JPH05117546A - Fluorine-based ultravilet curing resin coating - Google Patents
Fluorine-based ultravilet curing resin coatingInfo
- Publication number
- JPH05117546A JPH05117546A JP30536691A JP30536691A JPH05117546A JP H05117546 A JPH05117546 A JP H05117546A JP 30536691 A JP30536691 A JP 30536691A JP 30536691 A JP30536691 A JP 30536691A JP H05117546 A JPH05117546 A JP H05117546A
- Authority
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- Prior art keywords
- coating
- monomer
- weight
- acrylate
- fluorine
- 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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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、撥水性に富んだ透明な
フッ素系紫外線硬化樹脂塗料に関するものである。更に
詳しく述べると、フッ素アルキル基を側鎖に有するアク
リルモノマ−と特定の構造の三官能アクリレートモノマ
ーとを主成分とするモノマーを紫外線により硬化させる
撥水性に富んだ透明なフッ素系紫外線硬化樹脂塗料に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent fluorine-based ultraviolet curable resin coating material having a high water repellency. More specifically, a transparent fluorine-based ultraviolet-curable resin coating material rich in water repellency, which cures a monomer containing an acrylic monomer having a fluorinated alkyl group as a side chain and a trifunctional acrylate monomer having a specific structure as a main component with ultraviolet rays. Regarding
【０００２】[0002]
【従来の技術】フロロアルキル基を含む物質の固体表面
は、表面エネルギーが著しく低くなるため、高度の撥
水、撥油性を示し、摩擦係数が小さくなることはよく知
られている。又、フロロアルキル基を含む物質の耐候性
は、優れていることも良く知られている。この様な性質
を固体もしくは、各種の成形物の表面に与える事は、極
めて意味のある事である。この様な特徴は、ほんの表面
だけにフロロアルキル基を含む物質が存在すれば良く、
固体もしくは成形物全体がフロロアルキル基を含む物質
である必要はない。この様な観点から、フッ素樹脂コー
ティングが従来より種々の目的の為に行われてきた。し
かしながら、逆にフッ素樹脂は表面エネルギーが低いた
めに、コーティングする基材との密着性が悪く、焼付け
等の厳しい条件でしか充分な基材との密着性をあげるこ
とが難しいのが現状である。この為、密着性を良好にす
るために、コーティング樹脂中のフッ素含量を少なくす
る等の手段がとられてきた。しかし、高度の 撥水、撥
油性を必要とする用途には、コーティング樹脂中のフッ
素含量を増加させる必要がある。例えば、積雪の多い地
方の屋根に関して例を挙げる事が出来る。屋根への多量
の積雪は、時によって家屋を崩壊させる。これを少しで
も軽減させるため、屋根の傾斜を鋭くしたり、屋根の材
質に、フッ素樹脂コーティングを施す方法が採られる。
このコーティングを効果あらしめるためには、コーティ
ング樹脂中のフッ素含量を多くする必要がある事はいう
までもないことである。又、長期間この効果を持続させ
るためには、簡単に屋根の材質からコーティングが剥離
することがあってはならない。屋根の材質とコーティン
グ樹脂との密着性が極めて重要であることが分かる。こ
の様にフッ素含量が高く、且つ基材との密着性に優れ、
又、コーティングが簡単に施工できる有用な塗料が求め
られている。2. Description of the Related Art It is well known that the solid surface of a substance containing a fluoroalkyl group has a remarkably low surface energy and thus exhibits a high degree of water and oil repellency and a small friction coefficient. It is also well known that the weather resistance of a substance containing a fluoroalkyl group is excellent. It is extremely meaningful to give such properties to the surface of solid or various molded products. Such a characteristic is that a substance containing a fluoroalkyl group is present only on the surface,
It is not necessary that the solid or the entire molding be a substance containing a fluoroalkyl group. From such a viewpoint, fluororesin coating has been conventionally performed for various purposes. However, conversely, since the fluororesin has a low surface energy, the adhesion to the substrate to be coated is poor, and it is currently difficult to increase the adhesion to the substrate only under severe conditions such as baking. .. Therefore, in order to improve the adhesion, measures such as reducing the fluorine content in the coating resin have been taken. However, for applications that require a high degree of water and oil repellency, it is necessary to increase the fluorine content in the coating resin. For example, we can give an example for a roof in a region with a lot of snow. A large amount of snow on the roof sometimes causes houses to collapse. In order to reduce this as much as possible, a method of making the roof steep or applying a fluororesin coating to the material of the roof is adopted.
