JPH0594014A - Photosensitive resin composition for hologram - Google Patents
Photosensitive resin composition for hologramInfo
- Publication number
- JPH0594014A JPH0594014A JP25523491A JP25523491A JPH0594014A JP H0594014 A JPH0594014 A JP H0594014A JP 25523491 A JP25523491 A JP 25523491A JP 25523491 A JP25523491 A JP 25523491A JP H0594014 A JPH0594014 A JP H0594014A
- Authority
- JP
- Japan
- Prior art keywords
- hologram
- epoxy resin
- monomer
- parts
- photosensitive resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ホログラムに用いる感
光性樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a photosensitive resin composition used for holograms.
【０００２】[0002]
【従来の技術】従来のホログラム用感光性樹脂として
は、以下に示すものが知られている。第１の例として
は、低屈折率の不飽和エチレンモノマー、例えば、屈折
率1.47のブチルメタクリレート、重合の際、架橋剤とし
て作用するような前記モノマーと同程度の屈折率を有す
る不飽和エチレンモノマー、例えば、屈折率1.5 のエチ
レングリコールジメタクリレート、および高屈折率を有
し反応性が低い化合物、例えば、屈折率1.66の１−フェ
ニルナフタレンを主成分とし、開始剤としてベンゾイン
メチルエーテルを使用した感光性樹脂が挙げられる。2. Description of the Related Art As a conventional hologram photosensitive resin, the following are known. As a first example, an unsaturated ethylene monomer having a low refractive index, for example, butyl methacrylate having a refractive index of 1.47, an unsaturated ethylene monomer having a refractive index similar to that of the above-mentioned monomer which acts as a crosslinking agent during polymerization. , For example, ethylene glycol dimethacrylate having a refractive index of 1.5, and a compound having a high refractive index and low reactivity, for example, 1-phenylnaphthalene having a refractive index of 1.66 as a main component and benzoin methyl ether as an initiator. Resins may be mentioned.
【０００３】また、第２の例としては、低屈折率で反応
性が高いモノマーとしてシクロヘキシルメタクリレー
ト、高屈折率で反応性が低いモノマーとしてＮ−ビニル
カルバゾール、重合開始剤としてベンゾインメチルエー
テルを使用した感光性樹脂が挙げられる。As a second example, cyclohexyl methacrylate was used as a monomer having a low refractive index and high reactivity, N-vinylcarbazole was used as a monomer having a high refractive index and low reactivity, and benzoin methyl ether was used as a polymerization initiator. Examples include photosensitive resins.
【０００４】上記組成から成る感光液を２枚のガラス基
板で挟持して感光層とし、レーザーにてホログラムを記
録するものである。いずれの組成から作成した感光層に
おいても、体積ホログラムの露光を行うと、干渉縞の明
るい部分から高反応性物質の重合が行われ、重合により
生じる物質濃度の勾配から、高反応性物質は明るい部分
へ、低反応性物質は暗い部分へと拡散が生じる。このよ
うにして、干渉縞は、各々の物質の屈折率の差で記録さ
れ、ホログラムが形成される。A photosensitive liquid having the above composition is sandwiched between two glass substrates to form a photosensitive layer, and a hologram is recorded by a laser. When a volume hologram is exposed in any of the photosensitive layers formed from any composition, the highly reactive substance is polymerized from the bright part of the interference fringes, and the highly reactive substance is bright due to the gradient of the substance concentration generated by the polymerization. In the area, the low-reactivity substance diffuses into the dark area. In this way, the interference fringes are recorded by the difference in the refractive index of each substance, and the hologram is formed.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、このよ
うな従来のホログラム用感光性樹脂にあっては、第１の
例では、低反応性物質として使用している１−フェニル
ナフタレンが実際はほとんど反応性が無いものであり、
ホログラム完成後も低分子量の物質として残る組成とな
っていたため、保存安定性を確保する都合上好ましくな
いという問題点があった。However, in such a conventional photosensitive resin for holograms, in the first example, 1-phenylnaphthalene used as the low-reactivity substance is actually almost reactive. There is no
Since the composition remains as a low molecular weight substance after the hologram is completed, there is a problem that it is not preferable in terms of ensuring storage stability.
【０００６】また、第２の例では、低反応性物質として
使用しているＮ−ビニルカルバゾールが、ホログラムの
露光中もある程度重合が進む組成となっていたため、両
成分とも同時に重合が進んでしまい、干渉縞の分離が非
常に不完全なものとなるという問題点があった。In the second example, N-vinylcarbazole, which is used as a low-reactivity substance, has a composition in which the polymerization proceeds to some extent during the exposure of the hologram, so that both components simultaneously undergo polymerization. However, there is a problem that the separation of the interference fringes becomes very incomplete.
