JPH02136857A - Photosensitive resin composition - Google Patents
Photosensitive resin compositionInfo
- Publication number
- JPH02136857A JPH02136857A JP29009388A JP29009388A JPH02136857A JP H02136857 A JPH02136857 A JP H02136857A JP 29009388 A JP29009388 A JP 29009388A JP 29009388 A JP29009388 A JP 29009388A JP H02136857 A JPH02136857 A JP H02136857A
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive resin
- polymer
- pvcz
- resin composition
- styryl
- 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
- 239000011342 resin composition Substances 0.000 title claims description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims abstract description 6
- 150000002366 halogen compounds Chemical class 0.000 claims description 9
- 125000005504 styryl group Chemical group 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000975 dye Substances 0.000 abstract description 15
- 230000035945 sensitivity Effects 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 4
- 150000002367 halogens Chemical class 0.000 abstract 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 3
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 125000005842 heteroatom Chemical group 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 5
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 150000002497 iodine compounds Chemical class 0.000 description 3
- 229910052754 neon Inorganic materials 0.000 description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QOACTULVIZXIHU-UHFFFAOYSA-N C=C.Br.Br.Br.Br Chemical compound C=C.Br.Br.Br.Br QOACTULVIZXIHU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- -1 bromine compound Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 108091008695 photoreceptors Proteins 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- FXDUOKLAEGQUOS-UHFFFAOYSA-N 1,1,1,2,2,2-hexaiodoethane Chemical compound IC(I)(I)C(I)(I)I FXDUOKLAEGQUOS-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- APQXWKHOGQFGTB-UHFFFAOYSA-N 1-ethenyl-9h-carbazole Chemical class C12=CC=CC=C2NC2=C1C=CC=C2C=C APQXWKHOGQFGTB-UHFFFAOYSA-N 0.000 description 1
- IFYNAKGJQOOLPC-UHFFFAOYSA-N 3-(2-bromoethenyl)-9h-carbazole Chemical compound C1=CC=C2C3=CC(C=CBr)=CC=C3NC2=C1 IFYNAKGJQOOLPC-UHFFFAOYSA-N 0.000 description 1
- FCSHIKUMFOMECS-UHFFFAOYSA-N 3-(2-chloroethenyl)-9h-carbazole Chemical compound C1=CC=C2C3=CC(C=CCl)=CC=C3NC2=C1 FCSHIKUMFOMECS-UHFFFAOYSA-N 0.000 description 1
- MWOVWCGTSHZIDW-UHFFFAOYSA-N 3-(2-iodoethenyl)-9h-carbazole Chemical compound C1=CC=C2C3=CC(C=CI)=CC=C3NC2=C1 MWOVWCGTSHZIDW-UHFFFAOYSA-N 0.000 description 1
- MKWDKGYDWUZTPZ-UHFFFAOYSA-N 3-but-1-enyl-9h-carbazole Chemical compound C1=CC=C2C3=CC(C=CCC)=CC=C3NC2=C1 MKWDKGYDWUZTPZ-UHFFFAOYSA-N 0.000 description 1
- GBXFMOUYJFLJIG-UHFFFAOYSA-N 3-prop-1-enyl-9h-carbazole Chemical compound C1=CC=C2C3=CC(C=CC)=CC=C3NC2=C1 GBXFMOUYJFLJIG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業−にの利用分野）
本発明は感光性樹脂組成物に関し、更に詳しくは可視レ
ーザー光領域において優れた感度を打する感光性樹脂組
成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photosensitive resin composition, and more particularly to a photosensitive resin composition that exhibits excellent sensitivity in the visible laser light region.
（従来の技術及びその問題点）
エレクトロニクスの発達に伴う画像技術の向上により、
レーザー光走査による画像記録が望まれている。具体的
にはアルゴンレーザー（４８Ｓｎｍ、５１４．Ｓｎｍ）
、ヘリウム・ネオンレーザ−（６３２，Ｓｎｍ）で使用
出来る感光性樹脂が検討されている。これらの感光性樹
脂としては、例えば、重クロム酸ゼラチン系、光ラジカ
ル重合型ポリマー系、光イオン爪台型ポリマー系が知ら
れている。(Conventional technology and its problems) With the improvement of image technology accompanying the development of electronics,
Image recording by laser beam scanning is desired. Specifically, argon laser (48Snm, 514.Snm)
, photosensitive resins that can be used in helium-neon lasers (632, Snm) are being considered. As these photosensitive resins, for example, dichromate gelatin type, photo radical polymerization type polymer type, and photoionic nail platform type polymer type are known.
