JP2006225508A - Cationically photocurable composition and its cured product - Google Patents
Cationically photocurable composition and its cured product Download PDFInfo
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- JP2006225508A JP2006225508A JP2005040818A JP2005040818A JP2006225508A JP 2006225508 A JP2006225508 A JP 2006225508A JP 2005040818 A JP2005040818 A JP 2005040818A JP 2005040818 A JP2005040818 A JP 2005040818A JP 2006225508 A JP2006225508 A JP 2006225508A
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- curable composition
- compound
- photocationic curable
- parts
- photocationic
- Prior art date
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Landscapes
- Epoxy Resins (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、光カチオン硬化性組成物およびその光カチオン硬化性組成物から得られた硬化物に関する。具体的には、透明性、ガラスクリーナー耐性、ガラス、プラスチック樹脂基板などへの接着性、折り曲げ耐性（以下「屈曲性」と称する。）が良好な硬化膜を得ることができ、しかも少ない光照射量で硬化可能であることから、インク、コーティング材、に適用できる光カチオン硬化性組成物およびその硬化物に関する。 The present invention relates to a photocationic curable composition and a cured product obtained from the photocationic curable composition. Specifically, a cured film with good transparency, glass cleaner resistance, adhesion to glass, plastic resin substrate, etc., and bending resistance (hereinafter referred to as “flexibility”) can be obtained, and light irradiation is low. The present invention relates to a photocationic curable composition applicable to inks and coating materials and a cured product thereof.
紫外線等のエネルギー線を用いた硬化システムは、生産性の向上や近年の環境問題を解決する上で有力な方法となっている。現在の光硬化システムの主流は（メタ）アクリレート系材料を使用したラジカル硬化系であるが、エポキシ化合物やビニルエーテル、オキセタン等の材料を使用したカチオン硬化系材料は、（ａ）酸素による硬化阻害を受け難いため、表面および薄膜硬化性に優れる、（ｂ）硬化収縮が小さく、幅広い基材に対し良好な接着性を有する、（ｃ）活性種の寿命が長く光照射後も硬化が徐々に進むことから（暗反応）、残モノマー量を低く抑えることが可能である等、ラジカル硬化系に比べ優れた特長を有することから、近年、塗料、接着剤、ディスプレイ用シール剤、印刷インキ、立体造形、シリコーン系剥離紙、フォトレジスト、電子部品用封止剤等への応用が検討されている（例えば、非特許文献１参照）。
光カチオン硬化系で主に用いられる化合物としてはエポキシ化合物が挙げられ、中でもとりわけ反応性に富む脂環式エポキシ化合物が多用される（特許文献１参照）。該脂環式エポキシ化合物は、大気中においても酸素による硬化阻害を起こさないことからラジカル系に比べても優れた表面硬化性を有するが、重合の進行に伴い反応率が低下し内部の硬化性が不十分となり、十分な硬化物性が得られないと言う問題がある。また用いられる化合物の種類が少なく、得られる硬化物の物性を制御するには困難である。
Curing systems using energy rays such as ultraviolet rays have become an effective method for improving productivity and solving recent environmental problems. The current mainstream of photocuring systems is radical curing systems that use (meth) acrylate materials, but cationic curing materials that use materials such as epoxy compounds, vinyl ethers, oxetanes, etc. Excellent surface and thin film curability because it is difficult to receive, (b) small cure shrinkage, good adhesion to a wide range of substrates, (c) long life of active species, gradually curing after light irradiation (Dark reaction), and the amount of residual monomer can be kept low, so it has superior features compared to radical curing systems. In recent years, paints, adhesives, display sealants, printing inks, three-dimensional modeling Application to silicone-based release paper, photoresist, sealants for electronic parts, and the like are being studied (for example, see Non-Patent Document 1).
Examples of the compound mainly used in the photocation curing system include an epoxy compound, and among them, an alicyclic epoxy compound rich in reactivity is particularly used (see Patent Document 1). The alicyclic epoxy compound has excellent surface curability compared with radical systems because it does not cause curing inhibition by oxygen even in the atmosphere, but the reaction rate decreases with the progress of polymerization, and the internal curability is reduced. Is insufficient, and there is a problem that sufficient cured properties cannot be obtained. Moreover, since there are few kinds of compounds used, it is difficult to control the physical properties of the resulting cured product.
一方、熱硬化で広く用いられているグリシジル型エポキシ化合物は、前記脂環式エポキシ化合物に比べて種類は豊富であるが光カチオン硬化の場合には反応性が不十分であり、また安全性上問題があるＳｂＦ6やＡｓＦ6等の特殊な重合開始剤や、熱硬化を併用する等の方法を用いなければならない。これに対し、オキセタン化合物は光カチオン重合において、単独での開始反応は遅いものの成長反応速度が速い為、エポキシ化合物と併用することにより重合速度が向上することが知られている。しかしながら、この場合でも光硬化性は従来のラジカル系と比較すると未だ十分とは言えず、さらなる高感度化が必要である。この他、ビニルエーテル化合物が高いカチオン重合性を有することが知られているが、単独重合で得られた硬化膜は前記エポキシ化合物やオキセタンに比べ硬化収縮が大きく、基材との接着性が低下するという問題がある。 On the other hand, glycidyl-type epoxy compounds widely used in thermosetting are more abundant than alicyclic epoxy compounds, but in the case of photocationic curing, the reactivity is insufficient, and in terms of safety. It is necessary to use a special polymerization initiator such as SbF 6 or AsF 6 having a problem, or a method of using thermosetting together. On the other hand, oxetane compounds are known to improve the polymerization rate when used in combination with an epoxy compound because the oxetane compound has a slow initiation reaction but has a high growth reaction rate. However, even in this case, the photocurability is still not sufficient as compared with the conventional radical system, and further higher sensitivity is required. In addition, it is known that the vinyl ether compound has high cationic polymerizability, but the cured film obtained by homopolymerization has a larger shrinkage in curing than the epoxy compound or oxetane, and the adhesion to the substrate is reduced. There is a problem.
そこで前記脂環式エポキシ化合物にビニルエーテル化合物を併用することにより、エポキシ化合物の重合性を高め、且つ接着性を保持しようとする試みが数多くなされている（例えば、特許文献２および３参照）。さらに、この組合せからなる組成物を特定の用途、例えば、立体リソグラフィー用組成物（特許文献４参照）や、光ディスク用オーバーコート剤（特許文献５参照）、インクジェット記録方式用紫外線硬化性組成物（特許文献６参照）として使用する試みがなされている。しかしながら、このように単にエポキシ化合物にビニルエーテル化合物を併用した組成物では、確かにエポキシ化合物の反応性が若干向上するが、ビニルエーテル化合物の反応性が大きく低下し、結果として十分な硬化膜物性を得ることができない。これを改良する目的で上記試み（特許文献４、５）では、ビニルエーテル化合物として多官能のものを用いているが、その効果は未だ不十分である。 Therefore, many attempts have been made to increase the polymerizability of the epoxy compound and maintain the adhesiveness by using a vinyl ether compound in combination with the alicyclic epoxy compound (see, for example, Patent Documents 2 and 3). Furthermore, a composition comprising this combination is used for a specific application, for example, a composition for three-dimensional lithography (see Patent Document 4), an overcoat agent for an optical disk (see Patent Document 5), an ultraviolet curable composition for an ink jet recording system ( Attempts have been made to use it as (see Patent Document 6). However, in the composition in which the vinyl ether compound is simply used in combination with the epoxy compound as described above, the reactivity of the epoxy compound is slightly improved, but the reactivity of the vinyl ether compound is greatly reduced, and as a result, sufficient cured film properties are obtained. I can't. In the above attempts (Patent Documents 4 and 5) for the purpose of improving this, polyfunctional compounds are used as the vinyl ether compound, but the effect is still insufficient.
