JP2646205B2 - Method of forming photosensitive resin layer - Google Patents
Method of forming photosensitive resin layerInfo
- Publication number
- JP2646205B2 JP2646205B2 JP15566486A JP15566486A JP2646205B2 JP 2646205 B2 JP2646205 B2 JP 2646205B2 JP 15566486 A JP15566486 A JP 15566486A JP 15566486 A JP15566486 A JP 15566486A JP 2646205 B2 JP2646205 B2 JP 2646205B2
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive resin
- substrate
- less
- fine particles
- dispersed
- 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.)
- Expired - Fee Related
Links
- 229920005989 resin Polymers 0.000 title claims description 44
- 239000011347 resin Substances 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 30
- 239000000758 substrate Substances 0.000 claims description 34
- 239000007921 spray Substances 0.000 claims description 31
- 239000010419 fine particle Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- 239000012530 fluid Substances 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 3
- 239000003989 dielectric material Substances 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000002834 transmittance Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 238000004043 dyeing Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229920001342 Bakelite® Polymers 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- YVXDRFYHWWPSOA-BQYQJAHWSA-N 1-methyl-4-[(e)-2-phenylethenyl]pyridin-1-ium Chemical compound C1=C[N+](C)=CC=C1\C=C\C1=CC=CC=C1 YVXDRFYHWWPSOA-BQYQJAHWSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241001089723 Metaphycus omega Species 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000021120 animal protein Nutrition 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/18—Diazo-type processes, e.g. thermal development, or agents therefor
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optical Filters (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Liquid Crystal (AREA)
- Color Television Image Signal Generators (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は特に多色電気光学表示装置用電極基板の着色
画素形成に用いられる少なくとも顔料および不溶性染
料、高誘電体、導電体等の粉末が分散されて成る感光性
樹脂の現像法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention particularly relates to a method of forming at least a pigment and an insoluble dye, a powder of a high dielectric substance, a conductor and the like used for forming a colored pixel of an electrode substrate for a multicolor electro-optical display device. The present invention relates to a method for developing a dispersed photosensitive resin.
近年家庭用カラービデオカメラに対する関心が急速に
高まりつつある。In recent years, interest in home color video cameras has been rapidly increasing.
家庭用ビデオカメラは小型であること、軽量であるこ
と、そして、高価でないことが要求されており、このた
め、色相が異なる２種または３種以上の極めて微細なス
トライプが透明基板上に設けられたカラーフィルターを
撮像管に接着した単管式カラービデオカメラが用いられ
ている。また同様の目的でカラービデオカメラの固体撮
像素子の受光面上に直接密着するようにしてカラーフィ
ルターを設けた固体撮像式カラービデオカメラも提案さ
れている。Home video cameras are required to be small, lightweight, and inexpensive. For this reason, two or three or more very fine stripes having different hues are provided on a transparent substrate. A single-tube color video camera in which a color filter is adhered to an image pickup tube is used. For the same purpose, a solid-state imaging type color video camera provided with a color filter so as to be in close contact with a light receiving surface of a solid-state imaging device of a color video camera has also been proposed.
更に光電変換素子であるラインセンサ、エリアセンサ
ーなどの固体撮像素子の受光面に直接あるいは、間接的
に色分離フィルターを形成する方式も提案されている。
固体撮像素子としては、CCD,MOS,CID,CPDなどが用いら
れている。Further, there has been proposed a system in which a color separation filter is formed directly or indirectly on a light receiving surface of a solid-state imaging device such as a line sensor or an area sensor which is a photoelectric conversion device.
CCD, MOS, CID, CPD and the like are used as the solid-state imaging device.
また、液晶表示装置においても、表示される画像のカ
ラー化に対する関心が高まっており、そのための１つの
方法として、平行な一対の透明電極間に液晶材料を封入
し、透明電極を不連続な微細区域に分割するとともに、
この透明電極上の微細区域にそれぞれ赤、緑、青のいず
れか１色から選ばれたカラーを交互にパターン状に設け
る方式あるいは、基板上にカラーフィルターを形成した
後、透明電極を設ける方式が提案されている。このよう
にカラービデオカメラあるいは、カラー液晶表示装置な
どに用いられるカラーフィルターは、色相の異なる２種
または、３種以上の色に着色された極めて微細な領域を
透明基板あるいは、固体撮像素子上に設けることによっ
て形成されている。Also in liquid crystal display devices, interest in colorization of displayed images has been increasing. One method for that is to fill a liquid crystal material between a pair of parallel transparent electrodes and to form the transparent electrodes with discontinuous fineness. While dividing into areas,
A method of alternately providing a color selected from any one of red, green, and blue in a fine pattern on the transparent electrode in a pattern, or a method of forming a color filter on a substrate and then providing a transparent electrode. Proposed. As described above, a color filter used in a color video camera or a color liquid crystal display device has an extremely fine area colored in two or three or more different colors on a transparent substrate or a solid-state image sensor. It is formed by providing.
