JPH03111409A - Water-and oil-repellent photocurable resin - Google Patents
Water-and oil-repellent photocurable resinInfo
- Publication number
- JPH03111409A JPH03111409A JP25084989A JP25084989A JPH03111409A JP H03111409 A JPH03111409 A JP H03111409A JP 25084989 A JP25084989 A JP 25084989A JP 25084989 A JP25084989 A JP 25084989A JP H03111409 A JPH03111409 A JP H03111409A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- photocurable resin
- diacrylate
- fluorine
- water
- 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.)
- Granted
Links
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、撥水、撥油性を有する光硬化樹脂に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a photocurable resin having water and oil repellency.
（従来技術と問題点）
従来の光硬化樹脂は、紫外線硬化樹脂が半導体産業にお
けるフォトレジスト材、新聞の印刷基盤、ＵＶインク等
を中心として幅広い分野に利用されている。(Prior Art and Problems) Conventional photo-curing resins and ultraviolet-curing resins are used in a wide range of fields, including photoresist materials in the semiconductor industry, newspaper printing bases, UV inks, and the like.
この、紫外線硬化樹脂は、熱硬化樹脂に比較して、 （１）硬化時間が短くてすむ。Compared to thermosetting resin, this ultraviolet curing resin has (1) Curing time is short.
（２）操業費が安い。(2) Low operating costs.
等の優位性を有するために、飲料用アルミニウム缶の外
面塗装等従来熱硬化樹脂を使用していた分野においても
その使用が積極的に検討されている。Because of these advantages, their use is being actively considered in fields where thermosetting resins have traditionally been used, such as the exterior coating of aluminum beverage cans.
また、最近では、半導体のパターン形成において、より
微細な印刷を行うために、紫外線より波長の短い電子線
、Ｘ線等が注目されている。Furthermore, recently, in semiconductor pattern formation, electron beams, X-rays, and the like, which have wavelengths shorter than ultraviolet rays, are attracting attention in order to perform finer printing.
その他に、飲料用アルミニウム缶においても。In addition, aluminum cans for beverages are also used.
紫外線より進入が深い電子線による硬化方法も検討され
ている。Curing methods using electron beams, which penetrate deeper than ultraviolet rays, are also being considered.
これらの光硬化樹脂は、一般に、ウレタンアクリレート
系、エポキシアクリレート系の樹脂がよく使用されてい
るが、しかし、これらの樹脂は、炭化水素系の化合物で
あり、さらに分子中に極性基を有すること等から撥水、
撥油性は示さない。Generally, urethane acrylate-based and epoxy acrylate-based resins are often used as these photocurable resins, but these resins are hydrocarbon-based compounds and furthermore have polar groups in their molecules. Water repellent, etc.
Does not exhibit oil repellency.
例えば、エポキシアクリレート系の樹脂では分子中に水
酸基、エーテル結合などを、ウレタンアクリレート系の
樹脂では、ウレタン結合等を有しているために、耐水性
に劣るという問題があった。For example, epoxy acrylate resins have hydroxyl groups, ether bonds, etc. in their molecules, and urethane acrylate resins have urethane bonds, etc., so they have a problem of poor water resistance.
また、その他にこれらの樹脂は油を弾くいわゆる撥油性
はもたないため、それによって油汚れが付き易くさらに
一度付着した油汚れが取れにくいといった問題もあった
。In addition, since these resins do not have so-called oil repellency, they are susceptible to oil stains and are difficult to remove once they have adhered.
これより、電子材料などのコーテイング材として使用す
る用途においては、電子材料の性能低下の原因となった
り、あるいは外面塗装などに用いた場合、その塗膜の劣
化の原因となったり、また美観を著しく損ねるなどの問
題があった。Therefore, when used as a coating material for electronic materials, it may cause a decline in the performance of the electronic material, or when used for external painting, it may cause deterioration of the coating film, or it may impair the aesthetic appearance. There were problems such as significant damage.