Needless to say, it is necessary to increase the fluorine content in the coating resin in order to achieve this coating effect. Also, in order to maintain this effect for a long period of time, the coating must not easily peel off from the roof material. It can be seen that the adhesion between the roof material and the coating resin is extremely important. In this way, the fluorine content is high, and the adhesion to the substrate is excellent,
There is also a need for useful paints that can be easily coated.
【０００３】[0003]
【発明が解決しようとする課題】解決しようとする問題
点は、高度の撥水、撥油性を基材表面に与える為に、フ
ッ素含量が高く、且つ基材との密着性に優れ、又、コー
ティングが簡単に施工できる有用な塗料を得ることであ
る。The problem to be solved is to give a high degree of water repellency and oil repellency to the surface of the base material, so that the fluorine content is high and the adhesion to the base material is excellent. It is to obtain a useful paint whose coating can be applied easily.
【０００４】[0004]
【課題を解決するための手段】本発明は、このような上
述のフッ素樹脂系塗料を得べく検討を重ねた結果得られ
たものである。即ち、フッ素アルキル基を側鎖に有する
アクリルモノマ−と特定の構造の三官能アクリレートモ
ノマーとを主成分とするモノマーを紫外線により硬化さ
せるタイプの撥水性に富んだ透明なフッ素系紫外線硬化
樹脂塗料を得るに至った。以下、本発明を詳述する。The present invention was obtained as a result of repeated studies to obtain such a fluororesin-based coating material as described above. That is, a transparent fluorine-based ultraviolet curable resin coating rich in water repellency of a type in which a monomer mainly composed of an acrylic monomer having a fluorine alkyl group in a side chain and a trifunctional acrylate monomer having a specific structure is cured by ultraviolet rays. I got it. Hereinafter, the present invention will be described in detail.
【０００５】本発明のフッ素樹脂系塗料の主成分は、下
記化３（構造式１）で示されるフッ素アルキル基を側鎖
に有するアクリルモノマ−５０〜８０重量部、及び下記
化４（構造式２）で示される三官能アクリレート２０〜
５０重量部の混合物である。化３（構造式１）で示され
るフッ素アルキル基を側鎖に有するアクリルモノマ−
は、重合性の官能基がアクリル基であり、紫外線硬化に
適したものである。側鎖のフロロアルキル基は、目的と
するコーティングの撥水、撥油性の程度によるが本発明
では、通常、Ｒの炭素数は、Ｃ1〜Ｃ18のアルキル基が
使用される。Ｃ18を超えるアルキル基が用いられない理
由は、Ｃ18を超えるアルキル基の使用では、撥水、撥油
性は向上するが、コーティング薄膜の硬度が充分でなく
なる為であり、又、同様に、コーティング薄膜の耐熱性
も低下するためである。次に、フロロアルキル基Ｒfの
フッ素原子置換量は、本発明の目的が撥水、撥油性が大
きい事であり、この目的を満足させるためには、Ｒの炭
素数はＣ1〜Ｃ18のＣn（ｎ＝１〜１８）に対し、フッ素
原子の個数はｎ個以上が置換しているものが必要であ
る。ｎ個に満たないと目的とする充分な撥水、撥油性が
得られない為である。The main components of the fluororesin coating composition of the present invention are 50 to 80 parts by weight of an acrylic monomer having a fluoroalkyl group as a side chain represented by the following chemical formula 3 (structural formula 1), and the following chemical formula 4 (structural formula 2) trifunctional acrylate 20-
50 parts by weight of the mixture. Acrylic monomer having a fluorinated alkyl group represented by Chemical formula 3 (Structural Formula 1) in the side chain