一方、エポキシ化合物から成るカチオン系組成物に、水酸基含有化合物として脂肪族系多価アルコール（特許文献７、８参照）や、フェノール化合物（特許文献９、１０参照）を任意の成分として用いて硬化性を高める試みがなされているが、前者の場合エポキシ化合物の反応性は向上するものの硬化膜が脆弱化し、耐水性、耐摩擦性が劣化するという問題点があり、また、後者ではジヒドロキシベンゼン、トリヒドロキシベンゼン等のフェノール性芳香環１個あるいは２個のフェノール化合物、さらには分子中にメチロール基を有するレゾール型フェノール化合物が開示されているが、共に硬化性が不十分であり、特にレゾール型フェノール樹脂を用いた場合、硬化膜の硬度が徐々に低下するという問題がある。
また、特許文献１１にも、フェノール化合物を添加する技術が開示されているが、この場合も、フェノール化合物が、ラジカル禁止剤、または、酸化防止剤として作用することにより、不安定な開始剤を含むカチオン系組成物の長期の保存が可能となるものの、組成物の光硬化性そのものの向上は期待することできない。
On the other hand, a cationic composition comprising an epoxy compound is cured using an aliphatic polyhydric alcohol (see Patent Documents 7 and 8) or a phenol compound (see Patent Documents 9 and 10) as an optional component as a hydroxyl group-containing compound. In the former case, the reactivity of the epoxy compound is improved, but the cured film becomes brittle and the water resistance and friction resistance are deteriorated. In the latter case, dihydroxybenzene, A phenolic aromatic ring having one or two phenolic aromatic rings such as trihydroxybenzene, and a resol type phenolic compound having a methylol group in the molecule are disclosed, but both of them are insufficiently curable, particularly a resol type. When a phenol resin is used, there exists a problem that the hardness of a cured film falls gradually.
Also, Patent Document 11 discloses a technique of adding a phenol compound, but in this case as well, the phenol compound acts as a radical inhibitor or an antioxidant, thereby causing an unstable initiator. Although the cationic composition can be stored for a long period of time, it cannot be expected to improve the photocurability of the composition itself.
一方、硬化膜の耐摩擦性、耐候性の向上を目的にシラン化合物からなる感光性組成物が提案され、コーティング材、インクジェットプリンタ用インク、カラーフィルター用組成物等に用いる試みがされている（特許文献１２、１３、１４、１５参照）。しかし、これらはいずれも目的の感光性組成物を得る前段階に、アルコキシシラン類を縮重合させてポリアルコキシシランを得る工程を有し、合成時に使用される溶剤を含んだ状態で目的の感光性組成物を得たり、ポリアルコキシシランを溶解させるために積極的に溶媒を配合している。このため得られた感光性組成物は硬化性に問題を有し、さらに得られた硬化膜が剛直なため、基材への密着性、硬化膜の屈曲性について不十分である。 On the other hand, a photosensitive composition composed of a silane compound has been proposed for the purpose of improving the friction resistance and weather resistance of a cured film, and attempts have been made to use it for coating materials, ink for ink jet printers, compositions for color filters, and the like ( (See Patent Documents 12, 13, 14, and 15). However, all of these have a step of obtaining polyalkoxysilane by polycondensation of alkoxysilanes in a stage prior to obtaining the desired photosensitive composition, and containing the solvent used in the synthesis. In order to obtain a functional composition or to dissolve polyalkoxysilane, a solvent is actively added. For this reason, the obtained photosensitive composition has a problem in curability, and since the obtained cured film is rigid, the adhesion to the substrate and the flexibility of the cured film are insufficient.
また、ポリオルガノシリケートに光反応性官能基として（メタ）アクリロイル基を導入した化合物と多官能（メタ）アクリル酸エステルとを配合してなる感光性組成物（特許文献１６参照）が提案されているが、（メタ）アクリロイル基を主成分とするラジカル硬化であることから、光硬化性、基材への密着性に問題がある。
さらに、非溶剤系のシラン化合物含有感光性組成物も提案（特許文献１７参照）されている。該提案では、テトラアルコキシシランにカチオン反応性化合物とカチオン重合開始剤を配合してなるが、ここで用いているエチルシリケートは全てテトラエトキシシランの縮重合物（本発明の一般式（１）でｎ＞２である。）であり、本発明で使用するアルコキシシラン化合物とは本質的に異なる。このような縮重合物を用いると硬化性、硬化膜の透明性、硬化膜の屈曲性に問題がある。
In addition, a photosensitive composition (see Patent Document 16) obtained by blending a polyorganosilicate with a compound having a (meth) acryloyl group introduced as a photoreactive functional group and a polyfunctional (meth) acrylic ester is proposed. However, since it is radical curing having a (meth) acryloyl group as a main component, there are problems in photocurability and adhesion to a substrate.
Furthermore, a non-solvent silane compound-containing photosensitive composition has also been proposed (see Patent Document 17). In the proposal, tetraalkoxysilane is mixed with a cationic reactive compound and a cationic polymerization initiator, and all ethyl silicates used here are tetraethoxysilane polycondensates (general formula (1) of the present invention). n> 2, and is essentially different from the alkoxysilane compound used in the present invention. When such a condensation polymer is used, there are problems in curability, transparency of the cured film, and flexibility of the cured film.
本発明は、大気中でも速やかに光硬化し、ガラス、金属、樹脂等の基材に対する密着性が良好な光カチオン硬化性組成物、並びに該組成物からなるインクジェットインク、ハードコーティング材、およびそれらの硬化物を提供することを目的とする。 The present invention is a photocationic curable composition that is rapidly photocured in the air and has good adhesion to a substrate such as glass, metal, resin, etc., and an inkjet ink, a hard coating material comprising the composition, and their It aims at providing hardened | cured material.
本発明者等は、前記課題を解決するために鋭意検討した結果、特定の原料を組み合わせることにより、前記の課題を解決できることを見出し、本発明に至った。
即ち本発明は、（Ａ）下記一般式（１）で表されるアルコキシシラン化合物１００部に対して、（Ｂ）カチオン反応性化合物０．１〜１０００部、（Ｃ）光カチオン重合開始剤０．０５〜５０部、を含有してなることを特徴とする光カチオン硬化性組成物、である。
That is, the present invention relates to (A) 100 parts of an alkoxysilane compound represented by the following general formula (1), (B) 0.1 to 1000 parts of a cationic reactive compound, and (C) a photocationic polymerization initiator 0. 0.05 to 50 parts, a photocationic curable composition characterized by comprising:
本発明において、一般式（１）で表される（Ａ）アルコキシシラン化合物は、一般式（１）の要件を満たす化合物であれば特に制限するものではないが、一般式（１）で表される化合物のうちｎが２以下であることが必要であり、より具体的にはｎ＝１が５０％以上含まれることが望ましく、８０％以上がより好ましく、９０％以上がさらに好ましい。ｎの平均値は２以下であることが必須であり、１．５以下がよりに好ましく、さらに好ましくは１．２以下であり、最も好ましくは１である。ｎの平均値が２を越えると光照射により得られる硬化膜の透明性、基材への接着性が悪くなる。このようなアルコキシシラン化合物としては上記要件を満足するものであれば特に制限はないが、具体的には、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン等のテトラアルコキシシランを挙げることができる。好ましくはテトラエトキシシランが光硬化性の面で優れている。このようなテトラエトキシシラン化合物の市販品としては、コルコート２８Ｐ（コルコート社製）、ＫＢＥ−０４（信越化学工業社製）、ＴＳＬ−８１２５（ＧＥ東芝シリコーン社製）、ワッカーシリコーンＴＥＳ２８（旭ワッカーシリコーン社製）等を挙げることができる。 In the present invention, the (A) alkoxysilane compound represented by the general formula (1) is not particularly limited as long as it is a compound that satisfies the requirements of the general formula (1), but is represented by the general formula (1). N is required to be 2 or less, more specifically, n = 1 is desirably contained by 50% or more, more preferably 80% or more, and further preferably 90% or more. The average value of n is essential to be 2 or less, more preferably 1.5 or less, still more preferably 1.2 or less, and most preferably 1. When the average value of n exceeds 2, the transparency of the cured film obtained by light irradiation and the adhesion to the substrate are deteriorated. Such an alkoxysilane compound is not particularly limited as long as it satisfies the above requirements. Specifically, for example, tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc. Can be mentioned. Tetraethoxysilane is preferably excellent in terms of photocurability. Examples of such commercially available tetraethoxysilane compounds include Colcoat 28P (manufactured by Colcoat), KBE-04 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSL-8125 (manufactured by GE Toshiba Silicone), Wacker Silicone TES28 (Asahi Wacker Silicone). For example).
