CA1084326A - Substituted indolinium polymethine dyestuff sensitizer used with an organic photoconductor - Google Patents
Substituted indolinium polymethine dyestuff sensitizer used with an organic photoconductorInfo
- Publication number
- CA1084326A CA1084326A CA254,670A CA254670A CA1084326A CA 1084326 A CA1084326 A CA 1084326A CA 254670 A CA254670 A CA 254670A CA 1084326 A CA1084326 A CA 1084326A
- Authority
- CA
- Canada
- Prior art keywords
- sensitizer
- photoconductor
- unsubstituted
- alkyl
- insulating layer
- 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
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0664—Dyes
- G03G5/0666—Dyes containing a methine or polymethine group
- G03G5/0668—Dyes containing a methine or polymethine group containing only one methine or polymethine group
- G03G5/067—Dyes containing a methine or polymethine group containing only one methine or polymethine group containing hetero rings
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
- H05K3/065—Etching masks applied by electrographic, electrophotographic or magnetographic methods
Abstract
Abstract of the Disclosure This invention relates to a material for electrophotographic repro-duction, which comprises a conductive support having a sensitized photoconductive insulating layer thereon containing at least one photo-conductor and containing, as a sensitizer, a polymethine dyestuff cap-able of absorbing radiation of a wavelength within the spectral range of 400 to 550 nm.
Description
32~
The present invention relates to a material for electrophotoyra-phic reproduction, composed of a conductive support and a sensitized photoconcluctive insulating layer adhering thereto.
It already has been proposed, in German Patent No. 1,058,836, to use photoconductors for electrophotographic reproduction having a spectral sensitivity which is generally in the long wave ultra-vlolet region of about 350 to 450 nm.
Ill order to extend the spectral sensitivity range to about 650 nm, it has been proposed to use various dyestuffs of different chemical ' - :
types as sensitizers. Dyestuffs which are effective are, for example, the following, which are listed in the Schultæ Dyestuff Tables (7th Edition, Volume 1, I931): triarylmethane dyestuffs, such as Brilliant ,, Green (No. 760, p. 314), Victoria Blue B (No. 822, p. 347), Methyl Violet (No. 783, p. 327), Crystal Violet (No. 785, p. 329), Acid Violet~
6B (No. 831, p. 351); xanthene dyestuffs, i.e. rhodamines, such as Rhodamine B (No. 864, p. 365), Rhodamlne 6G (No.~866, p. 366), ~ `
Rhodamine G extra (No. 865, p. 366), Sulforhodamine B (No. 863, p.
364) and ~Fast Acid Eosin G (No. 870, p. 368), also phthalelns, such as Eosin S (No. 883, p. 375), Eosin A (No. 881, p. 374), Ery~hrosin (No.
886, p. 376), Phloxin (P~o. 890, p. 378). BengaL Rose (No. 889, p.
378), and Fluorescein (No. 880, p. 373); thiazine dyestuffs, such as methylene blue (No. 1038, p. 449); acricline dyestuffs, su~ as,Acridlne Yellovr (No. 901, p. 383), Acridine Orange (No. 908, p. 387) and T rypafiavin (No. 906, p. 386); Quinoline dyestuffs, such as Plnacyanole ~.
(No 924, p. 396) and Cryptocyanine (No. 927, p. 397); Quinone dy~-stuffs and ketone dyestuffs such as Alizarin (No. 1141, p. 499~, Aliza-rin red S (No. 1145, p. 502) and Quinizarin (No. 1148, p. 504); and , ~: .
cyanine dyestuffs.
. ,~ .
1~ ~'~ `'".
.
~8~3;26 The sensltization of the photoconductors is based in principle on the fact that the light energy available in the long wavelength range is absorbed by the sensitizers and transferred to the photoconductor molecule.
The object of the invention, by contrast, was to undertake sen- i sitization in the short wavelength absorption range of the photoconductor, i.e. in the blue range of the spectrum. Such sensitization hitherto has been regarded as undesirable, because it would prevent the reproduction of blue portions, e.g. of ink or ball-point pen paste, of an original.
The present invention provides a material for electrophotographic reproduction, which comprises a conductive support having a sensitized photo- ;~
conductive insulating layer thereon containing at least one photoconductor and containing as a sensitizer a polymethine dyestuff capable of absorbing radiation of a wavelength within the spectral range of from 400 to 550 nm, preferably 480 to 520 nm.
A particularly suitable sensitizer is a polymethine dyestuff capable of absorbing radiation of a wavelength within the specified spectral range and having the general formula I ~
~:
(C~1~)2 ;;
~: C- C= C-A ( 1 ) X
wherein A is an unsubstituted or alkyl, alkoxyI or aryl substituted indolyl group, an unsubstituted or alkyl, alkoxyl or aryl substituted benzthiazolyl-amino group, an unsubstituted or alkyl, alkoxyl or aryl substituted phenyl-amino gTOUp, or an unsubstituted or alkyl, alkoxyl or aryl substituted indollnyl ," ' .
,t ~
' ~' .. . . . .. . . . .. . . ..
:10~3 43Z6 K - 2 3 9 7 group, ancl X~ is a monovalellt anion, preferably a halide lon, more preferably a chloride ion.
The sensitiæer is prcferably either C. I. Basic Orange 21 (C.I.
98035 - Astrazone Orange G) of the forrnula II
(CH3)2 H
~J\ c - c = c - c --N~ H H3C - C
H3C ~ N
C 1 ~
or C. I. Basic Orange 22 (C.I. 48040 - Astrazone Orange R) of the formula III
~,.C - C =
H3C ~ H H /C~ ~ (tII) Cl 0 CH3 -As a result of the presence of the sensitizer, the~photoconduc~
tive layer becomes sensitive to blue light, which is necessary in par-ticular with regard to the use of argon ion lasers in reproduction tech-~ i : ~ . . . . .
nology, which has recently achieved great importance. Furthermore, in '. .. ~ ;, ~,.
~,special fields of reproduction technology, mounting sheets are used ~ ~ ~
: , with blue lines which are not reproduced during reproduction on litho-graphic silver fitm. Insofar as the silver film materials a~e to be re-placed by electrophotographic ~materials, it is necessary to sensitize , .
the latter to ùlue light.
Sorprislngly, it is possible~ according to the invention to sensi-tize organic photoconductors in a range close to their own natural ~ 3~
10~3432f.i K-2397 al~sorptioll r(lngt!s so ~llat a sensitivity i9 obtained which suhstantially corre~sporlds to the lithograpllic film.
Since the proportion o~ sensitizer compared with the proportion of photoconcluctor in an insulating layer is generally relatively small and is preferably about 0.01% by weight, calculated on the photoconductor weight, it was not to be expected that a sensitizer would cause an In-crease in the sensitivity of the photoconductor. This e~pectation is con-firmed by the fact that the use of known sensitizers suah as Thioflavln, Acridlne Orange, Trypaflavin or Acridine Yellow does not give a corres~
ponding increase. No~ was it intended to cause such an increase within the characteristic sensitivity range. Instead, all efforts were almed at extending the sensitivity into the yellow and red spectral ranges. ~ -The photoconductive insulating layer contains from about 0~01 to 10 per cent by weight of sensitizer, preferably about 5 per cent, calcu-lated on the total weight of the photoconductor component.
