JPH0375633A - Photosensitive material for recording visible laser beams - Google Patents

Photosensitive material for recording visible laser beams

Info

Publication number
JPH0375633A
JPH0375633A JP1210652A JP21065289A JPH0375633A JP H0375633 A JPH0375633 A JP H0375633A JP 1210652 A JP1210652 A JP 1210652A JP 21065289 A JP21065289 A JP 21065289A JP H0375633 A JPH0375633 A JP H0375633A
Authority
JP
Japan
Prior art keywords
formula
polymer
beams
visible laser
photosensitive material
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
JP1210652A
Other languages
Japanese (ja)
Inventor
Noriko Ikeda
紀子 池田
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 JP1210652A priority Critical patent/JPH0375633A/en
Publication of JPH0375633A publication Critical patent/JPH0375633A/en
Pending legal-status Critical Current

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  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)

Abstract

PURPOSE:To enhance sensitivity to visible laser beams, resolution,storage stability, and corrosion resistance by protecting the specified functional groups of a polymer, and removing the protective groups with acids generated by illumination with visible laser beams to restore the initial functional groups. CONSTITUTION:The photosensitive material comprises the polymer represented by formula I or II and an iron-allene complex represented by formula III, and in formula I, II, and III, each of R<1> - R<6> is H, alkyl, or the like; R<7> is alkylene; each of (n) and (m) is independently an integer of 5 - 500; and A is an aromatic hydrocarbon group. Said complex of formula III high in visible beams absorbance absorbs beams and generates acid to release the blocking substituents of the polymer of formula I or II and to restore the alkali-soluble poly(p-hydroxy-styrene), thus permitting exposed areas to be dissolved by the alkali development, therefore, a pattern to be formed with high sensitivity to beams in the visible wavelength region and in high resolution, and practicably sufficient storage stability and corrosion resistance to be obtained.

Description

【発明の詳細な説明】 〔概 要] 可視レーザ記録用感光材料に関し、 可視レーザに高感度であり、かつ解像性、保存安定性お
よび非腐食性に優れた感光材料を提供することを目的と
し、 下記式(I)又は(II)で表わされるポリマーと下記
式(III)で表わされる鉄アレーン錯体とで構成する
[Detailed Description of the Invention] [Summary] Regarding a photosensitive material for visible laser recording, the object is to provide a photosensitive material that is highly sensitive to visible laser and has excellent resolution, storage stability, and non-corrosion. It is composed of a polymer represented by the following formula (I) or (II) and an iron arene complex represented by the following formula (III).

6 (式中、pl、 RZ、 R3,R4,R5及びR6は
それぞれ独立に水素原子、アルキル基、アルケニル基又
はフェニル基を示し、R7はアルキレン基を示し、n及
びmはそれぞれ独立に5〜500の整数である。)R6 (式中、R1,R1,R3,R4,R%及びR&はそれ
ぞれ独立に水素原子、アルキル基、アルケニル基又はフ
ェニル基を示し、R?はアルキレン基を示し、n及びm
はそれぞれ独立に5〜500の整数である。)(式中、
Aは芳香族炭化水素基である。)〔産業上の利用分野〕 本発明は可視レーザ記録用感光材料に関する。
6 (wherein, pl, RZ, R3, R4, R5 and R6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group or a phenyl group, R7 represents an alkylene group, and n and m each independently represent 5 to is an integer of 500.) R6 (wherein R1, R1, R3, R4, R% and R& each independently represent a hydrogen atom, an alkyl group, an alkenyl group or a phenyl group, and R? represents an alkylene group, n and m
are each independently an integer from 5 to 500. ) (in the formula,
A is an aromatic hydrocarbon group. ) [Industrial Application Field] The present invention relates to a photosensitive material for visible laser recording.

可視レーザ記録用感光材料は凸版用、レリーフ像用およ
びフォトレジスト用などに広く適用されている。
Photosensitive materials for visible laser recording are widely used for letterpress printing, relief images, photoresists, and the like.