本発明のカチオン反応性化合物（Ｂ）は１分子中にカチオン反応性基を有していればよい。具体的には、エポキシ化合物、ビニルエーテル化合物、オキセタン化合物、オキソラン化合物、環状アセタール化合物、環状ラクトン化合物、チイラン化合物、チオビニルエーテル化合物、スピロオルソエステル化合物、エチレン性不飽和化合物、環状エーテル化合物、環状チオエーテル化合物、等を挙げることができ、これらのカチオン反応性化合物は単独でも二種以上組み合わせて使用しても良い。 The cation reactive compound (B) of this invention should just have a cation reactive group in 1 molecule. Specifically, epoxy compounds, vinyl ether compounds, oxetane compounds, oxolane compounds, cyclic acetal compounds, cyclic lactone compounds, thiirane compounds, thiovinyl ether compounds, spiro orthoester compounds, ethylenically unsaturated compounds, cyclic ether compounds, cyclic thioether compounds These cation-reactive compounds may be used alone or in combination of two or more.
これらのカチオン反応性化合物のうちビニルエーテル化合物が好ましい。例えば、エチレングリコールジビニルエーテル、ブタンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、シクロヘキサンジオールジビニルエーテル、トリメチロールプロパントリビニルエーテル、ペンタエリスリトールテトラビニルエーテル、グリセロールトリビニルエーテル、トリエチレングリコ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、ヒドロキシエチルビニルエーテル、ヒドロキシブチルビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、シクロヘキサンジオールモノビニルエーテル、９−ヒドロキシノニルビニルエーテル、プロピレングリコールモノビニルエーテル、ネオペンチルグリコールモノビニルエーテル、グリセロールジビニルエーテル、グリセロールモノビニルエーテル、トリメチロールプロパンジビニルエーテル、トリメチロールプロパンモノビニルエーテル、ペンタエリスリトールモノビニルエーテル、ペンタエリスリトールジビニルエーテル、ペンタエリスリトールトリビニルエーテル、ジエチレングリコールモノビニルエーテル、トリエチレングリコールモノビニルエーテル、テトラエチレングリコールモノビニルエーテル、トリシクロデカンジオールモノビニルエーテル、トリシクロデカンジメタノールモノビニルエーテル等を挙げることができる。 Of these cationic reactive compounds, vinyl ether compounds are preferred. For example, ethylene glycol divinyl ether, butanediol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerol trivinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, hydroxyethyl Vinyl ether, hydroxybutyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanediol monovinyl ether, 9-hydroxynonyl vinyl ether, propylene glycol monovinyl ether, neopentyl glycol monovinyl ether, glycerol divinyl ether, glycerol No vinyl ether, trimethylolpropane divinyl ether, trimethylolpropane monovinyl ether, pentaerythritol monovinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, tricyclodecanediol Examples thereof include monovinyl ether and tricyclodecane dimethanol monovinyl ether.
本発明のカチオン反応性化合物（Ｂ）において２種以上組み合わせて用いる場合、水酸基含有ビニルエーテル化合物とエポキシ化合物の組み合わせが好ましく、さらに好ましくはエポキシ化合物に脂環式エポキシ化合物を用いるのが良い。これらの化合物を組み合わせる場合、水酸基含有ビニルエーテルとエポキシ化合物をそれぞれ１種類づつ配合しても良いし、数種類づつ組み合わせて用いても良い。これらの化合物を組み合わせることにより、エポキシ化合物の硬化性を飛躍的に高めることができ、得られる硬化膜の透明性も良好で、基材への接着性も良好なる硬化膜を得ることができる。このうちエポキシ化合物としては、例えば、グリシジルエーテル型エポキシ化合物、脂環式エポキシ化合物等を挙げることができる。 When using in combination of 2 or more types in the cation reactive compound (B) of this invention, the combination of a hydroxyl-containing vinyl ether compound and an epoxy compound is preferable, It is good to use an alicyclic epoxy compound for an epoxy compound more preferably. When these compounds are combined, one kind each of hydroxyl group-containing vinyl ether and epoxy compound may be blended, or several kinds may be used in combination. By combining these compounds, it is possible to dramatically increase the curability of the epoxy compound, and it is possible to obtain a cured film having good transparency and good adhesion to the substrate. Among these, examples of the epoxy compound include a glycidyl ether type epoxy compound and an alicyclic epoxy compound.
グリシジルエーテル型エポキシ化合物の具体例としては、ビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、フェノールノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、水添ビスフェノールＡ型エポキシ化合物、ビスフェノールＡのアルキレンオキサイド付加体のジクリシジルエーテル、ビスフェノールＦのアルキレンオキサイド付加体のジクリシジルエーテル、水添ビスフェノールＡのアルキレンオキサイド付加体のジクリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ブタンジオールジグリシジルエーテル、ヘキサンジオールジグリシジルエーテル、シクロヘキサンジメタノールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピ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ジ及び／又はトリグリシジルエーテル、ペンタエリスリトールトリ及び／又はテトラグリシジルエーテル、ソルビトールヘプタ及び／又はヘキサグリシジルエーテル、レゾルシンジグリシジルエーテル、ジシクロペンタジエン・フェノール付加型グリシジルエーテル、メチレンビス（２，７−ジヒドロキシナフタレン）テトラグリシジルエーテル、１，６−ジヒドロキシナフタレンジグリシジルエーテル等を挙げることができる。 Specific examples of glycidyl ether type epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, and bisphenol A alkylene oxide adducts. Diglycidyl ether of dialkylidyl ether, alkylene oxide adduct of bisphenol F, diglycidyl ether of alkylene oxide adduct of hydrogenated bisphenol A, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, Butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexane dimethanol Diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane di and / or triglycidyl ether, pentaerythritol tri and / or tetraglycidyl ether, sorbitol hepta and / or hexaglycidyl ether, resorcin diglycidyl ether And dicyclopentadiene / phenol-added glycidyl ether, methylenebis (2,7-dihydroxynaphthalene) tetraglycidyl ether, 1,6-dihydroxynaphthalenediglycidyl ether, and the like.
脂環エポキシ化合物の具体例としては、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、２−（３，４−エポキシシクロヘキシル−５，５−スピロ−３，４−エポキシ）シクロヘキサン−メタ−ジオキサン、ビス（３，４−エポキシシクロヘキシルメチル）アジペート、ビニルシクロヘキセンジオキサイド、４−ビニルエポキシシクロヘキサン、ビス（３，４−エポキシ−６−メチルシクロヘキシルメチル）アジペート、３，４−エポキシ−６−メチルシクロヘキシル−３，４−エポキシ−６−メチルシクロヘキサンカルボキシレート、メチレンビス（３，４−エポキシシクロヘキサン）、ジシクロペンタジエンジエポキサイド、エチレングリコールジ（３，４−エポキシシクロヘキシルメチル）エーテル、エチレンビス（３，４−エポキシシクロヘキサンカルボキシレート）、プロピレンビス（３，４−エポキシシクロヘキサンカルボキシレート）、エポキシヘキサヒドロフタル酸ジオクチル、エポキシヘキサヒドロフタル酸ジ−２−エチルヘキシル、１，４−シクロヘキサンジメタノールジ（３，４−エポキシシクロヘキサンカルボキシレート）等が挙げられる。本発明の組成物に配合するエポキシ化合物としては、２官能以上の脂環式エポキシ化合物が反応性の面で優れていることから好適に使用される。 Specific examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane. -Meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexenedioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy- 6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) Ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), propylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4- And cyclohexanedimethanol di (3,4-epoxycyclohexanecarboxylate). As the epoxy compound to be blended in the composition of the present invention, a bifunctional or higher alicyclic epoxy compound is preferably used because of its excellent reactivity.
