JP2007204709A - Photo-curable paint and method for forming decorative coating using the same - Google Patents
Photo-curable paint and method for forming decorative coating using the same Download PDFInfo
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本発明は、漆、カシューオイル及び乾性油からなる群から選択された自動酸化塗膜成分を含有する装飾性に優れた光硬化性塗料、及び該塗料を用いた装飾性塗膜の形成方法に関する。 The present invention relates to a photocurable paint excellent in decorativeness containing an auto-oxidized coating film component selected from the group consisting of lacquer, cashew oil and drying oil, and a method for forming a decorative paint film using the paint. .
伝統的な漆塗装の硬化過程は、漆中に含まれる酵素（ラッカーゼ）によるウルシオールの脱水素反応及び空気中の酸素による自動酸化によるもので、反応が遅いために塗装工程は多大な手間と時間がかかる作業となっていた。このような低い作業性を改善するため、既に高分子化学の技術を導入しようとする試みが行われてきた。 The curing process of traditional lacquer coating is based on the dehydrogenation reaction of urushiol by the enzyme (laccase) contained in the lacquer and auto-oxidation by oxygen in the air. It was time-consuming work. In order to improve such low workability, attempts have already been made to introduce polymer chemistry technology.
例えば、アクリル酸エステル骨核を有するモノマーまたはオリゴマーを含む光重合型漆塗料や漆印刷インキが知られている（特許文献１，２参照）。また、カシューオイルのエポキシ誘導体より化学反応によりアクリル酸エステル誘導体に変換し、このモノマーからなる光重合型の塗料も提案されている（特許文献３参照）。
しかしながら、漆成分はアクリレートなどのモノマーの光重合を抑制するために、しばしば硬化不良を引き起こすことがあった。また、これらの塗料により形成された塗膜は、塗膜表面は基本的に平滑で、光沢等の変化による装飾効果を持たせることは困難である。
また、漆塗膜表面は基本的に平滑であり、積極的に光沢を変化させて塗膜の質感を変えたり、あるいは光沢の違いにより表面に装飾を施すには、サンドブラストなどによって表面に物理的な凹凸を付けたり、伝統的な蒔絵のように粉体や顔料を付着させる等、手間と時間のかかる方法を採用する必要があった。
However, the lacquer component often causes poor curing in order to suppress photopolymerization of monomers such as acrylates. Moreover, the coating film formed with these paints has a basically smooth coating surface, and it is difficult to give a decorative effect due to changes in gloss or the like.
In addition, the surface of the lacquer coating is basically smooth. To change the texture of the coating by actively changing the gloss, or to decorate the surface by the difference in gloss, the surface is physically applied by sandblasting etc. It was necessary to adopt a time-consuming and time-consuming method, such as adding irregularities and attaching powder and pigments like traditional lacquer paintings.
したがって、本発明はこれら従来技術の問題点を解消して、塗膜の硬化不良等の問題を生じず、短時間で塗膜を形成することができるとともに、塗膜を硬化させる際に塗膜自体に凹凸を発生させて装飾効果を発揮させることのできる光硬化性塗料、及び該塗料を使用した装飾性塗膜の形成方法を提供することを目的とする。 Therefore, the present invention eliminates the problems of these conventional techniques, does not cause problems such as poor curing of the coating film, can form the coating film in a short time, and when the coating film is cured, It is an object of the present invention to provide a photo-curable coating that can generate irregularities in itself and exhibit a decorative effect, and a method for forming a decorative coating film using the coating.
本発明者等は鋭意検討した結果、漆成分による重合抑制が起こりやすいラジカル重合性のアクリレートモノマー類に代えて、重合抑制の起こりにくいカチオン重合性モノマー類を利用することにより、上記課題が解決されることを発見し本発明を完成させたものである。 As a result of intensive studies, the present inventors have solved the above problem by using cationically polymerizable monomers that are unlikely to cause polymerization inhibition instead of radically polymerizable acrylate monomers that are liable to inhibit polymerization due to a lacquer component. And the present invention has been completed.
すなわち、本発明は、次の１〜７の構成を採用するものである。
１．（１）エポキシ化合物、オキセタン化合物及びビニルエーテル化合物からなる群から選択されたカチオン重合性化合物、（２）ヨードニウム塩及びスルホニウム塩からなる群から選択された光重合開始剤、及び（３）漆、カシューオイル及び乾性油からなる群から選択された自動酸化塗膜成分を含有することを特徴とする光硬化性塗料。
２．塗料全体を基準として、（１）カチオン重合性化合物１０〜９０重量％、（２）光重合開始剤０．２〜１５重量％、及び（３）自動酸化塗膜成分１０〜９０重量％を含有することを特徴とする１に記載の光硬化性塗料。
３．１又は２に記載された光硬化性塗料を被塗物表面に塗布した後に光照射し、塗膜を硬化させることを特徴とする装飾性塗膜の形成方法。
４．塗膜の完全硬化前に、塗膜表面に粉体を付着させることを特徴とする３に記載の装飾性塗膜の形成方法。
５．塗膜表面への光照射量を部分的に変化させることによって塗膜中の（３）自動酸化塗膜成分を相分離させ、塗膜表面に凹凸を形成することを特徴とする３に記載の装飾性塗膜の形成方法。
６．塗膜表面に模様を描いたマスク材を配置することによって、塗膜表面への光照射量を部分的に変化させることを特徴とする請求項５に記載の装飾性塗膜の形成方法。
７．塗膜表面に形成する凹凸の高さが０．１〜５００μｍであることを特徴とする請求項５又は６に記載の装飾性塗膜の形成方法。
That is, the present invention employs the following configurations 1 to 7.
1. (1) a cationic polymerizable compound selected from the group consisting of epoxy compounds, oxetane compounds and vinyl ether compounds, (2) a photopolymerization initiator selected from the group consisting of iodonium salts and sulfonium salts, and (3) lacquer and cashew A photocurable coating material comprising an auto-oxidation coating film component selected from the group consisting of oil and drying oil.
2. Contains (1) 10-90% by weight of cationically polymerizable compound, (2) 0.2-15% by weight of photopolymerization initiator, and (3) 10-90% by weight of auto-oxidized coating film component, based on the entire coating. 2. The photocurable paint according to 1, wherein
3. A method for forming a decorative coating film, which comprises applying the photocurable paint described in 1 or 2 to the surface of an object to be coated and then curing the coating film by irradiating light.