このような可視レーザ記録用感光材料の保持すべき特性
としては、(1)高感度であること、(2)高解像度を
有すること、(3)保存安定性に優れていること、(4
)アルカリ現像が可能なこと、及び(5)非腐食性に優
れていることなどが要求される。
The characteristics that such a photosensitive material for visible laser recording should maintain are (1) high sensitivity, (2) high resolution, (3) excellent storage stability, and (4)
) It is required to be capable of alkaline development, and (5) to be excellent in non-corrosion.

ここで用いるレーザ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であるArイオンレーザ
(波長7458.48B及び514nm )が望ましい
The laser used here is preferably an Ar ion laser (wavelength: 7458.48B and 514 nm), which is a gas laser that can stably produce high output and has an excellent coherence length.

〔従来の技術〕[Conventional technology]

可視レーザ記録用感光材料としては、可視光に対して十
分な感度を持つことが必要である。従来より、可視レー
ザ記録用感光材料の感度を増大させるために光重合開始
剤系について多くの研究がなされている。このような光
重合開始剤としてはベンゾイン及びその誘導体、置換又
は非置換の多核率ノン類などの多くの物質が既に知られ
ているが、特に可視光において十分な感度や解像性を有
するものは未だ知られていない。
A photosensitive material for visible laser recording must have sufficient sensitivity to visible light. Conventionally, many studies have been conducted on photopolymerization initiator systems in order to increase the sensitivity of photosensitive materials for visible laser recording. Many substances are already known as such photopolymerization initiators, such as benzoin and its derivatives, substituted or unsubstituted polynuclear compounds, etc., but those that have sufficient sensitivity and resolution, especially in visible light. is still unknown.

また、例えばN−フェニルグリシンのようなN−アリー
ル−α−デア5ノ酸各種の光吸収性化合物とを組み合わ
せた材料が知られている(例えば時開57−83501
号公報など参照)、シかしながら、この材料も感度や解
像性が十分ではなく、保存安定性も劣るなどの問題点が
ある。
Furthermore, materials are known in which N-aryl-α-dea-pentaenoic acids such as N-phenylglycine are combined with various light-absorbing compounds (for example, Jikai 57-83501
However, this material also has problems such as insufficient sensitivity and resolution, and poor storage stability.

そこで、レーザ照射で鉄アレーン錯体から発生した酸に
より、ブロック″した官能基をはずしてアルカリ可溶性
とする方法が開発されている(例えば特願昭63−13
800号出願など参照)。鉄アレーン錯体のアニオンと
してBF、−1PFth−1ASF&−又はSbF、−
が用いられている。しかしながら、ハロゲンである弗素
やりん、砒素及びアンチモンなどは金属への腐食性が高
く、このような腐食性が高い酸発生剤を用いると金属基
板や配線などを腐食する恐れがある。
Therefore, a method has been developed to make the iron arene complex soluble by removing the blocked functional groups using acid generated from the iron arene complex by laser irradiation (for example, Japanese Patent Application No. 1983-13).
(See Application No. 800, etc.) BF, -1PFth-1ASF&- or SbF, - as anion of iron arene complex
is used. However, halogens such as fluorine, phosphorus, arsenic, and antimony are highly corrosive to metals, and if such highly corrosive acid generators are used, there is a risk of corroding metal substrates, wiring, and the like.

(発明が解決しようとする課題) 従って、本発明は、前記した従来技術の問題点を解決し
て、可視レーザに高感度であり、かつ解像性、保存安定
性及び耐腐食性に優れたアルカリ現像型の感光材料を提
供することを目的とする。
(Problems to be Solved by the Invention) Therefore, the present invention solves the problems of the prior art described above, and provides a system that is highly sensitive to visible lasers and has excellent resolution, storage stability, and corrosion resistance. The purpose of the present invention is to provide an alkali-developable photosensitive material.

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

上記の目的は、本発明によれば、下記式(1)又は(I
I)で表わされるポリマーと下記式(nI)で表わされ
る鉄アレーン錯体とからなる可視レーザ記録用感光材料
によって達成される。
According to the present invention, the above object can be achieved by the following formula (1) or (I
This is achieved by a photosensitive material for visible laser recording comprising a polymer represented by I) and an iron arene complex represented by the following formula (nI).