本発明で使用するエネルギー線感受性の光カチオン重合開始剤（Ｃ）とは、エネルギー線照射によりカチオン重合を開始させる物質を発生させることが可能な化合物であり、特に好ましいものとしては光照射によりルイス酸を発生させるオニウム塩である。具体的には、ルイス酸のジアゾニウム塩、ルイス酸のヨードニウム塩、ルイス酸のスルホニウム塩等が挙げられ、これらはカチオン部分がそれぞれ芳香族ジアゾニウム、芳香族ヨードニウム、芳香族スルホニウムであり、アニオン部分がＢＦ4 -、ＰＦ6 -、ＳｂＦ6 -、［ＢＸ4］-（但しここで、Ｘは少なくとも２つ以上のフッ素又はトリフルオロメチル基で置換されたフェニル基）等により構成されたオニウム塩である。具体例としては、四フッ化ホウ素のフェニルジアゾニウム塩、六フッ化リンのジフェニルヨードニウム塩、六フッ化アンチモンのジフェニルヨードニウム塩、六フッ化ヒ素のトリ−４−メチルフェニルスルホニウム塩、四フッ化アンチモンのトリ−４−メチルフェニルスルホニウム塩、テトラキス（ペンタフルオロフェニル）ホウ素のジフェニルヨードニウム塩、アセチルアセトンアルミニウム塩とオルトニトロベンジルシリルエーテル混合体、フェニルチオピリジウム塩、六フッ化リンアレン−鉄錯体等を挙げることができる。 The energy ray-sensitive photocationic polymerization initiator (C) used in the present invention is a compound capable of generating a substance that initiates cationic polymerization by irradiation with energy rays. An onium salt that generates an acid. Specific examples include a diazonium salt of a Lewis acid, an iodonium salt of a Lewis acid, a sulfonium salt of a Lewis acid, and the like. In these, the cation portion is aromatic diazonium, aromatic iodonium, aromatic sulfonium, respectively, and the anion portion is An onium salt composed of BF 4 − , PF 6 − , SbF 6 − , [BX 4 ] − (wherein X is a phenyl group substituted with at least two fluorine or trifluoromethyl groups), etc. is there. Specific examples include phenyldiazonium salt of boron tetrafluoride, diphenyliodonium salt of phosphorus hexafluoride, diphenyliodonium salt of antimony hexafluoride, tri-4-methylphenylsulfonium salt of arsenic hexafluoride, antimony tetrafluoride Tri-4-methylphenylsulfonium salt, tetrakis (pentafluorophenyl) boron diphenyliodonium salt, acetylacetone aluminum salt and orthonitrobenzylsilyl ether mixture, phenylthiopyridium salt, phosphorus hexafluoride allene-iron complex, etc. be able to.
市販品としては、ＣＤ−１０１２（商品名：ＳＡＲＴＯＭＥＲ社製）、ＰＣＩ−０１９、ＰＣＩ−０２１（商品名：日本化薬社製）、オプトマーＳＰ−１５０、オプトマーＳＰ−１７０（商品名：旭電化社製）、ＵＶＩ−６９９０（商品名：ダウケミカル社製）、ＣＰＩ−１００Ｐ、ＣＰＩ−１００Ａ（商品名：サンアプロ社製）、ＴＥＰＢＩ−Ｓ（商品名：日本触媒社製）、Ｒ ＨＯＤＯＲＳＩＬ ＰＨＯＴＯＩＮＩＴＩＡＴＯＲ２０７４（商品名：Ｒｈｏｄｉａ社製）等を用いることができ、これらは単独でも２種以上を組み合わせて使用することもできる。これらのうちでもアニオン部位がＰＦ6 -が好ましく、さらに好ましくはアニオン部位がＰＦ6 -であるスルホニウム塩が安定性、硬化性、安全性の面で優れているので使用するのに好適である。 As commercial products, CD-1012 (trade name: manufactured by SARTOMER), PCI-019, PCI-021 (trade name: manufactured by Nippon Kayaku Co., Ltd.), Optmer SP-150, Optomer SP-170 (trade name: Asahi Denka) , UVI-6990 (trade name: manufactured by Dow Chemical Co., Ltd.), CPI-100P, CPI-100A (trade name: manufactured by Sun Apro), TEPBI-S (trade name: manufactured by Nippon Shokubai Co., Ltd.), R HODSIL PHOTOINITITOR 2074 ( (Trade name: manufactured by Rhodia Co., Ltd.) can be used, and these can be used alone or in combination of two or more. Among these, a sulfonium salt having an anion moiety of PF 6 − is preferable, and a sulfonium salt having an anion moiety of PF 6 − is more preferable in terms of stability, curability and safety.
本発明の光カチオン硬化性組成物には、さらに必要に応じて（メタ）アクリレートモノマー類やオリゴマー類およびビニル（メタ）アクリレート等のラジカル重合性化合物および光ラジカル開始剤、消泡剤、レベリング剤、重合禁止剤、ワックス類、酸化防止剤、非反応性ポリマー、微粒子無機フィラー、シランカップリング剤、光安定剤、紫外線吸収剤、帯電防止剤、スリップ剤等を添加することもできる。
本発明の光カチオン硬化性組成物には、加熱によりカチオン重合を開始させる物質を発生させる他の重合開始剤を本発明の本発明の光カチオン重合開始剤（Ｃ）と併用することもできる。他の重合開始剤の具体的な例としては、４，４’−ビス（ジエチルアミノ）ベンゾフェノン、２，４−ジエチルチオキサントン、イソプロピルチオキサントン、９，１０−ジエトキシアントラセン、９，１０−ジブトキシアントラセン等が挙げられる。
In the photocationic curable composition of the present invention, a radical polymerizable compound such as (meth) acrylate monomers and oligomers and vinyl (meth) acrylate, a photoradical initiator, an antifoaming agent, and a leveling agent are further included as necessary. Polymerization inhibitors, waxes, antioxidants, non-reactive polymers, fine particle inorganic fillers, silane coupling agents, light stabilizers, ultraviolet absorbers, antistatic agents, slip agents, and the like can also be added.
In the photocationic curable composition of the present invention, another polymerization initiator that generates a substance that initiates cationic polymerization by heating can be used in combination with the photocationic polymerization initiator (C) of the present invention. Specific examples of other polymerization initiators include 4,4′-bis (diethylamino) benzophenone, 2,4-diethylthioxanthone, isopropylthioxanthone, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and the like. Is mentioned.
その他、硬化性や硬化時の膜物性に悪影響を及ぼさない程度にカチオン重合性を示す他の化合物を添加することができる。これらの化合物としては、例えば前記以外の低分子量のエポキシ化合物を希釈剤として用いることでき、また環状ラクトン化合物、環状アセタール化合物、環状チオエーテル化合物、スピロオルソエステル化合物等が挙げられる。
また従来用いられている、エチレングリコール、プロピレングリコール、ジエチレングリコールやトリエチレングリコール等のポリエチレングリコールやポリプロピレングリコールと言ったジオール類、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の多価アルコール等を用いることもできる。
本発明で光カチオン硬化性組成物に光を照射する手段としては、所定の作業時間内で硬化させることができるものであれば特に制限はなく、例えば、超高圧水銀ランプ、高圧水銀ランプ、低圧水銀ランプ、メタルハライドランプ、キセノンランプ、パルスドキセノンランプ、無電極放電ランプ等が挙げられる。
In addition, other compounds exhibiting cationic polymerizability can be added to such an extent that the curability and film physical properties at the time of curing are not adversely affected. As these compounds, for example, low molecular weight epoxy compounds other than those mentioned above can be used as diluents, and cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiro orthoester compounds and the like can be mentioned.
Also, conventionally used diols such as polyethylene glycol such as ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol and polypropylene glycol, and polyhydric alcohols such as glycerin, trimethylolpropane and pentaerythritol can be used. .
The means for irradiating the photocationic curable composition with light in the present invention is not particularly limited as long as it can be cured within a predetermined working time. For example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure Examples include a mercury lamp, a metal halide lamp, a xenon lamp, a pulsed xenon lamp, and an electrodeless discharge lamp.
次に、本発明において用いられる光カチオン硬化性組成物中の各成分の組成割合について説明する。なお、以下に示される部は全て重量部を表す。
光カチオン硬化性組成物において配合する（Ｂ）光カチオン反応性化合物の含有量は、（Ａ）アルコキシシラン化合物１００部に対して０．１〜１０００部であり、好ましくは５〜８００部である。（Ｂ）光カチオン反応性化合物の含有量が０．１部未満であると、硬化性、硬化膜の透明性が不十分である。また１０００部を超えるとガラスクリーナー耐性が不十分となる。
本発明の光カチオン硬化性組成物における（Ｃ）光カチオン重合用開始剤の含有量は、（Ａ）アルコキシシラン化合物１００部に対して０．０５〜５０部であり、好ましくは１〜３０部、より好ましくは１〜１０部である。（Ｃ）光カチオン重合用開始剤の含有量が０．０５部未満であると十分な光硬化性が得られず、５０部を超えると十分なガラスクリーナー耐性が得られない。
Next, the composition ratio of each component in the photocationic curable composition used in the present invention will be described. In addition, all the parts shown below represent a weight part.