而して微細な領域を色相の異なる２種または３種以上
の色を着色するにはさまざまな方式が提案されている。Various schemes have been proposed for coloring a fine region with two or three or more colors having different hues.
例えば光の散乱による光透過率の低下を抑えられる所
定粒径分布を有する顔料を樹脂中に分散せしめた感光性
樹脂組成物を用いて着色画像を形成する方式が有る。For example, there is a method of forming a colored image using a photosensitive resin composition in which a pigment having a predetermined particle size distribution capable of suppressing a decrease in light transmittance due to light scattering is dispersed in a resin.
このような感光性樹脂組成物を用い、写真製版法によ
り形成した着色画像は旧来から行なわれてきた、感光性
樹脂を用いて写真製版法により、被染色層を形成したの
ち、該被染色層を染料を用いて所定の色に染色する染色
法による着色画像と比べ画質的に均一でかつ、感光性樹
脂層中に分散する色料が顔料であるが故に、物性面にお
いて優れているという特色を有する。Using such a photosensitive resin composition, a colored image formed by a photoengraving method has been used for a long time. After forming a layer to be dyed by a photoengraving method using a photosensitive resin, the dyed layer is formed. Is characterized by being uniform in image quality compared to a colored image by a dyeing method of dyeing a predetermined color using a dye, and being excellent in physical properties because the colorant dispersed in the photosensitive resin layer is a pigment. Having.
さらに旧来の染色法による着色画像に比べ、工程上で
は染色工程及び防染工程が省けるので、価格面・製品信
頼性の面で有利である。Further, compared to the colored image obtained by the conventional dyeing method, the dyeing step and the anti-dyeing step can be omitted in the process, which is advantageous in terms of price and product reliability.
一方、耐熱絶縁物、例えばガラス−エポキシ、ベーク
ライト、ポリエーテルスルホン、ポリイミド、或は種々
のセラミックス上に導電体粉末を分散させた感光性樹脂
を用いて、製版し、微細回路を形成する試みを行なわれ
ている。現在耐熱絶縁物上に回路形成する場合、予め、
銅箔を貼り付け、シルクスクリーン等による印刷でレジ
ストパターンを形成するか、または感光性樹脂を用い
て、製版し、レジストパターンを形成し、エッチングに
より余分な部分を除去する方法で行なわれている。この
方法では、レジストパターンの形成工程及びエッチング
工程が有るため工程数が多く低価格化への対応が難し
い。また、印刷でレジスト形成を行なう場合、その限界
精度が100μｍ程度であるため、100μ以下の精度を得る
用途には適用できない。On the other hand, plate-making is performed using a heat-resistant insulating material such as glass-epoxy, bakelite, polyethersulfone, polyimide, or a photosensitive resin in which conductive powder is dispersed on various ceramics, and an attempt is made to form a fine circuit. Is being done. At present, when forming circuits on heat-resistant insulation,
This method is performed by attaching a copper foil and forming a resist pattern by printing with a silk screen or the like, or making a plate using a photosensitive resin, forming a resist pattern, and removing an excess portion by etching. . In this method, since there are a resist pattern forming step and an etching step, the number of steps is large and it is difficult to cope with cost reduction. Further, when a resist is formed by printing, since the limit accuracy is about 100 μm, it cannot be applied to an application to obtain an accuracy of 100 μm or less.
近年、導電体を分散させた感光性樹脂を製版すること
により、微細回路や高誘電体を含む着色画像を形成する
ことが提案されている。In recent years, it has been proposed to form a colored image including a fine circuit and a high dielectric substance by making a plate of a photosensitive resin in which a conductor is dispersed.
しかしながら、微粒子を分散させた感光性樹脂を所定
の条件で製版してカラーフィルターや微細回路を得よう
とする非画線部に、微粒子が残存し、カラーフィルター
に関しては、非画線領域の微粒子残存部分が着色し、非
画線部の透過率が低下せしめられたり、或は微細回路に
関しては、非画線領域の導電粉末が短絡トラブルを生ぜ
しめることがある。However, fine particles remain in the non-image area where the photosensitive resin in which the fine particles are dispersed is subjected to plate making under predetermined conditions to obtain a color filter or a fine circuit. The remaining portion may be colored and the transmittance of the non-image area may be reduced, or in the case of a fine circuit, the conductive powder in the non-image area may cause a short circuit trouble.
