JPH0418455A - Hydrophilic photo-setting composition containing fluorine-containing anionic type surfactant - Google Patents
Hydrophilic photo-setting composition containing fluorine-containing anionic type surfactantInfo
- Publication number
- JPH0418455A JPH0418455A JP12079890A JP12079890A JPH0418455A JP H0418455 A JPH0418455 A JP H0418455A JP 12079890 A JP12079890 A JP 12079890A JP 12079890 A JP12079890 A JP 12079890A JP H0418455 A JPH0418455 A JP H0418455A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- resin
- anionic surfactant
- compound
- hydrophilic
- 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.)
- Pending
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000011737 fluorine Substances 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 title abstract description 4
- 125000000129 anionic group Chemical group 0.000 title abstract 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 13
- -1 perfluorooctylsulfonyl Chemical class 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 23
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 5
- 239000011253 protective coating Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 45
- 239000011347 resin Substances 0.000 description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 150000002222 fluorine compounds Chemical class 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007652 sheet-forming process Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、親水性を有する光硬化性組成物に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a photocurable composition having hydrophilic properties.
（従来技術とその問題点）
従来の光硬化性組成物は、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、印刷基盤、ｔＪＶインク、
塗料、接着剤、歯科材料等を中心として幅広い産業分野
に利用されている。(Prior art and its problems) Conventional photocurable compositions have been used as ultraviolet curable resins for photoresist materials in the semiconductor industry, printing substrates, tJV inks,
It is used in a wide range of industrial fields, mainly in paints, adhesives, dental materials, etc.
この紫外線硬化樹脂は、レジスト、印刷基盤等に使用さ
れているように、光の照射した部分だけが硬化するとい
う画像形成が可能である特徴の他に、一般に非溶媒系で
あるため公害を生じない点で優れ、硬化時間が秒単位で
あるため生産効率が高く、省力化が可能である。および
耐摩擦性、耐溶剤性、耐薬品性、硬さ等に優れるといっ
た特性を有するためにプラスチックのオーバーコーテイ
ング等これまでシリコーン系、および熱硬化性樹脂が使
用され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。This ultraviolet curing resin is used in resists, printing substrates, etc., and in addition to being able to form images by curing only the areas irradiated with light, it also causes pollution because it is generally non-solvent-based. The curing time is on the order of seconds, resulting in high production efficiency and labor savings. Because of its excellent properties such as abrasion resistance, solvent resistance, chemical resistance, and hardness, its use is now widespread in fields where silicone-based and thermosetting resins were previously used, such as overcoating of plastics. It is being actively considered.
これらの光硬化樹脂の成分は、一般に■光重合性オリゴ
マー、■反応性希釈剤、■光重合開始剤、■光重合開始
助剤、■着色剤、■その他の添加剤等の成分に分類され
るが、この中でも光重合性オリゴマーが主成分として用
いられており、樹脂の物性に最も大きな影響を有してい
る。The components of these photocurable resins are generally classified into components such as ■photopolymerizable oligomer, ■reactive diluent, ■photopolymerization initiator, ■photopolymerization initiation aid, ■coloring agent, and ■other additives. However, among these, photopolymerizable oligomers are used as the main component and have the greatest influence on the physical properties of the resin.
この光重合性オリゴマーとしては、様々な種類のものが
知られているが、その重合機構によって、一般にラジカ
ル重合型、光付加重合型、光カチオン重合型、酸硬化型
のオリゴマーに大別される。Various types of photopolymerizable oligomers are known, but they are generally classified into radical polymerization type, photoaddition polymerization type, photocation polymerization type, and acid curing type oligomers depending on their polymerization mechanism. .
これらオリゴマーは、分子中に極性基を有するものが多
いが、一般に特別価れた親木性は示さないため、用途に
よってはその使用が限定されるという問題があった。Although many of these oligomers have a polar group in their molecules, they generally do not exhibit special wood-philicity, which poses a problem in that their use is limited depending on the application.
