate is used as the curing catalyst. ing. However, when coating is performed using such a topcoat material, the curability and adhesion of the topcoat material may be insufficient depending on the type of the undercoat material, and desired physical properties may not be exhibited.
本発明は、このような点に鑑みなされたものであり、酸化硬化形樹脂を結合材とし、その硬化触媒として金属ドライヤーを含有する上塗材による塗装仕上げに適した塗装方法を提供することを目的とするものである。 The present invention has been made in view of these points, and an object of the present invention is to provide a coating method suitable for finishing with an overcoat material containing an oxidatively curable resin as a binder and a metal dryer as a curing catalyst. It is what.
このような問題を解決するため、本発明者らは鋭意研究を重ねた結果、特定のエポキシ系下塗材を塗付した後、酸化硬化形樹脂及び金属ドライヤーを含む上塗材を塗付する塗装方法に想到し、本発明の完成に至った。 In order to solve such problems, the present inventors have conducted extensive research. As a result, after applying a specific epoxy-based primer, a coating method comprising applying an overcoat material including an oxidation-curing resin and a metal dryer is applied. As a result, the present invention has been completed.
本発明は下記の特徴を有するものである。
１．基材に対し下塗材及び上塗材を順に塗付する塗装方法において、
前記下塗材は、可溶形エポキシ樹脂（Ａ）、及び、ポリアミドアミン（ｐ）に対してエポキシ基含有アクリル樹脂（ｑ）を、ポリアミドアミン（ｐ）中の活性水素とエポキシ基含有アクリル樹脂（ｑ）中のエポキシ基との当量比が１：０．０１〜１：０．２５となる割合で付加して得られるアミン化合物（Ｂ）を含むものであり、
前記上塗材は、酸化硬化形樹脂（Ｃ）、及び金属ドライヤー（Ｄ）を含むものであることを特徴とする塗装方法。
The present invention has the following characteristics.
1. In the coating method of applying the primer and the top coat to the base material in order,
The undercoat material comprises a soluble epoxy resin (A) and an epoxy group-containing acrylic resin (q) with respect to the polyamidoamine (p), active hydrogen in the polyamidoamine (p) and an epoxy group-containing acrylic resin ( an amine compound (B) obtained by addition at a ratio such that the equivalent ratio to the epoxy group in q) is 1: 0.01 to 1: 0.25,
The coating method, wherein the top coating material includes an oxidation-curing resin (C) and a metal dryer (D).
本発明の塗装方法によれば、硬化性、密着性等において安定した性能を具備する塗膜が形成できる。さらに、仕上がり性等においても有利な効果を得ることができる。 According to the coating method of the present invention, it is possible to form a coating film having stable performance in terms of curability and adhesion. Furthermore, advantageous effects can also be obtained in terms of finish.
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.
［基材］
本発明の塗装方法は、主に建築物、土木構築物等における躯体の保護のために適用することができる。塗装の対象となる基材としては、例えば、コンクリート、モルタル、スレート板、珪酸カルシウム板、ＡＬＣ板、押出成型板、スレート瓦、セメント瓦、新生瓦、磁器タイル、サイディングボード、金属、ガラス、木材、合板等が挙げられる。これら基材は、その表面に旧塗膜等を有するものであってもよい。
[Base material]
The coating method of the present invention can be applied mainly for the protection of the chassis in buildings, civil engineering structures and the like. Examples of the base material to be painted include concrete, mortar, slate plate, calcium silicate plate, ALC plate, extruded plate, slate tile, cement tile, new roof tile, porcelain tile, siding board, metal, glass, wood And plywood. These base materials may have an old coating film on the surface.
［下塗材］
本発明では、このような基材に対し、まず下塗材を塗付する。
本発明における下塗材は、可溶形エポキシ樹脂（Ａ）（以下「（Ａ）成分」という）、及びポリアミドアミン（ｐ）に対してエポキシ基含有アクリル樹脂（ｑ）を特定割合で付加して得られるアミン化合物（Ｂ）（以下「（Ｂ）成分」という）を必須成分として含むものである。
[Prime material]
In the present invention, an undercoat material is first applied to such a substrate.
The undercoat material in the present invention is obtained by adding an epoxy group-containing acrylic resin (q) at a specific ratio to a soluble epoxy resin (A) (hereinafter referred to as “component (A)”) and polyamidoamine (p). The resulting amine compound (B) (hereinafter referred to as “component (B)”) is included as an essential component.
本発明では、このような（Ａ）成分及び（Ｂ）成分を必須成分とする下塗材を使用することにより、上塗材塗装後の硬化性、密着性等において、優れた性能を得ることができる。このような効果が奏される理由は明確ではないが、（Ａ）成分の硬化剤として、エポキシ基含有アクリル樹脂（ｑ）によってポリアミドアミン（ｐ）が適度に高分子化された変性アミン化合物を用いることにより、その立体障害効果等によって下塗材の官能基と上塗材の金属ドライヤーとの相互作用が抑制されるため、上塗材の硬化過程において金属ドライヤーの効果が十分に発揮されるものと推測される。 In the present invention, by using such a primer that contains the component (A) and the component (B) as essential components, excellent performance can be obtained in curability, adhesion, and the like after the coating of the top coating material. . The reason why such an effect is achieved is not clear, but as a curing agent for component (A), a modified amine compound in which polyamidoamine (p) is appropriately polymerized by epoxy group-containing acrylic resin (q) is used. By using it, the interaction between the functional group of the primer and the metal dryer of the top coat is suppressed due to its steric hindrance effect, etc., so it is assumed that the effect of the metal dryer is fully exhibited in the curing process of the top coat Is done.
