DE1522717A1 - Imaging process using electrically light-sensitive particles - Google Patents

Description

DIPL.-ING. F.Weickmann, Ur. Ing.A-Weickmann, ljipl.-i.ng. in. weick-mann Dipl.-Phys. Dr. K. Fincke patent attorneys

8 MUNICH 27, MOHLSTRASSEJLRUFNUMMEaUJiMZaZ 1522717

RANK XEROX Ltd.
Rank Xerox House
338, Euston Road

London FW 1
ENGLAND

Imaging process rait with the help of electrically.light-sensitive Particle

The invention relates to imaging methods, and more particularly to the use of electrically photosensitive dyes in electrophotographic imaging processes.

There are already several types of electrophotographic ab-. Formation process known, the ■ electrically photosensitive dyes use. Uie, however, described in the application R 42 328

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"Ben, these experiences can still be improved: and it is great ^! " ■ '. wishes to enlarge the dye area from which a selection could then be made for carrying out such imaging processes. - -

The invention relates to electrophotographic imaging processes, the compounds of the general formula

1 13 12 11 · ■

H ". _Λ Ο

4 5 6 7 8 ■

use that can be substituted at suitable places, ■

The compounds of the above general formula belong to the class of substituted and unsubstituted l'riphenodioxazines. These compounds are also known as (1,4) Benzoxazine - (.?, 3 ~ b) phenoxazine; 5,12-moxa-7,14-diazopentacenes and triphenodioxazines. ■

Of the compounds according to the formula above, the the 6.13 places with a halogen and the 2.9 or 3.10 places substituted with an alkoyl or aryloyl for use'- ' preferred in electrophotographic imaging processes because they a particularly pure color and a very large light-sensitive have the ability. Of these, the most favorable 2,9-mbensyl-6,13-dichloro-triphenodioxazine have been found and 2,9 ~ diacetyl-6,1.5-dichl.or-triphenodioxazine ■ erv / icsen, These result in multicolored photoelectrophoretic Figures are the most frequently used combination

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of parbe and light sensitivity. "

-. ■ pa the .shade or hue of four dimensions and the spectral - um light-sensitive behavior depending on the use: ten 'substituents vary somewhat, one can get intermediate values of these Modifications obtained by mixing different compounds.

The compounds according to the above general formula and! Mixtures of these are particularly suitable as photosensitive dye particles for electrophoretic imaging processes, as described, for example, in application X 37 *

It has been shown that the compounds according to the above general formula when used in single or multicolored Electrophoretic imaging methods are particularly effective. : By her good. Spectral behavior and their great sensitivity to light result in dense, very good images. The dyes described here have surprisingly good color separation and image properties density properties. 'f

Together with the dyes, suitable substances can be used

^: v ■ '■ · ■■ .- ■.! ■■■■. te different colored photosensitive dye particles -. _v be exploited in order to Farbbildhers division one Farbstoffmis RECOVERY .. get into a Trägcrflltssigkeit. It has been found that: 2 to 10 Cev / 1 percent dye gives good results. Druch adding small amounts (in the range of 0.5 to 5 olprozentcr_ ^r) ".lektronendonatoren or suspensions for -äkzeptoren

Z I I I /

"sion, the sensitivity to light can be significantly increased,

.- .. The following examples describe the invention taking into account the use of compounds according to · the above general formula in elelctropliore tables. Imaging process. ^: Unless otherwise stated, parts and percentages are based on weight. . ■ '_..- _. .

. The. Examples serve to illustrate various preferred embodiments of the electrophoretic imaging process according to the invention. ■

All following examples 1-XVI v / grounding device with a _t performed, wherein the image carrier mixture NESA glass is brought to a through which the exposure takes place durchvden. The NESA glass surface is in series with a switch, a voltage source ..K nungsquelie and the conductive middle part of a role that on ^; its surface has a coating of baryta paper. The role

has an approximate diameter of 6, ^ 5 cm and becomes "with about } Moved 1.45 cm per second over the plate surface. The plate has a size of about 58 cm and is an exposure level of 86080 Iiux, measured against the uncoated ÜTESA glass

- surface, exposed. Unless otherwise stated, the

^: "Examples 1 Percentage by weight of the dye suspended in Sohio Odorless Solvent '344-0, imd the voltage applied is

: 2500 V. All dyes with. a relatively large particle size, as they are commercially available or manufactured are ground in a ball mill for 48 hours to get their

9Q9S40 / 1 32 p

Reduce the size in order to obtain a stable dispersion, which improves the sharpness of the images. The exposure takes place with a 3200 ° K lamp through a 0.30 graded gray wedge filter, to increase the sensitivity of the suspension to white light measure up. Yiratten filters are then used in separate experiments 29,61 and 47b placed individually on the light source to each the sensitivity of the suspension to red, green and blue Lies to measure.

