JPH02238455A - Photosensitive material for hologram recording - Google Patents

Photosensitive material for hologram recording

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Publication number
JPH02238455A
JPH02238455A JP5796189A JP5796189A JPH02238455A JP H02238455 A JPH02238455 A JP H02238455A JP 5796189 A JP5796189 A JP 5796189A JP 5796189 A JP5796189 A JP 5796189A JP H02238455 A JPH02238455 A JP H02238455A
Authority
JP
Japan
Prior art keywords
formula
copolymer
hologram
group
iii
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
Application number
JP5796189A
Other languages
Japanese (ja)
Inventor
Noriko Ikeda
紀子 池田
Motoaki Tani
元昭 谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujitsu Ltd
Original Assignee
Fujitsu Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fujitsu Ltd filed Critical Fujitsu Ltd
Priority to JP5796189A priority Critical patent/JPH02238455A/en
Publication of JPH02238455A publication Critical patent/JPH02238455A/en
Pending legal-status Critical Current

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Abstract

PURPOSE:To obtain the hologram material which has a high sensitivity to a visible light laser, is transparent, is excellent in environmental resistance and has high diffraction efficiency by constituting the photosensitive material of specific electron-donating polymers and iron/arylene complex. CONSTITUTION:This photosensitive material is constituted of the electron- donating polymers regulated by formula I to formula III, the copolymer IV of the formula I and the formula II, the copolymer V of the formula I and formula III, the copolymer VI of the formula II and the formula III, and the copolymer VII of the formula I and the formula II and the formula III, as well as the iron/arylene complex which generates an acid by absorbing 300 to 560nm light and is expressed by formula VIII. In the formula I to VII, R1 to R5 respectively independently denote a hydrogen atom, alkyl group, alkenyl group, phenyl group, etc. In the formula VIII, X<-> is BF4, PF6, AS6, or SbAS6; A denotes an arom. hydrocarbon group. The hologram which has the high sensitivity to the visible light laser, is transparent, is excellent in environmental resistance and has the high diffraction efficiency is formed in this way.

Description

【発明の詳細な説明】 〔概 要〕 ホログラム記録用感光材料に関し、 高感度、透明で、耐環境性に優れ、回折効率の高いホロ
グラム材料を得ることを目的とし、電子供与性ポリマと
鉄アレーン錯体とから構成する。
[Detailed Description of the Invention] [Summary] Regarding a photosensitive material for hologram recording, the purpose of the invention is to obtain a hologram material that is highly sensitive, transparent, has excellent environmental resistance, and has high diffraction efficiency. It consists of a complex.

〔産業上の利用分野〕[Industrial application field]

本発明は、ホログラム記録材料で、特に重合体における
光化学的架橋反応を利用してホログラムを記録する方式
を用いる新規な感光材料に関する。
The present invention relates to a hologram recording material, and particularly to a novel photosensitive material that uses a method of recording a hologram using a photochemical crosslinking reaction in a polymer.

ホログラムは、レーザなどの可干渉性光の記録のみなら
ず、情報の記録あるいはその回折現象を利用した光学素
子、たとえば、バーコードリーダ読み取り装置用ビーム
スキャナなどに用いられている. このホログラム素子を作製する際、ホログラム記録用材
料の有すべき特性としては、 (1)高感度であること、 (2)ホログラムの回折効率の高いこと、(3)高解像
度を有すること、 (4)ホログラムの耐環境性に優れていること、〈5》
透明性が優れていること、 などが要求される。
Holograms are used not only for recording coherent light such as lasers, but also for recording information or optical elements that utilize the diffraction phenomenon, such as beam scanners for barcode readers. When producing this hologram element, the characteristics that the hologram recording material should have are (1) high sensitivity, (2) high hologram diffraction efficiency, (3) high resolution, 4) The hologram has excellent environmental resistance, <5>
Excellent transparency is required.