しかしながら、重クロム酸ゼラチン系は耐湿性に難点が
あり、又、光ラジカル型は酸素のｍ合阻止作用を受は易
くオーバーコート層等の１夫が必要とされていた。又、
これらいずれの系もヘリウム・ネオンレーザ−で使用出
来ると報告されている例は極めて少なく、ヘリウム、ネ
オンレーザ−に対して優れた感度を有する新しい感光性
樹脂か望まれていた。However, the dichromate gelatin type has a drawback in moisture resistance, and the photo-radical type is susceptible to the action of inhibiting the combination of oxygen and requires a layer such as an overcoat layer. or,
There are very few reports that any of these systems can be used with helium/neon lasers, and a new photosensitive resin having excellent sensitivity to helium/neon lasers has been desired.
上記の問題点を解決するために新たな記録媒体として、
ポリビニルカルバゾール（以下ＰＶＣｚという）系ポリ
マー等の如く芳香族化合物を分子Ｓｎ構成１９１位とす
るポリマーに沃素化合物を増感剤として用いる感光体が
提案されている（例えば、特公昭５６−１６２０号公報
参照）。更に高性能ホログラムを得る技術も提案されて
いる（例えば、特公昭６２−１４８３１号公報参照）。As a new recording medium to solve the above problems,
Photoreceptors have been proposed in which an iodine compound is used as a sensitizer in a polymer such as a polyvinylcarbazole (hereinafter referred to as PVCz) polymer having an aromatic compound as the 191st position of the Sn structure in the molecule (for example, Japanese Patent Publication No. 1620/1983). reference). Furthermore, techniques for obtaining high-performance holograms have also been proposed (see, for example, Japanese Patent Publication No. 14831/1983).
しかしながら、このＰＶＣｚポリマー系においても５６
０ｎｍ迄しか感度がなく、ヘリウム・ネオンレーザ−で
使用出来る感光体ではながった。However, even in this PVCz polymer system, 56
It had sensitivity only down to 0 nm, and could not be used as a photoreceptor for helium/neon lasers.
従って本発明の［−１的は、ヘリウム・ネオンレーザ−
光領域において優れた感度を有する感光性樹脂組成物を
提供することである。Therefore, [-1] of the present invention is a helium neon laser.
An object of the present invention is to provide a photosensitive resin composition having excellent sensitivity in the optical region.
（問題点を解決するための手段） ■−記［］的は以上の本発明によって達成される。(Means for solving problems) (2) The objective [ ] is achieved by the present invention described above.
すなわち、本発明は、ＰＶＣｚ系ポリマー、ハロゲン化
合物及びスチリル系色素を含むことを特徴とする感光性
樹脂組成物である。That is, the present invention is a photosensitive resin composition characterized by containing a PVCz polymer, a halogen compound, and a styryl dye.
（作 用）
ＰＶＣｚ系ポリマーとハロゲン化合物からなる感光性樹
脂組成物に、増感剤としてスチリル系色素を添加するこ
とによって、８００ｎｍ迄の１ｆ視尤に感度を仔する感
光性樹脂組成物が提供され（好ましい実施態様）
次に好ましい実施態様を挙げて本発明を更に詳しく説明
する。(Function) By adding a styryl dye as a sensitizer to a photosensitive resin composition consisting of a PVCz polymer and a halogen compound, a photosensitive resin composition that is sensitive to 1f viewing up to 800 nm is provided. (Preferred Embodiments) Next, the present invention will be explained in more detail by citing preferred embodiments.
本発明において使用するＰＶＣｚ系ポリマーとしては、
ビニルカルバゾール、そのアルキル置換誘導体又はその
ハロゲン置換誘導体、カルバゾール基を側鎖に有するア
クリル酸誘導体や酢酸ビニル誘導体等の千ツマ−を主体
とするポリマーであり、具体的には、例えば、ＰＶＣｚ
、３−クロルビニルカルバゾールポリマー、３−ブロム
ビニルカルバゾールボリマー、３−ヨードビニルカルバ
ゾールポリマー、３−メチルビニルカルバゾールポリマ
ー、３−エチルビニル力ルバゾールボリマー、クロル化
ＰＶＣｚ、ブロム化ＰＶＣｚ及び下記の構造式（Ｉ）又
は（ＩＩ）で表されるモノマーからなるポリマー等が挙
げられる。The PVCz-based polymer used in the present invention includes:
Polymers mainly composed of vinylcarbazole, its alkyl-substituted derivatives or halogen-substituted derivatives, acrylic acid derivatives and vinyl acetate derivatives having carbazole groups in their side chains, and specifically, for example, PVCz.