例えば、その光硬化性組成物上に水性インクを用いて印
刷しようとした場合、樹脂がインクを弾いてその乗りが
悪い。またプラスチックのオーバーコーテイングとして
用いた場合、水滴が付着し易いことによる透明性の低下
、すなわち曇りの問題があり、光ディスク、家具等の保
護コーテイング材としての用途では、帯電性を示すため
に乾燥汚れが付着し易い等の問題があった。For example, when attempting to print on the photocurable composition using water-based ink, the resin repels the ink, making it difficult to print. In addition, when used as an overcoating for plastics, there is a problem of decreased transparency due to easy adhesion of water droplets, that is, cloudiness, and when used as a protective coating material for optical discs, furniture, etc., dry stains occur due to the electrostatic property. There were problems such as easy adhesion.
これらの問題を克服するために、光硬化性組成物中の表
面を親水性にする方法が検討されているが、その一つと
して１例えばポリオキシエチレン基を有するアクリレー
ト型化合物を用いる方法がある（特開平１−１４９５９
）。しかしこの方法では水洗いによってその特性が低下
する、および、樹脂本来の有する硬度が失われ、表面に
傷が付き易く、さらに摩耗によって表面の親水性が低下
するといった問題があった。In order to overcome these problems, methods of making the surface of the photocurable composition hydrophilic are being considered, one of which is, for example, a method of using an acrylate type compound having a polyoxyethylene group. (Unexamined Japanese Patent Publication No. 1-14959
). However, this method has problems in that its properties deteriorate when washed with water, the hardness inherent in the resin is lost, the surface is easily scratched, and the hydrophilicity of the surface decreases due to abrasion.
また、親水性を示す樹脂を表面に２層コーティングする
例もあるが（特開昭５６−１２３５０２） 、操作の煩
雑さがともない、さらに上記と同様の耐候性。There is also an example in which the surface is coated with two layers of hydrophilic resin (JP-A-56-123502), but this involves complicated operations and has the same weather resistance as above.
硬度などの特性は改良されていない。Properties such as hardness have not been improved.
一方、光硬化性樹脂の特性をフッ素化合物によって改良
する試みは数多く検討されている。例えば光ファイバー
の耐湿性改善の目的としてペルフルオロアルキル基を有
するアクリレート型化合物を用いる技術が多数報告され
ており（特開昭５８１８７４１４．６２−１８２７０１
．６３−２４３９０３．６３−４０１０３．６３−２４
８８０７、６３−２４９１１２．６４−３３５０６）
、これらは樹脂の主成分としてフッ素化合物を用いてい
る。On the other hand, many attempts have been made to improve the properties of photocurable resins using fluorine compounds. For example, many technologies have been reported that use acrylate compounds having perfluoroalkyl groups for the purpose of improving the moisture resistance of optical fibers (Japanese Patent Laid-Open No. 58187414.62-182701).
．． 63-243903.63-40103.63-24
8807, 63-249112.64-33506)
, these use a fluorine compound as the main component of the resin.
これに対し、フッ素化合物を添加物として光硬化性樹脂
に混合して表面改質を行う例として、ノニオン系界面活
性剤を用いて防汚性の改善を行う例もある（特開昭５９
−１３７９４３）が、これは親水性を示す極性基を有す
るフッ素化合物の添加によっても、その表面は撥水、撥
油性になることを示唆している。On the other hand, as an example of surface modification by mixing a fluorine compound as an additive into a photocurable resin, there is also an example of improving stain resistance using a nonionic surfactant (JP-A-59
-137943), which suggests that the addition of a fluorine compound having a hydrophilic polar group also makes the surface water and oil repellent.
このように、これまで光硬化性樹脂表面をフッ素化合物
の添加によって親水化するという試みはまだ行われてい
ない。Thus, no attempt has been made to make the surface of a photocurable resin hydrophilic by adding a fluorine compound.