下塗材を構成する成分のうち、（Ａ）成分としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂とフェノールノボラック樹脂との共重合型エポキシ樹脂、ジヒドロキシナフタレンのジグリシジルエーテル、モノ（ジ）ヒドロキシナフタレンノボラックのポリグリシジルエーテル、フェノール−ジビニルベンゼン架橋型フェノール樹脂のポリグリシジルエーテル、ビスフェノールＡ−ジビニルベンゼン架橋型フェノール樹脂のポリグリシジルエーテル、モノ（ジ）ヒドロキシナフタレン−ジビニルベンゼン架橋型フェノール樹脂のポリグリシジルエーテル等が挙げられる。 Among the components constituting the primer, the component (A) includes, for example, bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and bisphenol A. Novolak type epoxy resin such as novolak type epoxy resin, copolymer type epoxy resin of bisphenol A type epoxy resin and phenol novolak resin, diglycidyl ether of dihydroxynaphthalene, polyglycidyl ether of mono (di) hydroxynaphthalene novolak, phenol-divinyl Polyglycidyl ether of benzene crosslinked phenolic resin, polyglycidyl ether of bisphenol A-divinylbenzene crosslinked phenolic resin, mono (di) hydroxynaphth Len - polyglycidyl ethers of divinylbenzene crosslinked phenolic resins.
下塗材における（Ｂ）成分は、上記（Ａ）成分の硬化剤としてはたらくものである。この（Ｂ）成分は、ポリアミドアミン（ｐ）（以下「（ｐ）成分」という）と、エポキシ基含有アクリル樹脂（ｑ）（以下「（ｑ）成分」という）との反応により得られるものである。 The component (B) in the undercoat material serves as a curing agent for the component (A). This component (B) is obtained by a reaction between polyamidoamine (p) (hereinafter referred to as “(p) component”) and an epoxy group-containing acrylic resin (q) (hereinafter referred to as “(q) component”). is there.
このうち（ｐ）成分としては、公知または市販のポリアミドアミンが使用でき、具体的には、重合脂肪酸とポリアミンとの縮合反応生成物等が使用できる。このうち、重合脂肪酸としては、例えば、リノレイン酸、オレイン酸、リノール酸、エライジン酸、リシノレイン酸等の、分子中に不飽和結合を有する高級脂肪酸を重合させて得られるダイマー酸、トリマー酸等が挙げられる。また、ポリアミンとしては、脂肪族ジアミン類、アルキレンポリアミン類、ポリメチレンジアミン類、ポリアルキレンポリアミン類等が挙げられる。 Of these, as the component (p), a known or commercially available polyamidoamine can be used, and specifically, a condensation reaction product of a polymerized fatty acid and a polyamine can be used. Among these, as the polymerized fatty acid, for example, dimer acid, trimer acid and the like obtained by polymerizing a higher fatty acid having an unsaturated bond in the molecule such as linolenic acid, oleic acid, linoleic acid, elaidic acid, ricinoleic acid, etc. Can be mentioned. Examples of the polyamine include aliphatic diamines, alkylene polyamines, polymethylene diamines, and polyalkylene polyamines.
（ｑ）成分は、分子中に１個以上のエポキシ基を有するアクリル樹脂である。このような（ｑ）成分としては、例えば、エポキシ基含有単量体とアクリル系単量体との共重合物や、エポキシ樹脂とカルボキシル基含有アクリル樹脂との反応生成物等が使用できる。このうち、後者の反応生成物においては、エポキシ樹脂のエポキシ基とカルボキシル基含有アクリル樹脂のカルボキシル基との当量比において、エポキシ基が残存するように調製すればよい。エポキシ樹脂の比率は、通常、（ｑ）成分中に５〜５０重量％（好ましくは１０〜４０重量％）程度とすればよい。
（ｑ）成分におけるアクリル樹脂部分のガラス転移温度（Ｔｇ）は、通常−３０〜６０℃、好ましくは−１０〜４０℃程度に設定すればよい。（ｑ）成分のエポキシ当量は、通常１００〜１００００ｇ／ｅｑ、好ましくは３００〜５０００ｇ／ｅｑ、より好ましくは５００〜２０００ｇ／ｅｑ程度である。
The component (q) is an acrylic resin having one or more epoxy groups in the molecule. As such a component (q), for example, a copolymer of an epoxy group-containing monomer and an acrylic monomer, a reaction product of an epoxy resin and a carboxyl group-containing acrylic resin, or the like can be used. Of these, the latter reaction product may be prepared such that the epoxy group remains in the equivalent ratio of the epoxy group of the epoxy resin to the carboxyl group of the carboxyl group-containing acrylic resin. The ratio of the epoxy resin is usually about 5 to 50% by weight (preferably 10 to 40% by weight) in the component (q).
The glass transition temperature (Tg) of the acrylic resin portion in the component (q) is usually set to −30 to 60 ° C., preferably about −10 to 40 ° C. The epoxy equivalent of the component (q) is usually about 100 to 10000 g / eq, preferably 300 to 5000 g / eq, more preferably about 500 to 2000 g / eq.
（Ｂ）成分は、上記（ｐ）成分に対し、上記（ｑ）成分を（ｐ）成分のアミノ基が残存するように付加して得られるものである。ここで、（ｐ）に対する（ｑ）成分の割合は、（ｐ）成分中の活性水素と（ｑ）成分中のエポキシ基との当量比が１：０．０１〜１：０．２５（好ましくは１：０．０３〜１：０．２０）となるように設定する。本発明では、（Ｂ）成分中において、このような割合で（ｐ）成分と（ｑ）成分が複合化されることにより、下塗材中でのアクリル樹脂の立体障害作用が適度なものとなり、下塗材の官能基と上塗材の金属ドライヤーの直接的な接触が抑えられ、上塗材の硬化過程における金属ドライヤーの失活が抑制されるものと考えられる。その結果、上塗材塗装後の硬化性、密着性、仕上がり性、重ね塗り適性等において優れた効果を得ることができるのである。この割合よりも（ｑ）成分が少なすぎる場合は、アクリル樹脂による立体障害作用等が十分に発揮されず、上塗材の硬化性、密着性等における改善効果が得られにくくなる。逆に、（ｑ）成分が多すぎる場合は、下塗材の硬化性が不十分となり、基材と下塗材、または下塗材と上塗材の層間密着性や、下塗材の強度等にも悪影響を及ぼすこととなる。 The component (B) is obtained by adding the component (q) to the component (p) so that the amino group of the component (p) remains. Here, the ratio of the (q) component to the (p) is such that the equivalent ratio of the active hydrogen in the (p) component and the epoxy group in the (q) component is 1: 0.01 to 1: 0.25 (preferably Is set to be 1: 0.03 to 1: 0.20). In the present invention, the (p) component and the (q) component are combined in such a proportion in the component (B), so that the steric hindrance action of the acrylic resin in the primer becomes appropriate, It is considered that direct contact between the functional group of the undercoat material and the metal dryer of the topcoat material is suppressed, and the deactivation of the metal dryer in the curing process of the topcoat material is suppressed. As a result, it is possible to obtain excellent effects in curability, adhesion, finish, suitability for overcoating, and the like after coating the top coat material. When the amount of the component (q) is less than this ratio, the steric hindrance action or the like due to the acrylic resin is not sufficiently exhibited, and it becomes difficult to obtain an improvement effect on the curability and adhesion of the top coating material. On the other hand, if the amount of component (q) is too large, the curability of the primer will be insufficient, which will adversely affect the interlayer adhesion between the base material and the primer, or the primer and the primer, and the strength of the primer. Will be affected.