, 3-chlorovinylcarbazole polymer, 3-bromvinylcarbazole polymer, 3-iodovinylcarbazole polymer, 3-methylvinylcarbazole polymer, 3-ethylvinylcarbazole polymer, chlorinated PVCz, brominated PVCz and the following structures Examples include polymers made of monomers represented by formula (I) or (II).
（以下余白）
中ても未置換のＰＶＣｚは、その人丁、が８鴇てしかも
得られる感光性組成物の性能も特に優れたものであるか
らル実ト最適なものである。(Hereinafter in the margins) Among these, unsubstituted PVCz is the most suitable because of its properties and the performance of the resulting photosensitive composition.
に記ｐＶＣｚ系ポリマーは、例えば、フィルムとした際
の強度や宅軟性等の特性の制御のために、必要に応じて
、他の千ツマ−と共ＩＴ［合されていてもよい。そのよ
うな用途に用い得る他の千ツマ−としては、例えば、上
記ビニルカルバゾール類に加えて、酢酸ビニル等のビニ
ルエステル、アクリル酸、メタアクリル酸のエステル、
特に上記構造式（１）又は（ＩＩ）て表記されたエステ
ル類、スチレン及びスチレン誘導体等のラジカル重合に
よるＪい■合法によって」いＲ合し得るビニル糸上ツマ
−を挙げることがてきる。又、例えば、ポリスチレン、
スチレン−ブタジェンコポリマースチレン−水素化ブタ
ジェンコポリマー等の他のポリマーを感度を低下させず
に記録可能な範囲でブレンドして用いることもできる。The pVCz-based polymer described above may be combined with other polymers as necessary, for example, in order to control properties such as strength and flexibility when formed into a film. Other substances that can be used for such purposes include, in addition to the vinyl carbazoles mentioned above, vinyl esters such as vinyl acetate, esters of acrylic acid and methacrylic acid,
In particular, examples include vinyl threads that can be combined by the radical polymerization method of esters represented by the above structural formulas (1) or (II), styrene, and styrene derivatives. Also, for example, polystyrene,
Other polymers such as styrene-butadiene copolymer and styrene-hydrogenated butadiene copolymer can also be blended to the extent that recording is possible without reducing sensitivity.
尚、これらは所望の特性が得られるようにその添加割合
が選択して用いられる。Incidentally, the addition ratio of these materials is selected so as to obtain desired characteristics.
本発明の感光性樹脂組成物の主体をなすポリマー成分は
１本発明においてｐめハロゲン化合物、好ましくは沃素
化合物及び／又は臭素化合物によって輻射線に対して活
性にされている必要がある。かかるハロゲン化合物の好
ましいものとして具体的には、四状化炭素、ヨードホル
ム、四状化エチレン、トリヨードエタン、テトラヨード
エタン、ペンタヨードエタン、ヘキサヨードエタン、四
臭化炭素、四臭化エチレン等の沃素化合物及び臭素化合
物が挙げられる。これらのハロゲン化合物は前記ＰＶＣ
ｚ系ポリマーの１乃至１００川Ｊｘｔ％、好ましくは３
乃至２５重ｎｔ％の割合で上記ポリマーに添加する。In the present invention, the main polymer component of the photosensitive resin composition of the present invention must be made active to radiation by a p-halogen compound, preferably an iodine compound and/or a bromine compound. Preferred examples of such halogen compounds include carbon tetramonide, iodoform, ethylene tetrabromide, triiodoethane, tetraiodoethane, pentayodoethane, hexaiodoethane, carbon tetrabromide, ethylene tetrabromide, and the like. Examples include iodine compounds and bromine compounds. These halogen compounds are
1 to 100 Jxt% of the Z-based polymer, preferably 3
It is added to the above polymer in a proportion of 25% to 25% by weight.
