JPH01203403A - Photosensitive organic composition - Google Patents
Photosensitive organic compositionInfo
- Publication number
- JPH01203403A JPH01203403A JP2721588A JP2721588A JPH01203403A JP H01203403 A JPH01203403 A JP H01203403A JP 2721588 A JP2721588 A JP 2721588A JP 2721588 A JP2721588 A JP 2721588A JP H01203403 A JPH01203403 A JP H01203403A
- Authority
- JP
- Japan
- Prior art keywords
- organic
- peroxide
- ttf
- light
- visible light
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 9
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 229920000620 organic polymer Polymers 0.000 claims abstract 2
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 125000004001 thioalkyl group Chemical group 0.000 claims 1
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002978 peroxides Chemical class 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 239000003999 initiator Substances 0.000 description 11
- 238000001723 curing Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- -1 Ketone peroxide Chemical class 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- LZJCVNLYDXCIBG-UHFFFAOYSA-N 2-(5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine Chemical compound S1C(SCCS2)=C2SC1=C(S1)SC2=C1SCCS2 LZJCVNLYDXCIBG-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔概要〕
光でラジカルを発生し、重合、硬化、架橋などの反応を
開始させる光反応開始剤に関し、可視域に優れた感度を
もつ光反応開始剤を実用化することを目的とし、
有機過酸化物に対し、テトラチアフバレン或いはその誘
導体からなる色素を増感剤として加え、可視光領域で動
作する有機組成物を構成する。[Detailed Description of the Invention] [Summary] To commercialize a photoreaction initiator that generates radicals with light and initiates reactions such as polymerization, curing, and crosslinking, and has excellent sensitivity in the visible region. For this purpose, a dye consisting of tetrathiaphvalene or a derivative thereof is added as a sensitizer to an organic peroxide to form an organic composition that operates in the visible light region.
本発明は可視域に優れた感度をもつ感光性有機組成物に
関する。The present invention relates to a photosensitive organic composition having excellent sensitivity in the visible region.
ケトンパーオキサイド、パーオキシケタール。Ketone peroxide, peroxyketal.
ハイドロパーオキサイド、ジアルキルパーオキサイド、
ジアシルパーオキサイドなどの有機過酸化物は合成樹脂
や合成ゴムの重合開始剤、硬化剤または架橋剤として使
用されており、最近ではそのラジカル反応性を利用して
樹脂の改質剤としても使用されている。Hydroperoxide, dialkyl peroxide,
Organic peroxides such as diacyl peroxide are used as polymerization initiators, curing agents, or crosslinking agents for synthetic resins and synthetic rubbers, and recently, they have also been used as modifiers for resins by taking advantage of their radical reactivity. ing.
例えば、有機過酸化物が重合開始剤として適用される七
ツマ−を挙げると、塩化ビニル、スチレン、エチレン、
酢酸ビニル、テトラフロロエチレン、アクリロニトリル
などがある。For example, examples of organic peroxides used as polymerization initiators include vinyl chloride, styrene, ethylene,
Examples include vinyl acetate, tetrafluoroethylene, and acrylonitrile.
こ＼で、有機過酸化物が重合開始剤や架橋剤として作用
する理由は一般に熱によって開裂し、活性の有機ラジカ
ルを発生するからである。The reason why organic peroxides act as polymerization initiators and crosslinking agents is that they are generally cleaved by heat and generate active organic radicals.
然し、このように熱分解によって有機ラジカルを発生さ
せる方法は制御が難しいことが問題である。However, the problem with this method of generating organic radicals through thermal decomposition is that it is difficult to control.
一方、光でラジカル発生剤を活性化させ、重合。Meanwhile, the radical generator is activated by light and polymerized.
硬化、架橋などの反応を開始させる方法が検討されてい
る。Methods of initiating reactions such as curing and crosslinking are being studied.
本発明は可視光に感度を有する有機過酸化物系光反応開
始剤に関するものである。The present invention relates to an organic peroxide-based photoreaction initiator sensitive to visible light.
光照射によってラジカルを発生し、重合、硬化。 Generates radicals through light irradiation, polymerizes and hardens.
架橋などの反応を対しさせる光反応開始剤としてはアゾ
化合物やアジド化合物、多ハロゲン化合物などが知られ
ている。Azo compounds, azide compounds, polyhalogen compounds, and the like are known as photoreaction initiators that initiate reactions such as crosslinking.