Content of (B) photocation reactive compound mix | blended in a photocationic curable composition is 0.1-1000 parts with respect to 100 parts of (A) alkoxysilane compounds, Preferably it is 5-800 parts. . (B) When content of a photocation reactive compound is less than 0.1 part, sclerosis | hardenability and transparency of a cured film are inadequate. If it exceeds 1000 parts, the glass cleaner resistance becomes insufficient.
The content of the (C) photocationic polymerization initiator in the photocationic curable composition of the present invention is 0.05 to 50 parts, preferably 1 to 30 parts, relative to 100 parts of (A) alkoxysilane compound. More preferably, it is 1-10 parts. (C) If the content of the initiator for photocationic polymerization is less than 0.05 part, sufficient photocurability cannot be obtained, and if it exceeds 50 parts, sufficient glass cleaner resistance cannot be obtained.
本発明の光カチオン硬化性組成物には、加熱によりカチオン重合を開始させる物質を発生させる他の重合開始剤を本発明の（Ｃ）光カチオン重合開始剤と併用することもできる。これらの配合量は（Ａ）アルコキシシラン化合物１００部に対して、０．０１〜５０部であり、好ましくは１〜２０部である。
本発明の光カチオン硬化性組成物において、必要に応じて（メタ）アクリレートモノマー類やオリゴマー類およびビニル（メタ）アクリレート等のラジカル重合性化合物および光ラジカル開始剤、消泡剤、レベリング剤、重合禁止剤、ワックス類、酸化防止剤、非反応性ポリマー、微粒子無機フィラー、シランカップリング剤、光安定剤、紫外線吸収剤、帯電防止剤、スリップ剤等を添加することもできる。これらの配合量は（Ａ）アルコキシシラン化合物１００部に対して、０．０１〜１０部であり、好ましくは０．１部〜５部である。
本発明の光カチオン硬化性組成物に着色剤を添加することにより、光硬化型のインクジェット用インクとすることができる。インクジェットの印字方式では、インクの吐出安定性の観点から低粘度インクであることが必須要件となっている。本発明の光カチオン硬化型組成物は低粘度であるという特徴も有しており、優れた硬化性、基板密着性とあいまって、適当な着色剤と混合することにより光硬化型のインクジェット用インクとしても好適に用いることが可能である。
In the photocationic curable composition of the present invention, another polymerization initiator that generates a substance that initiates cationic polymerization by heating can be used in combination with the (C) photocationic polymerization initiator of the present invention. These compounding quantities are 0.01-50 parts with respect to 100 parts of (A) alkoxysilane compounds, Preferably it is 1-20 parts.
In the photocationic curable composition of the present invention, radically polymerizable compounds such as (meth) acrylate monomers and oligomers and vinyl (meth) acrylate and a photoradical initiator, an antifoaming agent, a leveling agent, and a polymerization as necessary. Inhibitors, waxes, antioxidants, non-reactive polymers, fine particle inorganic fillers, silane coupling agents, light stabilizers, ultraviolet absorbers, antistatic agents, slip agents, and the like can also be added. These compounding quantities are 0.01-10 parts with respect to 100 parts of (A) alkoxysilane compounds, Preferably they are 0.1-5 parts.
By adding a colorant to the photocationic curable composition of the present invention, a photocurable inkjet ink can be obtained. In the ink jet printing system, low viscosity ink is an essential requirement from the viewpoint of ink ejection stability. The photocationic curable composition of the present invention also has a feature of low viscosity, combined with excellent curability and substrate adhesion, and mixed with an appropriate colorant to form a photocurable ink jet ink. Can also be suitably used.
本発明において用いられる着色剤としては、有機顔料及び／又は無機顔料の種々のものが使用可能である。具体的には、酸化チタン、亜鉛華、鉛白、リトボンおよび酸化アンチモン等の白色顔料、アニリンブラック、鉄黒、およびカーボンブラック等の黒色顔料、黄鉛、黄色酸化鉄、ハンザイエロー（１００、５０、３０等）、チタンイエロー、ベンジンイエロー、およびパーマネントイエロー等の黄色顔料、クロームバーミロオン、パーマネントオレンジ、バルカンファーストオレンジ、およびインダンスレンブリリアントオレンジ等の橙色顔料、酸化鉄、パーマネントブラウン、およびパラブラウン等の褐色顔料、ベンガラ、カドミウムレッド、アンチモン朱、パーマネントレッド、ローダミンレーキ、アリザリンレーキ、チオインジゴレッド、ＰＶカーミン、モノライトフェーストレッド、およびキナクリドン系赤色顔料等の赤色顔料、コバルト紫、マンガン紫、ファーストバイレット、メチルバイオレットレーキ、インダンスレンブリリアントバイオレット、ジオキサジンバイオレット等の紫色顔料、群青、紺青、コバルトブルー、アルカリブルーレーキ、無金属フタロシアニンブルー、銅フタロシアニンブルー、インダンスレンブルーおよびインジゴ等の青色顔料、クロムグリーン、酸化クロム、エメラルドグリーン、ナフトールグリーン、グリーンゴールド、アシッドグリーンレーキ、マラカイトグリーンレーキ、フタロシアニングリーン、およびポリクロルブロム銅フタロシアニン等の緑色顔料、その他各種蛍光顔料、金属紛顔料、体質顔料等が挙げられる。本発明の光カチオン硬化性組成物中におけるこれらの顔料の含有量は１〜５０重量％であり、好ましくは５〜２５重量％である。 As the colorant used in the present invention, various organic pigments and / or inorganic pigments can be used. Specifically, white pigments such as titanium oxide, zinc white, lead white, litbon, and antimony oxide, black pigments such as aniline black, iron black, and carbon black, yellow lead, yellow iron oxide, and Hansa Yellow (100, 50 30), yellow pigments such as titanium yellow, benzine yellow, and permanent yellow, orange pigments such as chrome vermilon, permanent orange, balkan first orange, and indanthrene brilliant orange, iron oxide, permanent brown, and para Brown pigments such as brown, red pigments such as bengara, cadmium red, antimony vermilion, permanent red, rhodamine lake, alizarin lake, thioindigo red, PV carmine, monolite face tread, and quinacridone red pigment, cover Purple, manganese purple, first violet, methyl violet lake, indanthrene brilliant violet, dioxazine violet and other purple pigments, ultramarine blue, bitumen, cobalt blue, alkali blue lake, metal-free phthalocyanine blue, copper phthalocyanine blue, indan Blue pigments such as ren blue and indigo, green pigments such as chrome green, chromium oxide, emerald green, naphthol green, green gold, acid green rake, malachite green rake, phthalocyanine green, and polychlorobrom copper phthalocyanine, and various other fluorescent pigments , Metal powder pigments, extender pigments and the like. The content of these pigments in the photocationic curable composition of the present invention is 1 to 50% by weight, preferably 5 to 25% by weight.
上記顔料には必要に応じて顔料分散剤を用いてもよく、本発明で用いることができる顔料分散剤としては、例えば、高級脂肪酸塩、アルキル硫酸塩、アルキルエステル硫酸塩、アルキルスルホン酸塩、スルホコハク酸塩、ナフタレンスルホン酸塩、アルキルリン酸塩、ポリオキシアルキレンアルキルエーテルリン酸塩、ポリオキシアルキレンアルキルフェニルエーテル、グリセリンエステル、ソルビタンエステル、ポリオキシエチレン脂肪酸アミド等の活性剤、あるいはスチレン、スチレン誘導体、ビニルナフタレン誘導体、アクリル酸、アクリル酸誘導体、マレイン酸、マレイン酸誘導体、イタコン酸、イタコン酸誘導体、フマル酸、フマル酸誘導体から選ばれる２種以上の単量体から成るブロック共重合体、ランダム共重合体およびこれらの塩が挙げられる。
顔料の分散方法としては、例えば、ボールミル、サンドミル、アトライター、ロールミル、アジテータ、ヘンシェルミキサ、コロイドミル、超音波ホモジナイザー、パールミル、湿式ジェットミル、ペイントシェーカー等の各種分散機を用いることが出来る。また、顔料分散体の粗粒分を除去する目的で、遠心分離機やフィルターを用いてもよい。
顔料インク中の顔料粒子の平均粒径は、インク中での安定性、画像濃度、光沢感、耐光性等を考慮して選択するが、光沢向上、質感向上の観点からも粒径は適宜選択することが好ましい。
If necessary, a pigment dispersant may be used for the pigment. Examples of the pigment dispersant that can be used in the present invention include higher fatty acid salts, alkyl sulfates, alkyl ester sulfates, alkyl sulfonates, Activators such as sulfosuccinate, naphthalene sulfonate, alkyl phosphate, polyoxyalkylene alkyl ether phosphate, polyoxyalkylene alkyl phenyl ether, glycerin ester, sorbitan ester, polyoxyethylene fatty acid amide, or styrene, styrene Block copolymer comprising two or more monomers selected from derivatives, vinyl naphthalene derivatives, acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, fumaric acid derivatives, Random copolymer and the same Like salt of.