Sensitizers which are used according to the invention~ are poly~
methine dyestuffs which absorb in the spectrat range of 400 to 550 nm, preferaùly 480 to 520 nm, and the two orange dyestuffs mentioned;above are espe~cially preferred. Other dyestuffs which advantage~ously may be used include for example, C.l. Basic Yellow 11 (C.I. 48055), known as A6trazone Yellow 3G, C.I. Basic Yellow 12 (C.I. 48065), known as . .
Astrazone Yellow 5G, and Basic Yellow 52115 (C~Io 48060)/ ancl also the as yet unclassified relatecl dyestuffs Astrazone Orange 3R, Astrazone ...... . .
Yellow 7GLL, ~strazone Yellow GRL and Astra Yellow R.
;
An insulating photoconductive layer containing one of these ;~
sensitizers requires an energy of about 10~Wsec/cm2 for disoharge to half the value of the initial potential, which means for an organic photoconductive layer great sensitivity to light of 490 nm.
-: _ ~ _ It llas beQn ound thL~t in the production of printing forms this great s~nsitivity to light of the copying materials achi~3ves ever greater importance, since because o~ it the ac:cess time to the actual information ` can be shortened.
The electrophotogrdpllic material of the invention ls especially' intended for use in the electrophoto~raphic producton of prlnting forms and printed circuits, and the conductive support may be any material suitable for this purpose, for example, aluminum, zlnc, magnesium or copper plates or mutti-metal plates, and also cellulose products, for ~ ;
example, special papers, cellulose hydrate, cellulose acetate or cellu- '~ ' lose butyrate films, especially partially saponified cellulose acetate or .
butyrate films. Some plastic materials, for example, polyamides in film form or'metal-vaporized films, are suitable for use as supports.
Surface-aged atuminum foits have' proved particularly suitable.
. ~
The surface-aging process comprises mechanical or electrochemical roughening and, if required, ~subsequent anodlzing and treatment with polyvLnyl phosphonic acid, as~described, ~for exampLe~,~ ln C~erman Offen-legungsschrift No. 1,621,478.
Preferred photoconductors for use in the sensitizéd insulating layer are those mentioned in German Patent No. 1,120,875,~especially substituted vinyl oxazoles such as 2-vinyl-4-(2'-chlorophenyl)-5-(4"- '^
~' ~ diethyl-aminophenyl)-oxazole. Other suitable photoconductors include, for example, triphenylamine derivatives, higher condens~ed~matic com~
pounds, such as anthracene, benzo-condensed heterocyclic compounds, and pyrazoline or imidazole derivatives.
`~ Also suitable are triazote and oxadiazole derivatives, as dis-closed lnGermanPatents~Nos~. 1,060,260, and 1,058,836 2,5-bis-(4'-diethylaminophenylj-1,3,4-oxadiazole is particularly suitable, In . : .~ ' , -: :
-5- ~ ' `J ~
432~; K - 2 3 9 7 ion, vinyL ~lromatic polymers such as polyvinyl anthracene, poly-(l( el)c~p~lLhylelle~ poly-N-vinylcarbazole and copolymers of these com-pouncls arc suitable, provided they are suitable for a solubility differen-tiatioll with respect to the toner covered image areas and to the non-imac3e areas, in conjunction with a resin binding agent if requirecl. Also suitable are polycondensates of aromatic amlnes and alàehydes, EIS cle-scribed in German AuslegeschPift No. 1,197,325, and resins as de-scribed in German Offenlegungsschrift No. 2 ,137,288 .
The photoconductive layer preferably also contains one or more resin binders. With regard tothe film properties and adhesion, natural and/or synthetic resins are suitable for US8 as resin binders. In addition to the film-forming and electrical properties, and also adhesion to the support, solubility properties in particular play a special part in their selection. For practical purposes, the resin binding agents which are particularly suitable are those which are soluble in aqueous or alcoholic :
solvent systems, with the addition of acid or alkali if required. Aromatic ~;
or aliphatic, easily combu~stible;~solvents are excluded for physiologlcal ~ , , and safety reasons. The most suitable resin binding agents are high molecular substances carrying alkali-solubilizing groups. Such groups are, for example, acid anhydride, carboxyl, phenol, sulfonic acid, suL-fcnamSde or sulfonimide groups. Resin l:inding agents with high acid ~numbers are preferably used, since these are particularly easily soluble i n alkaline-aqueous~alcoholic solvent systems. Copolymers with anhy-~: -dride groups can be used with great success, since due to the absence of free ac~d grcups the dark conductivity of the electrophotographic layer is low, in spite of good solubility in alkali.
Copolymers of styrene and maleic anhydride, for example, those - ~ known under~the name Lytron(~, Monsanto Company, USA, are especially ~ ~432~; K- 2 3 9 7 suitable, also phenol reslns, for example those known under the narne Alnovol , Hoechst AG, Werk Albert, Germany, have proved very satis Eactory .
The following examples furth~r lllustrate the inventlon: ;
Comparison Example A solution is prepared containing 40 g of 2-vinyl-4-t2'~chloro-phenyl)-5-(4"-diethylaminophenyl)-c~azole and 60 g of a styrene/maleic anhydride copolymer in 300 g of ~lycol monomethyl ether, 470 ~ of tet-rahydrofuran, and 130 g of butyl acetate. Thç resulting stock solutLon ..
is divided into portlons of 150 g each. One of the portions remains un-sensitized . To each of the other five solutlons 0 . 6 ml of a 0 .1 per cent methanol solution of a dyestuff is added,~ usIng the known dyestuff sen-sitizers Thioflavin, Trypaflavin, Acridine Yellow and Acrldine Oran~e and ~, the sensltizer used according to the present Invention,~viz. Astrazone Orange R. The quantity of sensitizer~alded, calculated on the photocon-ductor weight, is 0.01 per cenlt. ~The solutions are cast~ in known manner .
lnto photoconductor layers and the sensiti~ity of these~layers at 490 nrn~
is determined. In the case of the known~dyestuff sensitlzers~Thioflavin, TrYpaflavin~Acridine Yellow and~Acrid~ne Orange, no aensitizing effect and enzuing incseazed sensitivity~over that of the pure~photoconductor layer can be detected. In the~case of Astrazone Orange R,~however, the sensitivity of the photoconduotor is unmlstakably increazed by a factor greater than 2.
ExamPle I
A zolution of 40 grams of ~2-vinyl-4-~2'-chlorophenyl)-5-~4"~
diethylaminophenyl)-o~azole,;47~grams~of a oopolymer of styrene and ~; maleic acid anhydride,~ 10~`gràms of a chlorocaoutchouc and 2 grams of , Astrazone Orange R (C,I. Basic Orange 22) in;S10 grams of tetrahydro~
;:
furan, 330 grams of methylglycol and iS0 grams of butyl acetate was 3Z 6, K-2 3 9 7 appli~cl to a 100~ thick aluminum foil, which had been rnechanically rougllened by wire brushing, with a brush depth of approximately 331.