一方、樹脂に親水性を与える方法として熱可塑性樹脂で
ある農業用塩化ビニルシートの防曇剤として、フッ素系
の界面活性剤を練り込む方法が報告されている（特公昭
５２−６２１４）が、シートの成形航にフッ素化合物が
添加され、その成形時の熱、および延伸がフン素化合物
の表面への拡散に大きく影響しているといわれている。On the other hand, as a method of imparting hydrophilicity to resin, a method has been reported in which a fluorine-based surfactant is kneaded as an antifogging agent into agricultural vinyl chloride sheets, which are thermoplastic resins (Japanese Patent Publication No. 52-6214). A fluorine compound is added during the sheet forming process, and the heat and stretching during the forming process are said to have a large effect on the diffusion of the fluorine compound to the surface.
これは、添加剤による樹脂表面の親水化は、添加剤が表
面に移行し、さらにその親水基を表面に向けて配向する
ことが必要とされ、そのために、まず添加物が表面に移
行するために熱を加えることが不可欠とされているため
で、このように現在フッ素化合物の添加による樹脂の表
面改質は、熱硬化性あるいは熱可塑性樹脂に限られてい
る。This is because making the resin surface hydrophilic with an additive requires the additive to migrate to the surface and further orient its hydrophilic groups toward the surface; This is because it is essential to apply heat to the resin, and thus surface modification of resins by adding fluorine compounds is currently limited to thermosetting or thermoplastic resins.
以上のように、従来は熱を必要としないで単にフッ素化
合物の添加によって光硬化性樹脂の表面を親水化すると
いうことは不可能と思われていた。As described above, it has hitherto been considered impossible to make the surface of a photocurable resin hydrophilic simply by adding a fluorine compound without requiring heat.
（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、ある特
定の構造を有するフッ素化合物を、主成分がラジカル重
合型のアクリレート系のオリゴマーである光硬化性組成
物中に添加した場合に、従来、添加剤の表面への移行に
不可欠とされていた熱を全く必要とせずに光硬化性組成
物に十分な親水性を与えることが可能であるという全く
新しい知見を得て、本発明に到った。(Findings related to solving the problem) As a result of intensive study of the above problem, the present inventors have developed a photocurable composition in which a fluorine compound having a specific structure is made of a radically polymerizable acrylate oligomer as a main component. A completely new finding that it is possible to impart sufficient hydrophilicity to a photocurable composition without requiring any heat, which was conventionally considered essential for the migration of additives to the surface. As a result, we have arrived at the present invention.
特に、従来、ペルフルオロアルキル基を有する化合物を
樹脂中に添加した場合、樹脂表面に撥水。In particular, conventionally, when a compound having a perfluoroalkyl group is added to a resin, the resin surface becomes water repellent.
撥油性、非粘着性などの効果を与えることが可能である
ことが知られていたが、分子末端に特定の親水性基を有
した化合物と主成分がラジカル重合型のアクリレート系
のオリゴマーである光硬化性組成物中との組合せにおい
ては、一般に知られている撥水、撥油性ではなく、逆に
高い親水性を与えることを見出した。It was known that it could provide effects such as oil repellency and non-adhesion, but it is a compound with a specific hydrophilic group at the end of the molecule and a radical polymerizable acrylate oligomer as the main component. It has been found that when combined with a photocurable composition, it imparts high hydrophilicity rather than the generally known water and oil repellency.
さらに、この含フツ素アニオン型界面活性剤の添加量が
少量で十分な効果が得られるため、硬度などの樹脂固有
の特性が低下しないという特性を有することを見出した
。Furthermore, it has been found that the fluorine-containing anionic surfactant has the property that a sufficient effect can be obtained even when the amount of the fluorine-containing anionic surfactant added is small, so that properties inherent to the resin such as hardness do not deteriorate.
（発明の構成）
本発明はアクリレート系のオリゴマーを主成分とし、一
般式
％式％（１）
（式中Ｒｒは、炭素数４〜１２のペルフルオロアルキル
基、ＸはＨ，ＮＨ，、Ｎａ、Ｌｉ、Ｋ）で表されるフッ
素系アニオン型界面活性剤を０．１〜１０重量パーセン
ト含有する親水性光硬化組成物を提供する。(Structure of the Invention) The present invention has an acrylate oligomer as a main component, and has the general formula % (1) (wherein Rr is a perfluoroalkyl group having 4 to 12 carbon atoms, X is H, NH, Na, A hydrophilic photocurable composition containing 0.1 to 10 weight percent of a fluorine-based anionic surfactant represented by Li, K) is provided.