As a method for dispersing the pigment, for example, various dispersing machines such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, and a paint shaker can be used. Further, a centrifuge or a filter may be used for the purpose of removing coarse particles of the pigment dispersion.
The average particle size of the pigment particles in the pigment ink is selected in consideration of the stability in the ink, image density, glossiness, light resistance, etc., but the particle size is also selected appropriately from the viewpoint of improving gloss and improving texture. It is preferable to do.
本発明を実施例などを用いて更に具体的に説明するが、本発明はこれら実施例などにより何ら限定されるものではない。実施例および比較例中の「部」は重量部を、％は重量％を意味する。なお、光カチオン硬化性組成物の光硬化性および硬化膜の物性評価は、以下の方法で行った。
＜光硬化性および硬化膜の物性評価＞
・タックフリー露光量（ＴＦＥＤ）：露光後被膜を指触観察し、表面が硬化し、ベタツキがなくなるのに必要な最小露光量を求めた。
・透明性観察：光カチオン硬化性組成物をガラス基板に塗布しＴＦＥＤで硬化した後、硬化膜の透明性を目視にて判断した。透明な場合は○、透明であるが硬化膜にしわが発生したものには△、白化した場合×で示す。
・ガラスクリーナー耐性：ガラス基板上に露光量２４０ｍＪ／ｃｍ2 で硬化した被膜にガラスクリーナーを塗布し、室温で１０分間放置した後、ガラスクリーナーを拭き取り、表面状態を目視にて観察し、表面はれがない場合○、はがれが生じた場合×とした。
・基板接着性：ガラスクリーナー耐性試験後、硬化膜に対し碁盤目テープ剥離（クロスカット）試験を行い、残存率（１００マス中１００全て剥離せずに残った場合○）の測定を行った。
・屈曲性：コロナ放電処理を表面に施した２軸延伸ポリプロピレン（ＯＰＰ）フィルム上に形成された硬化膜に対し、１８０度折り曲げ試験を行いクラック等のひび割れが生じたものは×、変化がなかったものは○とした。
The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, “parts” means parts by weight, and% means% by weight. The photocurability of the photocationic curable composition and the physical properties of the cured film were evaluated by the following methods.
<Evaluation of physical properties of photocurability and cured film>
-Tack-free exposure (TFED): The film after exposure was touched with a finger to determine the minimum exposure required to cure the surface and eliminate stickiness.
-Transparency observation: After apply | coating a photocationic curable composition to a glass substrate and hardening | curing with TFED, the transparency of the cured film was judged visually. In the case of being transparent, it is indicated by ◯, when it is transparent but wrinkled on the cured film, it is indicated by Δ, and when it is whitened, it is indicated by ×.
・ Glass cleaner resistance: A glass cleaner is applied to a film cured on a glass substrate at an exposure amount of 240 mJ / cm 2 , and left at room temperature for 10 minutes. Then, the glass cleaner is wiped off and the surface condition is visually observed. When there was no peeling, it was marked as ◯, and when peeling occurred x.
-Substrate adhesiveness: After a glass cleaner resistance test, the cured film was subjected to a cross-cut tape peeling (cross-cut) test, and the residual rate (when all 100 in 100 squares remained without peeling) was measured.
-Flexibility: No change when a 180 degree bending test was performed on a cured film formed on a biaxially stretched polypropylene (OPP) film that had been subjected to corona discharge treatment and cracks such as cracks occurred. The ones marked with ○.
［実施例１］
アルコキシシラン化合物としてＴＳＬ−８１２４（商品名：ＧＥ東芝シリコーン社製）５０部、カチオン反応性化合物としてトリメチロールプロパントリビニルエーテル（丸善石油化学工業社製）５０部、光カチオン重合開始剤としてヨードニウム塩型であるＦＸ−ＴＥＰＢＩ（商品名：日本触媒株式会社製）２部を十分混合することにより光カチオン硬化性組成物を得た。得られた組成物をガラス基材上にバーコーターを用いて膜厚１２μｍになるように塗工した後、４００Ｗ高圧水銀灯露光機（セン特殊光源社製）で露光し、塗膜の光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
［実施例２］
実施例１で用いたＴＳＬ−８１２４の代わりにＫＢＥ−０４（商品名：信越化学工業社製）５０部を用い光カチオン硬化性組成物を調整し、光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
[Example 1]
50 parts of TSL-8124 (trade name: manufactured by GE Toshiba Silicone) as an alkoxysilane compound, 50 parts of trimethylolpropane trivinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) as a cation-reactive compound, iodonium salt type as a photocationic polymerization initiator A photocationic curable composition was obtained by sufficiently mixing 2 parts of FX-TEPBI (trade name: manufactured by Nippon Shokubai Co., Ltd.). After coating the obtained composition on a glass substrate so as to have a film thickness of 12 μm using a bar coater, it is exposed with a 400 W high pressure mercury lamp exposure machine (manufactured by Sen Special Light Source Co., Ltd.), and the coating film is cured. The cured film physical properties were evaluated. The results are shown in Table 1.
[Example 2]
A photocationic curable composition was prepared by using 50 parts of KBE-04 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.) instead of TSL-8124 used in Example 1, and the photocurable and cured film properties were evaluated. It was. The results are shown in Table 1.
［実施例３］
実施例１で用いたトリメチロールプロパントリビニルエーテルの代わりにジエチレングリコールジビニルエーテル（丸善石油化学社製）１００部を用い光カチオン硬化性組成物を調整し、光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
［実施例４］
実施例１で用いたトリメチロールプロパントリビニルエーテルの代わりにトリメチロールプロパンジビニルエーテル（丸善石油化学工業社製）２５部を用い光カチオン硬化性組成物を調整し、光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
［実施例５］
実施例４の光カチオン硬化性組成物に、さらにシクロヘキサンジメタノールジビニルエーテル（日本カーバイド工業社製）５０部を添加することで光カチオン硬化性組成物を調整し、光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
[Example 3]
A photocationic curable composition was prepared using 100 parts of diethylene glycol divinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) instead of the trimethylolpropane trivinyl ether used in Example 1, and the photocurability and cured film physical properties were evaluated. . The results are shown in Table 1.
[Example 4]
A photocationic curable composition was prepared using 25 parts of trimethylolpropane divinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) in place of the trimethylolpropane trivinyl ether used in Example 1, and evaluation of photocurability and cured film physical properties was performed. Went. The results are shown in Table 1.
[Example 5]
The photocationic curable composition was prepared by adding 50 parts of cyclohexanedimethanol divinyl ether (manufactured by Nippon Carbide Industries Co., Ltd.) to the photocationic curable composition of Example 4 to obtain photocurable and cured film properties. Evaluation was performed. The results are shown in Table 1.