これらの問題を改善するために、樹脂中にシリコン系化
合物、フッ素系化合物を添加することも検討されている
。In order to improve these problems, adding silicon compounds and fluorine compounds to the resin is also being considered.
しかし、シリコン系化合物では、多少の耐水性の向上は
あるものの撥油性を与えることは困難である。一方、フ
ッ素系化合物は、その問題が多少改善されているものの
十分な特性を得るためには、１０パーセント以上、場合
によっては２０パ一セント程度まで添加する必要があり
、それによって樹脂本来の特性が低下したり、また価格
が高くなるといった問題があった。However, with silicone compounds, it is difficult to impart oil repellency, although water resistance may be improved to some extent. On the other hand, although this problem has been somewhat improved with fluorine compounds, in order to obtain sufficient properties, it is necessary to add 10% or more, and in some cases up to 20%, thereby improving the original properties of the resin. There were problems such as a decrease in the amount of electricity and an increase in the price.
さらに、フッ素系の化合物でも、その分子構造において
は、添加の効果が全く得られないものも珍しくなく、効
果的な添加剤がほとんど見つからない状態であった。Furthermore, it is not uncommon for fluorine-based compounds to have no effect at all due to their molecular structure, and it has been difficult to find effective additives.
（問題解決に係わる知見）
本発明者らは、上記の問題を鋭意検討した結果、ペルフ
ルオロアルキル基を有するジアクリレート型化合物を添
加した光硬化樹脂が上記の問題を解決することを見出し
本発明をなすに到った。(Findings related to problem solving) As a result of intensive study of the above problems, the present inventors discovered that a photocurable resin containing a diacrylate type compound having a perfluoroalkyl group solved the above problems, and developed the present invention. I arrived at the eggplant.
（発明の構成）
即ち、本発明は一般式
（式中Ｒｆは炭素数４〜１ｏのペルフルオロアルキル基
ｎｌは炭素数１〜５のアルキル基、Ｒ２は水素、また
はメチル基）で表わされる含フッ素ジアクリレート化合
物を含有することを特徴とする光硬化樹脂を提供する。(Structure of the Invention) That is, the present invention provides a fluorine-containing compound represented by the general formula (wherein Rf is a perfluoroalkyl group having 4 to 1 carbon atoms, nl is an alkyl group having 1 to 5 carbon atoms, and R2 is hydrogen or a methyl group). A photocurable resin containing a diacrylate compound is provided.
本発明はまた一般式
（式中Ｒ，は炭素数４〜ＩＯのペルフルオロアルキル基
、Ｒ２は水素またはメチル基、ｎは１〜３の整数で）で
表される含フッ素ジアクリレートを含有することを特徴
とする光硬化樹脂を提供する。The present invention also includes a fluorine-containing diacrylate represented by the general formula (wherein R is a perfluoroalkyl group having 4 to 10 carbon atoms, R2 is hydrogen or a methyl group, and n is an integer of 1 to 3). To provide a photocurable resin characterized by:
本発明において使用される前記（１）および（２）の化
合物は特願平１−１９０９２９ （特開平）および特願
平１−１９０９３０ （
特開平 ）に開示されている。The compounds (1) and (2) used in the present invention are disclosed in Japanese Patent Application No. 1-190929 (Japanese Unexamined Patent Application Publication No. 1999-1999) and Japanese Patent Application No. 1-190930 (Japanese Unexamined Patent Application Publication No. 1999-1992).
本発明が適用される母体樹脂は、光硬化性を有するもの
であればよく特に限定されないが、具体的な例として、
エポキシアクリレート、ウレタンアクリレート、ポリエ
ステルアクリレート、メラミンアクリレート、アミノア
ルキド、エポキシポリチオール等の樹脂があげられる。The base resin to which the present invention is applied is not particularly limited as long as it has photocurability, but specific examples include:
Examples include resins such as epoxy acrylate, urethane acrylate, polyester acrylate, melamine acrylate, amino alkyd, and epoxy polythiol.