4). 4. The method for forming a decorative coating film according to 3, wherein the powder is adhered to the surface of the coating film before the coating film is completely cured.
5). (3) The auto-oxidized coating film component in the coating film is phase-separated by partially changing the light irradiation amount to the coating film surface, and irregularities are formed on the coating film surface. A method for forming a decorative coating.
6). 6. The method for forming a decorative coating film according to claim 5, wherein the amount of light irradiation to the coating film surface is partially changed by arranging a mask material having a pattern on the coating film surface.
7). The method for forming a decorative coating film according to claim 5 or 6, wherein the height of the irregularities formed on the surface of the coating film is 0.1 to 500 µm.
本発明は、次のような顕著な効果を奏するものである。
（１）本発明のカチオン重合型光硬化性塗料では、重合反応への漆等の自動酸化塗膜成分の影響はほとんど見られないため、比較的少量の合成モノマーを漆等の自動酸化塗膜成分に添加することにより光硬化性塗料を調製することができる。
（２）塗膜の硬化は迅速で、しかも高度な質感を有し、美観の良好な硬化塗膜が得られる。
（３）適度に塗膜の硬化が進んだ段階で、金属粉体などを塗膜に付着させることにより、伝統的な蒔絵技術を完全に再現することができる。
（４）光照射条件を選択することにより、塗膜硬化の過程で高分子成分と漆等の自動酸化塗膜成分の相分離を発生させて塗膜に凹凸を形成し、塗膜の反射率等の外観を制御することが可能となる。また、この原理を利用することにより、塗膜に顔料や粉体を用いずに新たな装飾効果を付与することができる。
The present invention has the following remarkable effects.
(1) In the cationic polymerization type photocurable paint of the present invention, since the influence of an auto-oxidation coating film component such as lacquer on the polymerization reaction is hardly seen, a relatively small amount of a synthetic monomer is added to an auto-oxidation coating film such as lacquer. A photo-curable coating can be prepared by adding to the components.
(2) Curing of the coating film is rapid, and a cured coating film having a high texture and good aesthetics can be obtained.
(3) The traditional lacquer technique can be completely reproduced by adhering metal powder or the like to the coating film at a stage where the curing of the coating film has progressed moderately.
(4) By selecting the light irradiation conditions, phase separation of the polymer component and auto-oxidized coating film components such as lacquer is generated in the course of coating film formation, forming irregularities on the coating film, and the reflectance of the coating film And the like can be controlled. Further, by utilizing this principle, a new decorative effect can be imparted to the coating film without using a pigment or powder.
本発明では、光硬化性塗料を構成する成分として、（１）エポキシ化合物、オキセタン化合物及びビニルエーテル化合物からなる群から選択されたカチオン重合性化合物、（２）ヨードニウム塩及びスルホニウム塩からなる群から選択された光重合開始剤、及び（３）漆、カシューオイル及び乾性油からなる群から選択された自動酸化塗膜成分を使用する。 In the present invention, (1) a cationic polymerizable compound selected from the group consisting of an epoxy compound, an oxetane compound and a vinyl ether compound, and (2) a group consisting of an iodonium salt and a sulfonium salt are used as components constituting the photocurable coating. And (3) an auto-oxidation coating film component selected from the group consisting of lacquer, cashew oil and drying oil.
本発明では、（１）カチオン重合性化合物としてエポキシ化合物、オキセタン化合物及びビニルエーテル化合物からなる群から選択された化合物を使用する。これらの化合物としてはエポキシ構造、オキセタン構造、ビニルエーテル構造は、モノマー1分子当たり、1個、2個、3個、またはそれ以上の数の重合性基を含むものが利用でき、適宜に選択し架橋密度の調整をおこなう。
カチオン重合の反応基以外の分子構造は、重合前のインキの粘度や、硬化塗膜の硬度、しなやかさに影響することがある。特に、光硬化過程で塗膜中の漆等の（３）自動酸化塗膜成分との相分離を誘発させる際には、分子構造を選択することが重要である。塗膜の重合性と相分離の形態にあわせて、複数の（１）カチオン重合性モノマーを組み合わせて使用することもある。
In the present invention, (1) a compound selected from the group consisting of an epoxy compound, an oxetane compound and a vinyl ether compound is used as the cationic polymerizable compound. As these compounds, epoxy structures, oxetane structures, and vinyl ether structures containing one, two, three, or more polymerizable groups per monomer molecule can be used, and can be selected and crosslinked appropriately. Adjust the density.
The molecular structure other than the reactive group in the cationic polymerization may affect the viscosity of the ink before polymerization, the hardness of the cured coating film, and the flexibility. In particular, it is important to select the molecular structure when inducing phase separation with (3) auto-oxidation coating film components such as lacquer in the coating film in the photocuring process. A plurality of (1) cationic polymerizable monomers may be used in combination in accordance with the polymerizability of the coating film and the form of phase separation.
（１）カチオン重合性化合物として使用されるエポキシ化合物は、例えば分子末端にエポキシをもつグリシジル構造のもの、またはシクロヘキサン環のような脂環式骨核上にエポキシ基をもつものが利用できる。
このようなエポキシ化合物の例としては、ビスフェノール-Ａ-ジグリシジルエーテル、フェニルグリシジルエーテル、1,4-ブタンジオールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリフェニロールメタントリグリシジルエーテル、ポリ[（フェニルグリシジルエーテル）-co-ホルムアルデヒド]、ポリ（エチレン-co-メチルアクリレート-co-グリシジルメタクリレート）、3,4-エポキシシクロヘキシルメチル3,4-エポキシシクロヘキサンカルボキシレート、ビス（3,4-エポキシシクロヘキシルメチル）アジピン酸が挙げられる。
(1) As the epoxy compound used as the cationic polymerizable compound, for example, those having a glycidyl structure having an epoxy at the molecular terminal or those having an epoxy group on an alicyclic bone nucleus such as a cyclohexane ring can be used.
Examples of such epoxy compounds include bisphenol-A-diglycidyl ether, phenyl glycidyl ether, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, triphenylol methanetri Glycidyl ether, poly [(phenyl glycidyl ether) -co-formaldehyde], poly (ethylene-co-methyl acrylate-co-glycidyl methacrylate), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, bis (3 , 4-epoxycyclohexylmethyl) adipic acid.