以上の如きハロゲン化合物の添加量か少なすぎると得ら
れる感光性樹脂組成物の感度が低く、露光に長時間を要
するので好ましくなく、又、多すぎると感光性樹脂組成
物中に未分解のハロゲン化合物か残り、後にこれらを全
部除去する必要かあるため、感光性樹脂組成物中にボイ
ドを生じる要因となるので好ましくない。If the amount of the halogen compound added is too small, the sensitivity of the photosensitive resin composition obtained will be low and it will take a long time for exposure, which is undesirable. This is not preferable because some compounds remain and it is necessary to remove all of them later, which may cause voids to occur in the photosensitive resin composition.
本発明て使用する増感剤は複素環にスチリル基か結合し
、分子中の窒素原子が四級化され染料であり、具体的に
は、例えば、下記の構造式の染料が挙げられる。The sensitizer used in the present invention is a dye in which a styryl group is bonded to a heterocyclic ring and the nitrogen atom in the molecule is quaternized, and specific examples include dyes having the following structural formula.
［記スチリル系色素は感光性樹脂組成物中のポリマーに
対して１０−４乃至１０重量％、好ましくは１０−３乃
至５重量％の割合で添加される。添加油かｔ記範囲未満
であると増感作用が不十分であり、一方、−ト記範囲を
越える使用量では使用量の増加に従って増感作用が向上
することがなく、ボイドの発生等の問題も生じるので好
ましくない。[The above styryl dye is added in an amount of 10-4 to 10% by weight, preferably 10-3 to 5% by weight, based on the polymer in the photosensitive resin composition. If the amount of added oil is less than the range specified in (t), the sensitizing effect will be insufficient.On the other hand, if the amount used exceeds the range specified in (t), the sensitizing effect will not improve as the amount used increases, and voids may occur. This is not desirable as it may cause problems.
本発明の感光性樹脂組成物は、面記ＰＶＣｚ系ポリマー
、ハロゲン化合物及び増感剤をＰＶＣｚ系ポリマーの良
溶媒に溶解することによって得られる。ＰＶＣｚ系ポリ
マーに対する溶解性及び沸点等を考Ｊ遭すると、好まし
いイ１゛機溶剤とじては、例えば、ベンゼン、キシレン
、クロルベンセン、クロロホルム、ジクロルエタン、ジ
クロロエチレン、トリクロロエチレン、ピリジン、ジオ
キサン、テトラヒドロフラン或いはこれらの混合物が挙
げられる。The photosensitive resin composition of the present invention is obtained by dissolving a polygonal PVCz-based polymer, a halogen compound, and a sensitizer in a good solvent for the PVCz-based polymer. Considering the solubility and boiling point of the PVCz-based polymer, preferred organic solvents include, for example, benzene, xylene, chlorobenzene, chloroform, dichloroethane, dichloroethylene, trichloroethylene, pyridine, dioxane, tetrahydrofuran, or any of these. Mixtures may be mentioned.
ＰＶＣｚ系ポリマーの溶解はポリマーを面記有機溶剤中
に入れて必要に応して加熱し、濾過して不溶分を除き放
置して気泡を除去する等の通常の溶解操作でよく特に限
定されない。得られる溶液粘度は２０℃で好ましくは５
０乃至５，０００ｃｐｓ、更に好ましくは３００乃至２
，０００ｃｐｓの範囲である。Dissolution of the PVCz-based polymer is not particularly limited, and may be carried out by a conventional dissolution operation such as placing the polymer in the above-mentioned organic solvent, heating if necessary, filtering to remove insoluble matter, and leaving to remove air bubbles. The resulting solution viscosity is preferably 5 at 20°C.
0 to 5,000 cps, more preferably 300 to 2
,000 cps.
本発明の感光性樹脂組成物は」−記溶液状の他にフィル
ム状の形態てもよく、フィルム状の形態の場合には、上
述の感光性樹脂組成物の粘度を適当に調整し、これをガ
ラス板やプラスチックフィルムの如き適当な基材−Ｌに
塗膜を形成することによって１＋＋られる。この’ｆ５
１：ｒられるフィルムは１乃至２０μｍ程度の厚みであ
るのが好ましく、基材上に担持したままでも或は剥離し
た状態でもよ以上の如き本発明の感光性樹脂組成物は、
装置が簡便で１１つ安価であるヘリウム・ネオンレーザ
−光に十分な感度を有し、例えば、体Ｊ＋’１位相型ホ
ログラム、光散乱パターン、レリーフパターン等の形成
に有用である。The photosensitive resin composition of the present invention may be in the form of a film in addition to the solution form described above, and when it is in the form of a film, the viscosity of the above-mentioned photosensitive resin composition is appropriately adjusted. 1++ by forming a coating film on a suitable substrate L such as a glass plate or a plastic film. This 'f5
1: The film to be processed preferably has a thickness of about 1 to 20 μm, and the photosensitive resin composition of the present invention as described above can be applied while being supported on a substrate or in a peeled state.