基板に付着している非画線部微粒子は、比較的弱い力
で吸着しているので、物理的に除去する方法としては、
例えば、現像後柔かな布で払拭したり、更には指で軽く
擦る簡単な方法が考えられる。Since the non-image area fine particles adhering to the substrate are adsorbed by a relatively weak force, as a method of physically removing,
For example, a simple method of wiping with a soft cloth after development and further rubbing lightly with a finger can be considered.
しかしながら、カラーフィルターや微細回路の様に精
密なパターンにおいては、すべてのエリア内の非画線部
の微粒子を完全に払拭する事は不可能に近い。又量産
性、信頼性の面からも不十分な方法といえる。However, in a precise pattern such as a color filter or a fine circuit, it is almost impossible to completely remove the fine particles in the non-image area in all the areas. In addition, it can be said that this method is insufficient in terms of mass productivity and reliability.
本発明は非画線部に微粒子を残存せしめることなく高
精度に感光性樹脂製版する方法を提供するもので、第１
の発明は 粒径10μｍ以下で且つ平均粒径１μｍ以下の、顔料、不
溶性染料の微粒子が分散せしめられた、或いは粒径10μ
ｍ以下で且つ平均粒径１μｍ以下の高誘電体、導電体の
微粒子が分散せしめられた感光性樹脂組成物を基板上に
塗布するに際して、感光性樹脂または基板に密着性向上
処理を施しておき、この感光性樹脂組成物を基板上に塗
布して感光性樹脂層を形成しパターンの焼付けを行った
のち、二流体微噴霧ノズルを用いて気圧を0.7〜7.0Kgf/
cm2、液圧を0.7〜4.0Kgf/cm2に調整して、現像液をスプ
レーして現像することを特徴とする感光性樹脂層の形成
法。を要旨とするものであり、第２の発明は 『粒径10μｍ以下で且つ平均粒径１μｍ以下の、顔料、
不溶性染料の微粒子が分散せしめられた、或いは粒径10
μｍ以下で且つ平均粒径１μｍ以下の高誘電体、導電体
の微粒子が分散せしめられた感光性樹脂組成物を基板上
に塗布するに際して、感光性樹脂または基板に密着性向
上処理を施しておき、この感光性樹脂組成物を基板上に
塗布して感光性樹脂層を形成しパターンの焼付けを行っ
たのち、一流体微噴霧ノズルを用いて液圧を0.5〜10.0K
gf/cm2に調整して、現像液をスプレーして現像すること
を特徴とする感光性樹脂層の形成法。』を要旨とするも
のである。The present invention provides a method for making a photosensitive resin plate with high accuracy without leaving fine particles in a non-image area.
The invention is characterized in that fine particles of pigments and insoluble dyes having a particle size of 10 μm or less and an average particle size of 1 μm or less are dispersed or have a particle size of 10 μm.
m or less and an average particle diameter of 1 μm or less, when a photosensitive resin composition in which fine particles of a high dielectric substance and a conductor are dispersed is applied on a substrate, the photosensitive resin or the substrate is subjected to an adhesion improving treatment. After applying the photosensitive resin composition on a substrate to form a photosensitive resin layer and baking the pattern, using a two-fluid fine spray nozzle to adjust the pressure to 0.7 to 7.0 kgf /
cm 2, by adjusting the hydraulic pressure 0.7~4.0Kgf / cm 2, the method of forming the photosensitive resin layer, characterized by developing by spraying a developing solution. The second invention is “a pigment having a particle size of 10 μm or less and an average particle size of 1 μm or less,
Fine particles of insoluble dye dispersed or particle size 10
When applying a photosensitive resin composition in which fine particles of a high dielectric substance and an electric conductor having an average particle diameter of 1 μm or less are dispersed on a substrate, the photosensitive resin or the substrate is subjected to an adhesion improving treatment. After applying the photosensitive resin composition on a substrate to form a photosensitive resin layer and baking a pattern, using a one-fluid fine spray nozzle to adjust the liquid pressure to 0.5 to 10.0K
A method for forming a photosensitive resin layer, which comprises adjusting the gf / cm 2 and spraying a developer to perform development. ].
而して本発明において、感光性樹脂材料として、ゼラ
チン、カゼイン、グリューなどの動物性タンパク質系と
重クロム酸塩、クロム酸塩、ジアゾ化合物、ビスアジド
化合物を光架橋剤としたもの、ポリビニルアルコール／
スチルバゾリウム系の感光基を有する水溶性感光性樹脂
を用いることができる。Thus, in the present invention, as a photosensitive resin material, an animal protein system such as gelatin, casein, glue and the like, a bichromate, a chromate, a diazo compound, a bisazide compound as a photocrosslinking agent, polyvinyl alcohol /
A water-soluble photosensitive resin having a stilbazolium-based photosensitive group can be used.