6 (式中、R1,ip、 R3,R4,R’5及びR6は
それぞれ独立に水素原子、アルキル基(好ましくは炭素
数1〜5のアルキル基)、アルケニル基(好ましくは炭
素数2〜6のアルケニル基)又はフェニル基を示し、R
7はアルキレン基(好ましくは炭素数1〜lOのアルキ
レン基)を示し、n及びmはそれぞれ独立に5〜500
の整数である。) e A (式中、Aは芳香族炭化水素基である。)式(1)又は
(II)で表されるポリマーは、例えばポリ(p−ヒド
ロキシスチレン)の水酸基をトリオルガノシリル基又は
アルキレントリオルガノシリル基などによりブロックす
ることによって得られるポリマーである。
6 (wherein R1, ip, R3, R4, R'5 and R6 each independently represent a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), an alkenyl group (preferably an alkyl group having 2 to 6 carbon atoms) alkenyl group) or phenyl group, R
7 represents an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms), and n and m each independently represent 5 to 500
is an integer. ) e A (In the formula, A is an aromatic hydrocarbon group.) The polymer represented by formula (1) or (II) is, for example, a poly(p-hydroxystyrene) hydroxyl group replaced with a triorganosilyl group or an alkylene group. It is a polymer obtained by blocking with triorganosilyl groups or the like.

式(I[[)の鉄アレーン錯体は、300〜500n+
1の可視光を吸収して酸を発生する酸発生剤として作用
する。式(III)中、Aの芳香族炭化水素基としては
、例えば、ベンゼン、ナフタレン、ナフタセン、ピレン
およびナフタビレンなどの縮合芳香族環が好ましい。
The iron arene complex of the formula (I[[) has 300 to 500n+
Acts as an acid generator that absorbs visible light of 1 and generates acid. In formula (III), the aromatic hydrocarbon group of A is preferably a fused aromatic ring such as benzene, naphthalene, naphthacene, pyrene, and naphthabilene.

〔作用〕[Effect]

本発明では、ポリマー中の特定の官能基を保護しておき
、これを可視レーザ照射で発生した酸によりはずして元
の官能基に戻す機構を利用する。
The present invention utilizes a mechanism in which a specific functional group in a polymer is protected and then removed by an acid generated by visible laser irradiation to restore the original functional group.

すなわち、可視光の吸収能が大きい式(I[[)の鉄ア
レーン錯体が光を吸収して酸を発生し、式(1)または
式(II)のポリマーのブロックされた置換基がはずれ
て、アルカリ可溶性のポリ(Pヒドロキシスチレン)と
なる。アルカリ現像により露光部が溶解しポジパターン
が得られる。
In other words, the iron arene complex of formula (I [ , resulting in alkali-soluble poly(P-hydroxystyrene). The exposed areas are dissolved by alkaline development and a positive pattern is obtained.

この機能を、式(I)のポリマーを用いた場合について
示すと下記のとおりである。
This function is shown below when using the polymer of formula (I).

3 次に、この右辺のポリマーがアルカリ現像によって溶解
する。
3 Next, this polymer on the right side is dissolved by alkaline development.

保護基として用いるトリオルガノシリル基とアルキレン
トリオルガノシリル基は酸を触媒とする開裂速度が速く
、かつ酸が存在しない場合、即ち、露光しない限り極め
て安定である。また、酸発生剤のアニオンは腐食性が非
常に低い。このため、本発明の可視レーザ記録用感光材
料によれば、高感度、高解像度、高保存安定性及び非腐
食性が同時に得られる。
Triorganosilyl groups and alkylenetriorganosilyl groups used as protecting groups have a high rate of acid-catalyzed cleavage and are extremely stable in the absence of acid, that is, unless exposed to light. Furthermore, the anion of the acid generator has very low corrosivity. Therefore, according to the photosensitive material for visible laser recording of the present invention, high sensitivity, high resolution, high storage stability, and non-corrosion can be obtained at the same time.

以下に、実施例によって、本発明を更に詳しく説明する
が、本発明の範囲をこれらの実施例に限定するものでは
ないことはいうまでもない。
EXAMPLES The present invention will be explained in more detail below with reference to Examples, but it goes without saying that the scope of the present invention is not limited to these Examples.

