JPH02173007A - Photopolymer, photosensitive composition containing the same and formation of pattern by using the same composition - Google Patents
Photopolymer, photosensitive composition containing the same and formation of pattern by using the same compositionInfo
- Publication number
- JPH02173007A JPH02173007A JP32578588A JP32578588A JPH02173007A JP H02173007 A JPH02173007 A JP H02173007A JP 32578588 A JP32578588 A JP 32578588A JP 32578588 A JP32578588 A JP 32578588A JP H02173007 A JPH02173007 A JP H02173007A
- Authority
- JP
- Japan
- Prior art keywords
- pattern
- polymer compound
- photosensitive
- compound
- water
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- -1 azido aldehyde compound Chemical class 0.000 claims abstract description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- KWEXHDOBZQSNGR-UHFFFAOYSA-N CC(C)=O.CC(C)=O.NC(=O)C=C.NC(=O)C=C Chemical compound CC(C)=O.CC(C)=O.NC(=O)C=C.NC(=O)C=C KWEXHDOBZQSNGR-UHFFFAOYSA-N 0.000 claims description 5
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 5
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims 1
- 229920003169 water-soluble polymer Polymers 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- 229920002401 polyacrylamide Polymers 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- 238000006277 sulfonation reaction Methods 0.000 abstract description 2
- 230000000397 acetylating effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
Description
本発明は、感光性高分子化合物および組成物。
ならびにそれを用いたパターン形成法に係り、特にカラ
ーブラウン管の製造に用で好適な水溶性感光性組成物お
よびそれを用いたパターン形成法に関する。The present invention relates to photosensitive polymer compounds and compositions. The present invention also relates to a water-soluble photosensitive composition suitable for manufacturing color cathode ray tubes, and a pattern forming method using the same.
従来のパターン形成法の一例として、特開昭４８−９０
Ｌ ８５．特開昭５０−３３７６４にはカラーブラウ
ン管のブッラクマトリックスの製造方法およびこれに用
いる感光性組成物が記載されている。この方法は、相反
則不軌特性を有する感光性組成物、例えばアクリルアミ
ド−ジアセトンアクリルアミド共重合体等の高分子化合
物とビスアジド系架橋剤とからなる組成物を用いて光照
射区域より実質的に小面積のパターンを形成する方法で
ある。
これについて詳しく説明する。ブラックマトリックス型
カラーブラウン管は、パネル内面に赤、青、緑の蛍光体
ドツト又はストライプ等の蛍光体パターンを有し、その
間の空隙をカーボン等の非発光性光吸収性物質で埋めた
構造を有する。
以下、説明の便宜のためドツトの場合について。
その製造方法を述べる。
まずカラーブラウン管フェースプレート内面に、前記相
反則不軌特性を有する感光性組成物の塗膜を形成し、蛍
光体ドツトを形成する位置をシャドウマスクを介して露
光し、現像して感光性組成物のドツトを形成する。この
上にカーボンを塗布し。
ドツトを剥離液でその上のカーボンと共に除去する。か
くてブラックマトツリクスのホールが形成される。この
ホールに順次赤、青、緑の蛍光体ドツトを形成する。
相反則不軌特性を有する感光性組成物を用いているため
に、上記感光性組成物のドツトの面積、すなはち蛍光体
ドツトの面積は、シャドウマスクを介して光照射された
面積より実質的に小さい。
従ってこのシャドウマスを用いてカラーブラウン管を完
成すれば、上記シャドウマスクの穴を通って照射される
電子ビームの直径は、蛍光ドツトのそれより大きい、そ
れ故、製造したカラーブラウン管は明るく、コントラス
トに優れている。As an example of a conventional pattern forming method, Japanese Patent Application Laid-Open No. 48-90
L 85. JP-A-50-33764 describes a method for producing a black matrix for a color cathode ray tube and a photosensitive composition used therein. This method uses a photosensitive composition having reciprocity law failure characteristics, for example, a composition consisting of a polymer compound such as an acrylamide-diacetone acrylamide copolymer and a bisazide crosslinking agent, and uses a photosensitive composition that is substantially smaller than the light irradiated area. This is a method of forming an area pattern. This will be explained