画線部を強固にするためには、加熱等により感光性樹
脂溶媒を完全に除去し、露光は解像度低下が起こらない
範囲で十分に照射する必要がある。In order to strengthen the image area, it is necessary to completely remove the photosensitive resin solvent by heating or the like, and to sufficiently irradiate the exposure within a range where the resolution does not decrease.
次に感光性樹脂の基板への密着性を向上させるために
は、基板を表面処理（例えばUV-O3処理、シランカップ
ラー塗布、プライマー等の塗布）を行なったり、或は感
光性樹脂にシランカップラー等の密着性向上剤を0.1〜
１％添加すれば良い。Next, in order to improve the adhesion of the photosensitive resin to the substrate, the substrate is subjected to a surface treatment (for example, UV-O 3 treatment, silane coupler application, application of a primer or the like), or silane is applied to the photosensitive resin. 0.1 to less adhesion improver such as coupler
What is necessary is just to add 1%.
微粒子除去のために適したノズルは、スプレーパター
ン別に分類すると円環型ノズル、円形全面型ノズル、及
び扇型ノズルがあり、更に、流体別に、液体のみを扱っ
た一流体噴霧ノズルと、液体と気体を混合させる二流体
微噴霧ノズルとがある。ノズルは均一性、基板の大き
さ、経済性等を多角的に検討して最適なものを選定すれ
ば良い。Nozzles suitable for removing fine particles include annular nozzles, circular full-surface nozzles, and fan-shaped nozzles when classified by spray pattern.Furthermore, for each fluid, a one-fluid spray nozzle that handles only liquid, There is a two-fluid fine spray nozzle for mixing gas. The optimum nozzle may be selected by considering the uniformity, the size of the substrate, the economic efficiency, and the like from various viewpoints.
次に本発明において、二流体微噴霧ノズルを用いる場
合において、噴霧する気体の気圧を0.7〜7.0Kg f/cm2、
液体の液圧を0.7〜4.0Kg f/cm2に調整することが必要で
ある。この調整範囲の下限以下のときは微粒子の除去を
十分に行なうことができない。Next, in the present invention, when a two-fluid fine spray nozzle is used, the pressure of the gas to be sprayed is 0.7 to 7.0 kgf / cm 2 ,
It is necessary to adjust the liquid pressure of the liquid to 0.7 to 4.0 kg f / cm 2 . If it is below the lower limit of the adjustment range, the removal of fine particles cannot be performed sufficiently.
一方、上記調整範囲の上限以上のときは感光性樹脂膜
が剥離もしくは損傷せしめられる恐れがある。On the other hand, when it is above the upper limit of the adjustment range, the photosensitive resin film may be peeled or damaged.
次に一流体噴霧ノズルによる場合において、液圧は0.
5〜10.0Kg f/cm2に調整することが必要である。この調
整範囲の下限以下のときは微粒子の除去を十分に行なう
ことができない。一方、調整範囲の上限以上のときは感
光性樹脂膜が剥離もしくは損傷せしめられる恐れがあ
る。Next, in the case of a single fluid spray nozzle, the hydraulic pressure is 0.
It is necessary to adjust to 5 to 10.0 kg f / cm 2 . If it is below the lower limit of the adjustment range, the removal of fine particles cannot be performed sufficiently. On the other hand, when it is above the upper limit of the adjustment range, the photosensitive resin film may be peeled or damaged.
尚、スプレーの圧力による微粒子の除去速度依存性が
あるので、スプレーの圧力を均一にすることが必要であ
る。Note that the spray pressure depends on the removal speed of the fine particles, so it is necessary to make the spray pressure uniform.
非画線部に残存付着している微粒子は弱い力で吸着し
ているためにスプレーによる圧力により画線部を損うこ
となく非画線部に残存する微粒子を選択的に除去するこ
とができる。Fine particles remaining on the non-image area are adsorbed by a weak force, so that fine particles remaining on the non-image area can be selectively removed without damaging the image area by the pressure of the spray. .