Has a polymerizable functional group of an acrylic group and is suitable for ultraviolet curing. The side chain fluoroalkyl group depends on the degree of water repellency and oil repellency of the intended coating, but in the present invention, an alkyl group having a carbon number of R 1 to C 18 is usually used. Why can not the used alkyl group of greater than C 18, in the use of the alkyl group of greater than C 18, water repellency, oil repellency is improved, and because the hardness of the coating film becomes insufficient, and, similarly, This is because the heat resistance of the coating thin film also decreases. Next, the fluorine atom substitution amount of the fluoroalkyl group R f is that the object of the present invention is to have a large water repellency and oil repellency. To satisfy this object, the carbon number of R is C 1 to C 18. In contrast to C n (n = 1 to 18), the number of fluorine atoms needs to be replaced by n or more. This is because if the number is less than n, the desired sufficient water and oil repellency cannot be obtained.
【０００６】[0006]
【化３】 [Chemical 3]
【０００７】[0007]
【化４】 [Chemical 4]
【０００８】具体的な、フッ素アルキル基を側鎖に有す
るアクリルモノマ−のＲfの構造を次に示すと、ＣＦ3、
ＣＨＦ2、ＣＨ2Ｆ、ＣＨＦＣＦ3、ＣＨ2ＣＦ3、ＣＦ2Ｃ
Ｆ3、ＣＨ2ＣＦ2ＣＦ3、ＣＦ2ＣＦ2ＣＦ3、ＣＨ2ＣＦ2
ＣＦ2ＣＦ2ＣＦ2ＣＦ3、ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｃ
Ｆ3、ＣＨ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ3、Ｃ
Ｈ2（ＣＦ2）10ＣＦ3、ＣＦ2（ＣＦ2）10ＣＦ3、ＣＨ2
ＣＨ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ3、ＣＨ2ＣＨ
2（ＣＦ2）15ＣＦ3、ＣＦ2（ＣＦ2）16ＣＦ3、等を挙げ
ることが出来る。無論、本発明は、これらのみに限定さ
れない。一方、本発明では、該フッ素アルキル基を側鎖
に有するアクリルモノマ−の他に、下記化５（構造式
２）で示される三官能アクリレートが必須の成分として
用いられる。この化５（構造式２）で示される三官能ア
クリレートは、該フッ素アルキル基を側鎖に有するアク
リルモノマ−と重合官能基が同じであり、紫外線により
容易に共重合される。又、三官能性であるので、高度の
架橋構造を作ることを可能にし、コーティング薄膜の硬
度を上げるのに極めて有用である。更に、化５（構造式
２）で示される三官能アクリレートは、イソシアヌル酸
構造を有しており、耐候性に秀でていること、種々の基
材との密着性が優れていること、等の特徴も有してい
る。A specific structure of R f of an acrylic monomer having a side chain of a fluoroalkyl group is shown below, and CF 3 ,
CHF 2 , CH 2 F, CHFCF 3 , CH 2 CF 3 , CF 2 C
F 3 , CH 2 CF 2 CF 3 , CF 2 CF 2 CF 3 , CH 2 CF 2
CF 2 CF 2 CF 2 CF 3 , CF 2 CF 2 CF 2 CF 2 CF 2 C
F 3 , CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 , C
H 2 (CF 2 ) 10 CF 3 , CF 2 (CF 2 ) 10 CF 3 , CH 2
CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 , CH 2 CH
2 (CF 2) 15 CF 3 , CF 2 (CF 2) 16 CF 3, and the like. Of course, the present invention is not limited to these. On the other hand, in the present invention, a trifunctional acrylate represented by the following Chemical Formula 5 (Structural Formula 2) is used as an essential component in addition to the acrylic monomer having the fluorine alkyl group in the side chain. The trifunctional acrylate represented by Chemical Formula 5 (Structural Formula 2) has the same polymerization functional group as the acrylic monomer having the fluorine alkyl group in the side chain, and is easily copolymerized by ultraviolet rays. In addition, since it is trifunctional, it makes it possible to form a highly crosslinked structure and is extremely useful for increasing the hardness of the coating thin film. Furthermore, the trifunctional acrylate represented by Chemical Formula 5 (Structural Formula 2) has an isocyanuric acid structure, has excellent weather resistance, and has excellent adhesion to various base materials, etc. It also has the characteristics of.