中でも、特にフッ素系ジアクリレート型化合物と共重合
が可能なアクリレート系の樹脂が好ましい。Among these, acrylate resins that can be copolymerized with fluorine-based diacrylate compounds are particularly preferred.
本発明において一般式（１）および（２）で示されるペ
ルフルオロアルキル基を有するジアクリレート型化合物
を添加することによって得られる樹脂の撥水、撥油性は
添加剤のペルフルオロアルキル基によって発現されるも
のである。In the present invention, the water and oil repellency of the resin obtained by adding the diacrylate type compound having a perfluoroalkyl group represented by general formulas (1) and (2) is expressed by the perfluoroalkyl group of the additive. It is.
その正確な作用は明かではないが、一般式（１）および
（２）で示された化合物は、分子中にスルホンアミド結
合、またはエーテル結合という極性部分を有するために
、その極性部分が樹脂との相溶性、あるいはペルフルオ
ロアルキル基の表面への配向等になんらかの影響を与え
ているためと思われる。Although its exact action is not clear, the compounds represented by general formulas (1) and (2) have a polar moiety in the molecule called a sulfonamide bond or an ether bond, so the polar moiety is connected to the resin. This is thought to be due to some influence on the compatibility of the perfluoroalkyl group or the orientation of the perfluoroalkyl group on the surface.
添加剤として用いるジアクリレート型化合物中の２個の
アクリル基は、それが２官能性の重合性反応基として作
用し、単なる添加剤としてだけでなく、樹脂中の成分と
いわゆる共重合成分としても作用でき、また架橋剤的な
効果も有する。The two acrylic groups in the diacrylate type compound used as an additive act as bifunctional polymerizable reactive groups, and can be used not only as an additive but also as a so-called copolymerization component with the components in the resin. It also has the effect of a crosslinking agent.
これにより、少量の添加量で大きな効果を与えることが
可能であり、さらに樹脂成分と結合しているため、耐候
性に優れているという特徴を有する。As a result, it is possible to provide a large effect with a small amount of addition, and furthermore, since it is combined with the resin component, it has the characteristics of excellent weather resistance.
また、ペルフルオロアルキル基を有するジアクリレート
型化合物を樹脂中に添加する場合、ジアクリレート型化
合物をそのままか、あるいは樹脂との相溶性のよい溶媒
に溶解した形で行われる。Further, when a diacrylate type compound having a perfluoroalkyl group is added to the resin, the diacrylate type compound is added as it is or in a form dissolved in a solvent having good compatibility with the resin.
添加後は１通常の撹はんによって樹脂中に分散させれば
良いが、樹脂の粘度が大きく十分な撹はんが困難な場合
は、ジアクリレート型化合物を添加後、適当な溶媒を加
えて樹脂の粘度を低下させて十分に撹はんした後、低温
加熱あるいは減圧蒸発等の操作により溶媒を除去するこ
とが好ましい。After adding the diacrylate type compound, it can be dispersed in the resin using normal stirring, but if the viscosity of the resin is large and sufficient stirring is difficult, add an appropriate solvent after adding the diacrylate type compound. After lowering the viscosity of the resin and sufficiently stirring the resin, it is preferable to remove the solvent by heating at a low temperature or evaporating under reduced pressure.
一般式（１）または（２）の化合物の添加量は実質的に
限定はないが、実際的には全樹脂重量に対して０．０５
〜１０重量％である。The amount of the compound of general formula (1) or (2) added is not substantially limited, but in practice it is 0.05% based on the total resin weight.
~10% by weight.
また、本発明による樹脂は、撥水、撥油性、耐水性、防
汚性も示し、それに加えてその低表面エネルギーから非
粘着性、滑り性なども併せ持つ。Furthermore, the resin according to the present invention exhibits water repellency, oil repellency, water resistance, and stain resistance, and in addition, it also has non-adhesion and slip properties due to its low surface energy.