【０００７】[0007]
【課題を解決するための手段】本発明は、このような従
来の問題点に着目してなされたもので、不飽和エチレン
系モノマーとエポキシ樹脂を使用し、この不飽和エチレ
ン系モノマーとエポキシ樹脂との感光性を、増感剤など
を用いて波長に関して異ならせる。即ち、不飽和エチレ
ン系モノマーを、ある特定波長に対し感光性を有するよ
うにし、かつ、エポキシ樹脂を当該特定波長に対し感光
性を有さないようにすることにより、ホログラム形成時
における干渉縞の明るい部分と暗い部分との分離が効率
よく行えること、また、ホログラム形成後に紫外線また
は熱により、不飽和エチレン系モノマーとエポキシ樹脂
の両方を完全に重合させると保存安定性が向上すること
を知見したことに基づく。SUMMARY OF THE INVENTION The present invention has been made by paying attention to such conventional problems, and uses an unsaturated ethylene monomer and an epoxy resin. The unsaturated ethylene monomer and the epoxy resin are used. And the photosensitivity of are different with respect to the wavelength by using a sensitizer or the like. That is, by making the unsaturated ethylenic monomer photosensitive to a certain specific wavelength and making the epoxy resin insensitive to the certain specific wavelength, the interference fringes at the time of hologram formation are formed. It was found that the bright part and the dark part can be efficiently separated, and that the storage stability is improved by completely polymerizing both the unsaturated ethylenic monomer and the epoxy resin with ultraviolet rays or heat after forming the hologram. Based on that.
【０００８】従って、本発明の感光性樹脂組成物は、ラ
ジカル重合性を有し、常圧、20℃〜100 ℃の温度で液状
の不飽和エチレン系モノマー100 重量部に対し、光ラジ
カル重合開始剤と増感剤を0.05〜10重量部、エポキシ樹
脂を30〜100 重量部配合して成ることを特徴とする。Therefore, the photosensitive resin composition of the present invention has radical polymerizability and initiates radical photopolymerization with respect to 100 parts by weight of a liquid unsaturated ethylenic monomer at atmospheric pressure and a temperature of 20 ° C to 100 ° C. 0.05 to 10 parts by weight of an agent and a sensitizer and 30 to 100 parts by weight of an epoxy resin are blended.
【０００９】以下、本発明を詳細に説明する。本発明の
ホログラム用感光性樹脂組成物に用いる不飽和エチレン
系モノマーは常圧、20〜100 ℃で液体の、ラジカル重合
性を持つもので、２−エチルヘキシルアクリレート、２
−ヒドロキシエチルアクリレート、２−ヒドロキシエチ
ルメタクリレート、２−ヒドロキシプロピルアクリレー
ト、テトラヒドロフルフリルアクリレート、テトラヒド
ロキシフルフリルメタクリレート、フェノキシエチルア
クリレート、テトラヒドロフルフリルオキシエチルアク
リレート、テトラヒドロフルフリルオキシヘキサノリド
アクリレートなどの各種アクリレートが例示できる。ま
た、各種ウレタンアクリレート、エポキシアクリレー
ト、アクリルアミドであってもよい。The present invention will be described in detail below. The unsaturated ethylenic monomer used in the photosensitive resin composition for holograms of the present invention is a liquid having a radical polymerizable property at normal pressure and 20 to 100 ° C., and is 2-ethylhexyl acrylate, 2
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, tetrahydroxyfurfuryl methacrylate, phenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, etc. Acrylate can be illustrated. Also, various urethane acrylates, epoxy acrylates, and acrylamides may be used.
【００１０】上記不飽和エチレン系モノマーは、常温・
常圧での感光性樹脂の取扱いに際しモノマー状態を保持
する必要があるため、常圧、20〜100℃の温度で液状で
あることを要する。The unsaturated ethylenic monomer is
Since it is necessary to maintain the monomer state when handling the photosensitive resin under normal pressure, it is necessary that it be liquid at normal temperature and a temperature of 20 to 100 ° C.
【００１１】また、上記不飽和エチレン系モノマーの屈
折率は、1.55以下、好ましくは1.30〜1.55であるのが良
い。1.55以下とする理由は、ホログラム形成の一方の成
分であるエポキシ樹脂は、一般的に屈折率が約1.6 であ
り、また、このエポキシ樹脂と組合せて良好なホログラ
ムを形成するには、少なくとも0.05の屈折率差が必要だ
からである。The unsaturated ethylenic monomer has a refractive index of 1.55 or less, preferably 1.30 to 1.55. The reason for setting the ratio to 1.55 or less is that the epoxy resin, which is one component of hologram formation, generally has a refractive index of about 1.6, and in order to form a good hologram in combination with this epoxy resin, at least 0.05. This is because the difference in refractive index is necessary.