［実施例６］
アルコキシシラン化合物としてＴＳＬ−８１２４（商品名：ＧＥ東芝シリコーン社製）５０部、カチオン反応性化合物としてヒドロキシブチルビニルエーテル（丸善石油化学工業社製）６０部、ビスフェノールＦ（商品名：本州化学工業社製）１８０、光カチオン重合開始剤としてスルホニウム塩型であるＵＶＩ−６９９２（商品名：ダウ・ケミカル日本社製、約５０％プロピレンカーボネート溶液）１０部を十分混合することにより光カチオン硬化性組成物を得た。これをガラス基材上にバーコーターを用いて膜厚１２μｍになるように塗工した後、４００Ｗ高圧水銀灯露光機（セン特殊光源社製）で露光し、塗膜の光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
［実施例７］
実施例６で用いたビスフェノールＦの代わりに、ＵＶＲ６１０５（商品名：ダウ・ケミカル日本社製）１８０部を用い光カチオン硬化性組成物を調整し、光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
[Example 6]
50 parts of TSL-8124 (trade name: manufactured by GE Toshiba Silicone) as an alkoxysilane compound, 60 parts of hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) and bisphenol F (trade name: manufactured by Honshu Chemical Industry Co., Ltd.) as a cation reactive compound ) 180, UVI-6992 (trade name: manufactured by Dow Chemical Japan Co., Ltd., about 50% propylene carbonate solution), which is a sulfonium salt type as a photocationic polymerization initiator, is sufficiently mixed to prepare a photocationic curable composition. Obtained. This was coated on a glass substrate using a bar coater so as to have a film thickness of 12 μm, and then exposed with a 400 W high-pressure mercury lamp exposure machine (manufactured by Sen Special Light Source Co., Ltd.). Was evaluated. The results are shown in Table 1.
[Example 7]
In place of bisphenol F used in Example 6, 180 parts of UVR6105 (trade name: manufactured by Dow Chemical Japan Co., Ltd.) was used to prepare a photocationic curable composition, and the photocurability and cured film properties were evaluated. . The results are shown in Table 1.
［実施例８］
既知の手法でテトラエトキシシランの縮重合物を調製した。この縮重合物はｎ＝１が６２％、ｎ＝２が２５％であった。アルコキシシラン化合物としてＴＳＬ−８１２４（商品名：ＧＥ東芝シリコーン社製）４０部と当該縮重合物１０部、カチオン反応性化合物としてトリメチロールプロパントリビニルエーテル（丸善石油化学工業社製）５０部、光カチオン重合開始剤としてヨードニウム塩型であるＦＸ−ＴＥＰＢＩ（商品名：日本触媒株式会社製）２部を十分混合することにより光カチオン硬化性組成物を得た。これをガラス基材上にバーコーターを用いて膜厚１２μｍになるように塗工した後、４００Ｗ高圧水銀灯露光機（セン特殊光源社製）で露光し、塗膜の光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
［実施例９］
実施例８で用いたＴＳＬ−８１２４（商品名：ＧＥ東芝シリコーン社製）２５部とアルコキシシラン化合物の縮重合物２５部を用いる以外は実施例８と同様に光カチオン硬化性組成物を調合した。これをガラス基材上にバーコーターを用いて膜厚１２μｍになるように塗工した後、４００Ｗ高圧水銀灯露光機（セン特殊光源社製）で露光し、塗膜の光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
[Example 8]
A polycondensation product of tetraethoxysilane was prepared by a known method. This polycondensation product had n = 1 of 62% and n = 2 of 25%. 40 parts of TSL-8124 (trade name: manufactured by GE Toshiba Silicone) as an alkoxysilane compound and 10 parts of the condensation polymer, 50 parts of trimethylolpropane trivinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.), a photocation A photocationic curable composition was obtained by sufficiently mixing 2 parts of FX-TEPBI (trade name: manufactured by Nippon Shokubai Co., Ltd.) which is an iodonium salt type as a polymerization initiator. This was coated on a glass substrate using a bar coater so as to have a film thickness of 12 μm, and then exposed with a 400 W high-pressure mercury lamp exposure machine (manufactured by Sen Special Light Source Co., Ltd.). Was evaluated. The results are shown in Table 1.
[Example 9]
A photocationic curable composition was prepared in the same manner as in Example 8 except that 25 parts of TSL-8124 (trade name: manufactured by GE Toshiba Silicone) used in Example 8 and 25 parts of a polycondensation product of an alkoxysilane compound were used. . This was coated on a glass substrate using a bar coater so as to have a film thickness of 12 μm, and then exposed with a 400 W high-pressure mercury lamp exposure machine (manufactured by Sen Special Light Source Co., Ltd.). Was evaluated. The results are shown in Table 1.
［比較例１］
既知の手法でテトラエトキシシランの縮重合物を調製した。この縮重合物はｎ≧３が９３％であった。実施例１記載のＴＳＬ−８１２４（商品名：ＧＥ東芝シリコーン社製）の代わりに上記テトラエトキシシランの縮重合物５０部を用いる以外は実施例１と同様にして光カチオン硬化性組成物を調整した。これをガラス基材上にバーコーターを用いて膜厚１２μｍになるように塗工した後、４００Ｗ高圧水銀灯露光機（セン特殊光源社製）で露光し、塗膜の光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
［比較例２］
実施例１で用いたＴＳＬ−８１２４の代わりに比較例１で調製したテトラエトキシシランの縮重合物１００部、カチオン反応性化合物としてトリエチレングリコールジビニルエーテル（日本カーバイド社製）１００部、光カチオン重合開始剤としてヨードニウム塩型であるＦＸ−ＴＥＰＢＩ（商品名：日本触媒株式会社製）４部を十分混合することにより感光性組成物を得た。これをガラス基材上にバーコーターを用いて膜厚１２μｍになるように塗工した後、４００Ｗ高圧水銀灯露光機（セン特殊光源社製）で露光し、塗膜の光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
[Comparative Example 1]
A polycondensation product of tetraethoxysilane was prepared by a known method. This polycondensation product had 93% when n ≧ 3. A photocationic curable composition was prepared in the same manner as in Example 1 except that 50 parts of the polycondensation product of tetraethoxysilane was used instead of TSL-8124 (trade name: manufactured by GE Toshiba Silicone) described in Example 1. did. This was coated on a glass substrate using a bar coater so as to have a film thickness of 12 μm, and then exposed with a 400 W high-pressure mercury lamp exposure machine (manufactured by Sen Special Light Source Co., Ltd.). Was evaluated. The results are shown in Table 1.
[Comparative Example 2]
100 parts of a polycondensation product of tetraethoxysilane prepared in Comparative Example 1 instead of TSL-8124 used in Example 1, 100 parts of triethylene glycol divinyl ether (manufactured by Nippon Carbide) as a cationic reactive compound, photocationic polymerization A photosensitive composition was obtained by sufficiently mixing 4 parts of FX-TEPBI (trade name: manufactured by Nippon Shokubai Co., Ltd.) which is an iodonium salt type as an initiator. This was coated on a glass substrate using a bar coater so as to have a film thickness of 12 μm, and then exposed with a 400 W high-pressure mercury lamp exposure machine (manufactured by Sen Special Light Source Co., Ltd.). Was evaluated. The results are shown in Table 1.
［比較例３］
実施例３で用いたＴＳＬ−８１２４の代わりに比較例１で調製したテトラエトキシシランの縮重合物５０部を用いた以外は実施例３と同様にして光カチオン硬化性組成物を調整し、光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
［比較例４］
実施例４で用いたＴＳＬ−８１２４の代わりに比較例１で調製したテトラエトキシシランの縮重合物５０部を用い以外は実施例４と同様にして光カチオン硬化性組成物を調整し、光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
［比較例５］
アルコキシシラン化合物としてＴＳＬ−８１２４（商品名：ＧＥ東芝シリコーン社製）５０部、光カチオン重合開始剤としてヨードニウム塩型であるＦＸ−ＴＥＰＢＩ（商品名：日本触媒株式会社製）１部を十分混合することにより光カチオン硬化性組成物を得た。これをガラス基材上にバーコーターを用いて膜厚１２μｍになるように塗工した後、４００Ｗ高圧水銀灯露光機（セン特殊光源社製）で露光し、塗膜の光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
[Comparative Example 3]
A photocationic curable composition was prepared in the same manner as in Example 3 except that 50 parts of a tetraethoxysilane polycondensate prepared in Comparative Example 1 was used instead of TSL-8124 used in Example 3, and light The curability and the physical properties of the cured film were evaluated. The results are shown in Table 1.
[Comparative Example 4]
A photocationic curable composition was prepared in the same manner as in Example 4 except that 50 parts of the polycondensation product of tetraethoxysilane prepared in Comparative Example 1 was used instead of TSL-8124 used in Example 4, and photocuring was performed. And physical properties of the cured film were evaluated. The results are shown in Table 1.