実施例１ コーニング社7059材の４″φガラス基板にITOを2000
Å蒸着し、これを１％Ｒ・Ｂ・Ｓ洗浄液（純正化学
（株））に５分間攪拌しつつ浸漬し水洗した。以下の透
明着色感光性樹脂に1w.t.％のシランカップラー（sz630
0 トーレシリコーン（株））を添加した。Example 1 2000 ITO on 4 ″ φ glass substrate of Corning 7059
(5) Vapor deposition was performed, and the resultant was immersed in a 1% R, B, and S cleaning solution (Junsei Chemical Co., Ltd.) for 5 minutes while stirring, and washed with water. 1w.t.% of silane coupler (sz630
0 Toray Silicone Co., Ltd.).
この透明着色感光性樹脂を１μｍ以上の粒子をカット
して上記ガラス基板に回転塗布した。塗布条件は2000rp
mであった。This transparent colored photosensitive resin was cut into particles of 1 μm or more and spin-coated on the glass substrate. Application condition is 2000rp
m.
直ちに120℃にて50分間乾燥後、超高圧水銀ランプで
露光した。条件は赤と青の透明着色感光性樹脂について
は、50秒、緑は１分間照射した。このときの照度は13mW
/cm2だった。使用したパターンは、50μｍ□の格子状パ
ターンだった。 Immediately after drying at 120 ° C. for 50 minutes, exposure was performed with an ultra-high pressure mercury lamp. The conditions were such that the transparent colored photosensitive resin of red and blue was irradiated for 50 seconds and the green was irradiated for 1 minute. The illuminance at this time is 13mW
/ it was cm 2. The pattern used was a 50 μm square lattice pattern.
現像は第１図図示のような装置で行った。尚、当該図
において、（１）はスプレー装置本体、（２）は液体ノ
ズル、（３）は気体ノズル、（４）は感光性樹脂層を設
けた基板を示す。The development was carried out using an apparatus as shown in FIG. In this figure, (1) shows a spray device main body, (2) shows a liquid nozzle, (3) shows a gas nozzle, and (4) shows a substrate provided with a photosensitive resin layer.
スプレーノズルはスプレーイングシステムジャパン
（株）の二流体微噴霧ノズル（スプレー装置番号22）を
使用し、スプレー−基板間の距離を130mmに保ち、基板
は400rpmで回転させながら、室温の水を水圧2.0Kgf/c
m2、窒素の圧力を3.0Kgf/cm2現像を行った。尚、この
時、比較例として室温の水に45秒間浸漬法で現像も行っ
た。The spray nozzle uses a two-fluid fine spray nozzle (spray device No. 22) of Spraying System Japan Co., Ltd., keeping the distance between the spray and the substrate at 130 mm. 2.0Kgf / c
The development was carried out at 3.0 kgf / cm 2 with m 2 and nitrogen pressure. At this time, as a comparative example, development was also performed by immersion in water at room temperature for 45 seconds.
浸漬法で現像を行なった物については、現像できず、
未露光部がわずかに膨潤しただけであった。About the thing developed by the immersion method, it cannot be developed,
The unexposed areas only swelled slightly.
一方、スプレー方式では、完全にパターン形成でき、非
画線部の透過率は、透明着色感光性樹脂塗布前のITO付
ガラス基板を100％とした場合、各色のボトム透過率は
中心点で赤が96％、緑が96％、青が98％だった。On the other hand, in the spray method, the pattern can be completely formed, and the transmittance of the non-image area is 100% for the glass substrate with ITO before applying the transparent colored photosensitive resin, and the bottom transmittance of each color is red at the center point. 96%, green 96% and blue 98%.
実施例２ 住友ベークライト（株）製100μｍポリサルホンフィ
ルム（200mm×1000mm）に、導電体を分散させた感光性
樹脂をロールコーター（送り速度1m/mm）で塗布した。Example 2 A 100 μm polysulfone film (200 mm × 1000 mm) manufactured by Sumitomo Bakelite Co., Ltd. was coated with a photosensitive resin in which a conductor was dispersed by a roll coater (feed rate: 1 m / mm).
導電体を分散させた感光性樹脂の組成は以下の通りであ
る。The composition of the photosensitive resin in which the conductor is dispersed is as follows.
尚、この感光性樹脂は10,000rpmで遠心分離の後、5.0μ
ｍメンフランフィルターで過した。 In addition, this photosensitive resin was centrifuged at 10,000 rpm,
m passed through a membrane filter.
これを90℃にて30分間乾燥させた。この時の膜厚は約
25μｍだった。2KWメタルハロゲンランプ、1mの距離に
て、所望パターンを３分密着露光し、スプレーによる現
像およびフロー現像を行なった。This was dried at 90 ° C. for 30 minutes. The film thickness at this time is about
It was 25 μm. The desired pattern was contact-exposed for 3 minutes at a distance of 1 m with a 2 KW metal halogen lamp, and development by spraying and flow development were performed.
スプレーによる現像法は、以下のとうりである。 The developing method by spraying is as follows.