【０００９】[0009]
【化５】 [Chemical 5]
【００１０】本発明は、このように該フッ素アルキル基
を側鎖に有するアクリルモノマ−と該化５（構造式２）
で示される三官能アクリレートが必須の成分として用い
られるが本発明では、フッ素アルキル基を側鎖に有する
アクリルモノマ−５０〜８０重量部、及び化５（構造式
２）で示される三官能アクリレート２０〜５０重量部の
混合物を固形分モノマー１００重量部当り少なくとも７
０重量％以上含有することが必要である。フッ素アルキ
ル基を側鎖に有するアクリルモノマ−が８０重量部を超
えると、本発明の特徴である架橋効果、即ち、表面硬度
を高くすることができないだけでなく、耐熱性も低下す
る。しかし、５０重量部に満たないと、高度の撥水、撥
油性を基材表面に与えることが不可能になる。本発明で
は、上述の様に、該フッ素アルキル基を側鎖に有するア
クリルモノマ−と該化５（構造式２）で示される三官能
アクリレートの他に、３０％までの範囲で第三成分のモ
ノマーを用いることが出来る。この第三成分のモノマー
が用いられる理由は、コーティング薄膜の特性を改良す
るためである。即ち、屈折率を調節したり、より染色性
を高めたり、表面の艶を向上させたり、コーティング時
の流れ特性を改良したり、溶媒に対する溶解性を向上さ
せたり、紫外線による硬化速度を調節したりするためで
あり、種々の目的にあったモノマーが使用される。According to the present invention, the acrylic monomer having the fluorine alkyl group in the side chain as described above and the compound 5 (Structural formula 2)
In the present invention, the trifunctional acrylate represented by the formula (5) is used as an indispensable component, but in the present invention, 50 to 80 parts by weight of an acrylic monomer having a fluorine alkyl group in the side chain, and the trifunctional acrylate represented by Formula 5 (Structure 2) ~ 50 parts by weight of the mixture of at least 7 per 100 parts by weight of solids monomer.
It is necessary to contain 0% by weight or more. When the amount of the acrylic monomer having a fluorinated alkyl group in its side chain exceeds 80 parts by weight, not only the crosslinking effect, which is a feature of the present invention, that is, the surface hardness cannot be increased, but also the heat resistance is lowered. However, if the amount is less than 50 parts by weight, it becomes impossible to impart a high degree of water and oil repellency to the surface of the base material. In the present invention, as described above, in addition to the acrylic monomer having the fluoroalkyl group in the side chain and the trifunctional acrylate represented by Chemical Formula 5 (Structural Formula 2), the third component is used in a range of up to 30%. Monomers can be used. The reason for using this third component monomer is to improve the properties of the coating film. That is, the refractive index can be adjusted, the dyeability can be further increased, the surface gloss can be improved, the flow characteristics during coating can be improved, the solubility in solvents can be improved, and the curing rate by ultraviolet rays can be adjusted. The purpose is to use monomers suitable for various purposes.