一方、有機過酸化物は加熱によりラジカルを生ずる反応
開始剤として知られており、数多くの種類があるが、光
反応開始剤として使用できるものは限られており、多く
は光によるラジカル発生効率が低く、光反応開始剤とし
て使用することは実用上できない。On the other hand, organic peroxides are known as reaction initiators that generate radicals when heated, and although there are many types, only a limited number of them can be used as photoreaction initiators, and many have low radical generation efficiency due to light. It is practically impossible to use it as a photoreaction initiator.
また、無色あるいは淡黄色であるために紫外線でしか反
応を起こさせることができない。Also, because it is colorless or pale yellow, it can only be reacted with ultraviolet light.
そのため、光反応の利用分野として、ポリマーの合成、
光硬化型接着剤、印刷用製版、フォトレジストなどの用
途があるが、ポリマーの合成では紫外線に透明な容器を
用いる必要があり、光硬化型接着剤では紫外線ランプを
用い、また接着する材料も紫外線に透明である必要があ
る。Therefore, the fields of application of photoreaction include polymer synthesis,
Applications include light-curing adhesives, printing plates, and photoresists, but polymer synthesis requires the use of containers that are transparent to ultraviolet light, and light-curing adhesives require the use of ultraviolet lamps, and the materials to be bonded also need to be used. Must be transparent to UV light.
また印刷用製版の分野では、レーザプリンタと同様に可
視レーザを用いて画像を描画し、製版する方法がとられ
ているが、有機過酸化物は可視光に感度を持たないので
、か＼る用途には使用できない。In addition, in the field of printing plate-making, a visible laser is used to draw images and plate-making, similar to laser printers, but organic peroxides are not sensitive to visible light, so It cannot be used for any purpose.
以上の理由により可視光でラジカルを発生する有機過酸
化物が望まれている。For the above reasons, organic peroxides that generate radicals with visible light are desired.
先に記したようにポリマーの合成、光硬化型接着剤、印
刷用製版、フォトレジストなどの用途に広く使用できる
ようにするためには、可視光に優れた感度をもつ有機過
酸化物系の反応開始剤を開発することが課題である。As mentioned earlier, organic peroxides with excellent sensitivity to visible light must be used in a wide range of applications such as polymer synthesis, photocurable adhesives, printing plates, and photoresists. The challenge is to develop a reaction initiator.
上記の課題は加熱により開裂して有機ラジカルを発生し
、モノマーの重合開始剤やポリマーの硬化剤或いは架橋
剤として使用されている有機過酸化物に、テトラチアフ
バレン或いはその誘導体からなる色素を増感剤として加
え、可視光領域で光反応開始剤として動作させることに
より感光性有機組成物を構成する。The above problem can be solved by adding a dye consisting of tetrathiaphvalene or its derivative to an organic peroxide that is cleaved by heating to generate organic radicals and is used as a polymerization initiator for monomers, a curing agent for polymers, or a crosslinking agent. A photosensitive organic composition is constituted by adding it as a sensitizer and operating it as a photoreaction initiator in the visible light region.
本発明はテトラチアフバレン（以下略してＴＴＦ）或い
はこの誘導体からなる色素を添加することにより長波長
増感を行うものである。The present invention performs long wavelength sensitization by adding a dye made of tetrathiafuvalene (hereinafter abbreviated as TTF) or a derivative thereof.
ＴＴＦ或いはこの誘導体は有機超伝導物質として最近注
目されているが、光増感用として使用された例はない。Although TTF or its derivatives have recently attracted attention as organic superconducting materials, there have been no examples of their use for photosensitization.
・発明者等はＴＴＦ或いはその誘導体が分子内に大きな
電荷の偏りを有しており、優れた電子供与体として作用
すること、および可視光に吸収を有することに注目し、
光反応開始剤に対する波長増感作用を調べた。・The inventors noted that TTF or its derivatives have a large charge bias within the molecule, act as an excellent electron donor, and have absorption in visible light.
The wavelength sensitization effect on photoinitiators was investigated.
その結果、ＴＴＦ或いはその誘導体は有機過酸化物に対
して優れた増感剤として機能することを見出した。As a result, it was found that TTF or its derivative functions as an excellent sensitizer against organic peroxides.