After the evaporation of the solvent there remained a photoconductor layer with a thickness of 4-5~, which absorbed light in the blue spectral range witll a maximum at ~90 nm and became photoconduct~e. The energy re-quired to discharge the layer to half the charge potential was 10~W sec/
cm2. The layer was charged in the manner usual for electrophotography with a corona device to a surface potential of - 400 V and imagewise ex-posed with a modulated 10 mW argon ion laser having a wavelength of 488 nm. A printing form was produced by the process described ln German Auslegeschrift No. 1,117,391.
Example 2 A solution of 27 grams of 2-vinyl-4-(2'-chlorophenyl)-5-(4"-di-ethylaminophenyl)-oxazole, 38 grams of a copolymer of styrene and maleic acid anhydride, 12 grams of a chlorocaoutchouc and 1.35 grams of Astra- ~-zone Orange R (C~I. Basic Orange 22) in 410 grams of tetrahydrofuran, 260 grams of methylglycol and 120 grams of butyl acetate was applied to a 300 ~ thick aluminum foil which had ~been electrochemically roughened, anodized and treated with polyvinylphosphonic acid. After drying with warm air, the thickness of the layer was about 5~. The sensitivity corresponded to that of the laYer desctibed in Exampte 1. After charging and imagewise exposure with a modulated 15 mW argon ion laser, a printing form was produced by the proceas described in German Offenle-gungsschrift No. 2, 322, 046 .
Example 3 - A solution of 4S grarns of 2-vinyl-4-~2'-chlorophenyl)-5-(4"-di-ethylaminophenyl)-oxazole, 45 grams of a copolymer of styrene and maleic acid anhydride and 2.25 grams~of Astrazone Orange R (CoI~ Basic ~ K-2397 OrancJe 22) in 280 cJrams of tetrahydrofuran, 180 grams of methylylycol and 8~ rams of butyl acetate was prepared and used to coat a polyester film about 100~ thick having aluminum vaporized onto it. A~ter evapo- -ration of the solvent, there remained a photoconductor layer about 5~
thlck with a maximum sensltivity ln the blue spectral range. The film was charged with a corona device to about - 450 V and exposed in a repro-camera with 8 auto photo lamps of 500 watts each for 25 seconds.
The mountin~ of a printed circùit on a board printed with blue orientatlon lines served as the original. Due to the high sensitivity ~o light of the ..
photoconductor layer in the blue spectral range, these blue orientation lines were not reproduced on the copied film. After the development and removal of the photoconductor layer in the exposed areas accordlng to the process described in German ()ffenlegungsschrift No. 2, 322 ,047, the thin vaporized aluminum layer was removed by treatment with 2N
sodium hydroxide solutlon, and a~pri~ted~clrcuit was obtained.
~xample 4 The solution of photoconductor, blndirlg agent and sensiti er de~
scribed in Example l, lnstead of ~being~applied to a mechanically rough~
ened aluminum foil, was~ applled~to~a~zinc plate as conventionally used in relief printing. After evaporatlon ~f the ~sotvent, the about 4~1 thiak photoconductor layer whlch was sensitlve in the blue range was nega~
tively charged with a corona device tc about 450 V. The photoconductor layer was exposed with an image-modulated beam from~a 10 mW argon ion laser, and~ an energy~ cf~ about ~10 5 ~W-~sec/cm 2 was required to dis-charge the layer. The conversion into a~ printing form was carried out in the manner described ln German~ ~Auslegeschrift No. 1,117,391, by development with a toner powder, f~ing the~ toner powder by means of heat, and removing the photoconduct~:ar layer by the action of an ;
_ 9 _, , :
allialine aLcoholic solution. Etching to produce a relief printing form is carried out wlth diluted nitric acid in the manner usual for the production of electrotypes.
Example 5 The coating solution describled und0r Example 3 was used to coat a multi-metal plate made of aluminum/copper/chromium. After the dried layer had been charyed, it was exposed w1th a modulated argon lon laser in the manner described in Example 4. Development, fixing and decoat-ing were carried out in a conventional manner. Conversion lnto a print-in~ form was carried out by etching away the chromium layer in the areas affected by the laser li~ht by means of a commers;:ial chromium etching substance, thereby exposing copper, and subsequently dls501viny away the developed photoconductor image by means of methylene chloride.
The exposed chromium surface was water-accepting. The number of prints which could be obtained wlth the planographic printing form pro- :
duced was very large.
Exampl~ 6 A solution of 40 grams of 2,5-bis-(4'-diethylaminophenyl)-1,3,4-oxadSazole, 47 grams of a copolymer of styrene and maleic acid anhydrlde, 10 grams of a chlorocaoutchouc and 2.0 grams of Astrazone Orange R
(C.l. Basic Orange 22) in 520 grams of tetrahydrofuran, 330 grams of methylglycol and 150 grams of butyl acetate was applied to a 100~ thick aluminum foil which had its surface roughened by mechanical means.
: ~
After evaporation, the thickness of the electrophoto~raphic insulating layer was approximately S ~. The sensitivity of the layer was~ ~in the blue ~ ;
spectral range with a maximum at 480 nm. The energy re`quired to dis~
charge the layer to half the value of the initial potential was 8~W sec/
,: .
-10 - '' '''` K-2397
The present invention relates to a material for electrophotoyra-phic reproduction, composed of a conductive support and a sensitized photoconcluctive insulating layer adhering thereto.
It already has been proposed, in German Patent No. 1,058,836, to use photoconductors for electrophotographic reproduction having a spectral sensitivity which is generally in the long wave ultra-vlolet region of about 350 to 450 nm.
Ill order to extend the spectral sensitivity range to about 650 nm, it has been proposed to use various dyestuffs of different chemical ' - :
types as sensitizers. Dyestuffs which are effective are, for example, the following, which are listed in the Schultæ Dyestuff Tables (7th Edition, Volume 1, I931): triarylmethane dyestuffs, such as Brilliant ,, Green (No. 760, p. 314), Victoria Blue B (No. 822, p. 347), Methyl Violet (No. 783, p. 327), Crystal Violet (No. 785, p. 329), Acid Violet~
6B (No. 831, p. 351); xanthene dyestuffs, i.e. rhodamines, such as Rhodamine B (No. 864, p. 365), Rhodamlne 6G (No.~866, p. 366), ~ `
Rhodamine G extra (No. 865, p. 366), Sulforhodamine B (No. 863, p.
364) and ~Fast Acid Eosin G (No. 870, p. 368), also phthalelns, such as Eosin S (No. 883, p. 375), Eosin A (No. 881, p. 374), Ery~hrosin (No.
886, p. 376), Phloxin (P~o. 890, p. 378). BengaL Rose (No. 889, p.
378), and Fluorescein (No. 880, p. 373); thiazine dyestuffs, such as methylene blue (No. 1038, p. 449); acricline dyestuffs, su~ as,Acridlne Yellovr (No. 901, p. 383), Acridine Orange (No. 908, p. 387) and T rypafiavin (No. 906, p. 386); Quinoline dyestuffs, such as Plnacyanole ~.