（１）カチオン重合性化合物として使用されるオキセタン化合物の例としては、3-エチル-3-ヒドロキシメチルオキセタン、1,4-ビス｛［（3-エチル-3-オキセタニル）メトキシ］メチル｝ベンゼンが挙げられる。また、ビニルエーテル化合物としては、1,4,-シクロヘキサンジメタノールジビニルエーテル、ジエチレングリコールジビニルエーテルなどが挙げられる。 (1) Examples of oxetane compounds used as cationically polymerizable compounds include 3-ethyl-3-hydroxymethyloxetane and 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene. Can be mentioned. Examples of the vinyl ether compound include 1,4, -cyclohexanedimethanol divinyl ether and diethylene glycol divinyl ether.
また、（２）光重合開始剤としては、ヨードニウム塩、スルホニウム塩型のものが用いられる。開始剤の対アニオンはカチオン重合の反応速度に大きな影響を与えるが、AsF6 -、BF4 -、PF6 -、SbF6 -、CF3SO3 -などを用いることができる。
好ましい開始剤の例としては、ビス（4-tert-ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート、ビス（4-tert-ブチルフェニル）ヨードニウムヘキサフルオロホスフェート、ビス（4-ドデシルフェニル）ヨードニウムヘキサフルオロホスフェート、(4-フェニルチオフェニル)ジフェニルスルホニウムトリフルオロスルホネート、トリ-p-トリルスルホニウムヘキサフルオロホスフェート、（９−オキサ−９Ｈ-キサンテン−２−イル）フェニルヨードニウムヘキサフルオロホスフェート〔(9-Oxa-9H-xanthen-2-yl)phenyl idonium hexafluorophosphate〕、（９−オキサ−９Ｈ-キサンテン−２−イル）ジフェニルスルホニウムヘキサフルオロホスフェート〔(9-Oxa-9H-xanthen-2-yl)diphenyl sulfonium hexafluorophospahte〕が挙げられる。
(2) As the photopolymerization initiator, those of iodonium salt and sulfonium salt type are used. The counter anion of the initiator greatly affects the reaction rate of the cationic polymerization, but AsF 6 − , BF 4 − , PF 6 − , SbF 6 − , CF 3 SO 3 − and the like can be used.
Examples of preferred initiators include bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-dodecylphenyl) iodonium hexafluorophosphate, (4 -Phenylthiophenyl) diphenylsulfonium trifluorosulfonate, tri-p-tolylsulfonium hexafluorophosphate, (9-oxa-9H-xanthen-2-yl) phenyliodonium hexafluorophosphate [(9-Oxa-9H-xanthen-2 -yl) phenyl idonium hexafluorophosphate] and (9-oxa-9H-xanthen-2-yl) diphenylsulfonium hexafluorophosphate [(9-Oxa-9H-xanthen-2-yl) diphenyl sulfonium hexafluorophospahte].
本発明の光硬化性塗料を構成する成分の配合割合は、塗料全体を基準として、（１）カチオン重合性化合物１０〜９０重量％、通常は２５〜７０重量％、（２）光重合開始剤０．２〜１５重量％、通常は２〜８重量％、及び（３）自動酸化塗膜成分１０〜９０重量％、通常は２５〜７５重量％とすることが好ましい。（３）自動酸化塗膜成分として、天然漆をシリカゲルカラムで処理し（例えば、溶離液としてクロロホルム-アセトン（アセトン2-5容量％）を使用）精製したものを使用する場合には、（２）光重合開始剤は０．５〜１重量％程度に減量することが可能である。 The blending ratio of the components constituting the photocurable paint of the present invention is (1) 10 to 90% by weight, usually 25 to 70% by weight, (2) photopolymerization initiator based on the whole paint. It is preferably 0.2 to 15% by weight, usually 2 to 8% by weight, and (3) 10 to 90% by weight, usually 25 to 75% by weight of the auto-oxidized coating film component. (3) When using a natural lacquer treated with a silica gel column (for example, using chloroform-acetone (acetone 2-5% by volume) as an eluent) as an auto-oxidized coating film component, (2 ) The photopolymerization initiator can be reduced to about 0.5 to 1% by weight.
本発明の光硬化性塗料により形成する塗膜の厚さは０．５μｍ〜１ｍｍ程度、通常は１０〜１００μｍ程度である。照射光源としては、水銀灯、メタルハライドランプ、紫外光発光ダイオードなどを用いることができる。塗膜への積算照射光量（365nm）は、20mJ/cm2〜20J/cm2程度であり、通常は600mJ/cm2〜3J/cm2程度である。積算光量は、塗料の硬化速度に影響を及ぼし、特に光硬化過程で（３）自動酸化塗膜成分を相分離させる際には重要である。 The thickness of the coating film formed by the photocurable coating material of the present invention is about 0.5 μm to 1 mm, usually about 10 to 100 μm. As the irradiation light source, a mercury lamp, a metal halide lamp, an ultraviolet light emitting diode, or the like can be used. Cumulative amount of light irradiated to the coating film (365 nm) is 20mJ / cm 2 ~20J / cm 2 or so, usually a 600mJ / cm 2 ~3J / cm 2 approximately. The integrated light amount affects the curing speed of the paint, and is particularly important when (3) the auto-oxidized coating film component is phase-separated during the photocuring process.
本発明の光硬化性塗料は、（１）カチオン重合性化合物、（２）光重合開始剤及び（３）自動酸化塗膜成分を直接混合し、機械的な攪拌により均一に混練することにより調製できる。
（２）光重合開始剤の混和を容易にするため、少量のトルエン、テトラヒドロフラン、アセトン、プロピレンカーボネートなどの有機溶媒に開始剤を溶解した後、塗料混合物に添加してもよい。また開始剤の塗料混合物への溶解を促進するために浴型の超音波装置を利用することも可能である。
The photocurable paint of the present invention is prepared by directly mixing (1) a cationic polymerizable compound, (2) a photopolymerization initiator, and (3) an auto-oxidized coating film component, and kneading them uniformly by mechanical stirring. it can.