【００１２】次に、光ラジカル重合開始剤としては、ベ
ンゾインアルキルエーテル類、ケタール類、オキシムエ
ステル類、ベンゾフェノン、チオキサントン誘導体、キ
ノン、チオアクリドンなどの芳香族ケトン類、１，３−
ジ（ｔ−ブチルジオキシカルボニルベンゼン）、３，
３′，４，４′−テトラキス（ｔ−ブチルジオキシカル
ボニル）ベンゾフェノンなどのパーオキシ酸エステル、
ヨードニウム塩類、ジアニン、ローダミン、サフラニ
ン、マラカイトグリーン、メチレンブルーなどのアルキ
ルまたはアルキルほう酸塩、鉄−アレーン錯体、ビスイ
ミダゾール類、Ｎ−アリールグリシンなどが例示でき
る。また、増感剤としては、種々の可視光増感剤、例え
ば、ミヒラーズケトンなどの芳香族アミン、キサンテン
系色素、チオピリリウム塩、メロシニン・キノリン系色
素、クマリン・ケトクマリン系色素、アクリジンオレン
ジ、ベンゾフラビン、ジアニン、フタロシアニン、ポル
フィン、ローダミン、サフラニン、マラカイトグリー
ン、メチレングリーン、などを例示できる。上記光ラジ
カル重合開始剤と増感剤は、不飽和エチレン系モノマー
100重量部に対し、0.05〜10重量部の割合で用いる。配
合量が0.05重量部未満では、吸光量が少なく効果がな
く、10重量部を超えると、光の吸収が過剰となり、露光
のためのレーザー光がホログラム膜の深い部分まで到達
しなくなるため好ましくない。Next, as radical photopolymerization initiators, aromatic ketones such as benzoin alkyl ethers, ketals, oxime esters, benzophenone, thioxanthone derivatives, quinone and thioacridone, 1,3-
Di (t-butyldioxycarbonylbenzene), 3,
Peroxy acid esters such as 3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone,
Examples thereof include iodonium salts, dianine, rhodamine, safranine, malachite green, methylene blue and other alkyl or alkylborates, iron-arene complexes, bisimidazoles, N-arylglycines and the like. As the sensitizer, various visible light sensitizers, for example, aromatic amines such as Michler's ketone, xanthene dyes, thiopyrylium salts, merosinin / quinoline dyes, coumarin / ketocoumarin dyes, acridine orange, benzoflavin, Examples include dianine, phthalocyanine, porphine, rhodamine, safranine, malachite green, methylene green and the like. The above photo radical polymerization initiator and sensitizer are unsaturated ethylenic monomers.
It is used in a proportion of 0.05 to 10 parts by weight with respect to 100 parts by weight. If the blending amount is less than 0.05 parts by weight, the light absorption amount is small and there is no effect, and if it exceeds 10 parts by weight, the light absorption becomes excessive, and the laser light for exposure does not reach the deep portion of the hologram film, which is not preferable. ..
【００１３】さらに、エポキシ樹脂は、上記不飽和エチ
レン系モノマーとの関係から、400nm以下の紫外線で硬
化するものかまたは熱硬化型のものであるのがよい。ま
た、エポキシ樹脂は、上記不飽和エチレン系モノマー10
0 重量部に対し、30〜100 重量部の割合で用いる。30重
量部未満では、ホログラムの格子の高屈折率部分を形成
するための必要量に達せず、また、100 重量部を超える
と、最初のレーザーによる露光で重合が進行する成分が
半分以下となり、一旦形成された格子が不安定で乱れる
可能性があり好ましくない。Further, the epoxy resin is preferably a resin curable by ultraviolet rays of 400 nm or less or a thermosetting resin in view of the relationship with the unsaturated ethylenic monomer. Further, the epoxy resin is the above unsaturated ethylenic monomer 10
It is used in a proportion of 30 to 100 parts by weight with respect to 0 parts by weight. If it is less than 30 parts by weight, the amount required to form the high refractive index portion of the grating of the hologram cannot be reached, and if it exceeds 100 parts by weight, less than half the components in which polymerization proceeds by the first laser exposure, The lattice once formed may be unstable and disturbed, which is not preferable.