本発明における下塗材は、溶剤として非水系溶剤を用いるもので、当該非水系溶剤としては脂肪族炭化水素系溶剤を主成分とするものが好適である。このような脂肪族炭化水素系溶剤は、芳香族炭化水素系溶剤に比べ、低毒性であり、作業上の安全性が高く、さらには大気汚染に対する影響も小さいという特徴をもつものである。さらに、脂肪族炭化水素系溶剤は、適度な蒸発速度を有するため、本発明下塗材組成物の含浸補強性等に対しても有利にはたらくものである。脂肪族炭化水素系溶剤の比率は、全溶剤中５０重量％以上とすればよい。 The undercoat material in the present invention uses a non-aqueous solvent as a solvent, and the non-aqueous solvent preferably contains an aliphatic hydrocarbon solvent as a main component. Such an aliphatic hydrocarbon solvent has characteristics that it is less toxic than an aromatic hydrocarbon solvent, has high safety in operation, and has little influence on air pollution. Furthermore, since the aliphatic hydrocarbon solvent has an appropriate evaporation rate, it is advantageous for impregnation and reinforcement of the primer composition of the present invention. The ratio of the aliphatic hydrocarbon solvent may be 50% by weight or more in the total solvent.
脂肪族炭化水素系溶剤としては、例えば、ｎ−ヘキサン、ｎ−ペンタン、ｎ−オクタン、ｎ−ノナン、ｎ−デカン、ｎ−ウンデカン、ｎ−ドデカンのほか、テルピン油やミネラルスピリット等が例示できる。このような脂肪族炭化水素系溶剤の他に、必要に応じ、通常塗料に用いられる非水系溶剤を使用することも可能であるが、本発明では特に、トルエン、キシレンを含まず、引火点２１℃以上の消防法第四類第２石油類に該当するものが、安全衛生上好ましい。 Examples of the aliphatic hydrocarbon solvent include n-hexane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, terpin oil, mineral spirit, and the like. . In addition to such aliphatic hydrocarbon solvents, it is possible to use non-aqueous solvents that are usually used in paints as necessary. In the present invention, however, it does not contain toluene or xylene, and has a flash point of 21. Those that fall under the Fire Service Act Type 4 and Type 2 Petroleum above ℃ are preferred for safety and health.
下塗材には上述の成分の他、必要に応じ着色顔料、体質顔料、可塑剤、防腐剤、防黴剤、防藻剤、消泡剤、レベリング剤、顔料分散剤、沈降防止剤、たれ防止剤、艶消し剤、触媒、硬化促進剤等を、本発明の効果が阻害されない範囲内で混合することができる。
下塗材は、以上のような各成分を常法により均一に撹拌・混合して製造することができる。上塗材の形態は、流通時には（Ａ）成分を含む主剤と（Ｂ）成分を含む硬化剤からなる２液型の形態としておき、これらを塗装時に混合して使用することが望ましい。
In addition to the above-mentioned components for the primer, coloring pigment, extender pigment, plasticizer, antiseptic, antifungal agent, antialgae, antifoaming agent, leveling agent, pigment dispersant, antisettling agent, anti-sagging An agent, a matting agent, a catalyst, a curing accelerator, and the like can be mixed as long as the effects of the present invention are not inhibited.
The undercoat material can be produced by uniformly stirring and mixing the above-described components by a conventional method. As for the form of the top coat material, it is desirable to use a two-component form consisting of a main agent containing the component (A) and a curing agent containing the component (B) at the time of distribution, and these are mixed and used at the time of painting.
下塗材の固形分は、通常５〜６０重量％、好ましくは１０〜５０重量％である。固形分をこのような範囲内に設定すれば、含浸補強性とシール性のバランスが良好となり、密着性、仕上がり性、光沢性等の点で好適である。さらに塗装作業性を高めることもできる。 The solid content of the primer is usually 5 to 60% by weight, preferably 10 to 50% by weight. If the solid content is set within such a range, the balance between the impregnation reinforcing property and the sealing property becomes good, which is preferable in terms of adhesion, finish, glossiness, and the like. Furthermore, the paint workability can be improved.
本発明では、このような下塗材を前述の基材に塗付する。下塗材の塗装においては、例えば、刷毛塗装、ローラー塗装、スプレー塗装等の種々の方法を採用することができる。板状建材等を工場内で塗装する場合は、ロールコーター、フローコーター等を用いて塗装することもできる。塗付量については、通常５０〜５００ｇ／ｍ２、好ましくは８０〜３００ｇ／ｍ２程度である。
下塗材の塗回数は、基材の表面状態等によって適宜設定すればよいが、通常１〜２回である。本発明の下塗材では、このような少ない塗回数であっても、シール性に優れた塗膜が形成できる。
下塗材の乾燥時間は、通常３時間以上とすればよい。
In the present invention, such a primer is applied to the aforementioned base material. In painting the undercoat material, various methods such as brush painting, roller painting, and spray painting can be employed. When painting plate-like building materials in a factory, it can also be painted using a roll coater, a flow coater or the like. About a coating amount, it is 50-500 g / m < 2 > normally, Preferably it is about 80-300 g / m < 2 >.