(No 924, p. 396) and Cryptocyanine (No. 927, p. 397); Quinone dy~-stuffs and ketone dyestuffs such as Alizarin (No. 1141, p. 499~, Aliza-rin red S (No. 1145, p. 502) and Quinizarin (No. 1148, p. 504); and , ~: .
cyanine dyestuffs.
. ,~ .
1~ ~'~ `'".
.
~8~3;26 The sensltization of the photoconductors is based in principle on the fact that the light energy available in the long wavelength range is absorbed by the sensitizers and transferred to the photoconductor molecule.
The object of the invention, by contrast, was to undertake sen- i sitization in the short wavelength absorption range of the photoconductor, i.e. in the blue range of the spectrum. Such sensitization hitherto has been regarded as undesirable, because it would prevent the reproduction of blue portions, e.g. of ink or ball-point pen paste, of an original.
The present invention provides a material for electrophotographic reproduction, which comprises a conductive support having a sensitized photo- ;~
conductive insulating layer thereon containing at least one photoconductor and containing as a sensitizer a polymethine dyestuff capable of absorbing radiation of a wavelength within the spectral range of from 400 to 550 nm, preferably 480 to 520 nm.
A particularly suitable sensitizer is a polymethine dyestuff capable of absorbing radiation of a wavelength within the specified spectral range and having the general formula I ~
~:
(C~1~)2 ;;
~: C- C= C-A ( 1 ) X
wherein A is an unsubstituted or alkyl, alkoxyI or aryl substituted indolyl group, an unsubstituted or alkyl, alkoxyl or aryl substituted benzthiazolyl-amino group, an unsubstituted or alkyl, alkoxyl or aryl substituted phenyl-amino gTOUp, or an unsubstituted or alkyl, alkoxyl or aryl substituted indollnyl ," ' .
,t ~
' ~' .. . . . .. . . . .. . . ..
:10~3 43Z6 K - 2 3 9 7 group, ancl X~ is a monovalellt anion, preferably a halide lon, more preferably a chloride ion.
The sensitiæer is prcferably either C. I. Basic Orange 21 (C.I.
98035 - Astrazone Orange G) of the forrnula II
(CH3)2 H
~J\ c - c = c - c --N~ H H3C - C
H3C ~ N
C 1 ~
or C. I. Basic Orange 22 (C.I. 48040 - Astrazone Orange R) of the formula III
~,.C - C =
H3C ~ H H /C~ ~ (tII) Cl 0 CH3 -As a result of the presence of the sensitizer, the~photoconduc~
tive layer becomes sensitive to blue light, which is necessary in par-ticular with regard to the use of argon ion lasers in reproduction tech-~ i : ~ . . . . .
nology, which has recently achieved great importance. Furthermore, in '. .. ~ ;, ~,.
~,special fields of reproduction technology, mounting sheets are used ~ ~ ~
: , with blue lines which are not reproduced during reproduction on litho-graphic silver fitm. Insofar as the silver film materials a~e to be re-placed by electrophotographic ~materials, it is necessary to sensitize , .
the latter to ùlue light.
Sorprislngly, it is possible~ according to the invention to sensi-tize organic photoconductors in a range close to their own natural ~ 3~
10~3432f.i K-2397 al~sorptioll r(lngt!s so ~llat a sensitivity i9 obtained which suhstantially corre~sporlds to the lithograpllic film.
Since the proportion o~ sensitizer compared with the proportion of photoconcluctor in an insulating layer is generally relatively small and is preferably about 0.01% by weight, calculated on the photoconductor weight, it was not to be expected that a sensitizer would cause an In-crease in the sensitivity of the photoconductor. This e~pectation is con-firmed by the fact that the use of known sensitizers suah as Thioflavln, Acridlne Orange, Trypaflavin or Acridine Yellow does not give a corres~
ponding increase. No~ was it intended to cause such an increase within the characteristic sensitivity range. Instead, all efforts were almed at extending the sensitivity into the yellow and red spectral ranges. ~ -The photoconductive insulating layer contains from about 0~01 to 10 per cent by weight of sensitizer, preferably about 5 per cent, calcu-lated on the total weight of the photoconductor component.
Sensitizers which are used according to the invention~ are poly~
methine dyestuffs which absorb in the spectrat range of 400 to 550 nm, preferaùly 480 to 520 nm, and the two orange dyestuffs mentioned;above are espe~cially preferred. Other dyestuffs which advantage~ously may be used include for example, C.l. Basic Yellow 11 (C.I. 48055), known as A6trazone Yellow 3G, C.I. Basic Yellow 12 (C.I. 48065), known as . .
Astrazone Yellow 5G, and Basic Yellow 52115 (C~Io 48060)/ ancl also the as yet unclassified relatecl dyestuffs Astrazone Orange 3R, Astrazone ...... . .
Yellow 7GLL, ~strazone Yellow GRL and Astra Yellow R.
;
An insulating photoconductive layer containing one of these ;~
sensitizers requires an energy of about 10~Wsec/cm2 for disoharge to half the value of the initial potential, which means for an organic photoconductive layer great sensitivity to light of 490 nm.
-: _ ~ _ It llas beQn ound thL~t in the production of printing forms this great s~nsitivity to light of the copying materials achi~3ves ever greater importance, since because o~ it the ac:cess time to the actual information ` can be shortened.
The electrophotogrdpllic material of the invention ls especially' intended for use in the electrophoto~raphic producton of prlnting forms and printed circuits, and the conductive support may be any material suitable for this purpose, for example, aluminum, zlnc, magnesium or copper plates or mutti-metal plates, and also cellulose products, for ~ ;
example, special papers, cellulose hydrate, cellulose acetate or cellu- '~ ' lose butyrate films, especially partially saponified cellulose acetate or .
butyrate films. Some plastic materials, for example, polyamides in film form or'metal-vaporized films, are suitable for use as supports.
Surface-aged atuminum foits have' proved particularly suitable.
. ~
The surface-aging process comprises mechanical or electrochemical roughening and, if required, ~subsequent anodlzing and treatment with polyvLnyl phosphonic acid, as~described, ~for exampLe~,~ ln C~erman Offen-legungsschrift No. 1,621,478.
Preferred photoconductors for use in the sensitizéd insulating layer are those mentioned in German Patent No. 1,120,875,~especially substituted vinyl oxazoles such as 2-vinyl-4-(2'-chlorophenyl)-5-(4"- '^
~' ~ diethyl-aminophenyl)-oxazole. Other suitable photoconductors include, for example, triphenylamine derivatives, higher condens~ed~matic com~
pounds, such as anthracene, benzo-condensed heterocyclic compounds, and pyrazoline or imidazole derivatives.