【００１４】次に、本発明の感光性樹脂を用いたホログ
ラムの形成機構につき説明する。本発明の感光性樹脂組
成物において、紫外線（ＵＶ）による露光では不飽和エ
チレン系モノマーとエポキシ樹脂の両方の重合が行われ
る。しかし、アルゴンイオンレーザーなどの可視波長に
おける露光では増感剤（可視光増感剤）により光増感さ
れているラジカル重合開始剤を介して不飽和エチレン系
モノマーは重合するが、エポキシ樹脂は重合しない。Next, a hologram forming mechanism using the photosensitive resin of the present invention will be described. In the photosensitive resin composition of the present invention, both the unsaturated ethylenic monomer and the epoxy resin are polymerized by exposure to ultraviolet rays (UV). However, when exposed to visible wavelengths such as an argon ion laser, unsaturated ethylenic monomers polymerize via the radical polymerization initiator that is photosensitized by the sensitizer (visible light sensitizer), but the epoxy resin polymerizes. do not do.
【００１５】この理由は、エポキシ樹脂は、上記増感剤
ではほとんど増感されず、また、不飽和エチレン系モノ
マーの反応で発生するラジカルの影響も受けないからで
ある。従って、上記レーザーによるホログラム露光時に
は干渉縞の明るい部分から不飽和エチレン系モノマーが
重合し、この部分の不飽和エチレン系モノマーが不足す
るため、干渉縞の暗い部分に存在する不飽和エチレン系
モノマーは明るい部分に移動する。The reason for this is that the epoxy resin is hardly sensitized by the above-mentioned sensitizer and is not affected by the radicals generated by the reaction of the unsaturated ethylenic monomer. Therefore, when the hologram is exposed by the laser, the unsaturated ethylene-based monomer is polymerized from the bright portion of the interference fringes, and the unsaturated ethylene-based monomer in this portion runs short. Move to bright areas.
【００１６】一方、エポキシ樹脂は、重合せず干渉縞の
暗い部分に押し出され、この結果、不飽和エチレン系モ
ノマーとエポキシ樹脂の２成分は、干渉縞の明るい部分
と暗い部分とに分離する。以上の如く、不飽和エチレン
系モノマーを、ある特定の波長に対して感光性を有する
ようにし、かつ、エポキシ樹脂を当該波長に対して感光
性を有さないように調整することにより、干渉縞の明る
い部分と暗い部分との分離を効率よく行うことができ
る。On the other hand, the epoxy resin is not polymerized and is extruded to the dark portion of the interference fringes. As a result, the two components of the unsaturated ethylene monomer and the epoxy resin are separated into the light portion and the dark portion of the interference fringe. As described above, the interference fringes are adjusted by adjusting the unsaturated ethylenic monomer to have sensitivity to a specific wavelength and the epoxy resin to have no sensitivity to the wavelength. It is possible to efficiently separate the bright part and the dark part.
【００１７】また、ホログラム形成後に紫外線露光等を
行うことにより、不飽和エチレン系モノマーとエポキシ
樹脂の両方を完全に重合させ、保存安定性のよいホログ
ラムを形成することもできる。Further, it is possible to completely polymerize both the unsaturated ethylenic monomer and the epoxy resin by exposing the hologram to ultraviolet light after forming the hologram to form a hologram having good storage stability.
【００１８】[0018]
【実施例】以下、本発明を実施例により接続する。実施例１ ラジカル重合性の不飽和エチレン系モノマーとして、次
式EXAMPLES The present invention will be described below with reference to examples. Example 1 As a radically polymerizable unsaturated ethylenic monomer, the following formula
【化１】 で表される１官能性ウレタンアクリレート（ S.N.P.E.
社製、商品名 ACTICRYLCL960 ）を100 重量部（以下、
組成の比率は重量部で示す。）に対して、カチオン反応
性のＵＶ硬化型エポキシ樹脂（旭電化工業（株）製、商
品名オプトマーKR400 ）を30〜50、アクリレートと反応
するラジカル重合開始剤として、次式[Chemical 1] Monofunctional urethane acrylate represented by (SNPE
100 parts by weight (hereinafter referred to as "ACTICRYLCL960")
Composition ratios are given in parts by weight. ), A cation-reactive UV-curable epoxy resin (Asahi Denka Kogyo Co., Ltd., trade name Optomer KR400) is used as a radical polymerization initiator that reacts with 30 to 50 and an acrylate.