[Comparative Example 5]
50 parts of TSL-8124 (trade name: manufactured by GE Toshiba Silicone) as an alkoxysilane compound and 1 part of FX-TEPBI (trade name: manufactured by Nippon Shokubai Co., Ltd.) which is an iodonium salt type as a photocationic polymerization initiator are mixed sufficiently. Thus, a photocationic curable composition was obtained. This was coated on a glass substrate using a bar coater so as to have a film thickness of 12 μm, and then exposed with a 400 W high-pressure mercury lamp exposure machine (manufactured by Sen Special Light Source Co., Ltd.). Was evaluated. The results are shown in Table 1.
［比較例６］
比較例５で用いたＴＳＬ−８１２４の代わりに比較例１で調製したテトラエトキシシランの縮重合物５０部を用い光カチオン硬化性組成物を調整し、光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
［比較例７］
カチオン反応性化合物としてトリエチレングリコールジビニルエーテル（日本カーバイド社製）５０部、光カチオン重合開始剤としてヨードニウム塩型であるＦＸ−ＴＥＰＢＩ（商品名：日本触媒株式会社製）１部を十分混合することにより光カチオン硬化性組成物を得た。これをガラス基材上にバーコーターを用いて膜厚１２μｍになるように塗工した後、４００Ｗ高圧水銀灯露光機（セン特殊光源社製）で露光し、塗膜の光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
[Comparative Example 6]
A photocationic curable composition was prepared by using 50 parts of a polycondensation product of tetraethoxysilane prepared in Comparative Example 1 instead of TSL-8124 used in Comparative Example 5, and the photocurability and cured film properties were evaluated. It was. The results are shown in Table 1.
[Comparative Example 7]
Mix 50 parts of triethylene glycol divinyl ether (Nippon Carbide) as the cation-reactive compound and 1 part of FX-TEPBI (trade name: made by Nippon Shokubai Co., Ltd.) which is an iodonium salt type as the photocationic polymerization initiator. Thus, a photocationic curable composition was obtained. This was coated on a glass substrate using a bar coater so as to have a film thickness of 12 μm, and then exposed with a 400 W high-pressure mercury lamp exposure machine (manufactured by Sen Special Light Source Co., Ltd.). Was evaluated. The results are shown in Table 1.
［比較例８］
カチオン反応性化合物としてヒドロキシブチルビニルエーテル（丸善石油化学工業社製）２０部、ＵＶＲ６１０５（商品名：ダウ・ケミカル日本社製）５０部、光カチオン重合開始剤としてスルホニウム塩型であるＵＶＩ−６９９２（商品名：ダウ・ケミカル日本社製、約５０％プロピレンカーボネート溶液）３部を十分混合することにより光カチオン硬化性組成物を得た。これをガラス基材上にバーコーターを用いて膜厚１２μｍになるように塗工した後、４００Ｗ高圧水銀灯露光機（セン特殊光源社製）で露光し、塗膜の光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
［比較例９］
既知の手法でテトラエトキシシランの縮重合物を調製した。この縮重合物はｎ≧３が９３％であった。アルコキシシランとして当該縮合物を５０部用いる以外は実施例１と同様にして、光カチオン硬化性組成物を調合した。これをガラス基材上にバーコーターを用い膜厚１２μｍになるように塗工した後、４００Ｗ高圧水銀灯露光機（セン特殊光源社製）で露光し、塗膜の光硬化性および硬化膜物性の評価を行った。結果を表１に示す。
[Comparative Example 8]
Hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) 20 parts as a cation-reactive compound, UVR6105 (trade name: Dow Chemical Japan Co., Ltd.) 50 parts, UVI-6992 (product of sulfonium salt type as a photocationic polymerization initiator) A photocationic curable composition was obtained by sufficiently mixing 3 parts (name: Dow Chemical Japan, approximately 50% propylene carbonate solution). This was coated on a glass substrate using a bar coater so as to have a film thickness of 12 μm, and then exposed with a 400 W high-pressure mercury lamp exposure machine (manufactured by Sen Special Light Source Co., Ltd.). Was evaluated. The results are shown in Table 1.
[Comparative Example 9]
A polycondensation product of tetraethoxysilane was prepared by a known method. This polycondensation product had 93% when n ≧ 3. A photocationic curable composition was prepared in the same manner as in Example 1 except that 50 parts of the condensate was used as alkoxysilane. This was coated on a glass substrate using a bar coater so as to have a film thickness of 12 μm, and then exposed with a 400 W high-pressure mercury lamp exposure machine (manufactured by Sen Special Light Source Co., Ltd.). Evaluation was performed. The results are shown in Table 1.
本発明の光カチオン硬化性組成物は、透明性、ガラスクリーナー耐性、ガラス、プラスチック樹脂基板などへの接着性、折り曲げ耐性が良好な硬化膜を得ることができ、しかも少ない光照射量で硬化可能であることから、インクジェットプリンタ用インク、コーティング材、などに適用できる。 The photocationic curable composition of the present invention can provide a cured film with good transparency, glass cleaner resistance, adhesion to glass, plastic resin substrate, and bending resistance, and can be cured with a small amount of light irradiation. Therefore, it can be applied to ink for inkjet printers, coating materials, and the like.
Claims (12)
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| JP2005040818A JP2006225508A (en) | 2005-02-17 | 2005-02-17 | Cationically photocurable composition and its cured product |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056125A (en) * | 2005-08-24 | 2007-03-08 | Mitsubishi Rayon Co Ltd | Curing composition comprising carbon nano-tube and composite having cured coated film thereof |
| JP2008214576A (en) * | 2007-03-07 | 2008-09-18 | Nalux Co Ltd | Near-infrared-curable ink composition and printing method using the same |
| JP2008274216A (en) * | 2007-03-30 | 2008-11-13 | Fujifilm Corp | Polymerizable compound, polymer, ink composition, printed matter and inkjet recording method |
| JP2011153255A (en) * | 2010-01-28 | 2011-08-11 | Tokyo Printing Ink Mfg Co Ltd | Cationically photocurable composition and cured product |
| JP2012136631A (en) * | 2010-12-27 | 2012-07-19 | Riso Kagaku Corp | Nonaqueous pigment ink |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH101507A (en) * | 1996-06-17 | 1998-01-06 | Toyo Ink Mfg Co Ltd | Polymerizable composition and its cured substance |
| JP2000001648A (en) * | 1998-06-18 | 2000-01-07 | Jsr Corp | Photo-setting composition and cured film |
| JP2000327980A (en) * | 1999-05-18 | 2000-11-28 | Jsr Corp | Curable ink, its use and its curing |
| JP2001348515A (en) * | 2000-06-06 | 2001-12-18 | Kansai Paint Co Ltd | Curable composition and method for forming coating film of the same |
-
2005
- 2005-02-17 JP JP2005040818A patent/JP2006225508A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH101507A (en) * | 1996-06-17 | 1998-01-06 | Toyo Ink Mfg Co Ltd | Polymerizable composition and its cured substance |
| JP2000001648A (en) * | 1998-06-18 | 2000-01-07 | Jsr Corp | Photo-setting composition and cured film |
| JP2000327980A (en) * | 1999-05-18 | 2000-11-28 | Jsr Corp | Curable ink, its use and its curing |
| JP2001348515A (en) * | 2000-06-06 | 2001-12-18 | Kansai Paint Co Ltd | Curable composition and method for forming coating film of the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056125A (en) * | 2005-08-24 | 2007-03-08 | Mitsubishi Rayon Co Ltd | Curing composition comprising carbon nano-tube and composite having cured coated film thereof |
| JP2008214576A (en) * | 2007-03-07 | 2008-09-18 | Nalux Co Ltd | Near-infrared-curable ink composition and printing method using the same |
| JP2008274216A (en) * | 2007-03-30 | 2008-11-13 | Fujifilm Corp | Polymerizable compound, polymer, ink composition, printed matter and inkjet recording method |
| JP2011153255A (en) * | 2010-01-28 | 2011-08-11 | Tokyo Printing Ink Mfg Co Ltd | Cationically photocurable composition and cured product |
| JP2012136631A (en) * | 2010-12-27 | 2012-07-19 | Riso Kagaku Corp | Nonaqueous pigment ink |
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