ここで、ホログラムを光学素子として用いる場合には安
定して高い出力が得られ、コヒーレント長に優れたガス
レーザ(He−Neレーザ(633nn+)、Arレー
ザ(488na+) )光が望ましい。再生光として安
価なHe−Neレーザを用いることが多く、記録光とし
て色収差を抑えるために再生光と波長差の小さい光が望
ましい。しかし、従来の高分子感光材料はその感光域が
紫外部にあり、長波長になるほど感度は低下する.従っ
て、A『レーザ光を用いている. 〔従来の技術〕 ホログラム記録用感光材料としては、通常の写真材料に
使用されている銀塩に漂白処理を施したものや重クロム
酸ゼラチンが使用されている。これらの銀塩や重クロム
酸ゼラチンは、ほぼ可視光の全域に高い感度を有するも
のの、ゼラチン膜を結合剤として用いるために耐湿性、
耐熱性、耐感光性などの耐環境性が低いという問題点が
ある.これらの問題を解決することを目的とし、カルバ
ゾール環を含む重合体を主剤とし、有機ハロゲン化合物
を架橋剤とし、色素を増感剤とする高分子ホログラム記
録材料が提案されている(例えば、特公昭62−123
489など)。
Here, when using a hologram as an optical element, gas laser light (He--Ne laser (633nn+), Ar laser (488na+)), which can stably obtain high output and has an excellent coherence length, is desirable. An inexpensive He--Ne laser is often used as the reproduction light, and it is desirable that the recording light be light with a small wavelength difference from the reproduction light in order to suppress chromatic aberration. However, conventional photosensitive polymer materials have a photosensitive range in the ultraviolet region, and their sensitivity decreases as the wavelength increases. Therefore, A: ``Laser light is used.'' [Prior Art] As a photosensitive material for hologram recording, a bleached silver salt used in ordinary photographic materials and dichromate gelatin are used. These silver salts and dichromate gelatin have high sensitivity in almost the entire visible light range, but because they use a gelatin film as a binder, they have poor moisture resistance,
The problem is that it has low environmental resistance such as heat resistance and light sensitivity. Aiming to solve these problems, polymer hologram recording materials have been proposed that use a polymer containing a carbazole ring as a main ingredient, an organic halogen compound as a crosslinking agent, and a dye as a sensitizer (for example, Kosho 62-123
489 etc.).

上記高分子ホログラム記録材料は高分子用の光化学反応
機構として、色素は光励起し、増感物質として有機ハロ
ゲン化合物を分解する。分解した有機ハロゲン化合物は
イオン化し、主剤を架橋させるとともに、主剤と電荷移
動(CT)錯体を形成する。カルバゾール環はドナーと
して有機ハロゲン化合物はアクセプターとして働く。C
TtI体は光照射量が増加するに従い増加する。主剤と
して、ポリビニル力ルバゾール、有機ハロゲン化合物と
して沃素化合物を用いると、660nmに吸収極大を持
つ緑色のCT錯体を形成するので、He −Neレーザ
(633nae)に対する回折効率を低《している. 〔発明が解決しようとする課題〕 ポリビニル力ルバゾールを主剤とし、有機ハロゲン化合
物を架橋剤とする記録材料は耐環境性に優れたホログラ
ム記録材料であるが、可視光に低惑度で、crti体の
形成(透明性が低下する)によりHe−Neレーザに対
する回折効率を低くしていることが問題である。
In the polymer hologram recording material, the dye is photoexcited as a photochemical reaction mechanism for polymers, and the organic halogen compound is decomposed as a sensitizing substance. The decomposed organic halogen compound is ionized, crosslinks the main agent, and forms a charge transfer (CT) complex with the main agent. The carbazole ring acts as a donor and the organic halogen compound acts as an acceptor. C
The TtI body increases as the amount of light irradiation increases. When polyvinyl rubazole is used as the main agent and an iodine compound is used as the organic halogen compound, a green CT complex is formed that has an absorption maximum at 660 nm, which lowers the diffraction efficiency for the He-Ne laser (633 nae). [Problems to be Solved by the Invention] A recording material containing polyvinyl rubazole as a main ingredient and an organic halogen compound as a crosslinking agent is a hologram recording material with excellent environmental resistance, but it has a low degree of permeability to visible light and a CRTI body. The problem is that the diffraction efficiency for the He--Ne laser is reduced due to the formation of (reducing transparency).

そこで、可視光レーザに高感度で、透明で、耐環境性に
優れてかつ回折効率の高いホログラム材料を開発するこ
とが課題である。
Therefore, the challenge is to develop a hologram material that is highly sensitive to visible light lasers, transparent, has excellent environmental resistance, and has high diffraction efficiency.