従って、樹脂の耐湿性、防汚性、耐摩耗性の改善の他に
、金型、ノズル等の離型剤等への応用も可能である。Therefore, in addition to improving the moisture resistance, antifouling properties, and abrasion resistance of the resin, it is also possible to apply it as a mold release agent for molds, nozzles, etc.
（発明の具体的開示） 以下、実施例を挙げて本発明を具体的に説明する。(Specific disclosure of invention) The present invention will be specifically described below with reference to Examples.
（実施例１）
市販紫外線硬化樹脂（ユニデックＶ−４００１ＥＡ （
ウレタンアクリレート系）、大日本インキ（株）製）１
００ｇにフッ素系ジアクリレート型化合物として、を１
ｇ添加して十分に撹はんした。このようにして得られた
樹脂を市販スライド硝子（松浪硝子（株）製）に塗布し
た後、３００Ｗ高圧水銀灯（ウシオ電機（株）製ＵＭＡ
−３０１２−Ｎ４型）を用いて紫外線を１分間照射して
硬化した。(Example 1) Commercially available ultraviolet curing resin (UNIDEC V-4001EA (
Urethane acrylate type), manufactured by Dainippon Ink Co., Ltd.) 1
00g as a fluorine-based diacrylate type compound, 1
g was added and stirred thoroughly. After applying the resin thus obtained to a commercially available slide glass (made by Matsunami Glass Co., Ltd.), a 300W high-pressure mercury lamp (UMA made by Ushio Inc.) was applied.
-3012-N4 type) and was cured by irradiating ultraviolet rays for 1 minute.
このようにして得られた塗布膜の水とＮ、Ｎ−ジメチル
ホルムアミドとエチレングシコールモノエチルエーテル
の混合液（３５ｄｙｎｅ／ ｃｘｎ ）に対する表面接
触角を測定した。The surface contact angle of the thus obtained coating film with respect to a mixed solution (35 dyne/cxn) of water, N,N-dimethylformamide, and ethylene glycol monoethyl ether was measured.
（実施例２）
フッ素系ジアクリレート型化合物として、を用いた以外
は、実施例１と同様に実施し同様の評価を行った。(Example 2) The same procedure as in Example 1 was carried out and the same evaluation was performed, except that the fluorine-based diacrylate type compound was used.
（比較例１）
フッ素系ジアクリレート型化合物を用いずに、無添加の
樹脂を用いた以外は、実施例１と同様の評価を行った。(Comparative Example 1) The same evaluation as in Example 1 was performed except that an additive-free resin was used without using a fluorine-based diacrylate type compound.
（比較例２）
フッ素系ジアクリレート型化合物の代わりに、（三菱金
属（株）製、商標名ＭＦ−１３０）を用いた以外は、実
施例１と同様に実施し同様の評価を行った。(Comparative Example 2) The same procedure as in Example 1 was carried out and the same evaluation was performed, except that (manufactured by Mitsubishi Metals Co., Ltd., trade name MF-130) was used instead of the fluorine-based diacrylate type compound.
結果を、実施例１，２．比較例１の結果とあわせて第１
表に示す。The results are shown in Examples 1 and 2. Combined with the results of Comparative Example 1, the first
Shown in the table.
第１表
（実施例３）
市販紫外線硬化樹脂（ユニデイックＶ−５５００（エポ
キシアクリレート系）、大日本インキ（株）製）１００
ｇにフッ素系ジアクリレート型化合物として、し１１コ
を０．５ｇ添加して十分に撹はんした。このようにして
得られた樹脂を市販スライド硝子（松浪硝子）株）製）
に塗布した後、上記高圧水銀灯を用いて紫外線を３０秒
間照射して硬化した。Table 1 (Example 3) Commercially available ultraviolet curing resin (Unidaic V-5500 (epoxy acrylate type), manufactured by Dainippon Ink Co., Ltd.) 100
0.5 g of Shi11 was added as a fluorine-based diacrylate type compound to g and stirred thoroughly. The resin thus obtained was used as a commercially available slide glass (made by Matsunami Glass Co., Ltd.).