スプレーノズルは、スプレーイングシステムジャパン
（株）製二流体微噴霧ノズル（スプレー装置番号43）を
用い、気体は5.0Kg f/cm2の圧縮空気、液体は、4.0Kg f
/cm2の水を混合して、スプレーの圧力を得た。現像装置
は第３図の様な装置を用いた。尚、図において、（11）
はスプレー装置本体、（12）は液体ノズル、（13）は気
体ノズル、（10）は感光性樹脂層を設けた基板を示す。
第３図示のような装置を用い、フィルムから100mmの所
にスプレー装置を位置させ、現像時間は、ベルトの送り
速度で決める。この時の送り速度は0.5（m/分）とし
た。The spray nozzle used was a two-fluid fine spray nozzle manufactured by Spraying System Japan Co., Ltd. (spray device No. 43). The gas was 5.0 kgf / cm 2 of compressed air, and the liquid was 4.0 kgf.
/ cm 2 of water was mixed to obtain the spray pressure. The developing device used was as shown in FIG. In the figure, (11)
Denotes a spray device main body, (12) denotes a liquid nozzle, (13) denotes a gas nozzle, and (10) denotes a substrate provided with a photosensitive resin layer.
Using a device as shown in FIG. 3, a spray device is positioned at a position 100 mm from the film, and the developing time is determined by the feed speed of the belt. The feed speed at this time was 0.5 (m / min).
フロー現像は内径10mmφのパイプで、１（l/分）で室
温の水を送ったパイプはスプレーの位置に装着し、基板
より100mmの距離より水を落下させた。In the flow development, a pipe having an inner diameter of 10 mmφ and sending water at room temperature at 1 (l / min) was attached to a spray position, and water was dropped from a distance of 100 mm from the substrate.
フロー現像を行なったものは、外観レベルでは80μｍ
ライン＆スペースの解像性が得られた。フィルムの長辺
の両端部付近の電極間抵抗を計測したところ、数ＫΩ／
cm2台になった部分が有り、このままでは実用に供しな
いレベルだった。80 µm at the appearance level after flow development
Line & space resolution was obtained. When the resistance between the electrodes near both ends of the long side of the film was measured, several KΩ /
There was a part that became 2 cm, and it was at a level that was not practical for use as it was.
一方、スプレーで現像を行なったものは目視レベル
で、30μｍライン＆スペースの解像性が得られた。更に
電極間抵抗を計測したが、すべて数ＭΩ／cm2以上で、
フレキシブルな微細電極基板が得られた。On the other hand, those developed by spraying exhibited a resolution of 30 μm line and space at the visual level. Was further measured interelectrode resistance but, in all number M.OMEGA. / Cm 2 or more,
A flexible fine electrode substrate was obtained.
上記工程は、エッチングプロセスを用いず、工程的に
簡略化した微細電極基板製作がスプレーによる現像で可
能になった例である。尚、派生的に、スプレーによる現
像の水の流量は0.3l/時で、フローに比べ1/3になり、節
水効果も認められた。The above process is an example in which a fine electrode substrate can be manufactured in a simplified manner by spraying without using an etching process. Incidentally, the flow rate of the developing water by spraying was 0.3 l / h, which was 1/3 of the flow rate, and a water saving effect was also recognized.
コーニング社7059材の４″φガラス基板を硫酸過酸化
水素から成る洗浄液に浸漬、十分に水洗の後、１μｍ以
上の粒子をカットした顔料を分散して成る、赤・緑・青
の透明着色感光性樹脂を回転塗布した。塗布条件は2000
rpmであった。Transparent red, green, and blue colored photosensitive material composed of a Corning 7059 4 ″ φ glass substrate immersed in a cleaning solution composed of sulfuric acid and hydrogen peroxide, thoroughly washed with water, and then dispersed with a pigment with particles of 1 μm or more cut off. Resin was applied by spin coating under the conditions of 2000
rpm.
直ちに120℃にて50分間乾燥し、塗布膜厚を測定した
ところ、赤が1.02μｍ、緑が0.95μｍ、青が0.99μｍだ
った。Immediately after drying at 120 ° C. for 50 minutes, the coating film thickness was measured. As a result, red was 1.02 μm, green was 0.95 μm, and blue was 0.99 μm.
これらを超高圧水銀ランプで露光した。条件は赤と青
の透明着色感光性樹脂については、50秒間、緑は１分間
照射した。この時の照度は13mW/cm2だった。使用したパ
ターンは、50μｍ□の格子状パターンだった。These were exposed with an ultra-high pressure mercury lamp. The conditions were such that the transparent colored photosensitive resin of red and blue was irradiated for 50 seconds and the green was irradiated for 1 minute. The illuminance at this time was 13 mW / cm 2 . The pattern used was a 50 μm square lattice pattern.