〔課題を解決するための手段〕[Means to solve the problem]

上記の課題はレーザにて発生した酸により電子供与性で
あるボリマから水素を引き抜いて架橋する機構を利用す
ることにより、解決できる。
The above-mentioned problem can be solved by utilizing a mechanism in which hydrogen is extracted from an electron-donating polymer by an acid generated by a laser and crosslinked.

本発明によれば、即ち、 (1)下記(I)〜(VII)で規定される電子供与性
ポリマ (1) + (II)の共重合体      (rV)
(1) + (III)の共重合体      (V)
(If) + (III)の共重合体      (V
l)(1) + (n) + (II)の共重合体  
(■)(式中、R,〜R,はそれぞれ独立に水素原子、
アルキル基、アルケニル基、フェニル基、ニトリル基、
ハロゲン基、アミノ基または芳香族炭化水素を表す).
と、および (2)  300〜560nmの光を吸収して酸を発生
する、下記式で表される鉄アレーン錯体 壱。  X− (式中、X−はBFa−r PF4−+ AsFi− 
、またはSbF&−であり、Aは芳香族炭化水素基を表
す)から成ることを特徴とするホログラム記録用感光材
料が提供される。
According to the present invention, namely: (1) copolymer of electron-donating polymer (1) + (II) defined by the following (I) to (VII) (rV)
Copolymer of (1) + (III) (V)
(If) + (III) copolymer (V
l) Copolymer of (1) + (n) + (II)
(■) (wherein R, ~R, are each independently a hydrogen atom,
Alkyl group, alkenyl group, phenyl group, nitrile group,
(represents a halogen group, amino group or aromatic hydrocarbon).
and (2) iron arene complex 1 represented by the following formula, which absorbs light of 300 to 560 nm and generates acid. X- (wherein, X- is BFa-r PF4-+ AsFi-
, or SbF&-, where A represents an aromatic hydrocarbon group).

本発明において、芳香族炭化水素基の例は、ベンゼン、
ナフタレン、ナフタセン、ビレン、ナフタピレンなどの
残基である。
In the present invention, examples of aromatic hydrocarbon groups include benzene,
These are residues such as naphthalene, naphthacene, birene, and naphthapyrene.

〔作 用〕[For production]

本発明では、(2)の物質が光を吸収して酸f発生し、
(1)の水素原子が引き抜かれて、架橋が起こると考え
られる。下記のごとくの反応メカニズムに従う。
In the present invention, the substance (2) absorbs light and generates acid f,
It is thought that the hydrogen atom in (1) is extracted and crosslinking occurs. The reaction mechanism follows as shown below.

(式中、RHは上記(1)で示されるボリマである。) なお、当ホログラム材料は光照射量を増しても可視光域
に吸収を生ずることはない(CT錯体を形成することは
ない)ので、光照射量にかかわらず高い透明性を有する
ホログラムを形成できることがわかった。
(In the formula, RH is the volima shown in (1) above.) Furthermore, even if the amount of light irradiation is increased, this hologram material will not absorb in the visible light region (it will not form a CT complex). ), it was found that a hologram with high transparency could be formed regardless of the amount of light irradiation.

つぎに、ボリマに対する酸発生剤の添加量は実験の結果
、0.3〜13重量%が良いことがわかった。
Next, as a result of experiments, it was found that the amount of acid generator to be added to the volima is preferably 0.3 to 13% by weight.

A 酸 〔実施例〕 以下、実施例により本発明をさらに説明する。A acid 〔Example〕 The present invention will be further explained below with reference to Examples.

実施例l: (n)のボリマ:ボリビニルーN−メトキシ力ルバゾー
ル             10  g酸発生剤: 
(η6−ナフタレン)(η5−シクロペンタジエニル)
鉄(■)へキサフルオロホスフエイ ト       
                        0
.5g?9M:モノクロノレベンゼン    80  
gクロロホルム       80  gテトラヒド口
フラン    80  gこの組成の感光液を50 X
 50鶴で厚さl龍ガラス&+1上にスピンコートして
乾燥後の膜厚が5In@のホログラム用感光板を形成し
た。
Example 1: Volima of (n): Volivinyl-N-methoxy Rubazol 10 g Acid generator:
(η6-naphthalene) (η5-cyclopentadienyl)
Iron (■) hexafluorophosphate
0
.. 5g? 9M: Monochrome lebenzene 80
g Chloroform 80 g Tetrahydrofuran 80 g A photosensitive solution of this composition was mixed with 50
A photosensitive plate for a hologram having a film thickness of 5 In@ after drying was formed by spin-coating 50 Tsuru on a 1-thick glass &+1.