`~ Also suitable are triazote and oxadiazole derivatives, as dis-closed lnGermanPatents~Nos~. 1,060,260, and 1,058,836 2,5-bis-(4'-diethylaminophenylj-1,3,4-oxadiazole is particularly suitable, In . : .~ ' , -: :
-5- ~ ' `J ~
432~; K - 2 3 9 7 ion, vinyL ~lromatic polymers such as polyvinyl anthracene, poly-(l( el)c~p~lLhylelle~ poly-N-vinylcarbazole and copolymers of these com-pouncls arc suitable, provided they are suitable for a solubility differen-tiatioll with respect to the toner covered image areas and to the non-imac3e areas, in conjunction with a resin binding agent if requirecl. Also suitable are polycondensates of aromatic amlnes and alàehydes, EIS cle-scribed in German AuslegeschPift No. 1,197,325, and resins as de-scribed in German Offenlegungsschrift No. 2 ,137,288 .
The photoconductive layer preferably also contains one or more resin binders. With regard tothe film properties and adhesion, natural and/or synthetic resins are suitable for US8 as resin binders. In addition to the film-forming and electrical properties, and also adhesion to the support, solubility properties in particular play a special part in their selection. For practical purposes, the resin binding agents which are particularly suitable are those which are soluble in aqueous or alcoholic :
solvent systems, with the addition of acid or alkali if required. Aromatic ~;
or aliphatic, easily combu~stible;~solvents are excluded for physiologlcal ~ , , and safety reasons. The most suitable resin binding agents are high molecular substances carrying alkali-solubilizing groups. Such groups are, for example, acid anhydride, carboxyl, phenol, sulfonic acid, suL-fcnamSde or sulfonimide groups. Resin l:inding agents with high acid ~numbers are preferably used, since these are particularly easily soluble i n alkaline-aqueous~alcoholic solvent systems. Copolymers with anhy-~: -dride groups can be used with great success, since due to the absence of free ac~d grcups the dark conductivity of the electrophotographic layer is low, in spite of good solubility in alkali.
Copolymers of styrene and maleic anhydride, for example, those - ~ known under~the name Lytron(~, Monsanto Company, USA, are especially ~ ~432~; K- 2 3 9 7 suitable, also phenol reslns, for example those known under the narne Alnovol , Hoechst AG, Werk Albert, Germany, have proved very satis Eactory .
The following examples furth~r lllustrate the inventlon: ;
Comparison Example A solution is prepared containing 40 g of 2-vinyl-4-t2'~chloro-phenyl)-5-(4"-diethylaminophenyl)-c~azole and 60 g of a styrene/maleic anhydride copolymer in 300 g of ~lycol monomethyl ether, 470 ~ of tet-rahydrofuran, and 130 g of butyl acetate. Thç resulting stock solutLon ..
is divided into portlons of 150 g each. One of the portions remains un-sensitized . To each of the other five solutlons 0 . 6 ml of a 0 .1 per cent methanol solution of a dyestuff is added,~ usIng the known dyestuff sen-sitizers Thioflavin, Trypaflavin, Acridine Yellow and Acrldine Oran~e and ~, the sensltizer used according to the present Invention,~viz. Astrazone Orange R. The quantity of sensitizer~alded, calculated on the photocon-ductor weight, is 0.01 per cenlt. ~The solutions are cast~ in known manner .
lnto photoconductor layers and the sensiti~ity of these~layers at 490 nrn~
is determined. In the case of the known~dyestuff sensitlzers~Thioflavin, TrYpaflavin~Acridine Yellow and~Acrid~ne Orange, no aensitizing effect and enzuing incseazed sensitivity~over that of the pure~photoconductor layer can be detected. In the~case of Astrazone Orange R,~however, the sensitivity of the photoconduotor is unmlstakably increazed by a factor greater than 2.
ExamPle I
A zolution of 40 grams of ~2-vinyl-4-~2'-chlorophenyl)-5-~4"~
diethylaminophenyl)-o~azole,;47~grams~of a oopolymer of styrene and ~; maleic acid anhydride,~ 10~`gràms of a chlorocaoutchouc and 2 grams of , Astrazone Orange R (C,I. Basic Orange 22) in;S10 grams of tetrahydro~
;:
furan, 330 grams of methylglycol and iS0 grams of butyl acetate was 3Z 6, K-2 3 9 7 appli~cl to a 100~ thick aluminum foil, which had been rnechanically rougllened by wire brushing, with a brush depth of approximately 331.
After the evaporation of the solvent there remained a photoconductor layer with a thickness of 4-5~, which absorbed light in the blue spectral range witll a maximum at ~90 nm and became photoconduct~e. The energy re-quired to discharge the layer to half the charge potential was 10~W sec/
cm2. The layer was charged in the manner usual for electrophotography with a corona device to a surface potential of - 400 V and imagewise ex-posed with a modulated 10 mW argon ion laser having a wavelength of 488 nm. A printing form was produced by the process described ln German Auslegeschrift No. 1,117,391.
Example 2 A solution of 27 grams of 2-vinyl-4-(2'-chlorophenyl)-5-(4"-di-ethylaminophenyl)-oxazole, 38 grams of a copolymer of styrene and maleic acid anhydride, 12 grams of a chlorocaoutchouc and 1.35 grams of Astra- ~-zone Orange R (C~I. Basic Orange 22) in 410 grams of tetrahydrofuran, 260 grams of methylglycol and 120 grams of butyl acetate was applied to a 300 ~ thick aluminum foil which had ~been electrochemically roughened, anodized and treated with polyvinylphosphonic acid. After drying with warm air, the thickness of the layer was about 5~. The sensitivity corresponded to that of the laYer desctibed in Exampte 1. After charging and imagewise exposure with a modulated 15 mW argon ion laser, a printing form was produced by the proceas described in German Offenle-gungsschrift No. 2, 322, 046 .
Example 3 - A solution of 4S grarns of 2-vinyl-4-~2'-chlorophenyl)-5-(4"-di-ethylaminophenyl)-oxazole, 45 grams of a copolymer of styrene and maleic acid anhydride and 2.25 grams~of Astrazone Orange R (CoI~ Basic ~ K-2397 OrancJe 22) in 280 cJrams of tetrahydrofuran, 180 grams of methylylycol and 8~ rams of butyl acetate was prepared and used to coat a polyester film about 100~ thick having aluminum vaporized onto it. A~ter evapo- -ration of the solvent, there remained a photoconductor layer about 5~
thlck with a maximum sensltivity ln the blue spectral range. The film was charged with a corona device to about - 450 V and exposed in a repro-camera with 8 auto photo lamps of 500 watts each for 25 seconds.
The mountin~ of a printed circùit on a board printed with blue orientatlon lines served as the original. Due to the high sensitivity ~o light of the ..
photoconductor layer in the blue spectral range, these blue orientation lines were not reproduced on the copied film. After the development and removal of the photoconductor layer in the exposed areas accordlng to the process described in German ()ffenlegungsschrift No. 2, 322 ,047, the thin vaporized aluminum layer was removed by treatment with 2N
sodium hydroxide solutlon, and a~pri~ted~clrcuit was obtained.