Example I '.

About 7 parts of 2,9-dibenzyl-6,13-dichloro-triphenodioxazine will be in 100 parts SoMo Odorless. Solvent 34-40 suspended. "The. Mixture is smeared onto the liSSA glass slide and onto the roller electrode a negative voltage is applied. The plate will exposed through a Wratten filter 29 and the .Graukeilfilter so that the plate is exposed to red light. The results are shown in Table I.

_: .-..., '-.- Example II -

The experiment is carried out as in Example I, however Replace the Tratten filter 29 with a Wratten filter 61 so that the plate is exposed to green light. The results are listed in Table I.

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Example III

The experiment is carried out as in Example I, but the ■ Wratten filter 29 replaced by a Wratten filter 47b, so that . the plate is exposed to blue light. The. Results are in

Table I listed. . "'.;'.:

Example IV-

The experiment is carried out as in Example I, however . no color filter used so the plate is exposed to white light will. The results are shown in Table I.

Example V '■■

The experiment is carried out as in Example I, the voltage on However, the role is positive rather than negative. As in example I. a Wratten filter 29 is used to make the plate red light suspend. The results are shown in Table I.

Example Vl. ; ■■ '■■■.

The experiment is carried out as in Example V, but the Wratten filter 29 is replaced by a Wratten filter 61 so that the plate is exposed to green light. For the results, see Table I. ■ ' .

Example VII

'The experiment is carried out as in Example V, but the • Wratten filter 29 replaced by a Wratten filter 47b so that

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the plate is exposed to blue light. For the results see - Table I » _: -.

v. ■; '· .-. <rf ^; ■■■ '■■:. - .. ■■■■ -, ■■■■ ... '■

^ ■ ''. Example YIII

The search is carried out as in Example V, however. Icein Tratten uses filters so: that the plate. "Exposed to white light will. See Table I. '' for the results.

/.-:'■'■'■■■■-■. ' Example IX

- About 7 parts of 2,9- ⁱ -dioetyl-6,13 - diclilor-triphenodioxa2in are suspended in top parts of Sohio Odorless Solvent 344-0. The mixture is tested as in Example I * The Wratten filter 29 is used to expose the plate to red light. The results are shown in Table I.

r: - ■■ '; - Example X

i) The test is carried out as in Example IX, but is the · Tratten filter 29 is replaced by a Wratten filter 61, see above that the plates are exposed to green light. To the results -si ehe- tab hurry X. / ■ "

¹ V ::; ■ '.;'.- ■■ - Λ '■■■; Example XI

The Tersuch. is carried out as in Example IX, but is the Wratten filter 29 is replaced by a Wratten filter 47b, so that the plate is exposed to blue light. To the results

see table !. ■ '_ -.:'

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Example XII

The experiment is carried out as in Example IX, however no Tratten filter used, so the plate exposed to white light will. For the results, see Table I.

^: '. 'Example XIII

The experiment is carried out as in Example IX, but is on the roller electrode has a positive voltage instead of the negative voltage Tension laid. The plate is exposed through a written filter 29 ', so that it is exposed to red light. To the results see Table I. ■.

. -Example XIV '. ·

The experiment is carried out as in Example XIII, but the Wratten filter 29 is replaced by a Wratten filter 61 so that the plate is exposed to green Li ent, "For the results see Table I, / '■ .. ~ ' .

■■. · ■. ; ^_;: -; .- Example XV ";.