(2) In order to facilitate the mixing of the photopolymerization initiator, the initiator may be dissolved in a small amount of an organic solvent such as toluene, tetrahydrofuran, acetone, propylene carbonate, and then added to the coating mixture. It is also possible to use a bath-type ultrasonic device to promote dissolution of the initiator in the paint mixture.
本発明の光硬化性塗料を使用して塗膜を形成するには、通常の塗料と同様に、刷毛やゴムロールなどを使い、木材、金属、ガラス、セラミックス、プラスチックス等の被塗布物表面上に塗布することができる。また、本発明の光硬化性塗料のみで彩色を行うには、筆などによる塗布の他、シルクスクリーンなどの印刷法が適用可能である。 In order to form a coating film using the photo-curable paint of the present invention, a brush or a rubber roll is used on the surface of an object to be coated such as wood, metal, glass, ceramics, and plastics in the same manner as a normal paint. Can be applied. Moreover, in order to color only with the photocurable coating material of this invention, the printing methods, such as a silk screen other than application | coating with a brush, are applicable.
本発明によれば、光硬化性塗料を非塗物表面に塗布した後に光照射し、塗膜の完全硬化前に塗膜表面に金属、無機物、有機物等からなる粉体を付着させることにより、蒔絵風の装飾塗膜を形成することができる。
塗膜への粉体の固定による彩色は、未硬化塗膜へ光照射を行い、モノマーが重合反応により時間ととともに高分子化し、塗膜の粘度が相当に増大した時点で行う。このような彩色に適した時点は、塗膜の組成と照射条件に依存するが、光照射後10秒〜3時間程度経過した時点であり、通常は照射後1分から5分程度である。
According to the present invention, photoirradiation coating is applied to the surface of the non-coating material, followed by light irradiation, and before the coating film is completely cured, a powder made of metal, inorganic material, organic material, etc. is adhered to the coating surface. A decorative paint film with a lacquer painting style can be formed.
Coloring by fixing the powder to the coating film is performed when the uncured coating film is irradiated with light and the monomer is polymerized with time by the polymerization reaction, and the viscosity of the coating film is considerably increased. Although the time suitable for such coloring depends on the composition of the coating film and the irradiation conditions, it is the time when about 10 seconds to 3 hours have passed after the light irradiation, and usually about 1 to 5 minutes after the irradiation.
本発明によれば、塗膜表面への光照射量を部分的に変化させることによって塗膜中の（３）自動酸化塗膜成分を相分離させ、塗膜表面に凹凸を形成することができる。
光硬化反応中における相分離状態の形成は、（１）カチオン重合性モノマーと漆等の（３）自動酸化塗膜成分とは相溶性が高く、均質に混和するが、モノマーが高分子化するにつれて、漆等との相溶性が低下し、漆等が高分子成分の相から遊離してくることに由来する。塗膜中の漆等の（３）自動酸化塗膜成分は分子の拡散性、界面エネルギー等に依存して、ある一定の大きさの相を作り、塗膜に０．1μｍ〜1ｍｍ程度の規則構造（線状、棒状、点状など）を誘起する。この規則構造は、塗膜の透明度に影響を与えるだけでなく、塗膜表面に０．１〜５００μｍの高さの凹凸を生じさせ、塗膜の反射率を変化させることになる。
According to the present invention, by partially changing the light irradiation amount on the coating film surface, the (3) auto-oxidation coating film component in the coating film can be phase-separated to form irregularities on the coating film surface. .
The formation of the phase separation state during the photocuring reaction is (1) a cationically polymerizable monomer and (3) an auto-oxidized coating film component such as lacquer that is highly compatible and homogeneously mixed, but the monomer is polymerized. As a result, the compatibility with lacquer and the like decreases, and lacquer and the like are released from the phase of the polymer component. (3) Auto-oxidizing coating film components such as lacquer in the coating film form a phase of a certain size depending on the diffusibility of the molecule, interfacial energy, etc., and a rule of about 0.1 μm to 1 mm on the coating film Induces structure (linear, rod, dot, etc.). This regular structure not only affects the transparency of the coating film, but also causes irregularities with a height of 0.1 to 500 μm on the surface of the coating film, thereby changing the reflectance of the coating film.
このような規則構造の発生は、（１）カチオン重合性モノマーの重合速度とともに、（２）光重合開始剤の種類と含量、光の照射強度と積算光量に依存する。一般に、塗膜を急速に硬化させると、相分離の発生が抑制され均質な硬化膜を与えるので、同一の組成の塗料であっても照射条件を変えることによって、均質で平滑な硬化塗膜の調製と、相分離し凹凸のある硬化塗膜の調製を選択することができる。
従って、未硬化塗膜上の近接した位置に、文様を描いたマスクを置くなどにより、未硬化塗膜に到達する光に強度変化をつけると、硬化塗膜にはマスクの文様に従って反射率の違いが生じ、塗膜に文様の描写が実現される。
The occurrence of such a regular structure depends on (1) the polymerization rate of the cationic polymerizable monomer, and (2) the type and content of the photopolymerization initiator, the light irradiation intensity, and the integrated light quantity. In general, when the coating is cured rapidly, the occurrence of phase separation is suppressed and a uniform cured film is obtained. Therefore, even with a paint having the same composition, by changing the irradiation conditions, a uniform and smooth cured coating can be obtained. The preparation and the preparation of the cured coating film with phase separation and unevenness can be selected.
Therefore, if the intensity of light reaching the uncured coating is changed, for example, by placing a mask with a pattern on the uncured coating in close proximity, the reflectance of the cured coating will vary according to the mask pattern. A difference is made, and pattern depiction is realized on the coating film.
この時点では塗膜内部の漆等の（３）自動酸化塗膜成分は未硬化であるが、塗膜表面は十分な硬度を有し、内部の漆等の成分を遮閉しているので表面に移動することはなく、被塗布製品の取扱には特段の注意を必要としない。
（３）自動酸化塗膜成分としては、漆（主成分：ウルシオール）、カシューオイル（同：カルダノール）及び乾性油からなる群から選択された成分を使用することができる。これらの成分は、自動酸化によりゆっくりと硬化が進行する。自動酸化の促進には、ナフテン酸コバルト、２−エチルヘキサン酸コバルト（ＩＩ）のような脂溶性のコバルト塩等を微量添加することができる。
At this time, (3) auto-oxidized coating film components such as lacquer inside the coating film are uncured, but the surface of the coating film has sufficient hardness and blocks the components such as lacquer inside, so the surface There is no need to pay special attention when handling the coated product.