~xample 4 The solution of photoconductor, blndirlg agent and sensiti er de~
scribed in Example l, lnstead of ~being~applied to a mechanically rough~
ened aluminum foil, was~ applled~to~a~zinc plate as conventionally used in relief printing. After evaporatlon ~f the ~sotvent, the about 4~1 thiak photoconductor layer whlch was sensitlve in the blue range was nega~
tively charged with a corona device tc about 450 V. The photoconductor layer was exposed with an image-modulated beam from~a 10 mW argon ion laser, and~ an energy~ cf~ about ~10 5 ~W-~sec/cm 2 was required to dis-charge the layer. The conversion into a~ printing form was carried out in the manner described ln German~ ~Auslegeschrift No. 1,117,391, by development with a toner powder, f~ing the~ toner powder by means of heat, and removing the photoconduct~:ar layer by the action of an ;
_ 9 _, , :
allialine aLcoholic solution. Etching to produce a relief printing form is carried out wlth diluted nitric acid in the manner usual for the production of electrotypes.
Example 5 The coating solution describled und0r Example 3 was used to coat a multi-metal plate made of aluminum/copper/chromium. After the dried layer had been charyed, it was exposed w1th a modulated argon lon laser in the manner described in Example 4. Development, fixing and decoat-ing were carried out in a conventional manner. Conversion lnto a print-in~ form was carried out by etching away the chromium layer in the areas affected by the laser li~ht by means of a commers;:ial chromium etching substance, thereby exposing copper, and subsequently dls501viny away the developed photoconductor image by means of methylene chloride.
The exposed chromium surface was water-accepting. The number of prints which could be obtained wlth the planographic printing form pro- :
duced was very large.
Exampl~ 6 A solution of 40 grams of 2,5-bis-(4'-diethylaminophenyl)-1,3,4-oxadSazole, 47 grams of a copolymer of styrene and maleic acid anhydrlde, 10 grams of a chlorocaoutchouc and 2.0 grams of Astrazone Orange R
(C.l. Basic Orange 22) in 520 grams of tetrahydrofuran, 330 grams of methylglycol and 150 grams of butyl acetate was applied to a 100~ thick aluminum foil which had its surface roughened by mechanical means.
: ~
After evaporation, the thickness of the electrophoto~raphic insulating layer was approximately S ~. The sensitivity of the layer was~ ~in the blue ~ ;
spectral range with a maximum at 480 nm. The energy re`quired to dis~
charge the layer to half the value of the initial potential was 8~W sec/
,: .
-10 - '' '''` K-2397
2 ~ 3Z~
cm at ~7 nm. AEter being charged to - 450 V, the plate was exposed by rneans oE a 10 mW ar~on ion laser, the beam of whlch was modulated to corresponcl to the lmage. Conversion lnto a printing form was achiev-ed by developing and decoat1ng acco~dlng to Gerrnan Offenlegungsschrift No. 2,322,046. The plate produced high quality prints with a resolution of 6 lines/nm (60 screen) and an edltion of up to 100,000.
Example 7 ~
10 grams of 2,5-bls-(4'-diethylqminophenyl)-1,3,4-oxadiazole, 10 grams of a copolymer of styrene and maleia acld anhydride and 0.5 g of Astrazole Yellow 7 GLL were dissolved in 12~ grams of glycol mono-methylether, 30 grams of butyl acetate and 26 grams of butanone, and the solution was applied to a 100~ thlok aluminum foil mechanically rough-ened on the surface, in such a way that ~after~ evaporation of the solvent the thickness of the layer Was abQut S~. Th~ layer had a maximum spectral sens~tivity at 440 nm.~ ~The enè~r~y required to dlscharge the charged layer to half the~value ~ln~tial 'p~Otential was S~W sec/cm . ;
The layer was aharged, ~exposed ~a~ dev~loped~in~the usual~manner to produce a prlnting form. The mount~`lng D~a p~age of a newspaper senred as the original, using a support w~ blue orientation llnes.~ After re~
moval of the untoned, exposed areas o~he photoconduotor layer accord~
ing to German Offenlegungsschrift~No. 2,~322,047, a planographic printing form for newspaper~ print~n~; was 'o~tained. ~ ;
It will be obvious to those~ skilled'~in~the art that many modifi-oations may be made wlthln th~ sr~of ih,~present ~invention~;without ~eparting from~the spirit ~thereof, q~he~'inv~ention includes all~ suah madiflaatiaas .- j -. . ;
J
cm at ~7 nm. AEter being charged to - 450 V, the plate was exposed by rneans oE a 10 mW ar~on ion laser, the beam of whlch was modulated to corresponcl to the lmage. Conversion lnto a printing form was achiev-ed by developing and decoat1ng acco~dlng to Gerrnan Offenlegungsschrift No. 2,322,046. The plate produced high quality prints with a resolution of 6 lines/nm (60 screen) and an edltion of up to 100,000.
Example 7 ~
10 grams of 2,5-bls-(4'-diethylqminophenyl)-1,3,4-oxadiazole, 10 grams of a copolymer of styrene and maleia acld anhydride and 0.5 g of Astrazole Yellow 7 GLL were dissolved in 12~ grams of glycol mono-methylether, 30 grams of butyl acetate and 26 grams of butanone, and the solution was applied to a 100~ thlok aluminum foil mechanically rough-ened on the surface, in such a way that ~after~ evaporation of the solvent the thickness of the layer Was abQut S~. Th~ layer had a maximum spectral sens~tivity at 440 nm.~ ~The enè~r~y required to dlscharge the charged layer to half the~value ~ln~tial 'p~Otential was S~W sec/cm . ;
The layer was aharged, ~exposed ~a~ dev~loped~in~the usual~manner to produce a prlnting form. The mount~`lng D~a p~age of a newspaper senred as the original, using a support w~ blue orientation llnes.~ After re~
moval of the untoned, exposed areas o~he photoconduotor layer accord~
ing to German Offenlegungsschrift~No. 2,~322,047, a planographic printing form for newspaper~ print~n~; was 'o~tained. ~ ;
It will be obvious to those~ skilled'~in~the art that many modifi-oations may be made wlthln th~ sr~of ih,~present ~invention~;without ~eparting from~the spirit ~thereof, q~he~'inv~ention includes all~ suah madiflaatiaas .- j -. . ;
J
Claims (22)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A material for electrophotographic reproduction, which comprises a conductive support having a sensitized photoconductive insulating layer thereon containing at least one organic photoconductor and containing, as a sensitizer, a polymethine dyestuff which absorbs radiation of a wavelength within the spectral range of 400 to 550 nm and having the general formula wherein A is an unsubstituted or alkyl, alkoxyl or aryl substituted indolyl group, an unsubstituted or alkyl, alkoxyl or aryl substituted benzthiazolyl-amino group, an unsubstituted or alkyl, alkoxyl or aryl substituted phenyl-amino group, or an unsubstituted or alkyl, alkoxyl or aryl substituted indolinyl group, and X- is a monovalent anion.
2. A material as claimed in claim 1 wherein the sensitizer dyestuff is capable of absorbing radiation of a wavelength within the spectral range of 480 to 520 nm.
3. A material as claimed in claim 1 wherein X- is a halide ion.
4, A material as claimed in claim 3 wherein X- is a chloride ion.
5. A material as claimed in claim 1 wherein the sensitizer is C.I.
Basic Orange 21 (C.I. 48035).