The number of times of applying the undercoat material may be appropriately set depending on the surface condition of the base material, but is usually 1 to 2 times. With the undercoat material of the present invention, a coating film having excellent sealing properties can be formed even with such a small number of coatings.
The drying time of the primer is usually 3 hours or longer.
［上塗材］
本発明では、上記下塗材を塗付・乾燥した後、上塗材を塗付する。
本発明における上塗材では、樹脂成分として酸化硬化形樹脂（以下「（Ｃ）成分」という）を使用する。この（Ｃ）成分は、酸化重合可能な二重結合（酸化重合性基）によって、空気酸化し硬化乾燥するものである。（Ｃ）成分としては、酸化重合性基を有するものであれば特に限定されないが、具体的には以下に示すような樹脂が使用できる。
[Coating material]
In the present invention, after the primer is applied and dried, the top coat is applied.
In the top coating material in the present invention, an oxidation-curing resin (hereinafter referred to as “component (C)”) is used as a resin component. This component (C) is air-oxidized by an oxidatively polymerizable double bond (oxidatively polymerizable group) and cured and dried. The component (C) is not particularly limited as long as it has an oxidative polymerizable group, but specifically, the following resins can be used.
１）酸化重合性基を有するビニル単量体と、この単量体と共重合可能な他のビニル単量体とを共重合させて得られた樹脂。
２）エポキシ基含有ビニル単量体と、この単量体と共重合可能な他のビニル単量体とを共重合させた後、前記エポキシ基含有ビニル単量体に不飽和脂肪酸を付加させて得られた樹脂。
３）酸化重合性基を有するビニル単量体と、この単量体と共重合可能な他のビニル単量体とをアルキド樹脂にグラフト重合させて得られた樹脂。
1) A resin obtained by copolymerizing a vinyl monomer having an oxidative polymerizable group and another vinyl monomer copolymerizable with this monomer.
2) After copolymerizing an epoxy group-containing vinyl monomer and another vinyl monomer copolymerizable with this monomer, an unsaturated fatty acid is added to the epoxy group-containing vinyl monomer. Obtained resin.
3) A resin obtained by graft polymerization of a vinyl monomer having an oxidative polymerizable group and another vinyl monomer copolymerizable with this monomer onto an alkyd resin.
上記１）、３）における酸化重合性基を有するビニル単量体としては、例えばエポキシ基含有ビニル単量体に不飽和脂肪酸が付加されたビニル単量体が挙げられる。このビニル単量体は、エポキシ基と不飽和脂肪酸中のカルボキシル基との反応によって得られるものである。また、上記２）の樹脂は、樹脂中のエポキシ基に対する不飽和脂肪酸の付加反応によって得られるものである。エポキシ基と不飽和脂肪酸を反応させる際には、第３級アミンや第４級アンモニウム塩等の触媒を使用することができる。 Examples of the vinyl monomer having an oxidatively polymerizable group in the above 1) and 3) include a vinyl monomer obtained by adding an unsaturated fatty acid to an epoxy group-containing vinyl monomer. This vinyl monomer is obtained by a reaction between an epoxy group and a carboxyl group in an unsaturated fatty acid. The resin 2) is obtained by an addition reaction of an unsaturated fatty acid to an epoxy group in the resin. When the epoxy group and the unsaturated fatty acid are reacted, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used.
具体的にエポキシ基含有ビニル単量体としては、例えばグリシジル（メタ）アクリレート、β−メチルグリシジル（メタ）アクリレート、３，４−オキシシクロヘキシルプロピル（メタ）アクリレート、アリルグリシジルエーテル等が挙げられる。 Specific examples of the epoxy group-containing vinyl monomer include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-oxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether.
不飽和脂肪酸としては、例えば、亜麻仁油脂肪酸、桐油脂肪酸、魚油脂肪酸、脱水ヒマシ油脂肪酸、大豆油脂肪酸、ゴマ油脂肪酸、ケシ油脂肪酸、エノ油脂肪酸、サフラワー油脂肪酸、麻実油脂肪酸、ブドウ核油脂肪酸、トール油脂肪酸、ヒマワリ油脂肪酸、綿実油脂肪酸、トウモロコシ油脂肪酸、クルミ油脂肪酸等が挙げられる。 Examples of unsaturated fatty acids include linseed oil fatty acid, tung oil fatty acid, fish oil fatty acid, dehydrated castor oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, eno oil fatty acid, safflower oil fatty acid, hemp seed oil fatty acid, grape kernel oil Fatty acids, tall oil fatty acids, sunflower oil fatty acids, cottonseed oil fatty acids, corn oil fatty acids, walnut oil fatty acids and the like.
上記１）、３）における酸化重合性基を有するビニル単量体としては、ジシクロペンタジエンオキシアルキル（メタ）アクリレート等のジシクロペンタジエンオキシアルキル基含有ビニル単量体、アリル（メタ）アクリレート等のアリル基含有ビニル単量体を使用することもできる。 Examples of the vinyl monomer having an oxidatively polymerizable group in 1) and 3) above include dicyclopentadieneoxyalkyl group-containing vinyl monomers such as dicyclopentadieneoxyalkyl (meth) acrylate, and allyl (meth) acrylate. An allyl group-containing vinyl monomer can also be used.
上記３）におけるアルキド樹脂としては、多価アルコールと多価カルボン酸を重縮合させ、これを乾性油、不飽和脂肪酸等で変性したものが使用可能である。このうち多価アルコールとしては、例えばエチレングリコール、グリセリン、ペンタエリスリトール等が挙げられ、多価カルボン酸としては、例えば無水フタル酸、無水マレイン酸等が挙げられる。また、乾性油としては、例えば亜麻仁油、桐油、オイチシカ油、サフラワー油等が挙げられる。 As the alkyd resin in the above 3), those obtained by polycondensation of polyhydric alcohol and polycarboxylic acid and modified with drying oil, unsaturated fatty acid or the like can be used. Among these, examples of the polyhydric alcohol include ethylene glycol, glycerin, and pentaerythritol, and examples of the polyvalent carboxylic acid include phthalic anhydride and maleic anhydride. Examples of the drying oil include linseed oil, tung oil, sika deer oil, safflower oil, and the like.