(3) As an auto-oxidation coating film component, a component selected from the group consisting of lacquer (main component: urushiol), cashew oil (same: cardanol) and drying oil can be used. These components are slowly cured by auto-oxidation. For promotion of auto-oxidation, a trace amount of a fat-soluble cobalt salt such as cobalt naphthenate and cobalt (II) 2-ethylhexanoate can be added.
つぎに、実施例により本発明をさらに説明するが、以下の具体例は本発明を限定するものではない。
（実施例１）
（１）カチオン重合性モノマーとしてビスフェノール-Ａ-ジグリシジルエーテル（ＤＧ−１）６５重量部、（２）光重合開始剤としてビス（4-tert-ブチルフェニル）ヨードニウムヘキサフルオロホスフェート（Ｉ−１）５重量部、（３）自動酸化塗膜成分として生漆（Ｕｒ−１）３０重量部からなる光硬化性塗料を、ガラス基板上にアプリケータにより５０μｍの厚さに塗布した。高圧水銀灯（365nmにおける強度30mW/cm2,）で積算光量が１２００ｍＪ／ｃｍ２となるように紫外線を照射し、塗膜を硬化させた。
得られた硬化塗膜の重合状況を赤外分光光度計で評価し、エポキシのＣＨ伸縮振動（3000cm-1付近）の吸収が２０％以下に減少したことによりエポキシ成分の重合を確認した。
EXAMPLES Next, the present invention will be further described with reference to examples, but the following specific examples are not intended to limit the present invention.
Example 1
(1) 65 parts by weight of bisphenol-A-diglycidyl ether (DG-1) as a cationic polymerizable monomer, (2) bis (4-tert-butylphenyl) iodonium hexafluorophosphate (I-1) as a photopolymerization initiator A photo-curable coating composed of 5 parts by weight and (3) 30 parts by weight of raw lacquer (Ur-1) as an auto-oxidized coating film component was applied on a glass substrate to a thickness of 50 μm by an applicator. The coating film was cured by irradiating ultraviolet rays with a high-pressure mercury lamp (intensity 30 mW / cm 2 at 365 nm) so that the integrated light amount was 1200 mJ / cm 2 .
The polymerization state of the obtained cured coating film was evaluated with an infrared spectrophotometer, and the polymerization of the epoxy component was confirmed by the fact that the absorption of epoxy CH stretching vibration (near 3000 cm −1 ) decreased to 20% or less.
（実施例２〜１０）
実施例１と同様にして、（１）カチオン重合性モノマー、（２）光重合開始剤、（３）自動酸化塗膜成分として表１に記載の各化合物を使用し、実施例１と同様にして鉛筆硬度HBから2Hの硬化塗膜を得た。
硬化塗膜の重合状況は赤外分光光度計で評価し、エポキシのＣＨ伸縮振動（3000cm-1付近）の吸収の消失（または減少）よりエポキシ成分の重合を、また、ビニル基の伸縮振動1610cm-1付近）の消失よりビニル化合物の重合を確認した。これらの硬化塗膜において、（１）カチオン重合性モノマーに由来する赤外吸収の低下の程度は、漆等の（３）自動酸化塗膜成分を含まない塗料とほぼ同等であった。
(Examples 2 to 10)
In the same manner as in Example 1, (1) a cationic polymerizable monomer, (2) a photopolymerization initiator, and (3) each compound described in Table 1 as an auto-oxidation coating film component, and the same as in Example 1. Thus, a cured coating film having a pencil hardness of HB to 2H was obtained.
The state of polymerization of the cured coating film is evaluated with an infrared spectrophotometer. The polymerization of the epoxy component is caused by the disappearance (or decrease) of absorption of the CH stretching vibration (around 3000 cm -1 ) of the epoxy, and the stretching vibration of the vinyl group is 1610 cm. from loss of -1 vicinity) confirmed the polymerization of the vinyl compound. In these cured coating films, (1) the degree of reduction in infrared absorption derived from the cationic polymerizable monomer was almost the same as that of the paint not containing (3) auto-oxidation coating film components such as lacquer.
下記の表１、表２において、各記号はそれぞれ以下の化合物を表す。また、（）内の数値は各化合物の配合量（重量部）を表す。
（１）カチオン重合性モノマー
ＤＧ−１：ビスフェノール-Ａ-ジグリシジルエーテル
ＤＧ−２：エチレングリコールジグリシジルエーテル
ＥＣ−１：3,4-エポキシシクロヘキシルメチル3,4-エポキシシクロヘキサンカルボキシレート
ＤＶ：1,4,-シクロヘキサンジメタノールジビニルエーテル
ＯＸ：1,4-ビス｛［（3-エチル-3-オキセタニル）メトキシ］メチル｝ベンゼン
（２）光重合開始剤
Ｉ−１：ビス（4-tert-ブチルフェニル）ヨードニウムヘキサフルオロホスフェート
Ｉ−２：トリ-p-トリルスルホニウムヘキサフルオロホスフェート
Ｉ−３：（９−オキサ−９Ｈ-キサンテン−２−イル）ジフェニルスルホニウムヘキサフルオロホスフェート
（３）自動酸化塗膜成分
Ｕｒ−１：生漆， Ｕｒ−２：シリカゲルカラム精製漆
ＣＯ：カシューオイル
ＤＯ：乾性油
In the following Tables 1 and 2, each symbol represents the following compound. Moreover, the numerical value in () represents the compounding quantity (part by weight) of each compound.