【化２】 （式中のＲは−COOC(CH3)3を示す。）で表される３，
３′，４，４′−テトラ（ｔ−ブチルパーオキサイドカ
ルボニルベンゾフェノン）を２〜10、可視光増感色素と
して、次式[Chemical 2] 3 (R in formula -COOC (CH 3) shows a 3.) Represented by,
2'to 3 ', 4,4'-tetra (t-butyl peroxide carbonylbenzophenone), a visible light sensitizing dye of the following formula
【化３】 で表される３，３′−カルボニルビス（７−ジエチルア
ミノクマリン）を0.1 〜0.5 添加した。得られた混合物
を12時間攪拌して完全に溶解させ感光液とした。この感
光液を透明なガラス基板２枚で挟んで膜厚20〜80μm の
感光層とした。[Chemical 3] 0.1 to 0.5 of 3,3'-carbonylbis (7-diethylaminocoumarin) represented by The resulting mixture was stirred for 12 hours to be completely dissolved to obtain a photosensitive solution. This photosensitive solution was sandwiched between two transparent glass substrates to form a photosensitive layer having a film thickness of 20 to 80 μm.
【００１９】得られた感光層に紫外線を照射し、流動性
がなくなるまで前重合を行ない、アルゴンイオンレーザ
ーの488 nmで体積ホログラムの露光を行った。その後、
再び紫外線を照射し重合を完全に終了させて、保存安定
性のよい、明るいホログラムを得ることができた。The resulting photosensitive layer was irradiated with ultraviolet rays, prepolymerized until the fluidity disappeared, and the volume hologram was exposed with an argon ion laser at 488 nm. afterwards,
Ultraviolet rays were irradiated again to complete the polymerization, and a bright hologram having good storage stability could be obtained.
【００２０】本実施例による構成では、紫外線による露
光ではアクリレートとエポキシ樹脂の両方の重合が行な
われるが、アルゴンイオンレーザーの可視波長による露
光ではクマリン色素で可視光増感されているラジカル重
合開始剤を介してアクリレートは重合するが、エポキシ
はクマリン色素ではほとんど増感されず、アクリレート
の反応で発生するラジカルの影響も受けないため、重合
しない。このため、アルゴンイオンレーザーによるホロ
グラム露光時には干渉縞の明るい部分からアクリレート
が重合しこの部分のアクリレートが不足するため、干渉
縞の暗い部分に存在するアクリレートは明るい部分へと
移動する。エポキシは重合せず干渉縞の暗い部分へと押
し出され、アクリレートとエポキシ樹脂の２成分は干渉
縞の暗い部分と明るい部分とに分離する。以上のよう
に、ある特定の波長に対して感光性を有するようにした
アクリレートと、その特定の波長に対して感光性を有さ
ないエポキシを組み合わせることにより、分離の効率は
非常に向上した。また、ホログラム形成後に紫外線露光
を行ない、アクリレートとエポキシ樹脂の両方を完全に
重合させ保存安定性がよいホログラムとすることができ
た。前露光を行なって粘度を上げるのは、モノマーの拡
散速度を調整するためである。In the constitution of this embodiment, both the acrylate and the epoxy resin are polymerized by exposure to ultraviolet light, but the radical polymerization initiator is sensitized by visible light with the coumarin dye when exposed to visible light of an argon ion laser. The acrylate is polymerized through the coumarin, but the epoxy is hardly sensitized by the coumarin dye and is not affected by the radicals generated by the reaction of the acrylate, and thus is not polymerized. Therefore, during hologram exposure with an argon ion laser, the acrylate is polymerized from the bright portion of the interference fringes and the acrylate in this portion is insufficient, so that the acrylate present in the dark portion of the interference fringes moves to the bright portion. The epoxy does not polymerize and is extruded into the dark portion of the interference fringes, and the two components of acrylate and epoxy resin separate into the dark portion and the light portion of the interference fringe. As described above, the efficiency of separation was significantly improved by combining the acrylate, which was made photosensitive to a specific wavelength, and the epoxy, which was not photosensitive to the specific wavelength. Further, after the hologram was formed, UV exposure was performed to completely polymerize both the acrylate and the epoxy resin, and a hologram having good storage stability could be obtained. The reason why the viscosity is increased by performing the pre-exposure is to adjust the diffusion rate of the monomer.