Basic Orange 21 (C.I. 48035).
6. A material as claimed in claim I wherein the sensitizer is C.I.
Basic Orange 22 (C.I. 48040).
Basic Orange 22 (C.I. 48040).
7. A material as claimed in claim 1 wherein the sensitizer is C.I. Basic Yellow II (C.I. 48055), Basic Yellow 52115 (C.I. 48060), or C.I. Basic Yellow 12 (C.I. 48065).
8. A material as claimed in claim 1 wherein the sensitizer is Astrazone Orange 3R, Astrazone Yellow 7GLL, Astrazone Yellow GRL or Astra Yellow R.
9. A material as claimed in claim 1 wherein the photoconductive insulating layer contains 0.01 to 10 percent by weight of sensitizer, calculated on the total weight of the photoconductor.
10. A material as claimed in claim 9 wherein the photoconductive insulating layer contains about 5 percent by weight of sensitizer, cal-culated on the total weight of the photoconductor.
11. A material as claimed in claim 1 wherein the photoconductive insulating layer includes as a photoconductor an oxazole, triazole or oxadiazole derivative.
12. A material as claimed in claim 11 wherein the photoconductor is a substituted vinyl oxazole.
13. A material as claimed in claim 12 wherein the photoconductor is 2-vinyl-4-(2'-chlorophenyl)-5-(4"-diethylamanophenyl)-oxazole.
14. A material as claimed in claim 11 wherein the photoconductor is 2,5-bis-(4'-diethylaminophenyl)-1,3,4-oxadiazole.
15. A material as claimed in claim 1 wherein the conductive support comprises aluminum foil of which the surface adjacent the photoconductive insulating layer has been mechanically or electrochemically roughened.
16. A material as claimed in claim 15 wherein the surface of the aluminum foil has been electrochemically roughened, anodized, and treated with polyvinyl phosphonic acid.
17. A material as claimed in claim 1 wherein the photoconductive insulating layer includes as a binder a natural or synthetic resin.
18. A material as claimed in claim 17 wherein the binder comprises a polymeric material containing alkali-solubilizing groups.
19. A material as claimed in claim 18 wherein the binder comprises a polymeric material containing acid anhydride groups.
20. A material as claimed in claim 19 wherein the binder comprises a copolymer of styrene and maleic anhydride.
21. A process foir the production of a printing form or a printed cir-cuit, which includes imagewise exposing and developing a material as claimed in claim 1.
22. A printing form or a printed circuit comprising an imagewise ex-posed and developed photoconductive insulating layer which is on a conductive support, said layer containing at least one organic photoconductor with, as a sensitizer, a polymethine dyestuff which has absorbed radiation of a wave-length within the spectral range of 400 to 550 nm and which has a general formula wherein A is an unsubstituted or alkyl, alkoxy or aryl substituted indolyl group, an unsubstituted or alkyl, alkoxy or aryl substituted benzthiazolylamino group, an unsubstituted or alkyl, alkoxy or aryl substituted phenylamino group or an unsubstituted or alkyl, alkoxy or aryl substituted indolinyl group, and X- is a monovalent anion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752526720 DE2526720C3 (en) | 1975-06-14 | Electrophotographic reproduction material | |
| DEP2526720.3 | 1975-06-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1084326A true CA1084326A (en) | 1980-08-26 |
Family
ID=5949162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA254,670A Expired CA1084326A (en) | 1975-06-14 | 1976-06-11 | Substituted indolinium polymethine dyestuff sensitizer used with an organic photoconductor |
Country Status (20)
| Country | Link |
|---|---|
| US (1) | US4063948A (en) |
| JP (1) | JPS522437A (en) |
| AT (1) | AT347239B (en) |
| AU (1) | AU507694B2 (en) |
| BE (1) | BE842889A (en) |
| BR (1) | BR7603771A (en) |
| CA (1) | CA1084326A (en) |
| CH (1) | CH604219A5 (en) |
| DK (1) | DK142514C (en) |
| ES (1) | ES448823A1 (en) |
| FI (1) | FI59681C (en) |
| FR (1) | FR2314521A1 (en) |
| GB (1) | GB1553696A (en) |
| IE (1) | IE42855B1 (en) |
| IT (1) | IT1061763B (en) |
| LU (1) | LU75147A1 (en) |
| NL (1) | NL187249B (en) |
| NO (1) | NO142552C (en) |
| SE (1) | SE418121B (en) |
| ZA (1) | ZA763486B (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2014748B (en) * | 1978-02-07 | 1982-06-16 | Konishiroku Photo Ind | Electrophotographic material for obtaining toner image and process for forming printing plate by using the same |
| DE2817428A1 (en) * | 1978-04-21 | 1979-10-31 | Hoechst Ag | MATERIAL FOR ELECTROPHOTOGRAPHIC REPRODUCTION |
| US4387149A (en) * | 1978-10-13 | 1983-06-07 | Mitsubishi Paper Mills, Ltd. | Electrophotographic sensitive material having a dye sensitizer containing a carbonium atom |
| JPS5579451A (en) * | 1978-12-12 | 1980-06-14 | Mitsubishi Paper Mills Ltd | Sensitizer for electrophotographic organic photoconductor |
| DE3005695A1 (en) * | 1980-02-15 | 1981-08-20 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING A FLAT PRINT FORM BY ELECTROPHOTOGRAPHIC WAY |
| DE3024772A1 (en) * | 1980-06-30 | 1982-01-28 | Hoechst Ag, 6000 Frankfurt | ELASTIC, LAMINATE LIGHT SENSITIVE LAYER |
| DE3210576A1 (en) * | 1982-03-23 | 1983-10-06 | Hoechst Ag | ELECTROPHOTOGRAPHIC RECORDING MATERIAL |
| AU2239683A (en) * | 1982-12-16 | 1984-06-21 | Vickers Plc | Photoconductive compositions |
| JPS59216146A (en) * | 1983-05-24 | 1984-12-06 | Sony Corp | Electrophotographic sensitive material |
| DE3319654A1 (en) * | 1983-05-31 | 1984-12-06 | Hoechst Ag, 6230 Frankfurt | ELECTROPHOTOGRAPHIC RECORDING MATERIAL |