in detail. A black matrix color cathode ray tube has a phosphor pattern such as red, blue, and green phosphor dots or stripes on the inner surface of the panel, and has a structure in which the gaps between them are filled with a non-luminous light-absorbing substance such as carbon. . Below, for convenience of explanation, we will discuss the case of dots. The manufacturing method will be described below. First, a coating film of a photosensitive composition having the reciprocity law failure characteristic described above is formed on the inner surface of a color cathode ray tube face plate, and the positions where phosphor dots are to be formed are exposed to light through a shadow mask and developed to coat the photosensitive composition. Form a dot. Apply carbon on top of this. Remove the dots with a stripping solution along with the carbon on them. Thus, the hole of black matothrix is formed. Red, blue, and green phosphor dots are sequentially formed in this hole. Since a photosensitive composition having reciprocity law failure characteristics is used, the area of the dots of the photosensitive composition, that is, the area of the phosphor dots, is substantially larger than the area irradiated with light through the shadow mask. small. Therefore, if a color cathode ray tube is completed using this shadow mass, the diameter of the electron beam irradiated through the hole in the shadow mask will be larger than that of the fluorescent dot, so the manufactured color cathode ray tube will be bright and have a high contrast. Are better.
上記従来技術は、カラーブラウン管の大型化について配
慮されておらず、大型のカラーブラウン管製造の場合、
露光面が光源から離れるため露光面における照度が下が
り、露光に長時間を要するという問題があった。
本発明の目的は、高感度な感光性組成物およびそれを用
いたパターン形成法並びに放射線に高感度で感応する高
分子化合物を提供することにある。
さらに詳しく言えば、本発明の第１の目的はアジド基お
よび水溶性官能基を有するモノマー単位を少なくとも含
む高分子化合物を提供することにある。
また、第２の目的は、該感光性高分子化合物およびこれ
と反応して相反則不軌特性を示す水溶性高分子化合物か
らなる大型カラーブラウン管の製造に適した感光性組成
物を提供することにある。
第３の目的は、所望のパターンを形成しようとする面上
に、光照射区域より実質的に小さい面積のパターンを形
成するパターン形成方法を提供することにある。The above conventional technology does not take into consideration the enlargement of color cathode ray tubes, and when manufacturing large color cathode ray tubes,
Since the exposed surface is separated from the light source, the illuminance on the exposed surface decreases, resulting in a problem that exposure takes a long time. An object of the present invention is to provide a highly sensitive photosensitive composition, a pattern forming method using the same, and a polymer compound that is highly sensitive to radiation. More specifically, the first object of the present invention is to provide a polymer compound containing at least a monomer unit having an azide group and a water-soluble functional group. The second object is to provide a photosensitive composition suitable for manufacturing large-sized color cathode ray tubes, which is composed of the photosensitive polymer compound and a water-soluble polymer compound that reacts with the photosensitive polymer compound and exhibits reciprocity law failure characteristics. be. A third object is to provide a pattern forming method that forms a pattern on a surface on which a desired pattern is to be formed, the area of which is substantially smaller than the area irradiated with light.
本発明は上記目的を達成するために、感光性成分と水溶
性成分を高分子化合物中に導入した新規な感光性高分子
化合物を提供する。
共重合体において、２種類の七ツマ−を任意の比率で共
重合させることは困璽である。このため溶解性や感光性
などの点において特性上制約をうける。この点を解決す
るため１本発明においては単一モノマーを利用し、これ
に水溶性、感光性特性を持つように２種類の反応を順次
行なう、この場合、反応率は試薬量、反応条件で容易に
制御できる。
上記目的を達するうえで、感光性特性を出すためにはア
ジド基をもつ化合物を縮合させ、水溶性を出すためには
スルホン基を導入する。
上記縮合させるアジド化合物としては、４−アジドベン
ゼンアルデヒド−２−スルホン酸ナトリウム塩、４−ア
ジドシンナムアルデヒド−２−スルホン酸ナトリウム塩
などの芳香族アジドアルデヒド化合物が有効である。
また、水溶性を持たせるために高分子化合物のスルホン
化率は１０％以上であることが好ましい。
本発明の感光性組成物は、前述の如く上記高分子化合物
と、高分子化合物と反応して相反則不軌特性を示す水溶
性高分子化合物よりなる。両者の比率は、高分子化合物
の量が水溶性高分子化合物に対し１〜５０ｗｔ％の範囲
であることがより好ましく、５〜３０ｗｔ％の範囲であ
ることがより好ましい。
このような水溶性高分子化合物は、アークリルアミドー
ジアセトンアクリルアミド共重合体、ポリアクリルアミ
ド、ポリビニルピロリドン、ビニルピロリドン共重合体
等であり、塗膜としたとき０□透過性に優れるものが好
ましい。
本発明の感光性組成物は、上記水溶性高分子化合物と相
溶性を持つ他の水溶性高分子材料、例えばカルボキシメ
チルセルロース等を加えて用いることができる。これに
ついては前記の特開昭４８−９０１８５．特開昭５０−
３３７６４等に記載されている。
また、塗料としたときの特性の改良等のために、感光性
組成物にポリオキシエチレンアルキルエーテル等の界面
活性剤又はエチレングリコール等を加えること、基板と
の接着性改良のためにビニルトリス（β−メトキシエト
キシ）シラン等のカップリング剤を感光性組成物に加え
ることも前記の公報に記載されており、本発明の場合も
このような方法を用いることができる。
本発明のパターン形成方法は、気体の酸素の存在する条
件で露光を行なうことが必要である。またシュバルツシ
ルツ定数ｐの値がＯ＜ｐ ＜０．７６の範囲で露光する
ことが好ましいにこで、シュバルツシルツ定数と相反則
不軌特性については前記特開昭４８−９０１８５．特開
昭５０−３３７６４に記載されている。In order to achieve the above object, the present invention provides a novel photosensitive polymer compound in which a photosensitive component and a water-soluble component are introduced into the polymer compound. In copolymers, it is difficult to copolymerize two types of heptamers in arbitrary ratios. For this reason, they are subject to limitations in terms of properties such as solubility and photosensitivity. To solve this problem, the present invention uses a single monomer and sequentially performs two types of reactions to make it water-soluble and photosensitive.In this case, the reaction rate depends on the amount of reagents and reaction conditions. Easy to control. In order to achieve the above objectives, compounds having an azide group are condensed to provide photosensitive properties, and sulfone groups are introduced to provide water solubility. As the azide compound to be condensed, aromatic azido aldehyde compounds such as 4-azidobenzenaldehyde-2-sulfonic acid sodium salt and 4-azidocinnamaldehyde-2-sulfonic acid sodium salt are effective. Further, in order to provide water solubility, the sulfonation rate of the polymer compound is preferably 10% or more. As described above, the photosensitive composition of the present invention comprises the above-mentioned polymer compound and a water-soluble polymer compound that reacts with the polymer compound and exhibits reciprocity law failure characteristics. The ratio of the two is more preferably in the range of 1 to 50 wt%, and more preferably in the range of 5 to 30 wt%, based on the water-soluble polymer compound. Such water-soluble polymer compounds include acrylamide diacetone acrylamide copolymer, polyacrylamide, polyvinylpyrrolidone, vinylpyrrolidone copolymer, etc., and those having excellent 0□ permeability when formed into a coating film are preferred. The photosensitive composition of the present invention can be used in addition to other water-soluble polymer materials that are compatible with the above-mentioned water-soluble polymer compound, such as carboxymethyl cellulose. Regarding this, the above-mentioned Japanese Patent Application Laid-Open No. 48-90185. Japanese Patent Application Publication 1973-
33764 etc. Furthermore, in order to improve the properties when used as a paint, surfactants such as polyoxyethylene alkyl ether or ethylene glycol may be added to the photosensitive composition, and vinyl tris (β The above-mentioned publication also describes the addition of a coupling agent such as (methoxyethoxy)silane to the photosensitive composition, and such a method can also be used in the present invention. The pattern forming method of the present invention requires exposure to be performed under conditions where gaseous oxygen is present. Further, it is preferable to perform exposure in a range where the value of the Schwarzschild constant p is O<p<0.76.The Schwarzschild constant and the reciprocity law failure characteristic are described in the above-mentioned Japanese Patent Laid-Open No. 48-90185. It is described in Japanese Patent Application Laid-Open No. 50-33764.
本発明の高分子化合物は、超高圧水銀灯から発する励起
光の内、特に３６０ ｎｍ又は３６５止の波長の光をよ
く吸収する。またこの高分子化合物は、従来のビスアジ
ド化合物より高分子であり１分子中に多くのアジド基を
持つ。そのため同一の露光量において架橋点の数に対す
る架橋後の分子量の増加率が上がるので感光性組成物と
して高感度となる。さらに高分子化合物が水溶性基を有
するので水溶性である。The polymer compound of the present invention particularly well absorbs light having a wavelength of 360 nm or 365 nm out of the excitation light emitted from an ultra-high pressure mercury lamp. Furthermore, this polymer compound has a higher molecular weight than conventional bisazide compounds and has many azide groups in one molecule. Therefore, at the same exposure amount, the increase rate of the molecular weight after crosslinking with respect to the number of crosslinking points increases, resulting in high sensitivity as a photosensitive composition. Furthermore, since the polymer compound has a water-soluble group, it is water-soluble.
以下１本発明を実施例を用いて詳細に説明する。
実施例１
溶液ラジカル重合法で得たポリスチレン（平均分子量：
８０００） １０ ｇを二硫化炭素１００ ｍｌに溶
解した。この溶液を、無水塩化アルミニウム３０ ｇ、
二硫化炭素１００ ｍｌと塩化アセチル２０ ｇの溶解
した溶液に室温で攪拌しながら滴下した。その後加熱し
て２時間攪拌しながら還流させた。放冷した後、ろ別し
、不溶化物を乾燥した。これを粉末化した後、多量の氷
水で処理してよく水洗した後乾燥した。
上記で得たポリマー１０ｇにテトラクロロエタン２０
ｇを加え３０分間加熱した。放冷後、水冷しながらクロ
ルスルホン酸５０ ｇを徐々に加えて、室温で４時間攪
拌した。ついで塩化水素が発生しなくなるまで氷酢酸を
加え、多量の水中に注ぎ、不溶化物をろ別し、アセトン
、水で洗浄したのちＩＮ水酸化ナトリウム水溶液中で１
時間煮沸した。放冷後、塩化ナトリウムを加え高分子化
合物を塩析により析出させた。
つぎにこの高分子化合物１ｇ、４−アジドベンゼンアル
デヒド−２−スルホン酸ナトリウム塩２ｇ、水酸化ナト
リウム０．３ｇを水６０騰１に溶解した。そして室温に
４８時間放置し、塩化ナトリウムを１５ｇ加え析出した
沈殿物をろ別し、乾燥して、感光性高分子化合物を得た
。
次に、上記で得た感光性高分子化合物を用いて、以下の
組成の感光性組成物の溶液を調整した。これをガラス板
に０．７μｍの厚さに回転塗布し、乾燥して塗膜とした
。
組成：
ａ）アクリルアミド−ジアセトンアクリルアミド共重合
体（共重合比；アクリルアミド２．ジアセトンアクリル
アミド１） ・・・・・・２．０ ％ｂ）感
光性高分子化合物 ・・・・・・０．４ ％Ｃ
）シランカップリング剤 ・・・・・・０．００２
％ｄ）水 ・・・・・・残余
比較例として上記感光性高分子化合物に代えてビスアジ
ド化合物（４，４’−ジアジドスチルベン−２，２′−
ジスルホン酸二ナトリウム）を用いて前記と同様の塗膜
を形成した。
上記の塗膜に対して、超高圧水銀灯から光を２０秒照射
し、約４０℃の温水で、現像し、所定のホール（１６０
μｍ）のパターンを得るためにどれだけの照度（Ｖ／ｍ
”）で足りるかによって感度の評価を行なった。
比較例の場合１．４３Ｗ／ｍ”の照度が必要であったが
、本実施例の感光性高分子化合物を用いたときは、０．
４０１１／ｍ”の照度で同じホール径のパターンが得ら
れた。
実施例２
実施例１における組成のアクリルアミド−ジアセトンア
クリルアミド共重合体の代わりにポリビニルピロリドン
（ＧＡＦ社製に−９０）を用い、実施例１と同様の操作
によってパターンを形成することができた。
比較例として、上記感光性高分子化合物に代えてビスア
ジド化合物（４，４’−ジアジドスチルベン−２，２′
−ジスルホン酸二ナトリウム）を用いて塗膜形成を行な
った。上記の各塗膜に対して。
超高圧水銀灯から光を２０秒照射し、約４０℃の温水で
、現像し、所定のホール（１６０μ−）のパターンを得
るためにどれだけの照度（Ｖ／ｍ” ）で足りるかによ
って感度の評価を行なった。
比較例の場合１．４３１／ｍ”の照度が必要であったが
。
本実施例の感光性高分子化合物を用いたときは、０．５
２Ｗ／ｍ”の照度で同じホール径のパターンが得られた
。
実施例３
実施例１で合成した高分子化合物１ｇ、４−アジドシン
ナムアルデヒド−２−スルホン酸ナトリウム２ｇｅ水酸
化ナトリウム０．３ｇを水６０ｍ１に溶解した。そして
室温に４８時間放置し、塩化ナトリウムを１５ｇ加え析
出した沈殿物をろ別し、乾燥して、感光性高分子化合物
を得た。
次に、実施例１と同様の組成、操作によってパターンを
形成することができた。
比較例として、上記感光性高分子化合物に代えてビスア
ジド化合物（４，４’−ジアジドスチルベン−２，２′
−ジスルホン酸二ナトリウム）を用いて同様の塗膜形成
を行なった。
上記の各塗膜に超高圧水銀灯から光を２０秒照射し、約
４０℃の温水で、現像し、所定のホール（１６０μ履）
のパターンを得るためにどれだけの照度（１１／ｍ”）
で足りるかによって感度の評価を行なった。
比較例の場合１．４３１／ｗｉ”の照度が必要であった
が。
本実施例の感光性高分子化合物を用いたときは、０．５
９Ｗ／♂の照度で同じホール径のパターンが得られた。
（発明の効果］
本発明の感光性組成物は、高感度で相反則不軌特性を示
す、それ故、例えば大型のブラックマトリックス型カラ
ーブラウン管の製造等に用いて短時間で露光できるとい
う効果がある。また高精細ブラックマトリックス型カラ
ーブラウン管の製造等に用いてもシャドウマスクのホー
ル径が小さくなることによる露光面での照度低下を補う
ことができる効果がある。The present invention will be explained in detail below using examples. Example 1 Polystyrene obtained by solution radical polymerization (average molecular weight:
8000) was dissolved in 100 ml of carbon disulfide. This solution was mixed with 30 g of anhydrous aluminum chloride,
The mixture was added dropwise to a solution containing 100 ml of carbon disulfide and 20 g of acetyl chloride while stirring at room temperature. Thereafter, the mixture was heated and refluxed with stirring for 2 hours. After cooling, the mixture was filtered and the insolubilized material was dried. After pulverizing this, it was treated with a large amount of ice water, thoroughly washed with water, and then dried. 20 g of tetrachloroethane to 10 g of the polymer obtained above.
g was added and heated for 30 minutes. After cooling, 50 g of chlorosulfonic acid was gradually added while cooling with water, and the mixture was stirred at room temperature for 4 hours. Then, glacial acetic acid was added until no hydrogen chloride was generated, poured into a large amount of water, the insolubilized matter was filtered off, washed with acetone and water, and then dissolved in an IN aqueous solution of sodium hydroxide.
boiled for an hour. After cooling, sodium chloride was added to precipitate the polymer compound by salting out. Next, 1 g of this polymer compound, 2 g of 4-azidobenzenaldehyde-2-sulfonic acid sodium salt, and 0.3 g of sodium hydroxide were dissolved in 60 parts of water. The mixture was left at room temperature for 48 hours, 15 g of sodium chloride was added, and the precipitate was filtered out and dried to obtain a photosensitive polymer compound. Next, a solution of a photosensitive composition having the following composition was prepared using the photosensitive polymer compound obtained above. This was spin-coated onto a glass plate to a thickness of 0.7 μm and dried to form a coating film. Composition: a) Acrylamide-diacetone acrylamide copolymer (copolymerization ratio: acrylamide 2: diacetone acrylamide 1) 2.0% b) Photosensitive polymer compound 0. 4%C
) Silane coupling agent ・・・・・・0.002
%d) Water... As a remaining comparative example, a bisazide compound (4,4'-diazidostilbene-2,2'-
A coating film similar to that described above was formed using disodium disulfonate (disodium disulfonate). The above coating film was irradiated with light from an ultra-high-pressure mercury lamp for 20 seconds, developed with warm water at about 40°C, and placed in the designated hole (160°C).
How much illuminance (V/m) to obtain a pattern of μm)
Sensitivity was evaluated based on whether the illuminance of 1.43 W/m was sufficient in the comparative example, but when the photosensitive polymer compound of this example was used, the sensitivity was evaluated based on whether the illuminance of 1.43 W/m was sufficient.
A pattern with the same hole diameter was obtained at an illuminance of 4011/m''. Example 2 Polyvinylpyrrolidone (-90 manufactured by GAF) was used instead of the acrylamide-diacetone acrylamide copolymer having the composition in Example 1. A pattern could be formed by the same operation as in Example 1. As a comparative example, a bisazide compound (4,4'-diazidostilbene-2,2'
-Disodium disulfonate) was used to form a coating film. For each coating above. Irradiate the film with light from an ultra-high pressure mercury lamp for 20 seconds and develop with warm water at about 40℃. The comparison example required an illuminance of 1.431/m''. When using the photosensitive polymer compound of this example, 0.5
A pattern with the same hole diameter was obtained with an illuminance of 2 W/m''. Example 3 1 g of the polymer compound synthesized in Example 1, 2 ge of sodium 4-azidocinnamaldehyde-2-sulfonate, and 0.3 g of sodium hydroxide were added. It was dissolved in 60 ml of water.Then, it was left at room temperature for 48 hours, 15 g of sodium chloride was added, and the precipitate was filtered out and dried to obtain a photosensitive polymer compound. A pattern could be formed depending on the composition and operation.As a comparative example, a bisazide compound (4,4'-diazidostilbene-2,2'
-Disodium disulfonate) was used to form a similar coating film. Each of the above coatings was irradiated with light from an ultra-high pressure mercury lamp for 20 seconds, developed with warm water at about 40°C, and formed into a predetermined hole (160μ).
How much illuminance should be used to obtain the pattern (11/m”)
Sensitivity was evaluated based on whether it was sufficient. In the case of the comparative example, an illuminance of 1.431/wi" was required. When the photosensitive polymer compound of this example was used, the illuminance was 0.5
A pattern with the same hole diameter was obtained at an illuminance of 9 W/♂. (Effects of the Invention) The photosensitive composition of the present invention has high sensitivity and exhibits reciprocity law failure characteristics, and therefore has the effect of being able to be exposed in a short time when used, for example, in the manufacture of large black matrix type color cathode ray tubes. Also, when used in the manufacture of high-definition black matrix type color cathode ray tubes, etc., it has the effect of compensating for the decrease in illuminance on the exposed surface due to the smaller hole diameter of the shadow mask.