【００１１】しかしながら、これらモノマーは、紫外線
によって該フッ素アルキル基を側鎖に有するアクリルモ
ノマ−と該化５（構造式２）で示される三官能アクリレ
ートとに共重合可能なモノマーである必要があり、本発
明では、これらモノマーの官能基は、アクリル基である
ことが必要である。これら第三成分は、本発明の高度の
撥水、撥油性、高い耐候性、強い硬度などの諸特性を損
なわないために、３０％までの範囲で用いられる。この
様な第三成分の具体例を示すと、アクリル酸メチル、ア
クリル酸ブチル、アクリル酸フェニル、アクリル酸シク
ロヘキシル、２ーヒドロキシエチルアクリレート、エチ
レングリコールジアクリレート、ジエチレングリコール
ジアクリレート、トリエチレングリコールジアクリレー
ト、ポリエチレングリコールジアクリレート、１、４ー
ブタンジオールジアクリレート、１、６ーヘキサンジオ
ールジアクリレート、１、９ーノナンジオールジアクリ
レート、２、２ビス（４ーアクリロキシエトキシフェニ
ル）プロパン、２、２ビス（４ーアクリロキシジエトキ
シフェニル）プロパン、グリセリントリアクリレート、
トリメチロールプロパントリアクリレート、ペンタエリ
スリトールテトラアクリレート等の種々の単官能、多官
能アクリレートを挙げることが出来る。しかしながらこ
れらは一例であり、本発明はこれらのみに限定されな
い。However, these monomers must be monomers that can be copolymerized with an acrylic monomer having the fluorine alkyl group in the side chain and a trifunctional acrylate represented by Chemical Formula 5 (Structural Formula 2) by ultraviolet rays. In the present invention, the functional group of these monomers needs to be an acrylic group. These third components are used within a range of up to 30% so as not to impair various properties such as high water repellency, oil repellency, high weather resistance and strong hardness of the present invention. Specific examples of such a third component include methyl acrylate, butyl acrylate, phenyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, Polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 2,2bis (4-acryloxyethoxyphenyl) propane, 2,2bis (4-acryloxydiethoxyphenyl) propane, glycerin triacrylate,
Examples thereof include various monofunctional and polyfunctional acrylates such as trimethylolpropane triacrylate and pentaerythritol tetraacrylate. However, these are examples, and the present invention is not limited to these.
【００１２】次に、本発明では、紫外線硬化塗料とする
ために、これら特定組成の該フッ素アルキル基を側鎖に
有するアクリルモノマ−と該化５（構造式２）で示され
る三官能アクリレート、更に必要に応じてこれらモノマ
ーと共重合可能なアクリル基を官能基として持つモノマ
ー組成物が有機溶剤に溶解される。ここで用いられる有
機溶剤は、通常の紫外線硬化塗料が使用される溶剤を使
用することが出来、特に限定はない。即ち、各種のアル
コール、アルキルエステル、ケトン、エーテル、アミ
ド、芳香族ハイドロカーボン、等多種類の有機溶剤が目
的に応じて使用される。モノマー濃度は、これも目的に
応じた任意の濃度であり得るが通常５％〜６０％程度の
濃度が多用される。本発明では、これらモノマーを有機
溶剤に溶解させる際に、紫外線で分解し、ラジカル重合
を開始させる各種の重合開始剤は無論、塗膜の平滑性を
出させるレベリング剤、耐候性を向上させる為の抗酸化
剤、等の添加剤を加えることができることは言う迄もな
い。このようにして得られた本発明の塗料は、高度の撥
水、撥油性を基材表面に与えることが出来、フッ素含量
が高く、且つ基材との密着性に優れ、又、コーティング
が簡単に施工できる有用な塗料を提供するものである。
以下、本発明を実施例で説明する。Next, in the present invention, in order to obtain an ultraviolet-curable coating material, an acrylic monomer having the fluorine alkyl group of the specific composition in its side chain and a trifunctional acrylate represented by Chemical Formula 5 (Structural Formula 2), Further, if necessary, a monomer composition having an acrylic group capable of copolymerizing with these monomers as a functional group is dissolved in an organic solvent. The organic solvent used here may be a solvent used for ordinary UV-curable coatings and is not particularly limited. That is, various kinds of organic solvents such as various alcohols, alkyl esters, ketones, ethers, amides and aromatic hydrocarbons are used according to the purpose. The monomer concentration may be any concentration depending on the purpose, but a concentration of about 5% to 60% is usually used. In the present invention, when these monomers are dissolved in an organic solvent, various polymerization initiators that decompose with ultraviolet rays and initiate radical polymerization are, of course, leveling agents that bring out the smoothness of the coating film, and to improve weather resistance. It goes without saying that additives such as the antioxidants of 1) can be added. The coating material of the present invention thus obtained can impart a high degree of water repellency and oil repellency to the surface of the substrate, has a high fluorine content, is excellent in adhesion to the substrate, and is easy to coat. It provides a useful paint that can be applied to.