〔実施例] 2!Ju!1L (I)のポリマー:ポリ(p−1リオルガノメチルシロ
キシスチレン)10g 酸発生剤:炭酸水素化(η6ナフタレン)(η5シクロ
ペンタジェニル) 鉄(II )  0.5g?容斉り
:モノクロベンゼン        40gメチルイソ
ブチルケトン     40gテトラヒドロフラン  
     40gこの組成の感光液をシリコン基板上に
スピンコートシて乾燥後の膜厚5μmの感光板を形成し
た。
[Example] 2! Ju! 1L Polymer (I): Poly(p-1 liorganomethylsiloxystyrene) 10g Acid generator: Hydrocarbonated (η6 naphthalene) (η5 cyclopentagenyl) Iron (II) 0.5g? Appearance: Monochlorobenzene 40g Methyl isobutyl ketone 40g Tetrahydrofuran
40g of the photosensitive solution having this composition was spin-coated onto a silicon substrate to form a photosensitive plate having a film thickness of 5 μm after drying.

得られた感光板を、Arレーザを用いてフォトマスクを
通して露光し、現像液としてテトラメチルアンモニウム
ヒドロキシドを用いて、ポジ型のパターンを形成した。
The obtained photosensitive plate was exposed to light using an Ar laser through a photomask, and a positive pattern was formed using tetramethylammonium hydroxide as a developer.

その結果、25 mJ/clで10umラインの再現を
確認した。
As a result, it was confirmed that the 10 um line could be reproduced at 25 mJ/cl.

l動艷え (I)のポリマー:ポリ (p−トリオルガノメチルシ
ロキシスチレン)10g 酸発生剤:炭酸水素化(η6ピレン) (η5シクロペンタジェニル)鉄(II)  0.5g
溶剤:モノクロルベンゼン       40gメチル
イソブチルケトン     40gテトラヒドロフラン
       40g以下、実施例1と同様にしてポジ
型パターン形成したところ、10 mJ/ciで10μ
mラインの再現を確認した。
1 Polymer of moving part (I): Poly (p-triorganomethylsiloxystyrene) 10 g Acid generator: Hydrogenated carbonate (η6 pyrene) (η5 cyclopentadienyl) iron (II) 0.5 g
Solvent: Monochlorobenzene 40g Methyl isobutyl ketone 40g Tetrahydrofuran 40g or less A positive pattern was formed in the same manner as in Example 1, and 10μ at 10 mJ/ci
The reproduction of the m line was confirmed.

実Iu組よ (n)のポリマー:ポリ(p−トリメチルシリルメトキ
シスチレン)12g 酸発生剤:炭酸水素化(ηbピレン) (η5シクロペンタジェニル)&(II)  0.5g
溶剤:モノクロルベンゼン       40gメチル
イソブチルケトン     40gテトラヒドロフラン
       40g以下、実施例1と同様にしてポジ
型パターンを形成し、20 mJ/cfflで10II
I11ラインの再現を確認した。
Real Iu group (n) polymer: poly(p-trimethylsilylmethoxystyrene) 12 g Acid generator: hydrogen carbonate (ηb pyrene) (η5 cyclopentadienyl) & (II) 0.5 g
Solvent: Monochlorobenzene 40g Methyl isobutyl ketone 40g Tetrahydrofuran 40g or less, a positive pattern was formed in the same manner as in Example 1, and 10II was applied at 20 mJ/cffl.
The reproduction of the I11 line was confirmed.

夫旌班土 (II)のポリマー:ポリ (p−トリメチルシリルエ
トキシスチレン)            12g酸発
生剤:炭酸水素化(η6ピレン) (η5シクロペンタジェニル)&(II)  0.5g
ン容剤:モノクロルベンゼン       40gメチ
ルイソブチルケトン     40gテトラヒドロフラ
ン       40g以下、実施例1と同様にしてポ
ジ型パターンを形成し、15 mJ/cJで10μmラ
インの再現を確認した。
Polymer of Fuchengbanto (II): Poly (p-trimethylsilylethoxystyrene) 12g Acid generator: Hydrocarbonated (η6pyrene) (η5cyclopentadienyl) & (II) 0.5g
A positive pattern was formed in the same manner as in Example 1 using 40 g of monochlorobenzene, 40 g of methyl isobutyl ketone, and 40 g of tetrahydrofuran, and the reproduction of a 10 μm line was confirmed at 15 mJ/cJ.