本発明はまたアクリレート系のオリゴマーを主成分とし
、一般式
％式％（）
（式中Ｒｆ、Ｘは、前記に同じ）で表される含フツ素型
アニオン型界面活性剤を０．１〜１０重量パーセント含
有する親水性光硬化性組成物を提供する。The present invention also uses a fluorine-containing anionic surfactant containing an acrylate oligomer as a main component and having the general formula % (in which Rf and X are the same as above). A hydrophilic photocurable composition containing 10 weight percent is provided.
特に好ましい組成物は、一般式
％式％（）
（式中Ｘは、前記に同じ）で表されるペルフルオロオク
チルスルホニル型化合物を含有する。A particularly preferred composition contains a perfluorooctylsulfonyl type compound represented by the general formula %() (wherein X is the same as above).
本発明で使用される、含フツ素アニオン型界面活性剤は
、一般に、水に溶解した場合にそのペルフルオロアルキ
ル基を有する部分が陰イオンとして存在する。In the fluorine-containing anionic surfactant used in the present invention, the perfluoroalkyl group-containing moiety generally exists as an anion when dissolved in water.
本発明において、含フツ素アニオン型界面活性剤を添加
することによって得られる光硬化性組成物の親水性は、
この化合物中の分子末端に含まれる親水性基によって発
現される。In the present invention, the hydrophilicity of the photocurable composition obtained by adding a fluorine-containing anionic surfactant is as follows:
It is expressed by a hydrophilic group contained at the end of the molecule in this compound.
これは、この化合物が親水基を外側に向けて配向し、ま
たは表面に移行して存在する水に接触し、水の表面張力
を下げるためであると思わわる５ペルフルオロアルキル
基は、高い撥油性を示すために樹脂成分との相溶性が低
く、添加剤を熱を必要とすることなく表面に移行させる
効果を有するものと思われる。This is thought to be because this compound orients its hydrophilic groups outward or migrates to the surface to contact existing water and lower the surface tension of the water.The 5-perfluoroalkyl group has high oil repellency. It is thought that the compatibility with the resin component is low because of this, and that it has the effect of transferring the additive to the surface without requiring heat.
これは、本発明における含フツ素アニオン型界面活性剤
と同様の分子構造を有するが、このペルフルオロアルキ
ル基部分が通常の炭化水素である化合物、およびこのペ
ルフルオロアルキル基の炭素数が４未満の化合物では、
同様の効果は全く得られないことより推測される。This is a compound that has the same molecular structure as the fluorine-containing anionic surfactant of the present invention, but whose perfluoroalkyl group is a normal hydrocarbon, and a compound whose perfluoroalkyl group has less than 4 carbon atoms. So,
This is inferred from the fact that similar effects were not obtained at all.
それ故、このペルフルオロアルキル基の炭素数は４〜１
２のものが使用される。この炭素数が４未満であると、
上記のように思わしい効果が得られず、また１２を越え
ても、それ以下の場合と比較して特性の違いがほとんど
なく、単に価格を上昇させるばかりである。Therefore, the number of carbon atoms in this perfluoroalkyl group is 4 to 1.
2 are used. When this carbon number is less than 4,
As mentioned above, the desired effect cannot be obtained, and even if the number exceeds 12, there is almost no difference in characteristics compared to the case where the number is less than 12, and the price simply increases.
一方、含フツ素アニオン型界面活性剤を添加すべき光硬
化性樹脂は、ラジカル重合型で、アクリレート系のオリ
ゴマーを主成分とするものである。On the other hand, the photocurable resin to which the fluorine-containing anionic surfactant should be added is of the radical polymerization type and has an acrylate oligomer as its main component.
