JPH0261733B2 - - Google Patents
Info
- Publication number
- JPH0261733B2 JPH0261733B2 JP8632683A JP8632683A JPH0261733B2 JP H0261733 B2 JPH0261733 B2 JP H0261733B2 JP 8632683 A JP8632683 A JP 8632683A JP 8632683 A JP8632683 A JP 8632683A JP H0261733 B2 JPH0261733 B2 JP H0261733B2
- Authority
- JP
- Japan
- Prior art keywords
- casein
- photosensitive
- alkali
- water
- dichromate
- 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
Links
- 239000005018 casein Substances 0.000 claims description 43
- 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 claims description 43
- 235000021240 caseins Nutrition 0.000 claims description 43
- 239000003513 alkali Substances 0.000 claims description 31
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 17
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical group [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims description 8
- 235000013336 milk Nutrition 0.000 claims description 8
- 239000008267 milk Substances 0.000 claims description 8
- 210000004080 milk Anatomy 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical group [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000003899 bactericide agent Substances 0.000 claims 1
- 230000001235 sensitizing effect Effects 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 35
- 239000011248 coating agent Substances 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 238000000059 patterning Methods 0.000 description 16
- 206010034972 Photosensitivity reaction Diseases 0.000 description 15
- 238000005260 corrosion Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 15
- 230000036211 photosensitivity Effects 0.000 description 15
- 239000000758 substrate Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 239000000693 micelle Substances 0.000 description 9
- 238000011161 development Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910000655 Killed steel Inorganic materials 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 235000018102 proteins Nutrition 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 239000004328 sodium tetraborate Substances 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000546 pharmaceutical excipient Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 3
- 229940039790 sodium oxalate Drugs 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- -1 ammonium dichromate Chemical compound 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000020183 skimmed milk Nutrition 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 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
- G03C1/00—Photosensitive materials
- G03C1/66—Compositions containing chromates as photosensitive substances
Description
【発明の詳細な説明】
本発明は水溶性感光材料に関するもので、活性
光照射により光架橋反応を生じさせ、所望のパタ
ーニングを行う際、活性光照射前及び照射後に於
ける非照射部の熱的架橋反応を抑制し、安定な感
光特性を有する事が出来る水溶性カゼイン感光材
料に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-soluble photosensitive material, in which a photo-crosslinking reaction is caused by irradiation with actinic light, and when desired patterning is carried out, heat is applied to the non-irradiated area before and after irradiation with actinic light. The present invention relates to a water-soluble casein photosensitive material that can suppress crosslinking reactions and have stable photosensitive properties.
本発明を詳細に説明すれば、基板表面に感光性
レジスト組成物を塗布して被着させ、乾燥させて
得られる塗布膜を活性光により光像を露出し、露
光されたこの塗布膜を現像して非照射部分を除却
し、現像された被膜を加熱して残留部分に耐蝕性
を賦与する耐蝕性被膜の製造に於いて、上記感光
性レジスト組成物として水溶性感光材料を用い、
少なくともミルクカゼインと重クロム酸アルカリ
を含み、活性光による照射前及び照射後の塗布膜
の非照射部のカゼイン−クロム錯体の形成を抑制
する目的でクロム酸アルカリとホウ酸とを含む事
を特徴とする水溶性感光材料に関するものであ
る。 To explain the present invention in detail, a photosensitive resist composition is coated and adhered to the surface of a substrate, the resulting coating film is exposed to active light to form a photoimage, and the exposed coating film is developed. In the production of a corrosion-resistant coating in which the non-irradiated areas are removed and the developed coating is heated to impart corrosion resistance to the remaining areas, a water-soluble photosensitive material is used as the photosensitive resist composition,
Contains at least milk casein and alkali dichromate, and contains alkali chromate and boric acid for the purpose of suppressing the formation of casein-chromium complexes in the non-irradiated areas of the coating film before and after irradiation with active light. This invention relates to water-soluble photosensitive materials.
従来より耐蝕性被膜を製造する目的で、感光性
レジスト塗布膜を基板に被着させ乾燥を行つた
後、活性光照射により光像を露出し、泌照射部と
照射部その間に溶去剤に対する溶解度差を生じさ
せ、基板上に残留部分を形成する事はパターニン
グと呼ばれ、公知の方法である。感光性レジスト
被膜には、特に高感度、高解像度等の感光特性の
他に感光液状態並びに塗布膜状態に於ける保存安
定性、更には、合目的諸特性、例えば耐蝕性被
膜、広義にはマスクと考えている被膜の製造に於
いて、パターニング被膜に耐蝕性を賦与可能であ
る事、吸収性被膜、一般的には染色性被膜の製造
に於いてパターニング被膜に染着性を賦与可能で
ある事、或は種々の組み合せによる選択的かつ特
異的被膜の製造に於いてパターニング被膜に任意
の特性を賦与可能である事等が必要とされる。 Conventionally, for the purpose of producing a corrosion-resistant coating, a photosensitive resist coating film is applied to a substrate and dried, and then a photoimage is exposed by irradiation with actinic light, and an eluent is applied between the irradiated areas. Creating a solubility difference and forming a residual portion on the substrate is called patterning, and is a known method. In addition to photosensitive properties such as high sensitivity and high resolution, photosensitive resist coatings also have storage stability in the photosensitive liquid state and coated film state, as well as various desired properties such as corrosion-resistant coating, in a broad sense. In the production of coatings considered as masks, it is possible to impart corrosion resistance to the patterning coating, and in the production of absorbent coatings, generally dyeable coatings, it is possible to impart dyeability to the patterning coating. It is necessary to be able to impart arbitrary characteristics to a patterned film in the production of selective and specific films by certain things, or by various combinations.
耐蝕性被膜の代表的なものとしては、冷間圧延
炭素鋼やニツケル合金等の金薄板の両面に感光性
レジスト等を塗布被着させ、この塗布膜を密着焼
付法等によつてパターニングした後、加熱する事
によつて耐蝕性を賦与し、次いで耐蝕性被膜を設
けた金属薄板を所望通りに選択エツチングした
後、耐蝕性被膜を金属薄板から除去する事によ
り、カラーテレビ映像管に使用する孔開きマスク
や半導体集積回路チツプの導通ピンに使用するリ
ードフレーム等が製造されている。 A typical example of a corrosion-resistant film is to coat a thin gold plate made of cold-rolled carbon steel or nickel alloy with a photosensitive resist, etc., and then pattern the coated film using a contact baking method. , imparting corrosion resistance by heating, then selectively etching the metal sheet provided with the corrosion-resistant coating as desired, and then removing the corrosion-resistant coating from the metal sheet for use in color television picture tubes. Lead frames used for hole-opening masks and conducting pins of semiconductor integrated circuit chips are manufactured.
感光性レジストのなかでも、水溶性の感光性レ
ジストは、一般に重クロム酸アルカリと適当な高
分子成膜剤、例えば、グルー、PVA（ポリビニル
アルコール）、カゼイン等とを含んでおり、水溶
性感光材料の形で金属表面に塗布乾燥されて得ら
れるものである。カゼインとしてミルクカゼイン
を用い、賦感剤として重クロム酸アルカリとから
成る感光性レジストを用いる場合、常温常湿下に
於いて非照射部でカゼイン−クロム錯体の架橋が
熱的に起こる。感光性レジスト内に於ける活性光
照射前に発生するカゼイン−クロム錯体の熱的架
橋（以後暗反応と称す）及び、活性光照射後に発
生する非照射部に於けるカゼイン−クロム錯体の
光及び熱的架橋（以後残反応と称す）が問題とな
つており、感光性レジスト塗布被膜に所望のパタ
ーニングを行う場合、上記の暗反応、残反応によ
るカゼイン−クロム鎖体の架橋が起こり、パター
ニングの再現性に不均一性が認められている。 Among photosensitive resists, water-soluble photoresists generally contain alkali dichromate and a suitable polymeric film-forming agent, such as glue, PVA (polyvinyl alcohol), casein, etc. It is obtained in the form of a material that is applied to a metal surface and dried. When using a photosensitive resist consisting of milk casein as casein and alkali dichromate as a sensitizer, crosslinking of the casein-chromium complex occurs thermally in non-irradiated areas at room temperature and humidity. Thermal crosslinking of the casein-chromium complex in the photosensitive resist before irradiation with active light (hereinafter referred to as dark reaction), and the cross-linking of the casein-chromium complex in the non-irradiated area after irradiation with active light. Thermal crosslinking (hereinafter referred to as residual reaction) has become a problem, and when desired patterning is carried out on a photosensitive resist coated film, crosslinking of casein-chromium chains occurs due to the dark reaction and residual reaction described above, which impedes patterning. Inconsistency in reproducibility is observed.
市販感光液用カゼイン溶液中に含まれるミルク
カゼインは牛乳中のタンパク質で、脱脂乳に20℃
で酸を加えPHを4.6程度とした時に生ずる沈澱部
分である。このミルクカゼインに溶解剤として硼
砂、分散剤として界面活性剤、殺菌剤として石炭
酸等を加えたものが市販感光液用カゼイン溶液で
ある。この市販感光液用カゼイン溶液に、賦感剤
として重クロム酸アルカリ、例えば重クロム酸ナ
トリウム、重クロム酸カリウム、重クロム酸アン
モニウムが用いられるが、感光度と溶解性の点で
重クロム酸アンモニウムが一般的である。この様
にして調製した感光液から得られる塗布膜中で起
そる暗反応や残反応は、一般に賦感剤の重クロム
酸アルカリの濃度、塗布膜のPH、塗布膜の含水
量、保存環境の温度や湿度、抑制剤の存在等によ
つて影響される。 Milk casein, which is contained in casein solutions for commercial photosensitive liquids, is a protein found in milk, and is added to skim milk at 20°C.
This is the precipitated part that occurs when acid is added to bring the pH to about 4.6. A commercially available casein solution for photosensitive liquids is prepared by adding borax as a solubilizing agent, a surfactant as a dispersing agent, and carbolic acid as a sterilizing agent to this milk casein. In this casein solution for commercial photosensitive liquids, alkali dichromates such as sodium dichromate, potassium dichromate, and ammonium dichromate are used as excipients. is common. Dark reactions and residual reactions that occur in the coated film obtained from the photosensitive solution prepared in this way are generally caused by the concentration of the alkali dichromate used as the excipient, the pH of the coated film, the water content of the coated film, and the storage environment. It is affected by temperature, humidity, presence of inhibitors, etc.
従来法に於いては、感光性塗布膜基板を冷所保
存する方法、作業環境を低温化する方法、短時間
迅速作業を設定する方法、或は適当な抑制剤を共
存させる方法が採用されている。前三者は作業性
に於いて充分満足出来る方法とは言えず、主とし
て抑制剤共存方法が採用されている。例えば、重
クロム酸アルカリ感光性賦与剤の感光性がPHによ
つて変化する事に着目し、水酸化ナトリウム、水
酸化カリウム、水酸化アンモニウム、或は硼砂等
を添加してPHを7.0以上、普通8.0乃至9.0に調整す
るが、この様にPHを高くすると、感光性レジスト
の感光度が低下し、パターニングに要する時間
が、極めて長くなり作業性が悪くなる。 Conventional methods include storing the photosensitive coated film substrate in a cold place, lowering the temperature of the working environment, setting quick work for a short time, or coexisting with an appropriate inhibitor. There is. The former three methods cannot be said to be fully satisfactory in terms of workability, and the inhibitor coexistence method is mainly adopted. For example, we focused on the fact that the photosensitivity of an alkali dichromate photosensitizer changes depending on the pH, and added sodium hydroxide, potassium hydroxide, ammonium hydroxide, or borax to increase the pH to 7.0 or higher. Normally, it is adjusted to 8.0 to 9.0, but when the pH is raised in this way, the sensitivity of the photosensitive resist decreases, and the time required for patterning becomes extremely long, resulting in poor workability.
PH調整剤として一般的である水酸化アンモニウ
ムを感光液に添加する場合、塗布膜被着後にアン
モニア及び水の飛散が起こり、塗布膜としては感
光度の増大が望み得るが、感光度の経時変化に対
する不均一性が著しくなり、感光液保存性に優れ
たまた或る程度の感光度が得られるもののパター
ニングの再現性は悪い。 When ammonium hydroxide, which is a common PH adjuster, is added to a photosensitive solution, ammonia and water scatter after the coating film has been deposited, and although it is possible to increase the photosensitivity of the coating film, changes in photosensitivity over time may occur. Although the photosensitive solution has excellent storage stability and a certain degree of photosensitivity, the reproducibility of patterning is poor.
また、アルカリ金属水酸化物や硼砂の如きは、
感光性レジスト中にアルカリ金属イオンを増大さ
せ、系中のイオン濃度を増す結果、カゼインの様
な水溶性タンパク質コロイドの電解質的平衡系の
質的変化を引き起こす為、保存安定性に優れるも
ののパターニングを行う場合、暗・残両反応に於
けるカゼイン−クロム錯体の架橋を抑制する事は
困難であり、パターニングの再現性に不均一性が
認められる。 In addition, alkali metal hydroxides and borax, etc.
Increasing the alkali metal ions in the photosensitive resist increases the ion concentration in the system, which causes qualitative changes in the electrolyte equilibrium system of water-soluble protein colloids such as casein. When carried out, it is difficult to suppress crosslinking of the casein-chromium complex in both dark and residual reactions, and non-uniformity is observed in patterning reproducibility.
一般に重クロム酸アルカリ賦感水溶性カゼイン
感光液の感光性は、系中の酸性クロム酸イオンが
活性種であり、重クロム酸アルカリの濃度、温
度、PH値によつて、その濃度が決定される。重ク
ロム酸アルカリの濃度については低い程、暗・残
両反応に対する特性は優れるが、低過ぎると感光
度の低下を引き起こし所要露光時間が長くなる欠
点がある。また、市販感光液用カゼイン溶液は一
般にPH7.5乃至8.5であるが、カゼイン固型分の５
〜15重量％の重クロム酸アルカリを加えるとPH値
は、6.4乃至6.9となる。重クロム酸アルカリが多
量になると、PH値は低下し、暗・残両反応に対す
る特性は劣るが、PHが低い程感光度は増大し、所
要露光時間は短くなる。両者の兼ね合いから、一
般的には、４〜６重量％の重クロム酸アルカリの
添加が適当とされており、カゼイン感光液のPHは
6.7〜6.8となる。 In general, the photosensitivity of an alkali dichromate-sensitized water-soluble casein photosensitive solution is determined by the concentration of the alkali dichromate, temperature, and PH value, since acidic chromate ions in the system are the active species. Ru. The lower the concentration of alkali dichromate, the better the properties against both dark and residual reactions, but if it is too low, it has the drawback of lowering the photosensitivity and lengthening the required exposure time. In addition, casein solutions for commercially available photosensitive liquids generally have a pH of 7.5 to 8.5, but the casein solid content is
Addition of ~15% by weight of alkali dichromate results in a pH value of 6.4 to 6.9. When the amount of alkali dichromate increases, the pH value decreases and the characteristics against both dark and residual reactions are inferior, but the lower the pH, the higher the photosensitivity and the shorter the required exposure time. Considering the balance between the two, it is generally considered appropriate to add 4 to 6% by weight of alkali dichromate, and the pH of the casein photosensitive solution is
It will be 6.7 to 6.8.
一方高分子成膜剤であるミルクカゼインは、水
溶性タンパク質コロイドで、水溶性中ではミセル
の状態で存在し、分子量約６×108で、450〜
10000個の分子量約2.5×104のサブミセルから構
成されている。また、一般的にサブミセルの表面
は、リン酸基やカルボキシル基の様な極性基で覆
われており、内部に疎水性残基を含む構造を有
し、個々のサブミセルはリン酸カルシウムによつ
て結合し、巨大な球状ミセルを形成すると考えら
れている。また、カルシウムを含んだ系に於い
て、カルシウムに対して安定なカゼインと不安定
なカゼインとが相互作用し、極めて安定なミセル
を形成している事や、ゲル化、添加剤に対する感
受性、及び加熱或は電磁波等による他の構成成分
との相互作用等は、カゼインミセルを考える上で
は重要である。 On the other hand, milk casein, which is a polymeric film-forming agent, is a water-soluble protein colloid that exists in the form of micelles in water, with a molecular weight of approximately 6 x 10 8 and 450 ~
It is composed of 10,000 submicelles with a molecular weight of approximately 2.5×10 4 . In addition, the surface of submicelles is generally covered with polar groups such as phosphate groups and carboxyl groups, and has a structure containing hydrophobic residues inside, and each submicelle is bound by calcium phosphate. , and are thought to form giant spherical micelles. In addition, in systems containing calcium, calcium-stable casein and calcium-unstable casein interact to form extremely stable micelles, gelation, sensitivity to additives, and Interaction with other constituents due to heating, electromagnetic waves, etc. is important when considering casein micelles.
サブミセルの結合に関与するカルシウムは、コ
ロイド性リン酸カルシウムとして大部分存在する
が、例えばPHを下げるとコロイド性リン酸カルシ
ウムは分解し、粘度が増大して、カゼインミセル
の粒子は小さくなる。この意味に於いて、各種有
機酸アルカリ、例えば、酢酸ナトリウム、シユウ
酸ナトリウム、乳酸ナトリウム、サルチル酸ナト
リウム、酒石酸ナトリウム、クエン酸ナトリウム
等を、重クロム酸アンモニウム賦感カゼイン感光
液に添加すると粘度の増大が観測され、更に感光
性レジストのパターニングの再現性は、無添加の
ものよりも良好となる。 The calcium involved in submicelle binding is mostly present as colloidal calcium phosphate; for example, when the pH is lowered, colloidal calcium phosphate decomposes, increasing viscosity and reducing the size of casein micelle particles. In this sense, when various organic acid alkalis, such as sodium acetate, sodium oxalate, sodium lactate, sodium salicylate, sodium tartrate, and sodium citrate, are added to ammonium dichromate-sensitized casein photosensitive solution, the viscosity increases. An increase is observed, and furthermore, the reproducibility of the patterning of the photosensitive resist is better than that without additives.
特に、シユウ酸ナトリウム、クエン酸ナトリウ
ムの添加効果が優れ、感光性塗布膜に於ける暗反
応や残反応に対して、パターニングの再現性が良
い。 In particular, the effect of adding sodium oxalate and sodium citrate is excellent, and the reproducibility of patterning is good against dark reactions and residual reactions in photosensitive coating films.
改良された水溶性カゼイン感光液のひとつの例
としては、カゼイン固型分に対して、重クロム酸
アンモニウムを４〜６重量％、有機酸アルカリ、
例えば、クエン酸ナトリウム、シユウ酸ナトリウ
ム、或はクエン酸アンモニウム、シユウ酸アンモ
ニウム等を0.5〜5.0重量％、更に硼砂を添加して
PHを6.9に調整した組成であるが、これを塗布、
乾燥して得られる感光性レジストは、パターニン
グの再現性に於いて、或る程度の均一性を有して
いるが、感光度が低い事や塗布膜と基板の接着性
が悪い事等が欠点として指摘されている。 An example of an improved water-soluble casein photosensitive solution includes ammonium dichromate in an amount of 4 to 6% by weight, organic acid alkali,
For example, by adding 0.5 to 5.0% by weight of sodium citrate, sodium oxalate, ammonium citrate, ammonium oxalate, etc., and further adding borax.
The composition has a pH adjusted to 6.9, but when applied,
The photosensitive resist obtained by drying has a certain degree of uniformity in patterning reproducibility, but has drawbacks such as low photosensitivity and poor adhesion between the coating film and the substrate. It has been pointed out that
本発明は、従来の水溶性カゼイン感光液のかか
る欠点を改良した新規な水溶性カゼイン感光液に
関するもので、ミルクカゼインに、溶解剤、分散
剤、殺菌剤等を加え、更に賦感剤として重クロム
酸アルカリを加えて調整される水溶性カゼイン感
光液に、クエン酸アルカリとホウ酸を添加した水
溶性感光材料に関するものである。 The present invention relates to a new water-soluble casein photosensitive solution that improves the drawbacks of conventional water-soluble casein photosensitive solutions. This invention relates to a water-soluble photosensitive material in which alkali citrate and boric acid are added to a water-soluble casein photosensitive solution prepared by adding alkali chromate.
本発明に於いては、基板表面を市販感光液用カ
ゼイン水溶液に、重クロム酸アンモニウムを良し
とする重クロム酸アルカリと、クエン酸アルカ
リ、例えばクエン酸ナトリウム、或はクエン酸ア
ンモニウム、及びホウ酸とから成る水溶性感光材
料で被覆する。上記組成の感光性は実施例１或は
２で調整すると、PH値は約6.0乃至6.5になり、こ
れを塗布、乾燥して得られる感光性レジスト被膜
は、感光度が高く、パターニングに要する露光時
間が比較的短く、また、基板との接着性も良好で
ある。 In the present invention, the substrate surface is coated with a commercially available casein aqueous solution for photosensitive liquids, an alkali dichromate such as ammonium dichromate, an alkali citrate such as sodium citrate or ammonium citrate, and boric acid. coated with a water-soluble photosensitive material consisting of. When the photosensitivity of the above composition is adjusted according to Example 1 or 2, the PH value becomes about 6.0 to 6.5, and the photosensitive resist film obtained by coating and drying this composition has high photosensitivity and the exposure required for patterning The time required is relatively short, and the adhesion to the substrate is also good.
塗布膜を乾燥、露光、現像、耐蝕化して、所望
の耐蝕性被膜を形成した基板をエツチングし、耐
蝕性被膜を除去して得られる基板のエツチング加
工に於いては、加工鎖現性が良好で、暗反応や残
反応を伴う経時変化に対する加工寸法の安定性に
優れている。 The coating film is dried, exposed, developed, made corrosion resistant, the desired corrosion resistant coating is formed on the substrate, and the substrate obtained by etching the substrate has good processing chain development properties. It has excellent stability of processed dimensions against changes over time accompanied by dark reactions and residual reactions.
本発明を更に詳細に説明するならば、カゼイン
感光液の要素として、クエン酸アルカリを塗布膜
再溶液剤とし、ホウ酸を、感光度維持及び被膜改
質剤として利用する事に特徴がある。 To explain the present invention in more detail, it is characterized in that, as elements of the casein photosensitive liquid, alkali citrate is used as a coating film re-solution agent, and boric acid is used as a photosensitivity maintenance and film modifier.
先ずクエン酸アルカリは、カゼインミセルの結
合に関与するカルシウムイオンを選択的に除去
し、ミセルの形成能を小さくする事により、塗布
膜の再溶解性を向上させる。これは、クエン酸ア
ルカリとカゼインミセルとのイオン交換により、
比較的溶解度の高いクエン酸カルシウムと小さい
ミセルの集合体となつて、水溶液中に安定種とし
て共存出来る系になる事を示し、結果として、特
に非照射部の暗反応を抑制すること事になる。更
に、クエン酸アルカリは、塗布膜の推定PH値4.2
〜5.5の間に於いて緩衝作用を有し、水溶性タン
パク質コロイドであるミルクカゼインの電解質的
平衡を崩し難い点でも優れた効果がある。しか
し、多量に使用すると塗布膜と基板の接着が悪く
なり、水現像によつて露光部のレジストパターン
が流失する恐れがある点で、カゼイン固型分に対
してクエン酸アルカリは１〜15重量％が望まし
い。 First, alkali citrate selectively removes calcium ions involved in the binding of casein micelles and reduces the ability to form micelles, thereby improving the resolubility of the coating film. This is achieved through ion exchange between alkali citrate and casein micelles.
It was shown that calcium citrate, which has relatively high solubility, and small micelles form an aggregate that can coexist as a stable species in an aqueous solution, and as a result, dark reactions, especially in non-irradiated areas, are suppressed. . Furthermore, alkali citrate has an estimated pH value of 4.2 for the coating film.
-5.5, it has a buffering effect and is also excellent in that it does not easily disrupt the electrolyte balance of milk casein, which is a water-soluble protein colloid. However, if a large amount is used, the adhesion between the coating film and the substrate may deteriorate, and the resist pattern in the exposed area may be washed away by water development. % is desirable.
ホウ酸は解離定数が極端に小さいが、緩衡作用
を有する為、水素イオン供給可能でPHを調整する
働きがあり、感光度維持に大きく寄与する。更
に、非照射部に於ける光及び熱的なカゼイン−ク
ロム錯体の架橋の質的内容に於いて、ホウ酸を架
橋に一部関与し、残反応による架橋は露光部に比
較して、実質的に低く、水現像により容易に溶解
し易くなる。ホウ酸の添加量は、少量ではあまり
効果はなく、またカゼイン固型分に対して50重量
％以上では、塗布、乾燥によつて塗布膜中で晶折
し、結果として水現像によつて溶解しピンホール
を生じ易くなる点で、15〜45重量％が望ましい。 Boric acid has an extremely small dissociation constant, but since it has a buffering effect, it can supply hydrogen ions and has the function of adjusting pH, which greatly contributes to maintaining photosensitivity. Furthermore, regarding the qualitative content of optical and thermal crosslinking of the casein-chromium complex in the non-irradiated area, boric acid is partially involved in the crosslinking, and the crosslinking due to residual reaction is substantially less than that in the exposed area. It is easily dissolved by water development. If the amount of boric acid added is small, it will not have much effect, and if it exceeds 50% by weight based on the solid casein content, it will crystallize in the coating film during coating and drying, and as a result, it will dissolve during water development. The content is preferably 15 to 45% by weight since pinholes are more likely to occur.
また、従来法よりも賦感剤の重クロム酸アルカ
リ、特に溶解性に優れ重クロム酸アンモニウムの
濃度を高くする事が可能で、感光度の増大、基板
との接着性の向上に有効である。重クロム酸アン
モニウムの場合、カゼイン固型分に対して４〜18
重量％の添加が可能であるが、感光度を高め、接
着力を増す意味で、約９重量％が望ましく、濃度
を高くする事は、長期間の経過変化に対して充分
なパターニングの再現性が得られない。しかし、
作業性によつては、請求範囲以上の重クロム酸ア
ルカリの濃度も可能である。 In addition, it is possible to increase the concentration of the sensitizer alkali dichromate, especially ammonium dichromate, which has excellent solubility compared to conventional methods, which is effective in increasing photosensitivity and improving adhesion to the substrate. . In the case of ammonium dichromate, 4 to 18 based on casein solids
Although it is possible to add about 9% by weight in order to increase photosensitivity and adhesive strength, increasing the concentration will ensure sufficient patterning reproducibility against long-term changes. is not obtained. but,
Depending on workability, the concentration of alkali dichromate may be higher than the claimed range.
市販感光液用カゼイン溶液中の賦感剤、重クロ
ム酸アルカリとクエン酸アルカリ及びホウ酸は、
高分子成膜剤のカゼインを含めて、相互に関連し
合つている点で、感光性レジストの性能を種々変
化させる事が可能で、合目的な配合組成を設定し
た場合、感光性レジストのパターニングの再現性
は、極めて良好なものとなる。また、感光性レジ
ストのパターニングの再現性は、主として残反応
による影響を受け易く、暗反応の影響は、主とし
て基板と感光性レジストとの界面に強く現われ、
耐蝕性被膜化と引き続いてエツチングを行う場合
には、重要な意味を持つ。この意味で、クエン酸
アルカリは、主として暗反応に、ホウ酸は主とし
て残反応に寄与すると言える。更に、ホウ酸は重
クロム酸アルカリ賦感剤の活性種、酸性クロム酸
イオンの濃度の調節に寄与し、露光の際には感光
性レジストの感光度を維持する点で、重要な役割
を行う。 The excipients, alkali dichromate, alkali citrate, and boric acid in the casein solution for commercial photosensitive liquids are:
Including casein, a polymeric film-forming agent, it is possible to change the performance of photosensitive resist in various ways because they are related to each other, and when a suitable composition is set, patterning of photosensitive resist The reproducibility is extremely good. In addition, the reproducibility of patterning of photosensitive resists is easily affected mainly by residual reactions, and the effects of dark reactions appear strongly mainly at the interface between the substrate and the photosensitive resist.
This is important when etching is performed subsequent to the formation of a corrosion-resistant coating. In this sense, it can be said that alkali citrate mainly contributes to the dark reaction, and boric acid mainly contributes to the residual reaction. Furthermore, boric acid contributes to adjusting the concentration of acid chromate ion, an active species of the alkaline dichromate sensitizer, and plays an important role in maintaining the photosensitivity of the photosensitive resist during exposure. .
以下に本発明の実施例を示す。 Examples of the present invention are shown below.
実施例 １
固定分が約11％の市販感光液用カゼイン溶液
（東京応化工業製、商品名Ｇ−90S）1000mlに、
25％重クロム酸アンモニウム水溶性を40ml、クエ
ン酸ナトリウム４〜６ｇ及びホウ酸20〜30ｇを添
加した感光液を調製し、撹拌後、暗所に24時間放
置し、アルミキルド鋼板に塗布し乾燥後、温度24
〜27℃、湿度40〜60％の暗所で48時間保存し、活
性光照射してパターニングを行い同条件の暗所で
更に48時間保存した後、水現像を行い、得られた
パターニング被膜を測定した所、塗布乾燥直後に
活性光照射及び水現像を行つたパターニング被膜
と比較して大差のない塗布膜パターンを得る事が
出来た。Example 1 To 1000 ml of a commercial casein solution for photosensitive liquids (manufactured by Tokyo Ohka Kogyo, trade name G-90S) with a fixed content of about 11%,
A photosensitive solution was prepared by adding 40 ml of 25% aqueous ammonium dichromate, 4 to 6 g of sodium citrate, and 20 to 30 g of boric acid, stirred, left in a dark place for 24 hours, applied to an aluminum killed steel plate, and dried. , temperature 24
Store it in a dark place at ~27℃ and humidity 40-60% for 48 hours, pattern it by irradiating it with active light, store it in a dark place under the same conditions for an additional 48 hours, and then develop it with water to remove the resulting patterned film. As a result of measurements, it was possible to obtain a coating film pattern that was not significantly different from that of a patterned film in which active light irradiation and water development were performed immediately after coating and drying.
実施例 ２
固型分が約11％の市販感光液用カゼイン溶液
（東京応化工業製、商品名Ｇ−90S）1000mlに、
25％重クロム酸アンモニウム水溶性を40ml、クエ
ン酸アンモニウム３〜５ｇ、及びホウ酸20〜30dl
を添加した感光液を調製し、撹拌後、暗所に24時
間放置し、アルミキルド鋼板に塗布し、乾燥後、
温度24〜27℃、湿度40〜60％の暗所で48時間保存
し、活性光照射してパターニングを行い、同条件
の暗所で更に48時間保存した後、水現像を行い、
得られたパターニング被膜を測定した所、塗布、
乾燥直後に活性光照射及び水現像を行つたパター
ニング被膜と比較して大差のない塗布膜パターン
を得る事が出来た。Example 2 To 1000 ml of a commercial casein solution for photosensitive liquids (manufactured by Tokyo Ohka Kogyo, trade name G-90S) with a solid content of about 11%,
40 ml of 25% ammonium dichromate water soluble, 3-5 g of ammonium citrate, and 20-30 dl of boric acid
A photosensitive solution was prepared, stirred, left in a dark place for 24 hours, applied to an aluminum killed steel plate, and dried.
Store it in a dark place at a temperature of 24-27℃ and humidity 40-60% for 48 hours, pattern it by irradiating it with active light, store it in a dark place under the same conditions for an additional 48 hours, and then develop it with water.
The obtained patterned film was measured, coating,
It was possible to obtain a coated film pattern with no significant difference compared to a patterned film in which active light irradiation and water development were performed immediately after drying.
実施例 ３
実施例１或は実施例２で得られたパターニング
被膜を形成しているそれぞれのアルミキルド鋼板
を、耐蝕性被膜とする為に、200℃、10分間の加
熱を行い、放冷後、耐蝕性被膜の被着していない
裏面側を耐水性粘着シートにより保護し、
45゜Be′の塩化第二鉄溶液で45℃、10分間スプレー
エツチングを行つた後、粘着性保護シートを剥
し、耐蝕性被膜を苛性アルカリ浴で剥離させ除去
した。エツチングされたそれぞれのアルミキルド
鋼板上の加工部を測定した所、実施例１或は実施
例２のいずれに於いてもそれぞれの加工部に大き
な差は観測されなかつた。Example 3 In order to make each aluminum killed steel plate forming the patterned film obtained in Example 1 or Example 2 a corrosion-resistant film, it was heated at 200°C for 10 minutes, and after cooling, The back side to which the corrosion-resistant coating is not applied is protected by a water-resistant adhesive sheet,
After spray etching with a 45°Be' ferric chloride solution at 45°C for 10 minutes, the adhesive protective sheet was peeled off, and the corrosion-resistant coating was removed by peeling it off in a caustic alkaline bath. When the processed parts on each of the etched aluminium-killed steel plates were measured, no significant difference was observed between the respective processed parts in either Example 1 or Example 2.
Claims (1)
加え、更に賦感剤として重クロム酸アルカリを加
えて構成されるカゼイン感光液に、クエン酸アル
カリとホウ酸をカゼイン固型分に対して前者を１
〜15重量％、後者を15〜45重量％添加させてなる
水溶性感光材料。 ２ クエン酸アルカリがクエン酸ナトリウムで、
カゼイン固型分に対して２〜15重量％添加した特
許請求の範囲第１項記載の水溶性感光材料。 ３ クエン酸アルカリがクエン酸アンモニウム
で、カゼイン固型分に対して、１〜11重量％添加
した特許請求の範囲第１項記載の水溶性感光材
料。 ４ 重クロム酸アルカリが重クロム酸アンモニウ
ムで、カゼイン固型分に対して４〜18重量％添加
した特許請求の範囲第１項記載の水溶性感光材
料。[Scope of Claims] 1 A casein photosensitive solution consisting of milk casein, a solubilizing agent, a dispersing agent, a bactericidal agent, and an alkali dichromate as a sensitizing agent is added with an alkali citrate and boric acid to harden the casein. The former is 1 for the type
-15% by weight, and 15-45% by weight of the latter. 2 Alkaline citrate is sodium citrate,
The water-soluble photosensitive material according to claim 1, in which 2 to 15% by weight of casein is added based on the solid content of casein. 3. The water-soluble photosensitive material according to claim 1, wherein the alkali citrate is ammonium citrate and is added in an amount of 1 to 11% by weight based on the solid casein content. 4. The water-soluble photographic material according to claim 1, wherein the alkali dichromate is ammonium dichromate, which is added in an amount of 4 to 18% by weight based on the casein solid content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8632683A JPS59229552A (en) | 1983-05-17 | 1983-05-17 | Water soluble photosensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8632683A JPS59229552A (en) | 1983-05-17 | 1983-05-17 | Water soluble photosensitive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59229552A JPS59229552A (en) | 1984-12-24 |
| JPH0261733B2 true JPH0261733B2 (en) | 1990-12-20 |
Family
ID=13883709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8632683A Granted JPS59229552A (en) | 1983-05-17 | 1983-05-17 | Water soluble photosensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59229552A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100512077B1 (en) * | 2002-06-04 | 2005-09-05 | 일동화학 주식회사 | Casein composition for photoresist |
| KR100585536B1 (en) | 2004-06-07 | 2006-05-30 | 주식회사 루밴틱스 | Negative-type photoresist composition comprising casein, and process for preparing same |
-
1983
- 1983-05-17 JP JP8632683A patent/JPS59229552A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59229552A (en) | 1984-12-24 |
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