Hereinafter, the present invention will be described with reference to examples.
【００１３】[0013]
【実施例】 実施例（１） パーフロロオクチルアクリレート（ＣＨ2＝ＣＨＣ００
Ｃ8Ｆ17）４３重量部、下記化６（構造式２）でしめさ
れるトリアクリレート（東亜合成化学社製アロニックス
Ｍ-３１５）３５重量部、トリメチロールプロパントリ
アクリレート２２重量部を良く混合し、イソプロパノー
ル３００重量部に溶解させた。これに、紫外線重合開始
剤として、１ーヒドロキシシクロヘキシルフェニルケト
ンを０．８重量部加え、塗料モノマーとした。本発明の
この塗料を厚さ約１ｍｍの鉄板及び厚さ約１．２ｍｍの
アクリル板にコートし、約１０分間風乾させた。これに
照射距離１０ｃｍで８０Ｗの高圧水銀灯を１０秒間照射
したところ完全に固化した。固化後のアクリル板の可視
光線全光線透過率（ＡＳＴＭ Ｄ１００３ー５２）を求
めたところ９１％を示し、塗布膜は極めて透明であるこ
とが示された。次に、鉄板及びアクリル板上の塗膜の
ＪＩＳ Ｋ５４００（鉛筆引っかき試験）に準じる鉛筆
硬度を求めたところ、それぞれ５Ｈ及び３Ｈを示し強い
硬度を示した。又、ＪＩＳ Ｋ５４００（碁盤目試験）
に準じる密着テストを行ったところ、全く剥離は認めら
れず強い密着性を示した。次に、鉄板及びアクリル板上
の塗膜の水の表面接触角を協和界面科学（株）製接触角
計で求めたところ、それぞれ１０２度、１０４度、を示
し撥水性の高い表面を有していることが認められた。EXAMPLES Example (1) Perfluorooctyl acrylate (CH 2 = CHC00
C 8 F 17 ) 43 parts by weight, 35 parts by weight of triacrylate (Aronix M-315 manufactured by Toagosei Co., Ltd.) represented by the following chemical formula 6 (structural formula 2), and 22 parts by weight of trimethylolpropane triacrylate are mixed well. , Isopropanol was dissolved in 300 parts by weight. To this, 0.8 part by weight of 1-hydroxycyclohexyl phenyl ketone as an ultraviolet polymerization initiator was added to obtain a coating monomer. This coating material of the present invention was coated on an iron plate having a thickness of about 1 mm and an acrylic plate having a thickness of about 1.2 mm, and air-dried for about 10 minutes. When this was irradiated with a high-pressure mercury lamp of 80 W for 10 seconds at an irradiation distance of 10 cm, it was completely solidified. When the total visible light transmittance (ASTM D1003-52) of the acrylic plate after solidification was determined, it was 91%, showing that the coating film was extremely transparent. Next, the coating film on the iron plate and acrylic plate
When the pencil hardness according to JIS K5400 (pencil scratch test) was determined, it was 5H and 3H, respectively, indicating strong hardness. In addition, JIS K5400 (cross-cut test)
When an adhesion test was conducted in accordance with the above, no peeling was observed and strong adhesion was exhibited. Next, the water surface contact angles of the coating films on the iron plate and the acrylic plate were determined with a contact angle meter manufactured by Kyowa Interface Science Co., Ltd., and they were respectively 102 ° and 104 °, and had a highly water-repellent surface. It was recognized that