第１図はＴＴＦの構造式であり、第２図（Ａ）〜（Ｆ）
はこの誘導体の構造式である。Figure 1 shows the structural formula of TTF, and Figures 2 (A) to (F)
is the structural formula of this derivative.
すなわち、第２図（Ａ）はＴＴＦの水素原子をＣ１１！
基で置換したもの、また同図（Ｂ）はＣＦ３基で置換し
たもの、また同図（Ｃ）はベンゼン環が２個付加したも
の、同図（Ｄ）はベンゼン環の代わりに硫黄（Ｓ）を含
む複素環の付加したもの（ＢＥＤＴ−ＴＴＦ） 、また
同図（Ｅ）と（Ｆ）は片側にのみ環の付加したもので、
これらの色素は何れも増感剤として作用する。That is, in FIG. 2(A), the hydrogen atom of TTF is C11!
(B) shows one substituted with CF3 group, (C) shows one with two benzene rings added, and (D) shows one with sulfur (S) substituted for the benzene ring. ) (BEDT-TTF), and (E) and (F) in the same figure have a ring added only to one side,
All of these dyes act as sensitizers.
次に、光反応開始剤として働く有機過酸化物としては、
実験の結果、紫外線を吸収して反応する紫外線反応型の
ものは勿論ＴＴＦあるいはその誘導体と組み合わせて使
用できるが、通常では光反応を起こしにくいものでも使
用でき、殆ど総ての有機過酸化物が使用できることが判
った。Next, organic peroxides that act as photoreaction initiators include:
As a result of experiments, we found that ultraviolet-reactive types that absorb and react with ultraviolet light can of course be used in combination with TTF or its derivatives, but even substances that do not normally cause photoreactions can be used, and almost all organic peroxides can be used. It turned out that it can be used.
そしてＴＴＦ或いはその誘導体によって活性化して開裂
し、有機ラジカルを発生した有機過酸化物はポリマー或
いはモノマーに対し、熱や紫外線によって開裂した場合
と同様に作用する。The organic peroxide, which is activated and cleaved by TTF or its derivatives and generates organic radicals, acts on the polymer or monomer in the same way as when it is cleaved by heat or ultraviolet rays.
なお、このような怒光性有機組成物はシリコンゴムを始
めとして各種の合成ゴムや天然ゴム、ビニル系ポリマー
の架橋剤としても使用されるが、この場合に過酸化物と
してはジアルキルパーオキサイド系のものが適している
。Incidentally, such a photogenic organic composition is also used as a crosslinking agent for silicone rubber, various synthetic rubbers, natural rubbers, and vinyl polymers. is suitable.
実施例１：
試験管中の入れたメチルメタアクリレート１０１ｍ１に
有機過酸化物として１．１ ’、４．４′−テトラ（
ターシャリブチルパーオキシカルボニル）ベンゾフェノ
ン０．１重量％と増感剤としてＴＴＦの０．０５重量％
を溶解し、３００Ｗのタングステンランプ光を３０ｃｏ
＋の距離から１０分間に亙って照射した後、液体クロマ
トグラフ（ＧＰＣ）で分子量を測定したところ、ポリス
チレン換算で重量平均分子量（ＭＷ）として７００００
．分散度３．０のポリメチルメタクリレート（ＰＭＭＡ
）を得ることができた。Example 1: 1.1',4.4'-tetra(1.1',4.4'-tetra(
0.1% by weight of tert-butylperoxycarbonyl) benzophenone and 0.05% by weight of TTF as a sensitizer.
Melt and apply 300W tungsten lamp light to 30co
After irradiating for 10 minutes from a distance of +, the molecular weight was measured by liquid chromatography (GPC), and the weight average molecular weight (MW) in terms of polystyrene was 70,000.
．． Polymethyl methacrylate (PMMA) with a dispersity of 3.0
) was able to be obtained.
実施例２：
試験管中のスチレン１０ｍ１にターシャリブチルパーオ
キシアセテート０．０５重量％と第２図（Ａ）に示すメ
チル化ＴＴＦを０．０５重重量を溶解し、波長４２０ｎ
ａ＋以下の光をカットする紫外線フィルタを通し夕３０
０Ｗのタングステンランプの光を３０ｃｍの距離から１
０分間照射した後、ＧＰＣで分子量を測定したところ、
重量平均分子量（台−）として４００００のポリスチレ
ンを得ることができた。Example 2: Dissolve 0.05% by weight of tert-butyl peroxyacetate and 0.05% by weight of methylated TTF shown in FIG.