上塗材における（Ｃ）成分としては、上述のような樹脂をイソシアネート化合物、シリコーン化合物、アルコキシシラン化合物等で変性したものも使用できる。 As the component (C) in the top coating material, a resin obtained by modifying the above resin with an isocyanate compound, a silicone compound, an alkoxysilane compound, or the like can be used.
（Ｃ）成分の形態は、溶剤可溶形、非水分散形のいずれであってもよい。本発明では、両方の形態の樹脂を併用することもできる。（Ｃ）成分の重量平均分子量は、通常１００００〜５０００００、好ましくは２００００〜３０００００である。
（Ｃ）成分のガラス転移点は、通常−５℃〜７０℃、好ましくは０℃〜５０℃である。ガラス転移点が−５℃より低い場合は耐汚染性が不十分となり、７０℃より高いときは耐割れ性、耐久性等において満足な物性が得られ難くなる。
The form of component (C) may be either a solvent-soluble form or a non-aqueous dispersion form. In the present invention, both forms of resins can be used in combination. The weight average molecular weight of the component (C) is usually 10,000 to 500,000, preferably 20,000 to 300,000.
The glass transition point of (C) component is -5 degreeC-70 degreeC normally, Preferably it is 0 degreeC-50 degreeC. When the glass transition point is lower than −5 ° C., the stain resistance is insufficient, and when it is higher than 70 ° C., it is difficult to obtain satisfactory physical properties in terms of crack resistance and durability.
上塗材における金属ドライヤー（以下「（Ｄ）成分」という）は、上記酸化硬化形樹脂の硬化触媒としてはたらく成分である。（Ｄ）成分としては、コバルト系、マンガン系、ジルコニウム系、スズ系、鉛系、亜鉛系、銅系、鉄系、カルシウム系等の公知の有機金属化合物が使用できる。具体的には例えば、オクチル酸コバルト、ナフテン酸コバルト、オクチル酸マンガン、ナフテン酸マンガン、オクチル酸ジルコニウム、ナフテン酸ジルコニウム、オクチル酸スズ、ナフテン酸鉛、ナフテン酸亜鉛、ナフテン酸銅、ナフテン酸鉄、ナフテン酸カルシウム等が挙げられる。 A metal dryer (hereinafter referred to as “component (D)”) in the top coating material is a component that serves as a curing catalyst for the oxidation-curing resin. As the component (D), known organometallic compounds such as cobalt, manganese, zirconium, tin, lead, zinc, copper, iron, and calcium can be used. Specifically, for example, cobalt octylate, cobalt naphthenate, manganese octylate, manganese naphthenate, zirconium octylate, zirconium naphthenate, tin octylate, lead naphthenate, zinc naphthenate, copper naphthenate, iron naphthenate, Examples include calcium naphthenate.
（Ｄ）成分の混合比率は、（Ｃ）成分の固形分１００重量部に対し、通常、金属分で０．００１〜１０重量部、好ましくは０．０１〜５重量部である。 The mixing ratio of the component (D) is usually 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight in terms of the metal content with respect to 100 parts by weight of the solid content of the component (C).
上塗材では、上述の（Ｄ）成分と併せて、加水分解性シリル基含有ケチミン化合物（Ｅ）（以下「（Ｅ）成分」という）を用いることが望ましい。本発明では、このような（Ｅ）成分を用いることにより、塗膜形成時の硬化性を高めることができ、塗膜の経時的な色変化を抑制することもできる。さらに、この（Ｅ）成分は、塗り重ね時のリフティング抑制等にも有効に作用する。 In the top coating material, it is desirable to use a hydrolyzable silyl group-containing ketimine compound (E) (hereinafter referred to as “(E) component”) in combination with the above-mentioned component (D). In the present invention, by using such a component (E), the curability at the time of forming the coating film can be increased, and the color change with time of the coating film can also be suppressed. Furthermore, this component (E) also acts effectively on lifting suppression during coating.
（Ｅ）成分は、加水分解性シリル基と、化学式１に示すケチミン構造を有する化合物である。一般的には、カルボニル化合物（Ｏ＝ＣＲ１Ｒ２）（以下「（ｍ）成分」ともいう）と、１級アミノ基及び加水分解性シリル基を有する化合物（（以下「（ｎ）成分」ともいう）の反応により得られる化合物である。 The component (E) is a compound having a hydrolyzable silyl group and a ketimine structure represented by Chemical Formula 1. Generally, a carbonyl compound (O = CR 1 R 2 ) (hereinafter also referred to as “(m) component”) and a compound having a primary amino group and a hydrolyzable silyl group (hereinafter referred to as “(n) component”). It is a compound obtained by the reaction of (also called).
（化学式１）
−Ｎ＝ＣＲ１Ｒ２
（式中のＲ１、Ｒ２は、同じでも異なっていてもよく、水素原子、アルキル基、シクロアルキル基、フェニルアルキル基を示す。）
(Chemical formula 1)
-N = CR 1 R 2
(R 1 and R 2 in the formula may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenylalkyl group.)
（ｍ）成分としては、一般式：Ｏ＝ＣＲ１Ｒ２（式中のＲ１、Ｒ２は、同じでも異なっていてもよく、水素原子、アルキル基、シクロアルキル基、フェニルアルキル基を示す。）で示されるものであれば特に限定されないが、具体的には、アセトン、メチルエチルケトン、メチルイソプロピルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノン等のケトン類；アセトアルデヒド、ベンズアルデヒド等のアルデヒド類などを挙げることができる。 As the component (m), the general formula: O = CR 1 R 2 (wherein R 1 and R 2 may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenylalkyl group. )) Is not particularly limited, but specific examples include ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; aldehydes such as acetaldehyde and benzaldehyde. be able to.
（ｎ）成分としては、例えば、３‐アミノプロピルトリメトキシシラン、３‐アミノプロピルトリエトキシシラン、３‐アミノプロピルメチルジメトキシシラン、３‐アミノプロピルメチルジエトキシシラン、４‐アミノブチルトリメトキシシラン、４‐アミノブチルトリエトキシシラン、６‐アミノヘキシルトリプロポキシシラン、６‐アミノヘキシルトリブトキシシラン等が挙げられる。 Examples of the component (n) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, Examples include 4-aminobutyltriethoxysilane, 6-aminohexyltripropoxysilane, and 6-aminohexyltributoxysilane.