After coating, the coating was cured by irradiating ultraviolet rays for 30 seconds using the high-pressure mercury lamp.
このようにして得られた塗布膜の水と上記混合液に対す
る表面接触角を測定した。The surface contact angle of the coating film thus obtained with respect to water and the above-mentioned mixed liquid was measured.
（実施例４）
フッ素系ジアクリレート型化合物として、を用いた以外
は、実施例３と同様に実施し同様の評価を行った。(Example 4) The same procedure as in Example 3 was carried out and the same evaluation was performed, except that the fluorine-based diacrylate type compound was used.
（比較例３）
フッ素系ジアクリレート型化合物を用いずに、無添加の
樹脂を用いた以外は、実施例３と同様に実施し同様の評
価を行った。(Comparative Example 3) The same procedure as in Example 3 was carried out, and the same evaluation was performed, except that the fluorine-based diacrylate type compound was not used and an additive-free resin was used.
（比較例４）
フッ素系ジアクリレート型化合物の代わりに、しＩｌｔ
’１？”し、 ＩＮ Ｕ Ｍ、しｌ−１： Ｕ １１□
を用いた以外は、実施例３と同様に実施し同様の評価を
行った。結果を、実施例３，４、比較例３の結果とあわ
せて第２表に示す。(Comparative Example 4) Instead of the fluorine-based diacrylate type compound,
'1? “Shi, IN U M, Shil-1: U 11□
The same procedure as in Example 3 was carried out, except that the same evaluation was carried out as in Example 3. The results are shown in Table 2 together with the results of Examples 3 and 4 and Comparative Example 3.
第２表
（実施例５）
市販紫外線硬化樹脂（ＰＴＣ−５０Ｍ、瓦応化学（株）
製）１００ｇにフッ素系ジアクリレート型化合物として
。Table 2 (Example 5) Commercially available ultraviolet curing resin (PTC-50M, Kawaro Kagaku Co., Ltd.)
) as a fluorine-based diacrylate type compound.
を０．５ｇ添加して十分に撹はんした。このようにして
得られた樹脂を市販スライド硝子（松浪硝子（株）製）
に塗布した後、上記高圧水銀灯を用いて紫外線を３０秒
間照射して硬化した。0.5g of was added and thoroughly stirred. The resin thus obtained was used to make a commercially available slide glass (manufactured by Matsunami Glass Co., Ltd.).
After coating, the coating was cured by irradiating ultraviolet rays for 30 seconds using the high-pressure mercury lamp.
このようにして得られた塗布膜の水と上記混合液に対す
る表面接触角を測定した。The surface contact angle of the coating film thus obtained with respect to water and the above-mentioned mixed liquid was measured.
（比較例５）
フッ素系ジアクリレート型化合物を用いずに、無添加の
樹脂を用いた以外は、実施例５と同様に実施し同様の評
価を行った。(Comparative Example 5) The same procedure as in Example 5 was carried out, and the same evaluation was performed, except that the fluorine-based diacrylate type compound was not used and an additive-free resin was used.
結果を、実施例５の結果とあわせて第３表に示す。The results are shown in Table 3 together with the results of Example 5.