30 pm through an ultraviolet filter that cuts light below A+.
Light from a 0W tungsten lamp from a distance of 30cm
After irradiation for 0 minutes, the molecular weight was measured by GPC.
It was possible to obtain polystyrene having a weight average molecular weight (in units) of 40,000.
実施例３：
イソプレンゴム１０ｇと有機過酸化物であるジクミルパ
ーオキサイド０．５ｇと第２図（Ｄ）に示すＢＥＤＴ−
ＴＴＦの０．３ｇを４０ｇのキシレンに溶解し、これを
ガラス基板上にパーコータで塗布して厚さが１０μｍの
塗膜を形成した。Example 3: 10 g of isoprene rubber, 0.5 g of dicumyl peroxide, which is an organic peroxide, and BEDT- shown in FIG. 2 (D).
0.3 g of TTF was dissolved in 40 g of xylene, and this was applied onto a glass substrate using a percoater to form a coating film with a thickness of 10 μm.
この感光板の上を１００ＷのＡｒレーザビーム（波長４
８８ｎｍ）で１０ｎｕａ／ｓの速度で走査した。A 100W Ar laser beam (wavelength 4
88 nm) at a speed of 10 nua/s.
露光後にキシレンで現像したところ、レーザビームで走
査した部分が残留するレリーフ像が得られた。When developed with xylene after exposure, a relief image was obtained in which the portion scanned by the laser beam remained.
実施例４：
ポリビニルカルバゾール１０ｇとトリーターシャリブチ
ルパーオキシカルボニルベンゼン１．０ ｇと第２図（
Ｂ）に示すフルオロメチル化ＴＴＦの０゜３ｇを２００
ｇのクロールベンゼンに溶解し、スピンコード法により
厚さ２μ−の膜を形成した。Example 4: 10 g of polyvinylcarbazole and 1.0 g of treater-butylperoxycarbonylbenzene (Fig.
0°3 g of fluoromethylated TTF shown in B) was added to 200
g of chlorobenzene, and a film with a thickness of 2 μm was formed by spin coding.
この感光板をそれぞれ０．５ｍＷ／ｃａ＋ｚの強度の２
光束のＡｒレーザ光（４８８ｎｍ）で５分間に互って干
渉露光し、２０００本／１ｍのホログラムを露光した。This photosensitive plate was heated to 2
Interference exposure was performed for 5 minutes with Ar laser beams (488 nm) to expose 2000 holograms/1 m.
露光後にキシレンとトルエンの混合液に浸漬し、次いで
ペンタン中に浸漬することで現像した結果、波長６３３
ｎｍでの再生条件で６０％の回折効率を得ることができ
た。After exposure, it was developed by immersing it in a mixture of xylene and toluene, and then in pentane, resulting in a wavelength of 633.
A diffraction efficiency of 60% could be obtained under the regeneration conditions at nm.
本発明によれば、ラジカル反応開始剤として既に各種の
用途に使用されている有機過酸化物をＴＴＦ或いはこの
誘導体からなる色素と組み合わせると可視光に感度をも
つ光反応開始剤として使用できるので、ポリマーの光合
成を始め、光硬化型接着剤、印刷用製版、ホログラムな
ど各種の用途に使用することができる。According to the present invention, organic peroxides that have already been used in various applications as radical reaction initiators can be used as photoreaction initiators sensitive to visible light by combining them with dyes made of TTF or its derivatives. It can be used for a variety of purposes, including polymer photosynthesis, photocurable adhesives, printing plates, and holograms.
第１図はＴＴＦの構造式、 第２図（Ａ）〜（Ｆ）はＴＴＦの各種誘導体の構造式、 である。 Figure 1 shows the structural formula of TTF. Figure 2 (A) to (F) are the structural formulas of various derivatives of TTF, It is.