（Ｅ）成分の具体例としては、例えば、３‐メチルジメトキシシリル‐Ｎ‐（１，３‐ジメチル‐ブチリデン）プロピルアミン、３‐メチルジエトキシシリル‐Ｎ‐（１，３‐ジメチル‐ブチリデン）プロピルアミン、３‐エチルジエトキシシリル‐Ｎ‐（１，３‐ジメチル‐ブチリデン）プロピルアミン、３‐トリメトキシシリル‐Ｎ‐（１，３‐ジメチル‐ブチリデン）プロピルアミン、３‐トリエトキシシリル‐Ｎ‐（１，３‐ジメチル‐ブチリデン）プロピルアミン等が挙げられる。
（Ｅ）成分の混合比率は、（Ｃ）成分の固形分１００重量部に対し、通常０．１〜２０重量部、好ましくは０．２〜５重量部である。
Specific examples of the component (E) include, for example, 3-methyldimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-methyldiethoxysilyl-N- (1,3-dimethyl-butylidene) Propylamine, 3-ethyldiethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-triethoxysilyl- And N- (1,3-dimethyl-butylidene) propylamine.
(E) The mixing ratio of a component is 0.1-20 weight part normally with respect to 100 weight part of solid content of (C) component, Preferably it is 0.2-5 weight part.
上述の成分の他、上塗材には、通常塗料に配合することが可能な各種成分を本発明の効果に影響しない程度に配合することも可能である。このような成分としては、着色顔料、体質顔料、硬化剤、可塑剤、防腐剤、防黴剤、防藻剤、消泡剤、レベリング剤、顔料分散剤、沈降防止剤、たれ防止剤、皮張り防止剤、艶消し剤、紫外線吸収剤、光安定剤、酸化防止剤、低汚染化剤、触媒等が挙げられる。 In addition to the above-described components, various components that can be usually added to the paint can be added to the top coating material to such an extent that the effects of the present invention are not affected. Such components include coloring pigments, extender pigments, curing agents, plasticizers, antiseptics, antifungal agents, algaeproofing agents, antifoaming agents, leveling agents, pigment dispersants, anti-settling agents, anti-sagging agents, leather Examples thereof include anti-tensioning agents, matting agents, ultraviolet absorbers, light stabilizers, antioxidants, low-contaminating agents, and catalysts.
上塗材は、以上のような各成分を常法により均一に撹拌・混合して製造することができる。（Ｃ）成分の種類によっては、流通時に２液型の形態としておき、塗装時に混合して使用することも可能である。上塗材においては、下塗材と同様、非水系溶剤として脂肪族炭化水素系溶剤を主成分とするものが好適である。脂肪族炭化水素系溶剤の比率は、全溶剤中５０重量％以上とすればよい。 The top coating material can be produced by uniformly stirring and mixing the above-described components by a conventional method. Depending on the type of component (C), it is possible to use a two-component form at the time of distribution, and to mix and use at the time of painting. In the topcoat material, as in the case of the undercoat material, a non-aqueous solvent containing an aliphatic hydrocarbon solvent as a main component is suitable. The ratio of the aliphatic hydrocarbon solvent may be 50% by weight or more in the total solvent.
本発明における上塗材は、最終の仕上材として使用するものである。上塗材の塗装においては、例えば、刷毛塗装、ローラー塗装、スプレー塗装等の種々の方法を採用することができる。板状建材等を工場内で塗装する場合は、ロールコーター、フローコーター等を用いて塗装することもできる。塗装の際には、脂肪族炭化水素系溶剤等を用いて上塗材を適宜希釈することもできる。上塗材の塗付量は、通常１００〜５００ｇ／ｍ２、好ましくは１５０〜３００ｇ／ｍ２程度である。
上塗材の塗回数は、所望の仕上状態が得られるように適宜設定すればよい。本発明では、上塗材を２回以上の重ね塗りによって塗付した場合であっても、塗膜の浮き等が発生し難く、良好な仕上状態を得ることができる。
The top coating material in the present invention is used as a final finishing material. In the coating of the top coat material, for example, various methods such as brush coating, roller coating, and spray coating can be employed. When painting plate-like building materials in a factory, it can also be painted using a roll coater, a flow coater or the like. At the time of coating, the top coating material can be appropriately diluted with an aliphatic hydrocarbon solvent or the like. The coating amount of the top coating material is usually about 100 to 500 g / m 2 , preferably about 150 to 300 g / m 2 .
What is necessary is just to set suitably the frequency | count of coating of a top coat material so that a desired finishing state may be obtained. In the present invention, even when the top coating material is applied by two or more times of overcoating, it is difficult for the coating film to float and the like, and a good finished state can be obtained.
以下に実施例及び比較例を示し、本発明の特徴をより明確にする。 Examples and Comparative Examples are shown below to clarify the features of the present invention.
（下塗材１）
ポリアミドアミン（アミン価：２８０ＫＯＨｍｇ／ｇ、固形分：１００重量％）をミネラルスピリットに２０重量％溶解させて得た溶液に対し、エポキシ基含有アクリル樹脂（エポキシ樹脂とカルボキシル基含有アクリル樹脂との反応物、エポキシ樹脂比率：１５重量％、アクリル樹脂Ｔｇ：１８℃、エポキシ当量：８００ｇ／ｅｑ、固形分：６０重量％）を、活性水素とエポキシ基との当量比が１：０．１０となる割合で混合し、８０℃で２時間反応させた後、室温まで放冷することにより、変性アミン化合物を得た。
(Primer 1)
An epoxy group-containing acrylic resin (reaction between an epoxy resin and a carboxyl group-containing acrylic resin) was obtained by dissolving 20% by weight of polyamidoamine (amine value: 280 KOHmg / g, solid content: 100% by weight) in mineral spirit. Product, epoxy resin ratio: 15% by weight, acrylic resin Tg: 18 ° C., epoxy equivalent: 800 g / eq, solid content: 60% by weight), and the equivalent ratio of active hydrogen to epoxy group is 1: 0.10 After mixing at a ratio and reacting at 80 ° C. for 2 hours, the mixture was allowed to cool to room temperature to obtain a modified amine compound.