【００１４】実施例（２） パーフロロプロピレンアクリレート（ＣＨ2＝ＣＨＣ０
０Ｃ3Ｆ7 ）２０重量部、パーフロロオクチルアクリレ
ート４０重量部、及び、実施例（１）で使用したトリア
クリレート（東亜合成化学社製 アロニックス Ｍ-３１
５）２５重量部、２、２ビス（４ーアクリロキシジエト
キシフェニル）プロパン１５重量部を良く混合し、メチ
ルエチルケトン２０重量部、イソプロパノール１００重
量部、エチルセルソルブ２００重量部に溶解させ、更
に、紫外線重合開始剤として、メチルベンゾイルフォル
メート１．０重量部を添加し、モノマー溶液とした。こ
の塗料を厚さ約１ｍｍの鉄板及び厚さ約１．２ｍｍのア
クリル板にコートし、約１０分間風乾させた。これに実
施例（１）と同条件で紫外線を照射したところ、完全に
固化した。そして実施例（１）と同様の評価を行った。 結果 固化後のアクリル板の可視光線全光線透過率 ９１％ 鉛筆引っかき試験 鉄板 ５Ｈ アクリル板 ４Ｈ 碁盤目試験 鉄板 剥離なし アクリル板 剥離なし 塗膜の水の表面接触角 鉄板 １０４度 アクリル板 １００度 撥水性の高い表面を持った透明で硬度があり、密着性の
良好な塗膜が形成されていることが確認できた。Example (2) Perfluoropropylene acrylate (CH 2 ═CHC0
0C 3 F 7 ) 20 parts by weight, perfluorooctyl acrylate 40 parts by weight, and the triacrylate used in Example (1) (Aronix M-31 manufactured by Toagosei Kagaku KK).
5) 25 parts by weight, 15 parts by weight of 2,2 bis (4-acryloxydiethoxyphenyl) propane were mixed well and dissolved in 20 parts by weight of methyl ethyl ketone, 100 parts by weight of isopropanol, and 200 parts by weight of ethyl cellosolve, and further, As a UV polymerization initiator, 1.0 part by weight of methylbenzoyl formate was added to obtain a monomer solution. This paint was coated on an iron plate having a thickness of about 1 mm and an acrylic plate having a thickness of about 1.2 mm, and air-dried for about 10 minutes. When this was irradiated with ultraviolet rays under the same conditions as in Example (1), it solidified completely. Then, the same evaluation as in Example (1) was performed. Results Total visible light transmittance of acrylic plate after solidification 91% Pencil scratch test Iron plate 5H Acrylic plate 4H Cross-cut test Iron plate No peeling Acrylic plate No peeling Water contact angle of coating Iron plate 104 ° Acrylic plate 100 ° Water repellent It was confirmed that a coating film having a high surface and having transparency and hardness and good adhesion was formed.
【００１５】[0015]
【発明の効果】以上説明したように、本発明では、高度
の撥水、撥油性を基材表面に与える為に、フッ素含量が
高く、且つ基材との密着性に優れ、又、コーティングが
簡単に施工できる有用な塗料を得ることができる効果が
ある。As described above, according to the present invention, in order to impart a high degree of water repellency and oil repellency to the surface of the substrate, the fluorine content is high and the adhesion to the substrate is excellent. There is an effect that a useful paint that can be easily applied can be obtained.