The apparatus is simple and inexpensive, and has sufficient sensitivity to helium-neon laser light, and is useful for forming, for example, body J+'1 phase type holograms, light scattering patterns, relief patterns, etc.
上記本発明の感光性樹脂組成物の用途の１例と【７てホ
ログラム記録に用いる場合を説明する。One example of the use of the photosensitive resin composition of the present invention and the case where it is used for hologram recording will be described.
本発明の感光性樹脂組成物からなるホログラム記２ｊ媒
体は、上述の感光性樹脂組成物の粘度を適当に調整し、
これをガラス板やプラスチ・ｌクフイルムの如き適当な
基材上に塗膜をバニ成することによって得られる。The hologram recording medium 2j made of the photosensitive resin composition of the present invention can be prepared by appropriately adjusting the viscosity of the above-mentioned photosensitive resin composition,
This can be obtained by applying a coating film onto a suitable substrate such as a glass plate or plastic film.
以トの如くして形成した記録媒体に８００ｎｍ迄のコビ
ーレントな可視光である物体光と参照光の２光束の→■
−渉性レーザーを用いて露光を行う。Two beams of object light and reference light, which are coherent visible light up to 800 nm, are applied to the recording medium formed as described above →■
- Exposure is carried out using a chromatographic laser.
露光−Ｌ程に続いて、記録層を構成しているＰＶＣｚ系
ポリマーは勿論のこと、九反紀・により生成するポリマ
ーの架橋物を殆ど溶出させることのない溶媒中に浸漬し
て、記録層中から未反応のハロゲン化合物及びスチリル
系色素のみをほぼ完全に溶出除去して着色を除く。尚、
この工程は下記の膨潤工程を兼ねることができる。Following exposure-L, the recording layer is immersed in a solvent that hardly dissolves the PVCz-based polymer constituting the recording layer, as well as the cross-linked polymer produced by Kyushu. Unreacted halogen compounds and styryl dyes are almost completely eluted and removed to remove coloration. still,
This step can also serve as the swelling step described below.
次いで行う現像工程は、膨潤工程及び収縮工程の２ステ
ツプからなり、例えば、特公昭６２−０１４８３１号公
報に記載された方法と同様にして行うことができる。The subsequent developing step consists of two steps: a swelling step and a shrinking step, and can be carried out in the same manner as described in, for example, Japanese Patent Publication No. 62-014831.
上記で得られるホログラムフィルムは基板に接着したま
までも使用てき、基板から剥離したホログラムフィルム
としても１分に各種用途で使用可能である。The hologram film obtained above can be used as it is adhered to the substrate, or can be used for various purposes in one minute as a hologram film peeled from the substrate.
（効 果）
以上の如き本発明によれば、ＰＶＣｚ系ポリマーとハロ
ゲン化合物からなる感光性樹脂組成物に、増感剤として
スチリル系色素を添加することによって、８００ｎｍ迄
の可視光に感度を有する感光性樹脂組成物か提供される
。(Effects) According to the present invention as described above, by adding a styryl dye as a sensitizer to a photosensitive resin composition consisting of a PVCz polymer and a halogen compound, the composition is sensitive to visible light up to 800 nm. A photosensitive resin composition is provided.
（実施例）
次に実施例及び比較例を挙げて本発明を更に具体的に説
明する。(Example) Next, the present invention will be explained in more detail by giving examples and comparative examples.
実施例１
ｐＶＣｚ （ルビカンＭ−１７０，０ＡＳＦ社製）４．
５ｇ、四状化炭素０．３ｇ及びスチリル系色素（１１１
記例示染料Ｎｏ、３）０．１５ｇをクロルヘンゼン６０
ｇに暗所て溶解して本発明の溶液状感光性樹脂組成物を
得た。Example 1 pVCz (Rubican M-170, 0 manufactured by ASF) 4.