(1) Cationic polymerizable monomer DG-1: bisphenol-A-diglycidyl ether DG-2: ethylene glycol diglycidyl ether EC-1: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate DV: 1, 4, -cyclohexanedimethanol divinyl ether OX: 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene (2) photopolymerization initiator I-1: bis (4-tert-butylphenyl) ) Iodonium hexafluorophosphate I-2: tri-p-tolylsulfonium hexafluorophosphate I-3: (9-oxa-9H-xanthen-2-yl) diphenylsulfonium hexafluorophosphate (3) auto-oxidation coating film component Ur- 1: Raw lacquer, Ur-2: Silica gel column purified lacquer CO: Cashew oil DO: Sex oil
（実施例１１〜１３、比較例１〜３）
（１）カチオン重合性モノマー、（２）光重合開始剤、（３）自動酸化塗膜成分として表２に記載の各化合物を使用した光硬化性塗料を、アルミニウム皿上に薄く塗布した。ついで、高圧水銀灯（365nmにおける強度30mW/cm2）で塗膜に紫外線を連続照射した。
また、比較のために、（３）自動酸化塗膜成分である漆を使用せずに調製した光硬化性塗料を同様に塗布して、同様に紫外線を照射した。
これらの例において、発生する熱量と最大発熱時間は、それぞれ漆を添加しない例に匹敵するものであり、塗膜が迅速に重合することを確認した。発生する熱量の程度と最大発熱時間は、漆等の自動酸化塗膜成分を含まない塗料とほぼ同等であった。
(Examples 11-13, Comparative Examples 1-3)
(1) A cationically polymerizable monomer, (2) a photopolymerization initiator, and (3) a photocurable paint using each compound shown in Table 2 as an auto-oxidized coating film component was thinly applied on an aluminum dish. Subsequently, the coating film was continuously irradiated with ultraviolet rays with a high-pressure mercury lamp (intensity 30 mW / cm 2 at 365 nm).
For comparison, (3) a photocurable coating prepared without using lacquer, which is an auto-oxidized coating film component, was applied in the same manner and irradiated with ultraviolet rays in the same manner.
In these examples, the amount of heat generated and the maximum exothermic time are comparable to those in which lacquer is not added, and it was confirmed that the coating film rapidly polymerizes. The amount of generated heat and the maximum heat generation time were almost the same as those of a paint not containing an auto-oxidized coating film component such as lacquer.
（実施例１４）
（１）カチオン重合性モノマーとしてビスフェノールAジグリシジルエーテル45重量部、（２）光重合開始剤として(4-フェニルチオフェニル)ジフェニルスルホニウムヘキサフルオロホスフェート5重量部（トルエン溶液として添加）、及び（３）自動酸化塗膜成分として漆５０重量部を使用し、浴型超音波装置を用いて均質に混合し、光硬化型漆塗料を調製した。
ガラス上にアプリケータを用いてこの塗料を厚さ50μｍで塗布し、高圧水銀灯（30mW/cm2, 365nm）で40秒紫外線を照射した。照射後直ちに塗膜の完全硬化前に、１〜５μｍの金粉を塗膜表面に散布、または塗りつけた。塗膜は数分から数十分以内にほぼ完全硬化とともに、粉体は塗膜表面に固着され、蒔絵風の装飾塗膜が得られた。
(Example 14)
(1) 45 parts by weight of bisphenol A diglycidyl ether as a cationic polymerizable monomer, (2) 5 parts by weight of (4-phenylthiophenyl) diphenylsulfonium hexafluorophosphate (added as a toluene solution) as a photopolymerization initiator, and (3 ) 50 parts by weight of lacquer was used as an auto-oxidizing coating film component, and homogeneously mixed using a bath-type ultrasonic device to prepare a photo-curable lacquer paint.
This paint was applied to glass with a thickness of 50 μm using an applicator, and irradiated with ultraviolet light for 40 seconds with a high-pressure mercury lamp (30 mW / cm 2 , 365 nm). Immediately after the irradiation, before the coating film was completely cured, gold powder of 1 to 5 μm was sprayed or applied to the coating film surface. The coating film was almost completely cured within a few minutes to several tens of minutes, and the powder was fixed to the surface of the coating film, and a decorative paint film in a lacquered picture was obtained.
（実施例１５）
（１）カチオン重合性モノマーとして、3,4-エポキシシクロヘキシルメチル3,4-エポキシシクロヘキサン酸カルボキシレート22.5重量部、及び1,4-ビス｛［（3-エチル-3-オキセタニル）メトキシ］メチル｝ベンゼン22.5重量部、（２）光重合開始剤として、(4-フェニルチオフェニル)ジフェニルスルホニウムヘキサフルオロホスフェート5重量部（必要に応じてトルエン溶液として添加）、及び（３）自動酸化塗膜成分として漆５０重量部を使用し、浴型超音波装置を用いて均質に混合し、光硬化型漆塗料を調製した。ガラス、アルミニウム、または木材上に、アプリケータを用いてこの塗料を厚さ５０μｍで塗布した。高圧水銀灯（30mW/cm2, 365nm）で40秒紫外線を照射後、80％湿度下、室温で基板を放置すると、幅約５０μｍの微細な棒状の相を含む硬化塗膜が得られた。
(Example 15)
(1) As cationically polymerizable monomers, 2,2.5 parts of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane acid carboxylate and 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} 22.5 parts by weight of benzene, (2) as a photopolymerization initiator, 5 parts by weight of (4-phenylthiophenyl) diphenylsulfonium hexafluorophosphate (added as a toluene solution if necessary), and (3) as an auto-oxidation coating film component Using 50 parts by weight of lacquer and mixing homogeneously using a bath-type ultrasonic device, a photo-curable lacquer coating was prepared. This paint was applied to glass, aluminum, or wood at a thickness of 50 μm using an applicator. After UV irradiation for 40 seconds with a high-pressure mercury lamp (30 mW / cm 2 , 365 nm), when the substrate was left at room temperature under 80% humidity, a cured coating film containing a fine rod-like phase with a width of about 50 μm was obtained.
（実施例１６）
（１）カチオン重合性モノマーとして、ビスフェノール-Ａ-ジグリシジルエーテル４５重量部、（２）光重合開始剤として、(4-フェニルチオフェニル)ジフェニルスルホニウムヘキサフルオロホスフェート５重量部、及び（３）自動酸化塗膜成分として漆５０重量部を使用し、浴型超音波装置を用いて均質に混合し、光硬化型漆塗料を調製した。
ガラス基板上に、アプリケータを用いてこの塗料を厚さ５０μｍで塗布し、高圧水銀灯（30mW/cm2, 365nm）で40秒紫外線を照射後、80％湿度下、室温で基板を放置すると、幅約５０μｍの微細な棒状の漆成分が分離した相を含む硬化塗膜が得られた。得られた塗膜の実体顕微鏡写真を図１に示す。
(Example 16)
(1) 45 parts by weight of bisphenol-A-diglycidyl ether as a cationic polymerizable monomer, (2) 5 parts by weight of (4-phenylthiophenyl) diphenylsulfonium hexafluorophosphate as a photopolymerization initiator, and (3) Automatic Using 50 parts by weight of lacquer as an oxide coating film component, the mixture was homogeneously mixed using a bath-type ultrasonic device to prepare a photo-curable lacquer paint.