【００２１】実施例２ エチレングリコールジメタクリレトを100 に対しＵＶ硬
化型エポキシ樹脂（旭電化工業（株）製、商品名オプト
マーBYX304）を25〜50、ラジカル重合開始剤として３，
３′，４，４′−テトラ（ｔ−ブチルパーオキサイドカ
ルボニルベンゾフェノン）を３〜10、可視光増感色素と
して３，３′−カルボニルビス（７−ジエチルアミノク
マリン）を0.1 〜0.5 を溶解させて感光液とした。本実
施例においては、エチレングリコールジメタクリレート
はクマリン色素に増感されているため500 nm付近の可視
光でも紫外線でも重合が行なわれるが、エポキシ樹脂は
紫外線では重合が進むが、可視光では重合しない。この
ため、感光層を形成し体積ホログラムを実施例１と同様
の方法で作製すると、実施例１と同様の効果が得られ、
明るく保存安定性のよいホログラムを作ることができ
た。 Example 2 25 to 50 of UV curable epoxy resin (manufactured by Asahi Denka Kogyo Co., Ltd., trade name OPTOMER BYX304) to 100 of ethylene glycol dimethacrylate and 3 as a radical polymerization initiator.
Dissolve 3 ', 4,4'-tetra (t-butyl peroxide carbonylbenzophenone) in 3 to 10 and 3,3'-carbonylbis (7-diethylaminocoumarin) in 0.1 to 0.5 as a visible light sensitizing dye. It was used as a photosensitive liquid. In this example, ethylene glycol dimethacrylate is sensitized by a coumarin dye, so that it polymerizes with visible light or ultraviolet light around 500 nm, but the epoxy resin polymerizes with ultraviolet light but does not polymerize with visible light. .. Therefore, when the photosensitive layer is formed and the volume hologram is manufactured by the same method as in Example 1, the same effect as in Example 1 is obtained,
We were able to make a bright, storage-stable hologram.
【００２２】実施例３ ヒドロキシプロピルアクリレートを100 に対し、熱硬化
性エポキシ樹脂（ビスフェノールＡ型エポキシと硬化剤
（例えばエー・シー・アール（株）製、商品名Ｈ-3551
）を100 : 30〜60の比率で混合したもの）を25〜35、
ラジカル重合開始剤として３，３′，４，４′−テトラ
（ｔ−ブチルパーオキサイドカルボニルベンゾフェノ
ン）を４〜８、可視光増感剤として３，３′−カルボニ
ルビス（７−ジエチルアミノクマリン）を0.1 〜0.5 添
加し完全に溶解させた。次いで、実施例１と同様に感光
層を形成した。 Example 3 100 parts of hydroxypropyl acrylate, a thermosetting epoxy resin (bisphenol A type epoxy and a hardening agent (for example, AC R Co., Ltd., trade name H-3551)
) Mixed in a ratio of 100: 30-60)) 25-35,
3,3 ', 4,4'-Tetra (t-butyl peroxide carbonylbenzophenone) is used as a radical polymerization initiator 4-8, and 3,3'-carbonylbis (7-diethylaminocoumarin) is used as a visible light sensitizer. 0.1 to 0.5 was added and completely dissolved. Then, a photosensitive layer was formed in the same manner as in Example 1.
【００２３】本実施例では、アクリレートは紫外〜可視
の波長に感度を持つように増感されているが、エポキシ
は光では反応を行なわない。したがって、アルゴンイオ
ンレーザーの488 nmにてホログラム露光を行なうと実施
例１と同様の効果でアクリレートとエポキシが分離しホ
ログラムを形成することができた。その後、紫外線によ
る全面露光でアクリレートを完全に重合させ、さらに80
〜90℃で24時間以上加熱することによってエポキシが完
全に重合するので、明るい、保存安定性のよいホログラ
ムが得られた。In this embodiment, the acrylate is sensitized to have a sensitivity in the wavelength range from ultraviolet to visible, but the epoxy does not react with light. Therefore, when hologram exposure was performed with an argon ion laser at 488 nm, acrylate and epoxy were separated and a hologram could be formed with the same effect as in Example 1. Then, the entire surface is exposed to UV light to completely polymerize the acrylate.
Epoxy was completely polymerized by heating at ~ 90 ℃ for more than 24 hours, and a bright hologram with good storage stability was obtained.
【００２４】実施例４ 次式 Example 4 The following equation
【化４】 で表される１官能性のアクリリックウレタン（ＳＮＰＥ
社製、商品名 ACTICRYLCL959)を100 に対し、実施例３
と同じ熱硬化型エポキシ樹脂を25〜35、３，３′，４，
４′−テトラ（ｔ−ブチルパーオキサイドカルボニルベ
ンゾフェノン）をラジカル重合開始剤として３〜10、
３，３′−カルボニルビス（７−ジエチルアミノクマリ
ン）を0.1〜0.5 添加し完全に溶解させ感光液とした。
この感光液を透明なガラス基板２枚に挟んで感光層と
し、実施例３と同様の処理を行なうと、明るい、保存安
定性のよいホログラムが得られた。[Chemical 4] Monofunctional acrylic urethane represented by (SNPE
Example 3 against 100 manufactured by the company under the trade name ACTICRYLCL959)
The same thermosetting epoxy resin as 25-35, 3, 3 ', 4,
4'-tetra (t-butyl peroxide carbonylbenzophenone) as a radical polymerization initiator 3-10,
0.1 to 0.5 of 3,3'-carbonylbis (7-diethylaminocoumarin) was added and completely dissolved to obtain a photosensitive solution.