この樹脂の添加剤に対する挙動は明らかではないが、樹
脂の分子中に含まれる極性基が添加された含フツ素アニ
オン型界面活性剤の極性基との適度なバランスにおいて
後者の移動を促進するものと思われる。The behavior of this resin toward additives is not clear, but it promotes the migration of the latter when the polar groups contained in the resin molecule are in a suitable balance with the polar groups of the fluorine-containing anionic surfactant added. I think that the.
これは、同じラジカル重合型のオリゴマーを主成分とす
る光硬化性樹脂でもアクリレート型でないものにおいて
は思わしい効果を得ることが難しいことから推察される
。This is inferred from the fact that it is difficult to obtain the desired effect with photocurable resins that are not acrylate type, even if the photocurable resin is composed mainly of the same radical polymerizable oligomer.
さらに、２層コーティング、およびポリオキシエチレン
結合を有する化合物の添加など、従来の親水性を与える
ために用いられていた炭化水素系の化合物では、フッ素
系アニオン型界面活性剤の添加量が、樹脂全体量に比較
してきわめて少量であるために、樹脂が本来布する硬度
などの特性が変イヒしないという大きな利点を持つ。Furthermore, in conventional hydrocarbon-based compounds used to impart hydrophilic properties, such as two-layer coatings and the addition of compounds with polyoxyethylene bonds, the amount of fluorine-based anionic surfactants added to the resin Since the amount is extremely small compared to the total amount, it has the great advantage of not changing the original properties of the resin, such as hardness.
これは、上記の親水性を発現する機構ににおいて、添加
さｔた含フツ素アニオン型界面活性剤は樹脂中において
表面に徐々に移行して、接触する水の表面張力を著しく
下げるので、表面に存在する量が少量でも効果は大きい
。This is because the added fluorine-containing anionic surfactant gradually migrates to the surface of the resin and significantly lowers the surface tension of the water that comes into contact with the surface. Even if the amount present is small, the effect is large.
実用に際しては一般式（ＩＩ［）で表される化合物を含
む組成物が好ましい。これは、一般式（ＩＩ［）で示さ
れる化合物は、そのペルフルオロアルキル基の戻素数が
８個であり、電解フツ素化法などで工業的に大量に製造
されているため容易かつ比較的安価に得られるのに加え
、樹脂中に添加した場合、ペルフルオロオクチル基がこ
の化合物の表面への移行に十分な撥油性を示すためであ
る。In practical use, a composition containing a compound represented by general formula (II[) is preferred. This is because the compound represented by the general formula (II[) has 8 return primes in its perfluoroalkyl group, and is easily and relatively inexpensive because it is industrially produced in large quantities by electrolytic fluorination. This is because the perfluorooctyl group exhibits sufficient oil repellency to allow the compound to migrate to the surface when added to the resin.
本発明が適用できる樹脂は、主成分としてアクリレート
系オリゴマーのラジカル重合型の光硬化性樹脂であり、
具体的な例として、エポキシアクリレート系、ウレタン
アクリレート系、ポリエステルアクリレート系等の樹脂
があげられる。The resin to which the present invention can be applied is a radical polymerization type photocurable resin containing an acrylate oligomer as a main component,
Specific examples include epoxy acrylate, urethane acrylate, and polyester acrylate resins.
さらに、実用に際しては、含フツ素アニオン型界面活性
剤は、一般式（１）においてＸが水素、またはＮＨ４で
示される化合物が好ましい。Furthermore, in practical use, the fluorine-containing anionic surfactant is preferably a compound in which X is hydrogen or NH4 in the general formula (1).
これはＸがＮａ、に、Ｌｉで示される化合物より。This is from a compound where X is Na or Li.
一般に樹脂への溶解性に優れるため均一な塗膜が得られ
やすいからである。This is because they generally have excellent solubility in resins, so it is easy to obtain a uniform coating film.
また、その添加量は０．１〜１０重量％、好ましくは０
．５〜５重量％の間で変化する。０．１重量％未満では
思わしい効果が得られず、また１０重量％を越えると、
それ以下の場合と比較して特性にほとんど変化はなく、
また塗膜としての均一性が損われることが多く、基盤に
よっては塗膜が弾かれ濡れず、さらに硬度など樹脂本来
の性質が損われる場合も多い。Further, the amount added is 0.1 to 10% by weight, preferably 0.