この感光板を用い、二光束干渉露光光学系でArレーザ
によりホログラムを記録した。そして、トルエン・キシ
レン混合液中に5 sin浸漬して風乾した後、さらに
トルエン・キシレン混合液中に1+IIin浸漬して完
全に現像し、ついでN−ペンタン中に浸漬して収縮させ
てホログラムを形成した。
Using this photosensitive plate, a hologram was recorded using an Ar laser using a two-beam interference exposure optical system. Then, it was immersed in a toluene/xylene mixture for 5 sins and air-dried, then further immersed in a toluene/xylene mixture for 1+II in to develop completely, and then immersed in N-pentane to shrink to form a hologram. did.

その結果、40RIJ/一で回折効率76%のホログラ
ムを作ることができ、またホログラムは透明で可視光に
対する吸収は認められなかった。
As a result, it was possible to create a hologram with a diffraction efficiency of 76% at 40 RIJ/1, and the hologram was transparent and showed no absorption of visible light.

実施例2: (n)のボリマ:ポリビニルーN−ジアルキルアミノカ
ルバゾール         10  gfl1発生剤
:Cη1−ピレン)(η5−シクロペンタジエニル)鉄
(ff)へキサフルオ口ホスフエイ}        
                         
                     0.5 
 g溶 剤:モノクロルベンゼン    80  gク
ロロホルム       80  gテトラヒド口フラ
ン    80  g以下、実施例lと同様に行う。
Example 2: Bolima of (n): polyvinyl-N-dialkylaminocarbazole 10 gfl1 generator: Cη1-pyrene)(η5-cyclopentadienyl)iron(ff)hexafluorophosphate}

0.5
g Solvent: Monochlorobenzene 80 g Chloroform 80 g Tetrahydrofuran 80 g The following steps were carried out in the same manner as in Example 1.

その結果、40mJ/c+!で回折効率78%のホログ
ラムを作ることができ、またホログラムは透明で可視光
領域に対する吸収は認められなかった。
As a result, 40mJ/c+! It was possible to create a hologram with a diffraction efficiency of 78%, and the hologram was transparent and showed no absorption in the visible light region.

実施例3: (In)のボリマ:ポリ (p−ビニルフェニル2.3
−エボキシプ口ビルエーテル)  10  gM発生剤
:Cη6−ピレン)(η5−シクロペンタジエニル)鉄
(II)ヘキサフルオロアンチモネイ ト      
                         
 0.6g溶 剤:モノクロルベンゼン    80 
 gクロロホルム       80  gテトラヒド
口フラン    80  g以下、実施例lと同様に行
う。
Example 3: Bolima of (In): Poly (p-vinylphenyl 2.3
10 gM Generator: Cη6-pyrene)(η5-cyclopentadienyl)iron(II) hexafluoroantimonate

0.6g Solvent: Monochlorobenzene 80
g Chloroform 80 g Tetrahydrofuran 80 g Below, proceed as in Example 1.

その結果、50mJ/一で回折効率70%のホログラム
を作ることができ、またホログラムは透明で可視光領域
に対する吸収は認められなかった。
As a result, it was possible to create a hologram with a diffraction efficiency of 70% at 50 mJ/1, and the hologram was transparent and showed no absorption in the visible light region.

実施例4; (IV)のボリマ:スチレンとN−ビニル力ルバゾール
の共重合体          10  g酸発生剤.
(η6−ビレン)(η5−シクロペンタシエニル)鉄(
■)へキサフルオ口ホスフエイト          
                         
0.6 g溶剤:モノクロルベンゼン    80  
gクロロホルム       80  gテトラヒド口
フラン    80  g以下、実施例lと同様に行う
Example 4; (IV) Bolima: Copolymer of styrene and N-vinyl Rubazole 10 g Acid generator.
(η6-birene)(η5-cyclopentacyenyl)iron (
■) Hexafluorophosphate

0.6 g Solvent: Monochlorobenzene 80
g Chloroform 80 g Tetrahydrofuran 80 g Below, proceed as in Example 1.