When this photosensitive solution was sandwiched between two transparent glass substrates to form a photosensitive layer and the same treatment as in Example 3 was performed, a bright hologram having good storage stability was obtained.
【００２５】以上本発明を実施例により説明したが、本
発明はこれのみに限定されるものではなく、本発明の範
囲内で種々の変形が可能である。例えば、本発明で用い
る不飽和エチレンモノマーは実施例で示したアクリレー
トやメタクリレートに限られるものではなく、ラジカル
により重合が進み、カチオン重合しない不飽和エチレン
モノマーで、屈折率が1.3 〜1.55のものであれば、何で
も用いることができる。また、エポキシ樹脂としては、
実施例にあげたものに限らず、紫外線か熱のどちらかで
硬化するタイプで透明なものであれば何でも使用するこ
とができる。Although the present invention has been described above with reference to the embodiments, the present invention is not limited to this, and various modifications can be made within the scope of the present invention. For example, the unsaturated ethylene monomer used in the present invention is not limited to the acrylates and methacrylates shown in the examples, it is an unsaturated ethylene monomer that undergoes radical polymerization and does not undergo cationic polymerization, and has a refractive index of 1.3 to 1.55. Anything can be used if it exists. Also, as the epoxy resin,
Not limited to the examples, any type can be used as long as it is a type that is cured by either ultraviolet rays or heat and is transparent.
【００２６】[0026]
【発明の効果】以上説明してきたように、この発明によ
れば、その構成をラジカル重合を行なう不飽和エチレン
モノマー、ラジカル重合開始剤とこの重合開始剤に対す
る増感剤、紫外線または熱により硬化するエポキシ樹脂
としたため、特定の露光波長に対する感光性の違いか
ら、不飽和エチレンモノマーとエポキシ樹脂の２成分の
分離が効率よく行なわれ、紫外線による後露光や熱処理
により全ての成分を硬化できるため、非常に明るく保存
安定性に優れたホログラムを得ることができるという効
果が得られる。As described above, according to the present invention, the constitution is cured by an unsaturated ethylene monomer for radical polymerization, a radical polymerization initiator and a sensitizer for the polymerization initiator, ultraviolet rays or heat. Since the epoxy resin is used, the two components of the unsaturated ethylene monomer and the epoxy resin can be efficiently separated due to the difference in photosensitivity to a specific exposure wavelength, and all components can be cured by post-exposure or heat treatment with ultraviolet rays. The effect is that a hologram which is bright and has excellent storage stability can be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ０３Ｆ 7/038 ５０３ 7124−2Ｈ Ｇ０３Ｈ 1/02 8106−2Ｋ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location G03F 7/038 503 7124-2H G03H 1/02 8106-2K
Claims (1)
0 ℃の温度で液状の不飽和エチレン系モノマー100 重量
部に対し、光ラジカル重合開始剤と増感剤を0.05〜10重
量部、エポキシ樹脂を30〜100 重量部配合して成ること
を特徴とするホログラム用感光性樹脂組成物。1. Radical polymerizable, normal pressure, 20 ° C. to 10
It is characterized in that 0.05 to 10 parts by weight of a photo-radical polymerization initiator and a sensitizer and 30 to 100 parts by weight of an epoxy resin are mixed with 100 parts by weight of an unsaturated ethylenic monomer which is liquid at a temperature of 0 ° C. A photosensitive resin composition for hologram.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25523491A JPH0594014A (en) | 1991-10-02 | 1991-10-02 | Photosensitive resin composition for hologram |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25523491A JPH0594014A (en) | 1991-10-02 | 1991-10-02 | Photosensitive resin composition for hologram |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0594014A true JPH0594014A (en) | 1993-04-16 |
Family
ID=17275898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25523491A Pending JPH0594014A (en) | 1991-10-02 | 1991-10-02 | Photosensitive resin composition for hologram |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0594014A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0672953A2 (en) * | 1994-03-17 | 1995-09-20 | Toppan Printing Co., Ltd. | Photosensitive recording material, photosensitive recording medium, and process for producing hologram using this photosensitive recording medium |
| EP0697631A1 (en) * | 1994-07-29 | 1996-02-21 | Toppan Printing Co., Ltd. | Photosensitive recording material, photosensitive recording medium, and process for producing hologram using this photosensitive recording medium |
| US5858614A (en) * | 1993-04-12 | 1999-01-12 | Nippon Paint Co., Ltd. | Photosensitive composition for volume hologram recording |
| JP2005043862A (en) * | 2003-04-09 | 2005-02-17 | Konica Minolta Medical & Graphic Inc | Holographic recording composition, holographic recording medium and recording method thereof |