| DE3405487A1 (en) * | 1984-02-16 | 1985-08-22 | Hoechst Ag, 6230 Frankfurt | ELECTROPHOTOGRAPHIC RECORDING MATERIAL |
| DE3409888A1 (en) * | 1984-03-17 | 1985-09-19 | Hoechst Ag, 6230 Frankfurt | LIGHT-SENSITIVE RECORDING MATERIAL AND USE THEREOF IN A METHOD FOR PRODUCING A PRINTING FORM OR PRINTED CIRCUIT |
| DE3417951A1 (en) * | 1984-05-15 | 1985-11-21 | Hoechst Ag, 6230 Frankfurt | ELECTROPHOTOGRAPHIC RECORDING MATERIAL |
| DE3509147A1 (en) * | 1985-03-14 | 1986-09-18 | Hoechst Ag, 6230 Frankfurt | ELECTROPHOTOGRAPHIC RECORDING MATERIAL |
| DE3513747A1 (en) * | 1985-04-17 | 1986-10-23 | Hoechst Ag, 6230 Frankfurt | ELECTROPHOTOGRAPHIC RECORDING MATERIAL |
| DE3541534A1 (en) * | 1985-11-25 | 1987-05-27 | Hoechst Ag | POSITIVELY WORKING RADIATION-SENSITIVE MIXTURE |
| DE3617077A1 (en) * | 1986-05-21 | 1987-11-26 | Hoechst Ag | EMULSION FOR TREATING ELECTROPHOTOGRAPHICALLY PRODUCED FLAT PRINTING FORMS AND METHOD FOR PRODUCING THE FLAT PRINTING PLATES |
| DE3627758A1 (en) * | 1986-08-16 | 1988-02-18 | Basf Ag | METHOD FOR PRODUCING ELECTROPHOTOGRAPHIC RECORDING ELEMENTS |
| DE3627757A1 (en) * | 1986-08-16 | 1988-02-18 | Basf Ag | METHOD FOR PRODUCING FLAT PRINTING PLATES |
| DE3832903A1 (en) * | 1987-09-29 | 1989-04-06 | Fuji Photo Film Co Ltd | ELECTROPHOTOGRAPHIC PRINT PLATE |
| DE3800617A1 (en) * | 1988-01-12 | 1989-07-20 | Hoechst Ag | ELECTROPHOTOGRAPHIC RECORDING MATERIAL |
| JPH01158456A (en) * | 1988-09-30 | 1989-06-21 | Ricoh Co Ltd | Image recording device |
| JPH02140240U (en) * | 1989-04-26 | 1990-11-22 | ||
| DE4118434C2 (en) * | 1990-06-06 | 1996-01-04 | Mitsubishi Paper Mills Ltd | A method of electrophotographic reversible wet development |
| US5494764A (en) * | 1992-03-26 | 1996-02-27 | Mitsubishi Paper Mills Limited | Method for making printed circuit boards |
| US6645685B2 (en) * | 2000-09-06 | 2003-11-11 | Mitsubishi Paper Mills Limited | Process for producing printed wiring board |
| US20050091060A1 (en) * | 2003-10-23 | 2005-04-28 | Wing Thomas W. | Hearing aid for increasing voice recognition through voice frequency downshift and/or voice substitution |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2639282A (en) * | 1949-09-29 | 1953-05-19 | Eastman Kodak Co | Resin-dyes of the cyanine type |
| US2974141A (en) * | 1958-12-17 | 1961-03-07 | Gen Aniline & Film Corp | P-(2-pyrazolin-1-yl) styryl dyes |
| BE606888A (en) * | 1960-08-05 | 1900-01-01 | ||
| US3287114A (en) * | 1961-07-24 | 1966-11-22 | Azoplate Corp | Process for the sensitization of photoconductors |
| US3666464A (en) * | 1967-04-26 | 1972-05-30 | Itek Corp | Dye-sensitized photosensitive materials having improved photographic speed |
| JPS4946264B1 (en) * | 1969-01-17 | 1974-12-09 | ||
| JPS492638B1 (en) * | 1970-11-17 | 1974-01-22 | ||
| DE2214054A1 (en) * | 1972-03-23 | 1973-09-27 | Agfa Gevaert Ag | SENSITIZED ELECTROPHOTOGRAPHIC LAYERS |
| JPS5531463B2 (en) * | 1972-05-31 | 1980-08-18 |
-
1976
- 1976-06-09 AU AU14749/76A patent/AU507694B2/en not_active Expired
- 1976-06-10 US US05/694,712 patent/US4063948A/en not_active Expired - Lifetime
- 1976-06-10 CH CH735576A patent/CH604219A5/xx not_active IP Right Cessation
- 1976-06-11 GB GB24309/76A patent/GB1553696A/en not_active Expired
- 1976-06-11 DK DK260076A patent/DK142514C/en not_active IP Right Cessation
- 1976-06-11 NL NLAANVRAGE7606342,A patent/NL187249B/en not_active IP Right Cessation
- 1976-06-11 ZA ZA763486A patent/ZA763486B/en unknown
- 1976-06-11 ES ES448823A patent/ES448823A1/en not_active Expired
- 1976-06-11 LU LU75147A patent/LU75147A1/xx unknown
- 1976-06-11 NO NO762039A patent/NO142552C/en unknown
- 1976-06-11 BR BR7603771A patent/BR7603771A/en unknown
- 1976-06-11 IT IT49909/76A patent/IT1061763B/en active
- 1976-06-11 CA CA254,670A patent/CA1084326A/en not_active Expired
- 1976-06-11 FR FR7617720A patent/FR2314521A1/en active Granted
- 1976-06-11 FI FI761678A patent/FI59681C/en not_active IP Right Cessation
- 1976-06-11 IE IE1263/76A patent/IE42855B1/en unknown
- 1976-06-11 BE BE167876A patent/BE842889A/en not_active IP Right Cessation
- 1976-06-11 SE SE7606661A patent/SE418121B/en not_active IP Right Cessation
- 1976-06-14 AT AT433576A patent/AT347239B/en not_active IP Right Cessation
- 1976-06-14 JP JP51069648A patent/JPS522437A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NO142552C (en) | 1980-09-03 |
| AU507694B2 (en) | 1980-02-21 |
| DE2526720B2 (en) | 1977-06-30 |
| LU75147A1 (en) | 1978-01-18 |
| BR7603771A (en) | 1977-02-08 |
| AU1474976A (en) | 1977-12-15 |
| SE418121B (en) | 1981-05-04 |
| ATA433576A (en) | 1978-04-15 |
| IT1061763B (en) | 1983-04-30 |
| AT347239B (en) | 1978-12-11 |
| FR2314521A1 (en) | 1977-01-07 |
| NO762039L (en) | 1976-12-15 |
| DK260076A (en) | 1976-12-15 |
| ES448823A1 (en) | 1977-12-01 |
| FI59681B (en) | 1981-05-29 |
| NO142552B (en) | 1980-05-27 |
| ZA763486B (en) | 1977-05-25 |
| SE7606661L (en) | 1976-12-15 |
| NL7606342A (en) | 1976-12-16 |
| JPS522437A (en) | 1977-01-10 |
| CH604219A5 (en) | 1978-08-31 |
| DK142514B (en) | 1980-11-10 |
| FI761678A (en) | 1976-12-15 |
| NL187249B (en) | 1991-02-18 |
| IE42855B1 (en) | 1980-11-05 |
| BE842889A (en) | 1976-12-13 |
| IE42855L (en) | 1976-12-14 |
| DK142514C (en) | 1981-06-29 |
| DE2526720A1 (en) | 1976-12-16 |
| FI59681C (en) | 1981-09-10 |
| JPS6113223B2 (en) | 1986-04-12 |
| FR2314521B1 (en) | 1983-01-28 |
| GB1553696A (en) | 1979-09-26 |
| US4063948A (en) | 1977-12-20 |
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| MKEX | Expiry |