現像は第１図図示のような装置で行った。尚、当該図
において、（１）はスプレー装置本体、（２）は液体ノ
ズル、（３）は気体ノズル、（４）は感光性樹脂層を設
けた基板を示す。The development was carried out using an apparatus as shown in FIG. In this figure, (1) shows a spray device main body, (2) shows a liquid nozzle, (3) shows a gas nozzle, and (4) shows a substrate provided with a photosensitive resin layer.
スプレーノズルはスプレーイングシステムスジャパン
（株）の二流体微噴霧ノズル（スプレー装置番号22）を
使用し、スプレー−基板間の距離を130mmに保ち、基板
は400rpmで回転させながら80秒間現像を行った。The spray nozzle uses a two-fluid fine spray nozzle (spray device No. 22) of Spraying Systems Japan Co., Ltd., keeping the distance between the spray and the substrate at 130 mm, and developing the substrate for 80 seconds while rotating at 400 rpm. Was.
二流体のうち気体側は3.0（Kgf/cm2）の窒素を用い、
液体側は、室温の水を1.7、2.0、2.3、2.7（Kgf/cm2）
でギヤーポンプにより圧送した。また比較用として、室
温の水の中で45秒間浸漬現像も行った。The gas side of the two fluids uses 3.0 (Kgf / cm 2 ) nitrogen,
On the liquid side, 1.7, 2.0, 2.3, 2.7 (Kgf / cm 2 ) of room temperature water
And pumped by a gear pump. For comparison, immersion development was performed in water at room temperature for 45 seconds.
現像後、170℃にて60分間ベーキングを施し、膜厚を
測定したところ、赤0.97μｍ、緑が0.91μｍ、青が0.96
μｍで膜減りは、５％以内だった。After development, baking was performed at 170 ° C. for 60 minutes, and when the film thickness was measured, red was 0.97 μm, green was 0.91 μm, and blue was 0.96 μm.
At μm, the film loss was within 5%.
尚、赤・緑・青の透明着色感光性樹脂の組成は以下の
通りである。The composition of the red / green / blue transparent colored photosensitive resin is as follows.
第２図は緑色の透明着色感光性樹脂により製版したも
のの非画線部の透過率を示す。図において（５）は浸漬
法による現像時の非画線部透過率、（６）は水圧1.7Kgf
/cm2でスプレー現像したときの650nmの非画線部透過
率、（７）は水圧2.0Kgf/cm2でスプレー現像したときの
650nmの非画線部透過率、（８）は水圧2.3Kgf/cm2でス
プレー現像したときの650nmの非画線部透過率、（９）
は水圧2.7Kgf/cm2でスプレー現像したときの650nmの非
画線部透過率を示す。浸漬法で行ったものはボトム値85
％程度で、非画線部が着色されている様子が判る。それ
に対して水圧を上げてスプレー現像したときはボトム透
過率は中心点で90％を示した。同様に赤、及び青につい
ても、水圧を上げてスプレー現像したとき、ボトム透過
率は中心点で赤は90％、青は99％を示した。 FIG. 2 shows the transmittance of the non-image area of a plate made with a green transparent colored photosensitive resin. In the figure, (5) is the transmittance of the non-image area during development by the immersion method, and (6) is the water pressure of 1.7 kgf.
non-image area transmittance at 650 nm when spray-developed at / cm 2 , (7) is the value when spray-developed at 2.0 kgf / cm 2 water pressure
650 nm non-image area transmittance, (8) is 650 nm non-image area transmittance when spray-developed at a water pressure of 2.3 kgf / cm 2 , (9)
Indicates the non-image area transmittance at 650 nm when spray-developed at a water pressure of 2.7 kgf / cm 2 . Bottom value is 85 for immersion method
%, It can be seen that the non-image area is colored. On the other hand, when the water pressure was increased and spray development was performed, the bottom transmittance showed 90% at the center point. Similarly, when red and blue were spray-developed with increasing water pressure, the bottom transmittance at the center point was 90% for red and 99% for blue.
以上詳記した通り、本発明によれば、感光性樹脂の現
像とともに非画線部の微粒子の除去を行なうことができ
る。As described above in detail, according to the present invention, it is possible to remove the fine particles in the non-image area while developing the photosensitive resin.
第１図は現像機の模式図、第２図は緑色の透明着色感光
性樹脂を現像した後の非画線部透過率を示すグラフ、第
３図は基板移動式の現像機の模式図である。FIG. 1 is a schematic diagram of a developing machine, FIG. 2 is a graph showing transmittance of a non-image area after developing a green transparent colored photosensitive resin, and FIG. 3 is a schematic diagram of a developing machine of a substrate moving type. is there.