可溶形エポキシ樹脂（フェノールノボラック樹脂とビスフェノールＡ型エポキシ樹脂とダイマー酸との反応物、固形分：６０重量％、エポキシ当量：１２００ｇ／ｅｑ、溶剤：ミネラルスピリット）１００重量部に対し、ミネラルスピリット１２０重量部、シリコーン系消泡剤０．１重量部を混合し、次いで上記方法で得られた変性アミン化合物７５重量部を混合して下塗材１を得た。 Mineral spirit for 100 parts by weight of soluble epoxy resin (reaction product of phenol novolac resin, bisphenol A type epoxy resin and dimer acid, solid content: 60% by weight, epoxy equivalent: 1200 g / eq, solvent: mineral spirit) 120 parts by weight and 0.1 part by weight of a silicone-based antifoaming agent were mixed, and then 75 parts by weight of the modified amine compound obtained by the above method was mixed to obtain a primer 1.
（下塗材２）
変性アミン化合物において、ポリアミドアミンの活性水素とエポキシ基含有アクリル樹脂のエポキシ基との当量比を１：０．２０となる割合にした以外は、下塗材１と同様の方法で下塗材を製造し、下塗材２を得た。
(Prime material 2)
Under the modified amine compound, undercoat material was produced in the same manner as undercoat material 1 except that the equivalent ratio of active hydrogen of polyamidoamine and epoxy group of epoxy group-containing acrylic resin was set to 1: 0.20. Undercoat material 2 was obtained.
（下塗材３）
変性アミン化合物において、ポリアミドアミンの活性水素とエポキシ基含有アクリル樹脂のエポキシ基との当量比を１：０．０５となる割合にした以外は、下塗材１と同様の方法で下塗材を製造し、下塗材３を得た。
(Primer 3)
Under the modified amine compound, undercoat material was produced in the same manner as undercoat material 1 except that the equivalent ratio of active hydrogen of polyamidoamine and epoxy group of epoxy group-containing acrylic resin was set to 1: 0.05. Undercoat material 3 was obtained.
（下塗材４）
変性アミン化合物において、ポリアミドアミンの活性水素とエポキシ基含有アクリル樹脂のエポキシ基との当量比を１：０．００８となる割合にした以外は、下塗材１と同様の方法で下塗材を製造し、下塗材４を得た。
(Priming material 4)
Under the modified amine compound, undercoat material was produced in the same manner as undercoat material 1 except that the equivalent ratio of active hydrogen of polyamidoamine and epoxy group of epoxy group-containing acrylic resin was set to 1: 0.008. Undercoat material 4 was obtained.
（下塗材５）
アミン化合物としてポリアミドアミン（未変性品）を使用した以外は、下塗材１と同様の方法で下塗材を製造し、下塗材５を得た。
(Priming material 5)
Undercoat material 5 was obtained in the same manner as undercoat material 1 except that polyamidoamine (unmodified product) was used as the amine compound.
（上塗材１）
酸化硬化形樹脂として、スチレン・イソブチルメタクリレート・２−エチルヘキシルアクリレート・グリシジルメタクリレート共重合体の大豆油脂肪酸変性物（変性率２８重量％、重量平均分子量４００００、固形分５０重量％、ミネラルスピリット溶液）を２００重量部用意し、これに対し、酸化チタン８０重量部、増粘剤４重量部、消泡剤２重量部、金属ドライヤー（ナフテン酸コバルトとナフテン酸ジルコニウムの混合液（ミネラルスピリット溶液、Ｃｏ分０．３重量％、Ｚｒ分３重量％））８重量部を常法により混合して上塗材１を製造した。
(Coating material 1)
As oxidatively curable resin, modified soybean oil fatty acid of styrene / isobutyl methacrylate / 2-ethylhexyl acrylate / glycidyl methacrylate copolymer (modification rate 28 wt%, weight average molecular weight 40000, solid content 50 wt%, mineral spirit solution) 200 parts by weight were prepared. On the other hand, 80 parts by weight of titanium oxide, 4 parts by weight of thickener, 2 parts by weight of antifoaming agent, metal dryer (mixed solution of cobalt naphthenate and zirconium naphthenate (mineral spirit solution, Co content) 0.3 wt%, Zr content 3 wt%))) 8 parts by weight were mixed by a conventional method to prepare a top coating material 1.
（上塗材２）
酸化硬化形樹脂として、スチレン・イソブチルメタクリレート・２−エチルヘキシルアクリレート・グリシジルメタクリレート共重合体の大豆油脂肪酸変性物（変性率２８重量％、重量平均分子量４００００、固形分５０重量％、ミネラルスピリット溶液）を２００重量部用意し、これに対し、酸化チタン８０重量部、増粘剤４重量部、消泡剤２重量部、金属ドライヤー（ナフテン酸コバルトとナフテン酸ジルコニウムの混合液（ミネラルスピリット溶液、Ｃｏ分０．３重量％、Ｚｒ分３重量％））８重量部、３−トリエトキシシリル−Ｎ−（１，３−ジメチル−ブチリデン）プロピルアミン０．７重量部を常法により混合して上塗材２を製造した。
(Coating material 2)
As oxidatively curable resin, modified soybean oil fatty acid of styrene / isobutyl methacrylate / 2-ethylhexyl acrylate / glycidyl methacrylate copolymer (modification rate 28 wt%, weight average molecular weight 40000, solid content 50 wt%, mineral spirit solution) 200 parts by weight were prepared. On the other hand, 80 parts by weight of titanium oxide, 4 parts by weight of thickener, 2 parts by weight of antifoaming agent, metal dryer (mixed solution of cobalt naphthenate and zirconium naphthenate (mineral spirit solution, Co content) 0.3 wt%, Zr content 3 wt%)) 8 parts by weight, and 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine 0.7 parts by weight are mixed by a conventional method as a top coating material 2 was produced.