第３表Table 3
Claims (1)
基、Ｒ＾１は炭素数１〜５のアルキル基、Ｒ＾２は水素
、またはメチル基）で表わされる含フッ素ジアクリレー
ト化合物を含有することを特徴とする光硬化樹脂。 ２、一般式 ▲数式、化学式、表等があります▼（２） （式中Ｒ＿ｆは炭素数４〜１０のペルフルオロアルキル
基、Ｒ＾２は水素またはメチル基、ｎは１〜３の整数で
）で表される含フッ素ジアクリレートを含有することを
特徴とする光硬化樹脂。 ３、母材となる光硬化樹脂がアクリレート系樹脂である
ことを特徴とする請求項１または２に記載の光硬化樹脂
。 ４、含フッ素ジアクリレート化合物の含有量が０．０５
〜１０重量パーセントであることを特徴とする請求項１
または２に記載の光硬化樹脂。[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, R_f is a perfluoroalkyl group having 4 to 10 carbon atoms, and R^1 is an alkyl group having 1 to 5 carbon atoms. , R^2 is hydrogen or a methyl group) A photocurable resin containing a fluorine-containing diacrylate compound. 2. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (In the formula, R_f is a perfluoroalkyl group with 4 to 10 carbon atoms, R^2 is hydrogen or methyl group, and n is an integer from 1 to 3) A photocurable resin characterized by containing a fluorine-containing diacrylate represented by: 3. The photocurable resin according to claim 1 or 2, wherein the photocurable resin serving as the base material is an acrylate resin. 4. Content of fluorine-containing diacrylate compound is 0.05
Claim 1 characterized in that: ~10% by weight.
or the photocurable resin described in 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25084989A JP2643475B2 (en) | 1989-09-27 | 1989-09-27 | Photocurable resin with water and oil repellency |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25084989A JP2643475B2 (en) | 1989-09-27 | 1989-09-27 | Photocurable resin with water and oil repellency |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03111409A true JPH03111409A (en) | 1991-05-13 |
| JP2643475B2 JP2643475B2 (en) | 1997-08-20 |
Family
ID=17213921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25084989A Expired - Lifetime JP2643475B2 (en) | 1989-09-27 | 1989-09-27 | Photocurable resin with water and oil repellency |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2643475B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011125970A1 (en) * | 2010-04-05 | 2011-10-13 | 三菱レイヨン株式会社 | Active energy ray-curable resin composition, nano ridge/groove structure using same and production method for said structure, and water repellent article provided with nano ridge/groove structure |
| WO2012031058A3 (en) * | 2010-09-01 | 2012-06-28 | E. I. Du Pont De Nemours And Company | Processes for making high resolution, solvent resistant, thin elastomeric printing plates |
| US9541828B2 (en) | 2010-09-01 | 2017-01-10 | E I Du Pont De Nemours And Company | High resolution, solvent resistant, thin elastomeric printing plates |
-
1989
- 1989-09-27 JP JP25084989A patent/JP2643475B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011125970A1 (en) * | 2010-04-05 | 2011-10-13 | 三菱レイヨン株式会社 | Active energy ray-curable resin composition, nano ridge/groove structure using same and production method for said structure, and water repellent article provided with nano ridge/groove structure |
| US8703839B2 (en) | 2010-04-05 | 2014-04-22 | Mitsubishi Rayon Co., Ltd. | Active energy ray-curable resin composition, nano ridge/groove structure using same and production method for said structure, and water repellent article provided with nano ridge/groove structure |
| JP5648632B2 (en) * | 2010-04-05 | 2015-01-07 | 三菱レイヨン株式会社 | Active energy ray-curable resin composition, nano uneven structure using the same, method for producing the same, and water-repellent article provided with nano uneven structure |
| WO2012031058A3 (en) * | 2010-09-01 | 2012-06-28 | E. I. Du Pont De Nemours And Company | Processes for making high resolution, solvent resistant, thin elastomeric printing plates |
| CN103180783A (en) * | 2010-09-01 | 2013-06-26 | E.I.内穆尔杜邦公司 | Processes for making high resolution, solvent resistant, thin elastomeric printing plates |
| US8541162B2 (en) | 2010-09-01 | 2013-09-24 | E I Du Pont De Nemours And Company | High resolution, solvent resistant, thin elastomeric printing plates |
| US8877428B2 (en) | 2010-09-01 | 2014-11-04 | E I Du Pont De Nemours And Company | High resolution, solvent resistant, thin elastomeric printing plates |
| US9541828B2 (en) | 2010-09-01 | 2017-01-10 | E I Du Pont De Nemours And Company | High resolution, solvent resistant, thin elastomeric printing plates |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2643475B2 (en) | 1997-08-20 |
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