Apply this paint with a thickness of 50μm on a glass substrate using an applicator, irradiate with UV light for 40 seconds with a high-pressure mercury lamp (30mW / cm 2 , 365nm), then leave the substrate at 80% humidity and room temperature. A cured coating film containing a phase in which a fine rod-like lacquer component having a width of about 50 μm was separated was obtained. A stereoscopic microscope photograph of the obtained coating film is shown in FIG.
（実施例１７）
（１）カチオン重合性モノマーとして、3,4-エポキシシクロヘキシルメチル3,4-エポキシシクロヘキサンカルボキシレート４５重量部、（２）光重合開始剤として、(4-フェニルチオフェニル)ジフェニルスルホニウムヘキサフルオロホスフェート５重量部、及び（３）自動酸化塗膜成分として漆５０重量部を使用し、浴型超音波装置を用いて均質に混合し、光硬化型漆塗料を調製した。
ガラス基板上に、アプリケータを用いてこの塗料を厚さ５０μｍで塗布し、高圧水銀灯（30mW/cm2, 365nm）で40秒紫外線を照射後、80％湿度下、室温で基板を放置すると、幅約５０μｍの微細な棒状の漆成分が分離した相を含む硬化塗膜が得られた。得られた塗膜の実体顕微鏡写真を図２に示す。
(Example 17)
(1) 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate 45 parts by weight as a cationic polymerizable monomer, (2) (4-phenylthiophenyl) diphenylsulfonium hexafluorophosphate 5 as a photopolymerization initiator Part by weight, and (3) 50 parts by weight of lacquer was used as an auto-oxidized coating film component, and homogeneously mixed using a bath-type ultrasonic device to prepare a photo-curable lacquer paint.
Apply this paint with a thickness of 50μm on a glass substrate using an applicator, irradiate with UV light for 40 seconds with a high-pressure mercury lamp (30mW / cm 2 , 365nm), then leave the substrate at 80% humidity and room temperature. A cured coating film containing a phase in which a fine rod-like lacquer component having a width of about 50 μm was separated was obtained. A stereomicrograph of the obtained coating film is shown in FIG.
（実施例１８）
（１）カチオン重合性モノマーとして、3,4-エポキシシクロヘキシルメチル3,4-エポキシシクロヘキサンカルボキシレート４５重量部、（２）光重合開始剤として、(4-フェニルチオフェニル)ジフェニルスルホニウムヘキサフルオロホスフェート５重量部、及び（３）自動酸化塗膜成分として漆５０重量部を使用し、浴型超音波装置を用いて均質に混合し、光硬化型漆塗料を調製した。
アルミニウム基板上に、アプリケータを用いてこの塗料を厚さ５０μｍで塗布しし、高圧水銀灯（30mW/cm2, 365nm）で40秒紫外線を照射後、80％湿度下、室温で基板を放置すると、幅約５０μｍの微細な棒状の漆成分が分離した相を含む硬化塗膜が得られた。得られた塗膜表面の走査電子顕微鏡写真を図３に、また断面の走査電子顕微鏡写真を図４に示す。
(Example 18)
(1) 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate 45 parts by weight as a cationic polymerizable monomer, (2) (4-phenylthiophenyl) diphenylsulfonium hexafluorophosphate 5 as a photopolymerization initiator Part by weight, and (3) 50 parts by weight of lacquer was used as an auto-oxidized coating film component, and homogeneously mixed using a bath-type ultrasonic device to prepare a photo-curable lacquer paint.
When this paint is applied to an aluminum substrate with an applicator at a thickness of 50μm and irradiated with UV light for 40 seconds with a high-pressure mercury lamp (30mW / cm 2 , 365nm), the substrate is left at 80% humidity and room temperature. A cured coating film containing a phase in which a fine rod-like lacquer component having a width of about 50 μm was separated was obtained. FIG. 3 shows a scanning electron micrograph of the surface of the coating film obtained, and FIG. 4 shows a scanning electron micrograph of the cross section.
（実施例１９）
（１）カチオン重合性モノマーとして、3,4-エポキシシクロヘキシルメチル3,4-エポキシシクロヘキサン酸カルボキシレート22.5重量部、及び1,4-ビス｛［（3-エチル-3-オキセタニル）メトキシ］メチル｝ベンゼン22.5重量部、（２）光重合開始剤として、(4-フェニルチオフェニル)ジフェニルスルホニウムヘキサフルオロホスフェート5重量部、及び（３）自動酸化塗膜成分として漆５０重量部を使用して光硬化型漆塗料を調製し、ガラスにアプリケータを用いて塗料を厚さ５０μｍで塗布した。未乾燥塗膜と高圧水銀灯との間に、ガラス板上に金属蒸着で作成した光学格子（光遮閉部分の幅５０μｍ、光透過部分の幅５０μｍ）を未乾燥塗膜に近接させて設置した。この状態で紫外光（30mW/cm2, 365nm）を120秒照射した。80％湿度下、25℃で基板を10分間放置すると、スリットの配向に沿って、スリットの間隔と同一の幅５０μｍの微細な棒状の相を含む硬化塗膜が得られた。得られた塗膜の実体顕微鏡写真を図５に示す。
Example 19
(1) As cationically polymerizable monomers, 2,2.5 parts of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane acid carboxylate and 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} Photocuring using 22.5 parts by weight of benzene, (2) 5 parts by weight of (4-phenylthiophenyl) diphenylsulfonium hexafluorophosphate as a photopolymerization initiator, and (3) 50 parts by weight of lacquer as an auto-oxidized coating film component. A mold lacquer paint was prepared, and the paint was applied to glass at a thickness of 50 μm using an applicator. Between the wet film and the high-pressure mercury lamp, an optical grating (width 50 μm of the light shielding part, width 50 μm of the light transmission part) created by metal vapor deposition on the glass plate was placed close to the dry film. . In this state, ultraviolet light (30 mW / cm 2 , 365 nm) was irradiated for 120 seconds. When the substrate was allowed to stand for 10 minutes at 25 ° C. under 80% humidity, a cured coating film containing a fine rod-like phase having a width of 50 μm and the same spacing as the slit spacing was obtained. A stereomicrograph of the obtained coating film is shown in FIG.