Claims (2)
の、顔料、不溶性染料の微粒子が分散せしめられた、或
いは粒径10μｍ以下で且つ平均粒径１μｍ以下の高誘電
体、導電体の微粒子が分散せしめられた感光性樹脂組成
物を基板上に塗布するに際して、感光性樹脂または基板
に密着性向上処理を施しておき、この感光性樹脂組成物
を基板上に塗布して感光性樹脂層を形成しパターンの焼
付けを行ったのち、二流体微噴霧ノズルを用いて気圧を
0.7〜7.0Kgf/cm2、液圧を0.7〜4.0Kgf/cm2に調整して、
現像液をスプレーして現像することを特徴とする感光性
樹脂層の形成法。1. A high dielectric or conductive material having a particle diameter of 10 μm or less and an average particle diameter of 1 μm or less, in which fine particles of a pigment or an insoluble dye are dispersed, or a particle diameter of 10 μm or less and an average particle diameter of 1 μm or less. When applying the photosensitive resin composition in which the fine particles are dispersed on a substrate, the photosensitive resin or the substrate is subjected to an adhesion improving treatment, and the photosensitive resin composition is applied on the substrate to form a photosensitive resin. After forming a layer and printing the pattern, the air pressure is increased using a two-fluid fine spray nozzle.
0.7~7.0Kgf / cm 2, to adjust the hydraulic pressure in 0.7~4.0Kgf / cm 2,
A method for forming a photosensitive resin layer, which comprises developing by spraying a developer.
の、顔料、不溶性染料の微粒子が分散せしめられた、或
いは粒径10μｍ以下で且つ平均粒径１μｍ以下の高誘電
体、導電体の微粒子が分散せしめられた感光性樹脂組成
物を基板上に塗布するに際して、感光性樹脂または基板
に密着性向上処理を施しておき、この感光性樹脂組成物
を基板上に塗布して感光性樹脂層を形成しパターンの焼
付けを行ったのち、一流体微噴霧ノズルを用いて液圧を
0.5〜10.0Kgf/cm2に調整して、現像液をスプレーして現
像することを特徴とする感光性樹脂層の形成法。2. A method of dispersing fine particles of a pigment or an insoluble dye having a particle size of 10 μm or less and an average particle size of 1 μm or less, or a high dielectric or conductive material having a particle size of 10 μm or less and an average particle size of 1 μm or less. When applying the photosensitive resin composition in which the fine particles are dispersed on a substrate, the photosensitive resin or the substrate is subjected to an adhesion improving treatment, and the photosensitive resin composition is applied on the substrate to form a photosensitive resin. After the layer is formed and the pattern is baked, the fluid pressure is reduced using a one-fluid fine spray nozzle.
A method for forming a photosensitive resin layer, comprising adjusting to 0.5 to 10.0 kgf / cm 2 and spraying a developing solution to perform development.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15566486A JP2646205B2 (en) | 1986-07-02 | 1986-07-02 | Method of forming photosensitive resin layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15566486A JP2646205B2 (en) | 1986-07-02 | 1986-07-02 | Method of forming photosensitive resin layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6310157A JPS6310157A (en) | 1988-01-16 |
| JP2646205B2 true JP2646205B2 (en) | 1997-08-27 |
Family
ID=15610892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15566486A Expired - Fee Related JP2646205B2 (en) | 1986-07-02 | 1986-07-02 | Method of forming photosensitive resin layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2646205B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2627018B2 (en) * | 1990-09-12 | 1997-07-02 | 富士写真フイルム株式会社 | Plate making method of waterless lithographic printing plate |
| US5443942A (en) * | 1990-11-28 | 1995-08-22 | Canon Kabushiki Kaisha | Process for removing resist |
| JP5153332B2 (en) * | 2005-07-04 | 2013-02-27 | 株式会社 エルフォテック | Method and apparatus for forming high definition pattern |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3937175A (en) * | 1973-12-26 | 1976-02-10 | American Hoechst Corporation | Pulsed spray of fluids |
| US3953265A (en) * | 1975-04-28 | 1976-04-27 | International Business Machines Corporation | Meniscus-contained method of handling fluids in the manufacture of semiconductor wafers |
| JPS57208135A (en) * | 1981-06-18 | 1982-12-21 | Fujitsu Ltd | Spray type resist developing apparatus |
| JPS60129707A (en) * | 1983-12-16 | 1985-07-11 | Agency Of Ind Science & Technol | Color filter |
-
1986
- 1986-07-02 JP JP15566486A patent/JP2646205B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6310157A (en) | 1988-01-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |