EP0759906A1 - Sel de stilbazolium, sa preparation et son utilisation - Google Patents

Sel de stilbazolium, sa preparation et son utilisation

Info

Publication number
EP0759906A1
EP0759906A1 EP96907768A EP96907768A EP0759906A1 EP 0759906 A1 EP0759906 A1 EP 0759906A1 EP 96907768 A EP96907768 A EP 96907768A EP 96907768 A EP96907768 A EP 96907768A EP 0759906 A1 EP0759906 A1 EP 0759906A1
Authority
EP
European Patent Office
Prior art keywords
group
salt
following formula
sbq
ion
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.)
Withdrawn
Application number
EP96907768A
Other languages
German (de)
English (en)
Inventor
Lee Soon Park
Bong Chul Kim
Yoon Soo Han
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Orion Electric Co Ltd Korea
Original Assignee
Orion Electric Co Ltd Korea
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1019950005821A external-priority patent/KR0148718B1/ko
Priority claimed from KR1019950005822A external-priority patent/KR960035150A/ko
Application filed by Orion Electric Co Ltd Korea filed Critical Orion Electric Co Ltd Korea
Publication of EP0759906A1 publication Critical patent/EP0759906A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D215/14—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Definitions

  • the present invention relates to novel stilbazolium salt, and preparation and use thereof. More specifically, the present invention relates to novel stilbazolium salt prepared by using terephthalaldehydem ⁇ n ⁇ dialkylacetal, processes for preparation thereof, and use of thus prepeured stilbazolium salt for preparation of a photosensitive resin.
  • Stilbazolium salt (“SbQ salt”) forms a photosensitive resin of high sensitivity (“PVA-SbQ type resin”) when it is combined with polyvinyl alcohol (“FVA”) .
  • FVA polyvinyl alcohol
  • the PVA-ADC (ammonium dichromate) type photosensitive resin or FVA-Diazo type photosensitive resin has been commonly used as a photosensitive resin for fluorescent slurry of color Braun tube.
  • the PVA-ADC type or PVA-Diazo type resin has been recently substituted with the PVA-SbQ type resin because it exhibits from several to several dozens of more folds of activities as compared to the conventional FVA-ACD type or FVA-diazo type photosensitive resin, and thus the former two types are presently considered as highly valuable for the purposes of fixation of enzyme, screen printing, preparation of color picture tube, color filter or the like.
  • a photosensitive liquid using the PVA-SbQ type resin has a great advantage in that it causes very little environmental pollution unlike the conventional photosensitive resin.
  • the conventional PVA-ADC type photosensitive resin contains chromium, a type of heavy metal, and FVA-diazo type photosensitive resin contains a large amount of toxic diazo compound in order to increase sensitivity, so that both resins axe serious environmental hazards.
  • the FVA- SbQ type resin is presently being used as a substitute for the PVA-ADC or FVA-diazo type resin.
  • the problem with the PVA-SbQ type resin is that the process of preparing SbQ salt, used as a raw material of the resin, is complicated and inefficient. Therefore, development of a process for efficient preparation of SbQ salt is required in the art.
  • TA terephthalaldehyde
  • the first process comprises reacting a compound of picoline type or methylquinoline type with terephthalaldehyde; purifying the product thus obtained; and reacting the product with an alkylating agent to synthesize SbQ salt.
  • the process has problems in that 1) an excess amount of TA is used in order to avoid dimeric byproduct, 2) the material used in the purifying process is very toxic, and 3) a complicated process comprising 7 steps (i.e., (a) removing the unreacted TA by using aqueous hydrochloric acid, (b) removing the unreacted TA by ii- q -i-n benzene, (c) neutralizing with aqueous sodium hydroxide, (d) drying SbQ and dimeric byproducts, (e) removing the dimeric-byproducts by using ethyl acetate, (f) removing the ethyl acetate and drying SbQ, and (g) synthesizing SbQ salt by using dimethyl sulfate) are required.
  • the second process comprises reacting a compound of picoline type or methylquinoline type with an alkylating agent, adding TA to the reaction mixture to prepare SbQ salt.
  • multi-step purifying process has been somewhat simplified, but the problem of using an excessive amount of TA still remains.
  • the process for purifying SbQ salt according to the second process comprises the steps of (a) removing the dimeric byproduct frcm the reaction mixture, (b) treating reaction mixture with a mixed solvent of ethanol »n acetone, and (c) filtering and drying SbQ salt.
  • the complicated purifying processes have been simplified somewhat in this three-step process, a method of removing the dimeric byproducts has not been described.
  • TDA time difference analysis
  • the present invention provides a stilbazolium salt ("SbQ- A salt”) as a photoreactive compound wh ch is represented by the following formula (1) or (1A) :
  • R* and j being identical to or different from each other, independently represents hydrogen atom, alk l group, aryl group, allyl group, aralkyl group or allylalkyl group, wherein hydr ⁇ xyl group, ami e group, carboxylic group, ether bond, double bond, or the like may be included in each group; and X ' represents halogen ion, sulfate ion, phosphate ion, methosulfate ion, methanesulf ⁇ nate ion or p-toluenesulfonate ion.
  • the present invention provides two processes for preparing the aforementioned novel SbQ-A salt.
  • the first process of the present invention comprises the steps of reacting a compound of picoline type or methylquinoline type with TEA, and purifying the reaction product to obtain pale yellow crystals, and dispersing the crystals thus obtained in water, and adding an alkylating agent of the following formula (3) thereto to obtain the stilbazolium salt.
  • the second process of the present invention comprises the steps of reacting a compound of picoline type or methylqui ⁇ noline type with an alkylating agent of the following formula (3) to form a picolinium salt or methylquinolinium salt, and aHrK-ng TDA to the solution thus obtained, and heating under reflux to obtain clear yellow SbQ-A salt.
  • Compounds of picoline type or methylquinoline type include ⁇ , ⁇ or ⁇ -picoline or 2-, 3-, 4-, 6-, 7- or 8- methylquinoline.
  • TDA used in the preparation of SbQ-A salt of the present invention is a compound represented by the following formula (2) :
  • R- represents hydrogen atom, alkyl group, aryl group or allyl group
  • each R 2 may be of the same group and each of the three groups may include hydroxyl group, amide group, carboxylic group, ether bond, double bond, or the like.
  • a representative example is terephthalaldehydem ⁇ nodiethylacetal.
  • the alkylating agent used in the formation of SbQ-A salt of the present invention is a compound represented by the following formula (3) :
  • R represents hydrogen atom, alkyl group, aryl group, allyl group, aralkyl group or allylalkyl group, wherein hydroxyl group, amide group, carboxylic group, ether bond, double bond, or the like may be included in each group; and
  • X ' represents halogen atom, sulfate group, phosphate group, metho ⁇ sulfate group, methanesulf ⁇ nate group or p-toluenesulfonate group.
  • the solvent used in the synthesis of SbQ-A salt according to the first process described above is not restricted, and a mixed solvent of acetic anhydride and acetic acid should preferably be used.
  • the temperature of the reaction can be aried depending on the solvent used. The temperature should be between room temperature and 180°C, and the reaction time should be between 1 hour to 24 hours, preferably 7 to 11 hours.
  • the solvent used in the synthesis of SbQ-A salt accord ng to the second process described above include polar solvents such as methyl alcohol, ethyl alcohol, or the like.
  • Usable catalysts include acids and bases.
  • sodium hydroxide, sodium ethoxide, sodium acetate or amine compounds may be used as a base catalyst.
  • Use of weak bases rather than strong bases, is more efficient and preferable.
  • a representative example is piperidine.
  • a compound of picoline type or methylquinoline type and TDA are heated under reflux in a mixed solvent of acetic anhydride and acetic acid for 1 to 24 hours, a large amount of water is added thereto, and the resultant solution is neutralized with dilute alkaline solution to give pale yellow precipitate.
  • the precipitate is filtered, and washed with methyl alcohol, isopropyl alcohol, or the like, and filtered and dried to obtain crystals of compound represented by following formula (4) or (4A) :
  • R j is defined as above.
  • a compound of which the acetal site of formula (4) or (4A) has been converted to aldehyde may be detected in a small amount if such acidic solvent was used.
  • SbQ salt, not SbQ-A salt is formed.
  • the formation of the compound having the converted aldehyde group is caused by water produced by a condensation reaction between picoline or methylquinoline compound and TDA, and acidic solvent.
  • a base catalyst is used instead of acidic catalyst since the acetal site of the formula (4) or (4A) may stably co-exist with basic compound though it is fragile to acidic compound.
  • Aphotosensitive resin is preparedby adding acid catalyst such as phosphoric acid to the aqueous solution of the salt and then reacting it with aqueous FVA solution.
  • a compound of picoline or methylquinoline type is dissolved in a methyl alcohol solvent and the solution is cooled at low temperature.
  • An alkylating agent such as dimethyl sulfate is slowly added thereto to form a picolinium salt or methylquinolini.um salt.
  • TDA is added, and the mixture is heated under reflux for 30 minutes to about 24 hours.
  • Methyl alcohol solvent is removed therefrom by using a rotary evaporator, and the residue is washed with acetone to form a deposit of clear yellow SbQ-A salt crystals. The crystals are filtered and dried to give SbQ-salt having a structural formula or (1) or (1A) as described above.
  • the second process of the present invention is different from the first process in that (a) it comprises different reaction orders of the reactants used for preparing SbQ-A salt from those of the first process, and (b) the aldehyde formation of the acetal site caused by the use of acid catalyst in the first process does not occur.
  • the second process for preparing SbQ-A salt according to the present invention is more efficient than the first process.
  • a process for removing the dimeric byproducts also is essential because the production thereof cannot be completely avoided even if a large amount of TA is used.
  • the process for removing the unreacted TA as well as that for removing the dimeric byproducts is unnecessary in the processes of the present invention, by using TDA instead of TA, whereby the overall process is shortened.
  • TDA acetal group of TDA which protects aldehyde group from H-i- ta-r formation
  • TDA itself exists as a liquid phase at room temperature so that the purifying steps after the SbQ-A salt formation may become easy.
  • the polymerization degree of the polyvinyl alcohol (completely orpartially saponified polyvinyl acetate) used for preparing the photosensitive resin by the use of SbQ-A salt according to the process described above, is preferably 300 - 3000, and sapon fication rate thereof is preferably 75% or more.
  • the reaction of SbQ-A salt with FVA in the presence of acid catalyst must be performed in a darkroom because the reaction mixture itself exhibits high photosensitivity as the reaction proceeds.
  • the reaction temperature is preferably 0 to 100°C, and the reaction time of 1 to 50 hours is sufficient. Since the finished reaction mixture has high photosensitivity, the photosensitivity may be tested with the reaction mixture, or it may be tested after re-precipitating in acetone, methanol, dioxane or the like, extracting with methanol by the use of Soxhlet device and drying.
  • the photosensitive resin thus obtained even if the incorporated ratio of photosensitive group is only 1 mol%, exhibits from several to several dozen-folds of activities, as compared to the conventional PVA-ADC type or FVA-diazo type resin. Maximum absorption range appears around 340 nm.
  • FVA-SbQ can be prepared by using the same 2 reactors of the conventional processes, though TDA has an acetal group at an end unlike TA.
  • Both processes for preparing SbQ-A need only one reactor, and SbQ-A salt may be used, together with an aqueous FVA solution separately prepared, for the preparation of FVA-SbQ photosensitive liquid in one reactor. It is because an aldehyde formation of the acetal occurs by an acid catalyst during the reaction of SbQ-A salt with FVA, even if one side of TDA is comprised of acetal, and the aldehyde can be re- acetalized by reacting with two hydroxyl groups in FVA.
  • the acid catalyst has two roles of altering the acetal in SbQ-A salt to aldehyde and of re-acetalizing the altered aldehyde, so that the consumption of the acid catalyst may be reduced. More specifically, one reactor is needed to prepare SbQ-A in the first process, and another reactor is needed to prepare SbQ-A salt by the reaction of SbQ-A with an alkylating agent. An aqueous solution of FVA which have been prepared separately is added to the aqueous solution containing SbQ-A salt, and the mixture is reacted in a darkroom to obtain an aqueous PVA-SbQ solution.
  • SbQ-A salt is more efficient than that of SbQ salt. Since the acetal group of SbQ-A salt can be readily converted to an aldehyde group in acidic solution and then can be re-acetalized by reacting with the hydroxy group of FVA, the problems associated with the conventional processes do not exist in the reaction with FVA.
  • the process of the present invention is able to prepare PVA-SbQ more efficiently than by the conventional processes, allowing a large scale manufacture of PVA-SbQ resin.
  • the product obtained by filtering the precipitation was dispersed in a cold (5°C) mixed solution of 5 % by weight of pure water and 95 % by weight of is ⁇ propyl alcohol, and the dispersion was stirred for 1 hour to remove the unreacted reactants and other solvents, filtered again, and dried to obtain 16 g of 2-[2-(4-di- ethylacetylphe ⁇ yl)ethenyl]pyridine ( .p. 234-238°C) .
  • 2-Methylquinoline (12.63 g) was dissolved in methyl alcohol (16.26 ml) , and the solution was cooled in an ice-salt bath.
  • Brcmobutane (21.54 g) was slowly added to the solution to proceed with formation of a quinolinium salt.
  • terephthalaldehydemono- (dibenzylacetal) (47 g) was added thereto, and the mixture was heated under reflux for 11 hours.
  • the photosensitive liquid wherein the reaction had been completed was re-precipitated in acetone and extracted with methanol solvent by using Soxhlet device for 8 hours. After extraction and drying, the product was dissolved in distilled water, and the light-absorbing range was examined. The product exhibited a maximum absorbance at 341 nm.
  • the photosensitive liquid itself which had not been passed through the re-precipitation and extraction steps also showed high photosensitivity.
  • the photosensitive liquid where the reaction had been completed was treated with the same method as Example 10 and absorption range thereof was examined. It also showed a maximum absorbance at 341 n .
  • the photosensitive liquid itself which had not been passed through the treatment steps after reaction also showed high photosensitivity.
  • FVA (20 g) was added to water (230 ml) , and dissolved by stirring at roam temperature for 4 hours. The remaining FVA undissolved was removed by using a fine wire net.
  • l-methyl-2- [2- (4-diethylace- tylphenyl)ethenyl]quinolinium iodide (2.13 g) prepeured in Example 9 was added and dissolved, and then 80 % by weight of phosphoric acid (1.03 g) was added thereto. Stirring was continued for 35 hours in a darkroom while maintaining the room temperature to prepare a photosensitive resin.
  • the photosensitive liquid where the reaction had been completed was re-precipitated in acetone and extracted with methanol solvent by using Soxhlet device for 8 hours. After extraction and drying, the product was dissolved in distilled water, and the light-absorbing range was examined. The product exhibited a maximum absorbance at 341 nm.
  • the photosensitive liquid itself which had not been passed through the re-precipitation and extraction steps also showed high photosensitivity.
  • Polyvinyl acetate (FVA) 500 g having polymerization degree of 1700 and saponification ratio of 87 % was dissolved in distilled water (7 ml), and l-methyl-4- [p- (2,2- dimethoxyeth ⁇ xy)styryl]pyridinium p-toluenesulfonate (55 mg) was dissolved therein.
  • phosphoric acid 500 mg was added, and the mixture was stirred at 60°C for 15 hours.
  • the resultant yellow reaction mixture was added to a large amount of acetone to precipitate resin.
  • the resin was sufficiently washed twice with methanol, and dried in vacuo to obtain 420 mg of the product.
  • the resin exhibited a maximum absorption peak at 370 nm in an aqueous solution, and the incorporation ratio of stilbazolium group was 0.71 mol%.
  • the resin film showed 9-fold increase of sensitivity as compared to cinnamon vinyl.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Materials For Photolithography (AREA)

Abstract

Sel de stilbazolium répondant à la formule (1) ou (1A), dans lesquelles R1, R2 et X- ont les notations définies dans la première revendication; son procédé de préparation à l'aide de téréphtalaldéhydemonodialkylacétal; et utilisation du sel de stilbazolium ainsi obtenu dans la préparation d'une résine photosensible.
EP96907768A 1995-03-20 1996-03-20 Sel de stilbazolium, sa preparation et son utilisation Withdrawn EP0759906A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
KR9505822 1995-03-20
KR9505821 1995-03-20
KR1019950005821A KR0148718B1 (ko) 1995-03-20 1995-03-20 스틸바졸리움염 및 그 제조 방법
KR1019950005822A KR960035150A (ko) 1995-03-20 1995-03-20 감광성 수지의 제조 방법
PCT/KR1996/000035 WO1996029312A1 (fr) 1995-03-20 1996-03-20 Sel de stilbazolium, sa preparation et son utilisation

Publications (1)

Publication Number Publication Date
EP0759906A1 true EP0759906A1 (fr) 1997-03-05

Family

ID=26630922

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96907768A Withdrawn EP0759906A1 (fr) 1995-03-20 1996-03-20 Sel de stilbazolium, sa preparation et son utilisation

Country Status (4)

Country Link
EP (1) EP0759906A1 (fr)
JP (1) JPH09510739A (fr)
CN (1) CN1148850A (fr)
WO (1) WO1996029312A1 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999003154A1 (fr) * 1997-07-11 1999-01-21 University Of Southern California Generateurs de charges prevus dans des films minces heterolamellaires multicouches
WO2004078136A2 (fr) 2003-03-03 2004-09-16 Mycosol, Inc. Sels de pyridinium, composes et procedes d'utilisation
CN101216668B (zh) * 2007-12-29 2010-06-09 范俊 一种n-甲基-对甲酰基苯乙烯基吡啶甲基硫酸盐的工业合成方法
WO2012085835A2 (fr) 2010-12-20 2012-06-28 L'oreal Composition liquide et stérile pour le comblement des rides
WO2013190465A2 (fr) 2012-06-19 2013-12-27 L'oreal Procédé cosmétique pour former une couche à la surface d'un ongle ou faux ongle
WO2013190466A2 (fr) 2012-06-19 2013-12-27 L'oreal Procédé cosmétique de maquillage des yeux
WO2013190464A2 (fr) 2012-06-19 2013-12-27 L'oreal Procédé cosmétique de maquillage et/ou de traitement de la surface de la peau
WO2013190469A2 (fr) 2012-06-19 2013-12-27 L'oreal Procédé cosmétique pour le maquillage et/ou le soin des lèvres
FR3035588B1 (fr) 2015-04-29 2017-05-19 Oreal Composition topique pour ameliorer la duree dans le temps d'un effet immediat de maquillage et/ou de soin
FR3046072B1 (fr) 2015-12-23 2018-05-25 L'oreal Procede de traitement des matieres keratiniques au moyen d'une composition comprenant un polymere photodimerisable modifie
FR3090364B1 (fr) 2018-12-21 2021-06-18 Oreal Composition comprenant un polymere photodimerisable modifie et un agent alcalin et/ou un derive amine d’alcoxysilane et procede de traitement mettant en œuvre la composition
FR3131201A1 (fr) 2021-12-23 2023-06-30 L'oreal Procédé pour démaquiller des fibres kératiniques ayant été préalablement traitées par une composition comprenant un polymère photoréticulable
FR3131317A1 (fr) 2021-12-23 2023-06-30 L'oreal Polymères photodimérisables comprenant au moins un groupement polyoxyalkyléné, composition les comprenant et procédé de traitement cosmétique
FR3131200A1 (fr) 2021-12-23 2023-06-30 L'oreal Composition comprenant un polymère photoréticulable et un agent colorant

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JPS56147804A (en) * 1980-04-17 1981-11-17 Agency Of Ind Science & Technol Photosensitive resin material for forming fluorescent surface of cathode ray tube
JPS5827073A (ja) * 1981-08-12 1983-02-17 Koden Electronics Co Ltd 方向探知機
JPH0791883B2 (ja) * 1986-06-26 1995-10-09 正 門田 モルタル充填式鉄筋継手スリ−ブ
JPS6354938A (ja) * 1986-08-27 1988-03-09 Dainichi Color & Chem Mfg Co Ltd ペロブスカイト型触媒の製造方法
US4728175A (en) * 1986-10-09 1988-03-01 Ovonic Imaging Systems, Inc. Liquid crystal display having pixels with auxiliary capacitance

Non-Patent Citations (1)

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Title
See references of WO9629312A1 *

Also Published As

Publication number Publication date
WO1996029312A1 (fr) 1996-09-26
MX9605668A (es) 1998-05-31
CN1148850A (zh) 1997-04-30
JPH09510739A (ja) 1997-10-28

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