．． Varies between 5 and 5% by weight. If it is less than 0.1% by weight, the desired effect cannot be obtained, and if it exceeds 10% by weight,
There is almost no change in the characteristics compared to the case below,
Furthermore, the uniformity of the coating film is often impaired, and depending on the substrate, the coating film is repelled and does not get wet, and the original properties of the resin, such as hardness, are often impaired.
一方、一般式（Ｉ〜■）で表される化合物において、Ｘ
がＨである化合物は、樹脂中の水酸基やアミノ基といっ
た官能基と反応することがあるので、それが問題となる
場合は、一般式（■〜■）でＸがＨ以外の化合物を用い
ることが好ましい。On the other hand, in the compound represented by the general formula (I to ■),
Compounds in which is H may react with functional groups such as hydroxyl groups and amino groups in the resin, so if this is a problem, use a compound in which X is other than H in the general formula (■ to ■). is preferred.
また、添加方法は特に限定されず、さらに、その基材へ
の塗布方法も特に限定されない。Further, the method of addition is not particularly limited, and furthermore, the method of applying it to the base material is also not particularly limited.
具体的な塗布方法としては、浸漬法、スプレー法、ロー
ル法等の一般に用いられる塗布方法をそのまま使用する
ことができる。As a specific coating method, commonly used coating methods such as a dipping method, a spray method, and a roll method can be used as they are.
また、本発明の樹脂は、その親水性によって、防曇性、
帯電防止性、基材への密着性の改善、およびその上さら
に樹脂をコーティングするような場合の濡れ性の改善な
どが可能となる。In addition, the resin of the present invention has antifogging properties due to its hydrophilicity.
It is possible to improve the antistatic property, the adhesion to the base material, and the wettability when coating with a resin.
これによって、例えばプラスチックのオーバーコーテイ
ング用に用いる場合の曇り防止、および光ディスク、家
具などのオーバーコーテイングで乾燥汚れがつきにくい
等の性質を与えることが可能である。This makes it possible to provide properties such as prevention of fogging when used for overcoating plastics, and resistance to dry stains when overcoating optical discs, furniture, and the like.
（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（ＳＡＣＲＥＸ：日本石油■製：エ
ポキシアクリレート型）５０ｇにフッ素系アニオン型界
面活性剤として、
Ｃ，Ｆ□７Ｓ○３Ｈ
を１．５ｇ添加して十分に攪拌した。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■製）に塗布
した後、高圧水銀灯を用いて紫外線を１０秒間照射して
硬化した。Example 1 1.5 g of C,F□7S○3H as a fluorine-based anionic surfactant was added to 50 g of a commercially available ultraviolet curable resin (SACREX: manufactured by Nippon Oil Corporation, epoxy acrylate type) and thoroughly stirred. The resin thus obtained was applied to a commercially available slide glass (manufactured by Matsunami Glass) and cured by irradiating it with ultraviolet rays for 10 seconds using a high-pressure mercury lamp.
このようにして得られた塗布膜の水との接触角を測定し
た。The contact angle of the coating film thus obtained with water was measured.
実施例２
フッ素系アニオン型界面活性剤として
ＣＬＯＦ２１ＳＯ３ＮＨ４
を２．５ｇ用いた以外は、実施例１と同様の評価を行っ
た。Example 2 The same evaluation as in Example 1 was performed except that 2.5 g of CLOF21SO3NH4 was used as the fluorine-based anionic surfactant.
実施例３
フッ素系アニオン型界面活性剤として
Ｃ，Ｆ工、ＳＯ□Ｋ
を３．０ｇ用いた以外は、実施例１と同様の評価を行っ
た。Example 3 The same evaluation as in Example 1 was performed except that 3.0 g of C, F, SO□K was used as the fluorine-based anionic surfactant.
比較例１
フッ素系アニオン型界面活性剤を用いないで、未添加の
紫外線硬化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 a fluorine-based anionic surfactant was not used and an unadded ultraviolet curable resin was used.
比較例２ フッ素系アニオン型界面活性剤として ＣＦ３ＣＯ２Ｈ を用いた以外は、実施例１と同様の評価を行った。Comparative example 2 As a fluorine-based anionic surfactant CF3CO2H The same evaluation as in Example 1 was performed except that .
比較例３
フッ素系アニオン型界面活性剤を用いずにステアリン酸
を用いた以外は、実施例］、と同様の評価を行った。Comparative Example 3 The same evaluation as in Example] was performed except that stearic acid was used without using a fluorine-based anionic surfactant.
実施例１〜３、比較例１．２の結果をあわせて第１表に
示す。The results of Examples 1 to 3 and Comparative Examples 1.2 are also shown in Table 1.
第１表
傍Ｍ色
実施例１ １３゜
実施例２ ４２゜
実施例３ ３４゜
比較例１ ８６゜
比較例２ ９３゜
比較例３ ８９゜
実施例４
市販紫外線硬化樹脂（Ｖ −４００１Ｅ Ａ ：大日本
インキ■製：ウレタンアクリレート型）５０ｇにフッ素
系アニオン型界面活性剤として、
Ｃ７Ｆ１．Ｃ○２Ｈ
を０．５ｇ添加して十分に攪拌した。このようにして得
られた樹脂を市販ポリカーボネート板に塗布した後、高
圧水銀灯を用いて紫外線を１分間照射して硬化した。First surface side M color Example 1 13° Example 2 42° Example 3 34° Comparative example 1 86° Comparative example 2 93° Comparative example 3 89° Example 4 Commercially available ultraviolet curing resin (V-4001E A: Large Nippon Ink ■: Urethane acrylate type) 50g as a fluorine-based anionic surfactant, C7F1. 0.5 g of C○2H was added and thoroughly stirred. The resin thus obtained was applied to a commercially available polycarbonate plate, and then cured by irradiating it with ultraviolet rays for 1 minute using a high-pressure mercury lamp.
このようにして得られた塗布膜の水に対する表面接触角
を測定した。接触角は３８°てあった。The surface contact angle of the coating film thus obtained with respect to water was measured. The contact angle was 38°.
比較例４
フッ素系化合物を用いずに、炭化水素系化合物として
ＣＨＣＨ２＝ＣＨＣ０２（ＣＨ２ＣＨ２０）□ＣＣＨ＝
ＣＨ２（第−工業製薬味製： Ｐ Ｅ−４００）を用い
た以外は、実施例４と同様の評価を行った。接触角は６
５°であった。Comparative Example 4 CHCH2=CHC02(CH2CH20)□CCH= as a hydrocarbon compound without using a fluorine compound
The same evaluation as in Example 4 was performed except that CH2 (manufactured by Dai-Kogyo Yakuhin Aji: PE-400) was used. The contact angle is 6
It was 5°.
実施例５
市販紫外線硬化樹脂（アロニツクスＭ−６２００：東亜
合成■製：ポリエステルアクリレート型）３０ｇにフッ
系陰イオン型界面活性剤として、Ｃ，Ｆ、Ｓ○、Ｈ
を３．０ｇ添加して十分に攪拌した。このようにして得
られた樹脂を市販アクリル板に塗布した後、高圧水銀灯
を用いて紫外線を１０秒間照射して硬化した。Example 5 Adding 3.0 g of C, F, S○, H as a fluorine-based anionic surfactant to 30 g of a commercially available ultraviolet curable resin (Aronics M-6200 manufactured by Toagosei ■: polyester acrylate type) was sufficient. The mixture was stirred. The resin thus obtained was applied to a commercially available acrylic plate, and then cured by irradiating it with ultraviolet rays for 10 seconds using a high-pressure mercury lamp.
このようにして得られた塗布膜の水に対する表面接触角
を測定した。接触角は２９°あった。The surface contact angle of the coating film thus obtained with respect to water was measured. The contact angle was 29°.