5 g, 0.3 g of carbon tetramonide, and styryl dye (111
Exemplary dye No. 3) 0.15g of chlorhenzene 60
g in the dark to obtain a solution photosensitive resin composition of the present invention.
上記組成物を１００μｍのポリエステルフィルムベース
に膜厚２μｍになるように塗布及び乾燥してフィルム状
の本発明の感光性樹脂組成物を得た。The above composition was coated on a 100 μm polyester film base to a film thickness of 2 μm and dried to obtain a film-like photosensitive resin composition of the present invention.
このフィルムにネガフィルムを密着させ、ヘリウム・ネ
オンレーザ−を用いて露光を行った。A negative film was brought into close contact with this film, and exposure was performed using a helium-neon laser.
次に上記フィルムをベンゼン溶媒に５秒間間浸清した後
、メチルアルコールに５秒間間浸消して乾燥させると非
露光領域が不透明になり反射で見ると鮮明なポジの可視
パターンが得られた。The film was then immersed in a benzene solvent for 5 seconds, then in methyl alcohol for 5 seconds and allowed to dry, leaving the unexposed areas opaque and providing a clear positive visible pattern when viewed in reflection.
実Ｊｊ’ｔｓ例２
実施例１においてベンゼン溶媒による処理を３分間行っ
た。その結果非露光領域が溶出除去され、乾燥後には透
明なレリーフパターンが形成された。Actual Jj'ts Example 2 In Example 1, the treatment with benzene solvent was performed for 3 minutes. As a result, the non-exposed areas were eluted and removed, and after drying, a transparent relief pattern was formed.
実施例３
実施例１と同様の材料でホログラムの記録を行った。露
光後３２℃のトルエンに１分間及びｎ−へブタンに１分
間浸漬した後乾燥させて体積位相望ホログラムを得た。Example 3 A hologram was recorded using the same material as in Example 1. After exposure, it was immersed in toluene at 32° C. for 1 minute and n-hebutane for 1 minute, and then dried to obtain a volume phase telescopic hologram.
実施例４
実施例１における染料に代えてｔ１ｅｒ記例示染料Ｎｏ
、 １乃値２．４乃至１１を使用し、他は実施例１と
同様にして、実施例１と同様な結果が得られた。Example 4 In place of the dye in Example 1, t1er exemplified dye No.
, 1 to 2.4 to 11 were used, and the other conditions were the same as in Example 1, and the same results as in Example 1 were obtained.
比較例１
スチリル系色素を除いた系を用いて実施例１と同様にし
て記録を行ったところポジの可視パターンは形成されな
かった。Comparative Example 1 When recording was carried out in the same manner as in Example 1 using a system excluding the styryl dye, no positive visible pattern was formed.
Claims (3)
合物及びスチリル系色素を含むことを特徴とする感光性
樹脂組成物。(1) A photosensitive resin composition comprising a polyvinylcarbazole polymer, a halogen compound, and a styryl dye.
樹脂組成物。(2) The photosensitive resin composition according to claim 1, which contains a solvent and is in the form of a solution.
光性樹脂組成物。(3) The photosensitive resin composition according to claim 1, which is formed into a film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29009388A JPH02136857A (en) | 1988-11-18 | 1988-11-18 | Photosensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29009388A JPH02136857A (en) | 1988-11-18 | 1988-11-18 | Photosensitive resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02136857A true JPH02136857A (en) | 1990-05-25 |
Family
ID=17751707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29009388A Pending JPH02136857A (en) | 1988-11-18 | 1988-11-18 | Photosensitive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02136857A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5422204A (en) * | 1991-07-19 | 1995-06-06 | Canon Kabushiki Kaisha | Photo-crosslinkable resin composition and hologram recording medium |
| WO2008108406A1 (en) * | 2007-03-05 | 2008-09-12 | Fujifilm Corporation | Compound for photoresist, photoresist solution, and etching method using the photoresist solution |
-
1988
- 1988-11-18 JP JP29009388A patent/JPH02136857A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5422204A (en) * | 1991-07-19 | 1995-06-06 | Canon Kabushiki Kaisha | Photo-crosslinkable resin composition and hologram recording medium |
| WO2008108406A1 (en) * | 2007-03-05 | 2008-09-12 | Fujifilm Corporation | Compound for photoresist, photoresist solution, and etching method using the photoresist solution |
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