| EP1612623A1 (en) * | 2003-04-09 | 2006-01-04 | Konica Minolta Medical & Graphic Inc. | Holographic recording medium and recording method using the same |
| JP2007034334A (en) * | 2006-10-30 | 2007-02-08 | Nippon Paint Co Ltd | Photosensitive composition for volume hologram recording, and recording medium and method for forming volume hologram using the same |
| US7727679B2 (en) | 2005-01-07 | 2010-06-01 | Nitto Denko Corporation | Optical refractive index-modifying polymer composition, hologram recording material and method of controlling refractive index |
| JP2011118075A (en) * | 2009-12-02 | 2011-06-16 | Dainippon Printing Co Ltd | Method for producing hologram |
| US8034514B2 (en) | 2005-03-08 | 2011-10-11 | Nippon Steel Chemical Co., Ltd. | Photosensitive resin composition for volume phase hologram recording and optical information recording medium using the same |
| US8163443B2 (en) | 2006-03-09 | 2012-04-24 | Nippon Steel Chemical Co., Ltd. | Photosensitive resin composition for volume phase hologram recording and optical information recording medium using the same |
-
1991
- 1991-10-02 JP JP25523491A patent/JPH0594014A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5858614A (en) * | 1993-04-12 | 1999-01-12 | Nippon Paint Co., Ltd. | Photosensitive composition for volume hologram recording |
| KR100296083B1 (en) * | 1994-03-17 | 2001-11-05 | 후지다 히로미찌 | Method of manufacturing hologram using photosensitive recording material, photosensitive recording medium and this photosensitive recording medium |
| EP0672953A3 (en) * | 1994-03-17 | 1996-03-27 | Toppan Printing Co Ltd | Photosensitive recording material, photosensitive recording medium, and process for producing hologram using this photosensitive recording medium. |
| US5698345A (en) * | 1994-03-17 | 1997-12-16 | Toppan Printing Co., Ltd. | Photosensitive recording material, photosensitive recording medium, and process for producing hologram using this photosensitive recording medium |
| EP0672953A2 (en) * | 1994-03-17 | 1995-09-20 | Toppan Printing Co., Ltd. | Photosensitive recording material, photosensitive recording medium, and process for producing hologram using this photosensitive recording medium |
| EP0697631A1 (en) * | 1994-07-29 | 1996-02-21 | Toppan Printing Co., Ltd. | Photosensitive recording material, photosensitive recording medium, and process for producing hologram using this photosensitive recording medium |
| US6045953A (en) * | 1994-07-29 | 2000-04-04 | Toppan Printing Co., Ltd. | Photosensitive recording material, photosensitive recording medium, and process for producing hologram using this photosensitive recording medium |
| EP1612623A1 (en) * | 2003-04-09 | 2006-01-04 | Konica Minolta Medical & Graphic Inc. | Holographic recording medium and recording method using the same |
| JP2005043862A (en) * | 2003-04-09 | 2005-02-17 | Konica Minolta Medical & Graphic Inc | Holographic recording composition, holographic recording medium and recording method thereof |
| EP1612623A4 (en) * | 2003-04-09 | 2007-04-04 | Konica Minolta Med & Graphic | Holographic recording medium and recording method using the same |
| US7727679B2 (en) | 2005-01-07 | 2010-06-01 | Nitto Denko Corporation | Optical refractive index-modifying polymer composition, hologram recording material and method of controlling refractive index |
| US8034514B2 (en) | 2005-03-08 | 2011-10-11 | Nippon Steel Chemical Co., Ltd. | Photosensitive resin composition for volume phase hologram recording and optical information recording medium using the same |
| US8163443B2 (en) | 2006-03-09 | 2012-04-24 | Nippon Steel Chemical Co., Ltd. | Photosensitive resin composition for volume phase hologram recording and optical information recording medium using the same |
| JP2007034334A (en) * | 2006-10-30 | 2007-02-08 | Nippon Paint Co Ltd | Photosensitive composition for volume hologram recording, and recording medium and method for forming volume hologram using the same |
| JP2011118075A (en) * | 2009-12-02 | 2011-06-16 | Dainippon Printing Co Ltd | Method for producing hologram |
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