〔発明の効果〕〔Effect of the invention〕

以上説明したように、本発明の可視レーザ記録用感光材
料は、可視光領域において従来の感光材料よりも高い感
度および解像度でパターンを形成することができ、かつ
実用的に十分な保存安定性および非腐食性を有する。
As explained above, the photosensitive material for visible laser recording of the present invention can form a pattern with higher sensitivity and resolution than conventional photosensitive materials in the visible light region, and has practically sufficient storage stability and Non-corrosive.

Claims (1)

【特許請求の範囲】 1、下記式( I )又は(II)で表わされるポリマーと
下記式(III)で表わされる鉄アレーン錯体とからなる
可視レーザ記録用感光材料。 ▲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) (式中、R^1、R^2、R^3、R^4、R^5及び
R^6はそれぞれ独立に水素原子、アルキル基、アルケ
ニル基又はフェニル基を示し、R^7はアルキレン基を
示し、n及びmはそれぞれ独立に5〜500の整数であ
る。) ▲数式、化学式、表等があります▼(III) (式中、Aは芳香族炭化水素基である。)
[Claims] 1. A photosensitive material for visible laser recording comprising a polymer represented by the following formula (I) or (II) and an iron arene complex represented by the following formula (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1, R^2, R^3, R^4, R^5 and R^6 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or a phenyl group, R^7 represents an alkylene group, and n and m each independently represent an integer from 5 to 500.) ▲ Numerical formula, chemical formula , tables, etc.▼(III) (In the formula, A is an aromatic hydrocarbon group.)
JP1210652A 1989-08-17 1989-08-17 Photosensitive material for recording visible laser beams Pending JPH0375633A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1210652A JPH0375633A (en) 1989-08-17 1989-08-17 Photosensitive material for recording visible laser beams

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1210652A JPH0375633A (en) 1989-08-17 1989-08-17 Photosensitive material for recording visible laser beams

Publications (1)

Publication Number Publication Date
JPH0375633A true JPH0375633A (en) 1991-03-29

Family

ID=16592856

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1210652A Pending JPH0375633A (en) 1989-08-17 1989-08-17 Photosensitive material for recording visible laser beams

Country Status (1)

Country Link
JP (1) JPH0375633A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2145765A1 (en) * 2008-07-18 2010-01-20 FUJIFILM Corporation Resin composition for laser engraving, image forming material, relief printing plate precursor for laser engraving. relief printing plate, and method of producing relief printing plate
US8273520B2 (en) 2008-01-29 2012-09-25 Fujifilm Corporation Resin composition for laser engraving, relief printing plate precursor for laser engraving, relief printing plate and method of producing the same
US8278387B2 (en) 2008-03-28 2012-10-02 Fujifilm Corporation Resin composition for laser engraving, image forming material, relief printing plate precursor for laser engraving, relief printing plate, and method of manufacturing relief printing plate

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8273520B2 (en) 2008-01-29 2012-09-25 Fujifilm Corporation Resin composition for laser engraving, relief printing plate precursor for laser engraving, relief printing plate and method of producing the same
US8278387B2 (en) 2008-03-28 2012-10-02 Fujifilm Corporation Resin composition for laser engraving, image forming material, relief printing plate precursor for laser engraving, relief printing plate, and method of manufacturing relief printing plate
EP2145765A1 (en) * 2008-07-18 2010-01-20 FUJIFILM Corporation Resin composition for laser engraving, image forming material, relief printing plate precursor for laser engraving. relief printing plate, and method of producing relief printing plate
US8367300B2 (en) 2008-07-18 2013-02-05 Fujifilm Corporation Resin composition for laser engraving, image forming material, relief printing plate precursor for laser engraving, relief printing plate, and method of producing relief printing plate

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