Claims (1)
加熱により開裂して有機ラジカルを発生し得る有機過酸
化物と、下記の構造式で示されるテトラチアフバレン或
いはその誘導体を含み、可視光により前記ポリマー又ま
たはモノマーが重合或いは架橋可能であることを特徴と
する感光性有機組成物。 ▲数式、化学式、表等があります▼ ここで、Ｒ＿１〜Ｒ＿４はＨまたはＣ＿１〜Ｃ＿３のア
ルキル基またはチオアルキル基で、Ｒ＿１と Ｒ＿２、Ｒ＿３とＲ＿４はそれぞれ環状になっていても
よい。[Claims] A crosslinkable or polymerizable organic monomer or organic polymer;
Contains an organic peroxide that can be cleaved by heating to generate organic radicals, and tetrathiafuvalene or a derivative thereof represented by the structural formula below, and the polymer or monomer can be polymerized or crosslinked by visible light. A photosensitive organic composition characterized by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R_1 to R_4 are H or an alkyl group or thioalkyl group of C_1 to C_3, and R_1 and R_2 and R_3 and R_4 may each be cyclic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2721588A JPH01203403A (en) | 1988-02-08 | 1988-02-08 | Photosensitive organic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2721588A JPH01203403A (en) | 1988-02-08 | 1988-02-08 | Photosensitive organic composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01203403A true JPH01203403A (en) | 1989-08-16 |
Family
ID=12214878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2721588A Pending JPH01203403A (en) | 1988-02-08 | 1988-02-08 | Photosensitive organic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01203403A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064747A (en) * | 1989-07-24 | 1991-11-12 | Fuji Photo Film Co., Ltd. | Sensitizers for photocrosslinkable polymers |
| JPH03296759A (en) * | 1990-04-17 | 1991-12-27 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
-
1988
- 1988-02-08 JP JP2721588A patent/JPH01203403A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064747A (en) * | 1989-07-24 | 1991-11-12 | Fuji Photo Film Co., Ltd. | Sensitizers for photocrosslinkable polymers |
| JPH03296759A (en) * | 1990-04-17 | 1991-12-27 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0500321B1 (en) | High speed aqueous solvent developable photopolymer compositions | |
| Crivello et al. | Photopolymer materials and processes for advanced technologies | |
| Ravve et al. | Light-associated reactions of synthetic polymers | |
| Ledwith | Photoinitiation of polymerisation | |
| JP5486141B2 (en) | Photoinitiated reaction | |
| KR900002124A (en) | Photoresist composition and photoresist using the same and method for producing hologram stable to light | |
| Yagci et al. | Phenacyl onium salt photoinitiators: Synthesis, photolysis, and applications | |
| JPH01203403A (en) | Photosensitive organic composition | |
| JPH11202740A (en) | Refractive index distribution forming material and holographic dry plate | |
| Kani et al. | Photosensitization of Base-Developable Poly (phenylhydrosilane) with 3, 3 ‘, 4, 4 ‘-Tetra (tert-butylperoxycarbonyl) benzophenone. Mechanism of the Drastic Photosensitization in Terms of Photoinduced Electron Transfer | |
| JP2651725B2 (en) | Photosensitive resin composition, photoreceptor, and method for producing volume phase hologram using same | |
| JPS60247639A (en) | Photoinsolubilizable photosensitive material | |
| HORITO et al. | Photochemistry and acid sensitivity of pyrimidine polymers | |
| JP2727852B2 (en) | Photopolymerization initiator composition | |
| US3110592A (en) | Method of making photographic polymeric resist images | |
| JPH05230121A (en) | Photosensitive composition | |
| Williams et al. | Photopolymerization and photocrosslinking of polymers | |
| JPH03223861A (en) | Novel resist material | |
| JPH06175565A (en) | Hologram recording material and production of volume phase type hologram by using the recording material | |
| KR100252217B1 (en) | Base resin for photoresist using ultra-violet ray for fabrication of semiconductor device, its manufacturing method and photoresist using ultra-violet ray comprosing the base resin | |
| JPH06202543A (en) | Production of volume phase type hologram | |
| JP4724941B2 (en) | Photosensitive composition for volume hologram recording and photosensitive medium for volume hologram recording | |
| Ericsson et al. | Novel degradable methacrylate‐and p‐vinylphenoxy‐based oligomers, 2. Photopolymerization and acid‐catalysed degradation | |
| JPH0816784B2 (en) | Visible light resin composition | |
| Kannurpatti et al. | Photochemistry of polymers: photopolymerization fundamentals and applications |