Claims (1)
ル基、ＸはＨ、Ｎａ、ＮＨ＿４、Ｌｉ、Ｋ）で表される
含フッ素アニオン型界面活性剤を０．１〜１０重量％含
有する親水性光硬化組成物。 ２、含フッ素アニオン型界面活性剤が一般式Ｃ＿８Ｆ＿
１＿７ＳＯ＿３Ｘ（II） （式中Ｘは、前記に同じ）で表されるペルフルオロオク
チルスルホニル型化合物である請求項１に記載の光硬化
性組成物。 ３、アクリレート系のオリゴマーを主成分とし、一般式 Ｒ＿ｆＣＯ＿２Ｘ（III） （式中Ｒ＿ｆ、Ｘは、前記に同じ）で表される含フッ素
アニオン型界面活性剤を０．１〜１０重量％含有する親
水性光硬化性組成物。[Claims] 1. The main component is an acrylate oligomer, with the general formula R_fSO_3X(I) (wherein R_f is a perfluoroalkyl group having 4 to 12 carbon atoms, and X is H, Na, NH_4, Li, K ) A hydrophilic photocurable composition containing 0.1 to 10% by weight of a fluorine-containing anionic surfactant. 2. The fluorine-containing anionic surfactant has the general formula C_8F_
The photocurable composition according to claim 1, which is a perfluorooctylsulfonyl compound represented by 1_7SO_3X(II) (wherein X is the same as defined above). 3. The main component is an acrylate oligomer, and contains 0.1 to 10% by weight of a fluorine-containing anionic surfactant represented by the general formula R_fCO_2X(III) (wherein R_f and X are the same as above) Hydrophilic photocurable composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12079890A JPH0418455A (en) | 1990-05-10 | 1990-05-10 | Hydrophilic photo-setting composition containing fluorine-containing anionic type surfactant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12079890A JPH0418455A (en) | 1990-05-10 | 1990-05-10 | Hydrophilic photo-setting composition containing fluorine-containing anionic type surfactant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0418455A true JPH0418455A (en) | 1992-01-22 |
Family
ID=14795261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12079890A Pending JPH0418455A (en) | 1990-05-10 | 1990-05-10 | Hydrophilic photo-setting composition containing fluorine-containing anionic type surfactant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0418455A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997004033A1 (en) * | 1995-07-21 | 1997-02-06 | Mitsubishi Rayon Co., Ltd. | Photopolymerizable composition and optical disc having hardened coating made from the composition |
| JP2006052260A (en) * | 2004-08-10 | 2006-02-23 | Lintec Corp | Coating composition, coated film, method for producing the coated film, and optical recording medium |
| JP2009179836A (en) * | 2008-01-30 | 2009-08-13 | Mitsubishi Materials Corp | Method of absorbing perfluoroalkane sulfonyl fluoride |
| JP2018524443A (en) * | 2015-06-22 | 2018-08-30 | アームストロング ワールド インダストリーズ インコーポレーテッド | Soil dirt prevention powder coating |
-
1990
- 1990-05-10 JP JP12079890A patent/JPH0418455A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997004033A1 (en) * | 1995-07-21 | 1997-02-06 | Mitsubishi Rayon Co., Ltd. | Photopolymerizable composition and optical disc having hardened coating made from the composition |
| US6066684A (en) * | 1995-07-21 | 2000-05-23 | Mitsubishi Rayon Co., Ltd. | Photopolymerizable composition and optical disk having cured coating thereof |
| US6296916B1 (en) | 1995-07-21 | 2001-10-02 | Juichi Fujimoto | Photopolymerizable composition and optical disk having cured coating thereof |
| JP2006052260A (en) * | 2004-08-10 | 2006-02-23 | Lintec Corp | Coating composition, coated film, method for producing the coated film, and optical recording medium |
| JP2009179836A (en) * | 2008-01-30 | 2009-08-13 | Mitsubishi Materials Corp | Method of absorbing perfluoroalkane sulfonyl fluoride |
| JP2018524443A (en) * | 2015-06-22 | 2018-08-30 | アームストロング ワールド インダストリーズ インコーポレーテッド | Soil dirt prevention powder coating |
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