Claims (1)
アルキル基を側鎖に有するアクリルモノマ−５０〜８０
重量部、及び化２（構造式２）で示される三官能アクリ
レート２０〜５０重量部の混合物を固形分モノマー１０
０重量部当り少なくとも７０重量％以上含有する撥水性
に富んだ透明なフッ素系紫外線硬化樹脂塗料 【化１】 【化２】 1. An acrylic monomer having a fluoroalkyl group represented by the following Chemical Formula 1 (Structural Formula 1) in its side chain: 50 to 80
Parts by weight and a mixture of 20 to 50 parts by weight of a trifunctional acrylate represented by Chemical Formula 2 (Structural Formula 2) as solid content monomer 10.
Transparent fluorine-containing UV-curable resin coating material rich in water repellency, containing at least 70% by weight per 0 part by weight. [Chemical 2]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30536691A JPH05117546A (en) | 1991-10-24 | 1991-10-24 | Fluorine-based ultravilet curing resin coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30536691A JPH05117546A (en) | 1991-10-24 | 1991-10-24 | Fluorine-based ultravilet curing resin coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05117546A true JPH05117546A (en) | 1993-05-14 |
Family
ID=17944248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30536691A Pending JPH05117546A (en) | 1991-10-24 | 1991-10-24 | Fluorine-based ultravilet curing resin coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05117546A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1234847A2 (en) | 2001-02-19 | 2002-08-28 | Kuraray Co., Ltd. | Method of curing a mixture comprising an ionizing radiation curing resin, and surface modifying technique |
| JP2003025520A (en) * | 2001-07-16 | 2003-01-29 | Fukuvi Chem Ind Co Ltd | Molded article excellent in antistaining properties and method for manufacturing the same |
| US20120214893A1 (en) * | 1997-02-03 | 2012-08-23 | Cytonix Llc | Hydrophobic Coating Compositions and Articles Coated With Said Compositions |
| WO2019124341A1 (en) * | 2017-12-22 | 2019-06-27 | 第一工業製薬株式会社 | Copolymer, water and oil repellent, and coating agent |
| CN112004838A (en) * | 2018-06-06 | 2020-11-27 | 富士胶片株式会社 | Modifier, composition, hard coat film, article provided with hard coat film, and image display device |
-
1991
- 1991-10-24 JP JP30536691A patent/JPH05117546A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120214893A1 (en) * | 1997-02-03 | 2012-08-23 | Cytonix Llc | Hydrophobic Coating Compositions and Articles Coated With Said Compositions |
| US8785556B2 (en) * | 1997-02-03 | 2014-07-22 | Cytonix, Llc | Hydrophobic coating compositions and articles coated with said compositions |
| EP1234847A2 (en) | 2001-02-19 | 2002-08-28 | Kuraray Co., Ltd. | Method of curing a mixture comprising an ionizing radiation curing resin, and surface modifying technique |
| JP2003025520A (en) * | 2001-07-16 | 2003-01-29 | Fukuvi Chem Ind Co Ltd | Molded article excellent in antistaining properties and method for manufacturing the same |
| WO2019124341A1 (en) * | 2017-12-22 | 2019-06-27 | 第一工業製薬株式会社 | Copolymer, water and oil repellent, and coating agent |
| JP2019112531A (en) * | 2017-12-22 | 2019-07-11 | 第一工業製薬株式会社 | Copolymer, water and oil repellent, and coating agent |
| CN112004838A (en) * | 2018-06-06 | 2020-11-27 | 富士胶片株式会社 | Modifier, composition, hard coat film, article provided with hard coat film, and image display device |
| CN112004838B (en) * | 2018-06-06 | 2022-09-13 | 富士胶片株式会社 | Modifier, composition, hard coat film, article provided with hard coat film, and image display device |
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