（実施例２０）
（１）カチオン重合性モノマーとして、3,4-エポキシシクロヘキシルメチル3,4-エポキシシクロヘキサン酸カルボキシレート４５重量部、（２）光重合開始剤として、ビス（4-tert-ブチルフェニル）ヨードニウムヘキサフルオロホスフェート5重量部、及び（３）自動酸化塗膜成分として漆５０重量部を使用して光硬化型漆塗料を調製し、ガラスにアプリケータを用いて塗料を厚さ５０μｍで塗布した。
レーザープリンタで任意の図を印刷したポリスチレンフィルムを光マスクとして、未硬化塗膜の直上に配置した。光マスクの上方より高圧水銀灯（光マスク上で30mW/cm2, 365nm）で180秒紫外線を照射した。塗膜を80％湿度下、室温で基板を放置すると、塗膜は数十分で硬化し、その際、光マスクの図に対応した図柄が硬化塗膜上に現れた。光マスクの透明部分は、塗膜の平滑な部分として、また半透明部分は、凹凸のある部分として転写された。得られた塗膜の実体顕微鏡写真を図６に示す。
(Example 20)
(1) As cationically polymerizable monomer, 45 parts by weight of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane acid carboxylate, (2) As a photopolymerization initiator, bis (4-tert-butylphenyl) iodonium hexafluoro A photocurable lacquer paint was prepared using 5 parts by weight of phosphate and (3) 50 parts by weight of lacquer as an auto-oxidized coating film component, and the paint was applied to glass at a thickness of 50 μm using an applicator.
A polystyrene film on which an arbitrary figure was printed with a laser printer was used as a photomask, and was placed immediately above the uncured coating film. UV light was irradiated from above the light mask with a high-pressure mercury lamp (30 mW / cm 2 , 365 nm on the light mask) for 180 seconds. When the substrate was allowed to stand at room temperature under 80% humidity, the coating film was cured in several tens of minutes. At that time, a pattern corresponding to the figure of the photomask appeared on the cured coating film. The transparent part of the optical mask was transferred as a smooth part of the coating film, and the translucent part was transferred as an uneven part. A stereomicrograph of the obtained coating film is shown in FIG.
Claims (7)
The method for forming a decorative coating film according to claim 5 or 6, wherein the height of the irregularities formed on the surface of the coating film is 0.1 to 500 µm.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008255292A (en) * | 2007-04-09 | 2008-10-23 | National Institute Of Advanced Industrial & Technology | Japanese lacquer and method for forming decorative coat using the same |
| EP2025903A1 (en) | 2007-08-06 | 2009-02-18 | Nissan Motor Co., Ltd. | Internal combustion engine |
| KR101240302B1 (en) * | 2011-03-31 | 2013-03-07 | 전용복 | Oriental lacquer coating method on glass board and glass board made by the same that |
| JP5607044B2 (en) * | 2009-06-02 | 2014-10-15 | 山本化成株式会社 | Iodonium-based photopolymerization initiator, method for producing the same, and photocurable composition containing the same |
| JP2015111034A (en) * | 2013-11-11 | 2015-06-18 | パナソニックＩｐマネジメント株式会社 | Household electric appliance and decorative sheath material used for the same |
| JP2016090193A (en) * | 2014-11-10 | 2016-05-23 | パナソニックＩｐマネジメント株式会社 | Home electric appliance and decoration exterior plate used for the same |
| JP7438514B2 (en) | 2020-08-04 | 2024-02-27 | 華南農業大学 | Pure vegetable oil polymer by photoinduced cationic polymerization, its preparation method and applications |
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| JP2016211786A (en) * | 2015-05-11 | 2016-12-15 | パナソニックＩｐマネジメント株式会社 | Household electric appliance and interior material used for the same |
| CN107532843A (en) * | 2015-05-11 | 2018-01-02 | 松下知识产权经营株式会社 | Home appliance |
| JP2016211787A (en) * | 2015-05-11 | 2016-12-15 | パナソニックＩｐマネジメント株式会社 | Household electric appliance and decorative sheath material used for the same |
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| JPS53128644A (en) * | 1977-04-16 | 1978-11-09 | Yasuyo Hiuga | Adhesives for making flat and tenacious design of golddclad tusks horns stones and metals |
| JPH05230421A (en) * | 1991-03-01 | 1993-09-07 | Sigma:Kk | Method for treating metallic material with resin-japanese lacquer mixture |
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| JPS53128644A (en) * | 1977-04-16 | 1978-11-09 | Yasuyo Hiuga | Adhesives for making flat and tenacious design of golddclad tusks horns stones and metals |
| JPH05230421A (en) * | 1991-03-01 | 1993-09-07 | Sigma:Kk | Method for treating metallic material with resin-japanese lacquer mixture |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008255292A (en) * | 2007-04-09 | 2008-10-23 | National Institute Of Advanced Industrial & Technology | Japanese lacquer and method for forming decorative coat using the same |
| EP2025903A1 (en) | 2007-08-06 | 2009-02-18 | Nissan Motor Co., Ltd. | Internal combustion engine |
| JP5607044B2 (en) * | 2009-06-02 | 2014-10-15 | 山本化成株式会社 | Iodonium-based photopolymerization initiator, method for producing the same, and photocurable composition containing the same |
| KR101240302B1 (en) * | 2011-03-31 | 2013-03-07 | 전용복 | Oriental lacquer coating method on glass board and glass board made by the same that |
| JP2015111034A (en) * | 2013-11-11 | 2015-06-18 | パナソニックＩｐマネジメント株式会社 | Household electric appliance and decorative sheath material used for the same |
| JP2016090193A (en) * | 2014-11-10 | 2016-05-23 | パナソニックＩｐマネジメント株式会社 | Home electric appliance and decoration exterior plate used for the same |
| JP7438514B2 (en) | 2020-08-04 | 2024-02-27 | 華南農業大学 | Pure vegetable oil polymer by photoinduced cationic polymerization, its preparation method and applications |
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