（実施例１）
上述の方法で得られた下塗材１と上塗材１を用い、以下の試験を行った。結果を表１に示す。
Example 1
The following tests were performed using the undercoat material 1 and the topcoat material 1 obtained by the method described above. The results are shown in Table 1.
・仕上がり性
下塗材１を珪酸カルシウム板に塗付量１５０ｇ／ｍ２で刷毛塗りした。標準状態にて３時間養生後、上塗材１を塗付量２００ｇ／ｍ２で刷毛塗りした。標準状態にて７日養生後、塗膜表面の鏡面光沢度（測定角度：６０度）を測定することにより仕上がり性を評価した。評価基準は、鏡面光沢度７０以上を「○」、鏡面光沢度６０以上７０未満を「△」、鏡面光沢度６０未満を「×」とした。
- finish subbing material 1 was brushed with coat-weight 150 g / m 2 on calcium silicate plate. After curing for 3 hours in the standard state, the top coating material 1 was applied with a brush at a coating amount of 200 g / m 2 . After curing for 7 days in the standard state, the finish was evaluated by measuring the specular gloss (measurement angle: 60 degrees) of the coating film surface. The evaluation criteria were “◯” for a mirror glossiness of 70 or more, “Δ” for a mirror glossiness of 60 or more and less than 70, and “x” for a mirror glossiness of less than 60.
・密着性
下塗材１をスレート板に塗付量１００ｇ／ｍ２で刷毛塗りした。標準状態にて３時間養生後、上塗材１を塗付量２００ｇ／ｍ２で刷毛塗りし、標準状態にて７日養生した。以上の方法で得られた試験板を５０℃温水に２４時間浸漬した後、碁盤目テープ法（４×４ｍｍ・２５マス）により密着性を評価した。評価基準は、破断が認められなかったものを「○」、破断面積が５／２５未満であったものを「△」、破断面積が５／２５以上であったものを「×」とした。
· Adhesion undercoating material 1 was brushed with coat-weight 100 g / m 2 to slate. After curing for 3 hours in the standard state, the top coating material 1 was applied with a brush at a coating amount of 200 g / m 2 and cured for 7 days in the standard state. After the test plate obtained by the above method was immersed in warm water at 50 ° C. for 24 hours, adhesion was evaluated by a cross-cut tape method (4 × 4 mm · 25 squares). Evaluation criteria were “◯” when no fracture was observed, “Δ” when the fracture area was less than 5/25, and “x” when the fracture area was 5/25 or more.
・重ね塗り適性
下塗材１をブリキ板に塗付量８０ｇ／ｍ２で刷毛塗りし、標準状態にて３時間乾燥養生した。次いで、上塗材１を塗付量１２０ｇ／ｍ２で刷毛塗りし、所定時間（１６時間、４８時間）乾燥養生後、再度上塗材１を塗付量１２０ｇ／ｍ２で刷毛塗りした。このときの塗膜の表面状態を観察し、異常が認められなかったものを「○」、異常（溶解または浮き）が認められたものを「×」として評価を行った。
-Overcoat suitability The undercoat material 1 was brush-coated on a tin plate at an application amount of 80 g / m 2 and dried and cured in a standard state for 3 hours. Next, the top coating material 1 was brushed at a coating amount of 120 g / m 2 , dried for a predetermined time (16 hours, 48 hours), and then the top coating material 1 was brushed again at a coating amount of 120 g / m 2 . The surface state of the coating film at this time was observed, and the evaluation was made with “O” indicating no abnormality and “X” indicating abnormality (dissolving or floating).
（実施例２）
上述の方法で得られた下塗材２と上塗材１を用い、実施例１と同様の試験を行った。結果を表１に示す。
(Example 2)
The same test as in Example 1 was performed using the primer 2 and the topcoat 1 obtained by the above-described method. The results are shown in Table 1.
（実施例３）
上述の方法で得られた下塗材３と上塗材１を用い、実施例１と同様の試験を行った。結果を表１に示す。
(Example 3)
The same test as in Example 1 was performed using the primer 3 and the topcoat 1 obtained by the above method. The results are shown in Table 1.
（実施例４）
上述の方法で得られた下塗材３と上塗材２を用い、実施例１と同様の試験を行った。結果を表１に示す。
Example 4
The same test as in Example 1 was performed using the primer 3 and the primer 2 obtained by the above-described method. The results are shown in Table 1.
（比較例１）
上述の方法で得られた下塗材４と上塗材１を用い、実施例１と同様の試験を行った。結果を表１に示す。
(Comparative Example 1)
The same test as in Example 1 was performed using the primer 4 and the topcoat 1 obtained by the above-described method. The results are shown in Table 1.
（比較例２）
上述の方法で得られた下塗材５と上塗材１を用い、実施例１と同様の試験を行った。結果を表１に示す。
(Comparative Example 2)
The same test as in Example 1 was performed using the primer 5 and the topcoat 1 obtained by the above method. The results are shown in Table 1.
Claims (1)
前記下塗材は、可溶形エポキシ樹脂（Ａ）、及び、ポリアミドアミン（ｐ）に対してエポキシ基含有アクリル樹脂（ｑ）を、ポリアミドアミン（ｐ）中の活性水素とエポキシ基含有アクリル樹脂（ｑ）中のエポキシ基との当量比が１：０．０１〜１：０．２５となる割合で付加して得られるアミン化合物（Ｂ）を含むものであり、
前記上塗材は、酸化硬化形樹脂（Ｃ）、及び金属ドライヤー（Ｄ）を含むものであることを特徴とする塗装方法。 In the coating method of applying the primer and the top coat to the base material in order,
The undercoat material comprises a soluble epoxy resin (A) and an epoxy group-containing acrylic resin (q) with respect to the polyamidoamine (p), active hydrogen in the polyamidoamine (p) and an epoxy group-containing acrylic resin ( an amine compound (B) obtained by addition at a ratio such that the equivalent ratio to the epoxy group in q) is 1: 0.01 to 1: 0.25,
The coating method, wherein the top coating material includes an oxidation-curing resin (C) and a metal dryer (D).
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