その結果、45mJ/ajで回折効率72%のホログラ
ムを作ることができ、またホログラムは透明で可視光領
域に対する吸収は認められなかった。
As a result, a hologram with a diffraction efficiency of 72% could be produced at 45 mJ/aj, and the hologram was transparent and no absorption in the visible light region was observed.

実施例5: (V)のポリマ:スチレンとp−ビニルフェニルー2.
3−エボキシプ口ビルエーテルの共重合体      
                 10  g酸発生
剤: (η6−ビレン)(η5−シクロペンタジエニル
)鉄(n)ヘキサフルオロアンチモネイ ト     
                         
  0.6g溶剤:モノクロルベンゼン    80 
 gクロロホルム       80  gテトラヒド
口フラン    80  g以下、実施例lと同様に行
う。
Example 5: Polymer (V): styrene and p-vinylphenyl2.
3-Eboxypyl ether copolymer
10 g acid generator: (η6-birene)(η5-cyclopentadienyl)iron(n) hexafluoroantimonate

0.6g Solvent: Monochlorobenzene 80
g Chloroform 80 g Tetrahydrofuran 80 g Below, proceed as in Example 1.

その結果、50mJ/cjで回折効率70%のホログラ
ムを作ることができ、またホログラムは透明で可視光領
域に対する吸収は認められなかった。
As a result, a hologram with a diffraction efficiency of 70% could be produced at 50 mJ/cj, and the hologram was transparent and no absorption in the visible light region was observed.

〔発明の効果〕〔Effect of the invention〕

本発明に係る記録材料を使用すれば、可視光レーザに対
して高惑度で、従来の記録材料よりも透明で耐環境性が
優れ、かつ高い回折効率を持つホログラムを形成するこ
とができる。
By using the recording material according to the present invention, it is possible to form a hologram that is highly sensitive to visible light lasers, is more transparent than conventional recording materials, has superior environmental resistance, and has high diffraction efficiency.

Claims (1)

【特許請求の範囲】 1、(1)下記( I )〜(VII)で規定される電子供与
性ポリマ ▲数式、化学式、表等があります▼( I ) ▲数式、化学式、表等があります▼(II) ▲数式、化学式、表等があります▼(III) ( I )+(II)の共重合体(IV) ( I )+(III)の共重合体(V) (II)+(III)の共重合体(VI) ( I )+(II)+(III)の共重合体(VII) (式中、R_1〜R_5はそれぞれ独立に水素原子、ア
ルキル基、アルケニル基、フェニル基、ニトリル基、ハ
ロゲン基、アミノ基または芳香族炭化水素を表す)と、
および (2)300〜560nmの光を吸収して酸を発生する
、下記式で表される鉄アレーン錯体 ▲数式、化学式、表等があります▼ (式中、X^−はBF_4^−、PF_6^−、AsF
_6^−、またはSbF_6^−であり、Aは芳香族炭
化水素基を表す) から成ることを特徴とするホログラム記録用感光材料。
[Claims] 1. (1) Electron-donating polymer defined by the following (I) to (VII) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) Copolymer of (I) + (II) (IV) Copolymer of (I) + (III) (V) (II) + (III) ) copolymer (VI) (I) + (II) + (III) copolymer (VII) (wherein R_1 to R_5 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a nitrile group) group, halogen group, amino group or aromatic hydrocarbon);
and (2) an iron arene complex represented by the following formula that absorbs light in the range of 300 to 560 nm and generates acid. There are mathematical formulas, chemical formulas, tables, etc.▼ (wherein, X^- is BF_4^-, PF_6 ^-, AsF
_6^- or SbF_6^-, where A represents an aromatic hydrocarbon group.
JP5796189A 1989-03-13 1989-03-13 Photosensitive material for hologram recording Pending JPH02238455A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP5796189A JPH02238455A (en) 1989-03-13 1989-03-13 Photosensitive material for hologram recording

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP5796189A JPH02238455A (en) 1989-03-13 1989-03-13 Photosensitive material for hologram recording

Publications (1)

Publication Number Publication Date
JPH02238455A true JPH02238455A (en) 1990-09-20

Family

ID=13070609

Family Applications (1)

Application Number Title Priority Date Filing Date
JP5796189A Pending JPH02238455A (en) 1989-03-13 1989-03-13 Photosensitive material for hologram recording

Country Status (1)

Country Link
JP (1) JPH02238455A (en)

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