Claims (1)
ものにアジド基を含むアルデヒド化合物を組み合わせて
成ることを特徴とする感光性高分子化合物。 ２、請求項第１項記載の感光性高分子化合物とアクリル
アミド−ジアセトンアクリルアミド共重合体またはポリ
ビニルピロリドンから成ることを特徴とする感光性高分
子化合物。 ３、所望のパターンを形成しようとする面上に請求項第
２項記載の感光性組成物の塗膜を形成する工程、該感光
性組成物の塗膜に酸素の存在する条件において所望のパ
ターン露光を行なう工程、上記塗膜を現像して光照射区
域より実質的に小さい面積のパターンを形成する工程を
有することを特徴とするパターン形成方法。 ４、請求項第３項記載のパターン形成しようとする面が
カラーブラウン管のフェースプレートの内面であること
を特徴とするパターン形成方法。[Scope of Claims] 1. A photosensitive polymer compound comprising a combination of acetylated and sulfonated polystyrene and an aldehyde compound containing an azide group. 2. A photosensitive polymer compound comprising the photosensitive polymer compound according to claim 1 and an acrylamide-diacetone acrylamide copolymer or polyvinylpyrrolidone. 3. Forming a coating film of the photosensitive composition according to claim 2 on a surface on which a desired pattern is to be formed, forming the desired pattern in the presence of oxygen in the coating film of the photosensitive composition. A pattern forming method comprising the steps of exposing to light, and developing the coating film to form a pattern having an area substantially smaller than the area irradiated with light. 4. The pattern forming method according to claim 3, wherein the surface on which the pattern is to be formed is an inner surface of a face plate of a color cathode ray tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32578588A JPH02173007A (en) | 1988-12-26 | 1988-12-26 | Photopolymer, photosensitive composition containing the same and formation of pattern by using the same composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32578588A JPH02173007A (en) | 1988-12-26 | 1988-12-26 | Photopolymer, photosensitive composition containing the same and formation of pattern by using the same composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02173007A true JPH02173007A (en) | 1990-07-04 |
Family
ID=18180581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32578588A Pending JPH02173007A (en) | 1988-12-26 | 1988-12-26 | Photopolymer, photosensitive composition containing the same and formation of pattern by using the same composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02173007A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0770314A (en) * | 1993-07-07 | 1995-03-14 | Minnesota Mining & Mfg Co <3M> | Azide polymer guided by dipolarophile |
| US5725978A (en) * | 1995-01-31 | 1998-03-10 | Basf Aktiengesellschaft | Water-soluble photosensitive resin composition and a method of forming black matrix patterns using the same |
| US5866296A (en) * | 1996-01-25 | 1999-02-02 | Toyo Gosei Co., Ltd. | Photosensitive resin composition |
| US6140007A (en) * | 1997-04-30 | 2000-10-31 | Toyo Gosei Kogyo Co., Ltd. | Photosensitive compositions and pattern formation method |
| US6342330B2 (en) | 1998-09-24 | 2002-01-29 | Toyo Gosei Kogyo Co., Ltd. | Photosensitive compositions and pattern formation method |
| JP2008522014A (en) * | 2004-12-01 | 2008-06-26 | トヨタ テクニカル センター，ユー．エス．エー．，インコーポレイティド | A novel proton exchange membrane using cycloaddition reaction between azide and alkyne-containing components |
-
1988
- 1988-12-26 JP JP32578588A patent/JPH02173007A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0770314A (en) * | 1993-07-07 | 1995-03-14 | Minnesota Mining & Mfg Co <3M> | Azide polymer guided by dipolarophile |
| US5725978A (en) * | 1995-01-31 | 1998-03-10 | Basf Aktiengesellschaft | Water-soluble photosensitive resin composition and a method of forming black matrix patterns using the same |
| US5990269A (en) * | 1995-01-31 | 1999-11-23 | Basf Aktiengesellschaft | Copolymer of vinylpyrrolidone and vinylimidazole |
| US5866296A (en) * | 1996-01-25 | 1999-02-02 | Toyo Gosei Co., Ltd. | Photosensitive resin composition |
| US6140007A (en) * | 1997-04-30 | 2000-10-31 | Toyo Gosei Kogyo Co., Ltd. | Photosensitive compositions and pattern formation method |
| US6342330B2 (en) | 1998-09-24 | 2002-01-29 | Toyo Gosei Kogyo Co., Ltd. | Photosensitive compositions and pattern formation method |
| JP2008522014A (en) * | 2004-12-01 | 2008-06-26 | トヨタ テクニカル センター，ユー．エス．エー．，インコーポレイティド | A novel proton exchange membrane using cycloaddition reaction between azide and alkyne-containing components |
| JP4806683B2 (en) * | 2004-12-01 | 2011-11-02 | トヨタ テクニカル センター，ユー．エス．エー．，インコーポレイティド | A novel proton exchange membrane using cycloaddition reaction between azide and alkyne-containing components |
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