The experiment is carried out as in Example XIII, except that it is carried out that: -Wratten PiIt er 29 replaced by a V / rat th filter 47b, so that the plate is exposed to blue light. For the results, see Table 1, - ■■ "- ■ '.". '"

■ ^; '■' ■. ■■. ', .. Example XVI. ".. V.:

The experiment is carried out as in Example XIII, but is carried out

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no Wratten filter used, so the plate is exposed to white light will. For the results see table

T a b e 1 1 e

■ □ „, · „ ^ „τ roll chip- Wratten light- G-speed- - _nnYn example _nung ^ j _Pilter color / W] &

-2500 29 Red no —— 2, -—- --- -2500 ■; 61 green 1345 2.0 1, ,8th 0.2 -2500 47b blue 5380 —_ __ 4th 0.6 -2500 without White - 64.6 2.0 J, 8th 0.2 +2500 29 Red no 1, - - - ■ - +2500 61 , green . 5380 0.3; - 0 0.6 +2500 47b " blue 21520 _— ; - 6th 0.6 +2500 without White 10760 ■ 0.3 - 0.6 -2500 29 Red 10760 - - 0.4 -2500 61 green 3230 5.0 O 0.1 -2500 47b blue 538.0 ■ , - - 0.1 -2500 without White 2690 3.0 7, 0 0.2 +2500 29 Red no —_ -_ - _— +2500 61 green 3230 1.7 7, 0 0.2 +2500 47b blue 538Ό - 0.2 +2500 without White 3230 1/7 0 0.2

The Electrophorepic Sensitivity of Different Dyes e for red, green, blue and white light is according to the normal photographic process. The results are shown in the table: I. In the table shows the first Split the sorrows of the example. The second column shows the positive or negative voltage applied to the roller electrode

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■ .. ■ ■ i: ■ - ίο - ■. ■ ---; ■ - ■■ - .-. · ■.

in V, The VTratten! Tilter inserted between the light source and the HESA plate are listed in the third column. The ' fourth column contains the light colors falling on the plate, In the fifth column the photographic speed is the photosensitive mixture given in lux. The photographic Speed results from an optical density curve versus the logarithm of the exposure in lux. Ss is f · c. 0.3 gamma 'of the lower speed and fc 0.3 gamma of the upper - speed. The gamma plotted in column 6 is a standard photographic designation relating to the slope of the above curve. The maximum achieved and minimum reflective density is in each column and S plotted. In some examples, in which the sensitivity ' The resistance of the composition to the special light color is low, gamma and I) "" "are not measurable. Like the table too

May.

can be seen, the tested dyes are in the electrophoresis -see- sense particularly sensitive to green light. Bs can be seen that the dyes have particularly little effect on red and blue Address the light. You respond to something in the blue light.

In the following playing IVII - XXI is an equal amount of three different colored dyes containing suspension by dispersing the dyes in finely divided form in Söhio. Odorless Solvent 3440 made so that the dyes make up about 8 percent by weight of the mixture. This mixture is referred to as "tri-icing". The mixtures are each tested by brushing them onto a FISA glass slide and exposing them as in Example I. "Ss is used instead of the gray wedge filter

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and the Tratten filter placed a multicolored "Kodachrora" slide between the light source and the plate. As a result, a multicolored image is projected onto the plate as the roller moves over the surface of the coated NESÄ glass carrier. A barite paper barrier electrode is used and the roller is at the negative voltage of 2500 V with respect to the carrier. The roller is moved six times over the carrier. It is cleaned after each time. The power supply and exposure are maintained during the six-time movement. After the six-time movement is completed, the density and color separation * of the image obtained are estimated.

> ■ _ ■ Example XVII '. ■' ■■:

The dye suspension consists of a magenta dye, V'2 "19 ^ dibenzoyl-6,13-dichloro-triphenodi-oxazine; a cyan dye, Oyan GKTI ¹ , the beta form of copper plithal ο cyanins, 0 * I. Sr. 74160, from Oollway Colors . Company; and a yellow dye ;, S, 13r2ioxodinaphtho (1, 2-2 ', 3') -furan-6-carbox-m-; chloranilide, prepared according to the in the application R 42 328 ITb / "_; 12CL specified \ Yerfahren. This tri-blend is exposed to a multicolored image and gives a full color image of good density and color separation.

:. ^ '' ζ. ; . Example XYIII

The dye suspension consists of a magenta colored dye, 2,9-diacetyl-6,13-dlchloro-tripherLodioxazine; a cyan -

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dye, cyan, 3,3'-ethoxy-4, 4'-diphenyl-bis (1 "~ azo-2" -hydroxy-3 "-naplithanilide), CI I ¹ Tr. 21180, from Harmon Colors; and Algol αβΓο GG, 1, 2,5,6-Ms (O, G'-diphenyl) -thiazol-anthra- ■ cliinon, GI No. 67300 from General Dye Stuffs.This tri-position becomes a multicolored picture exposed and gives a full color image of good density and very good color separation.

Example XIX

& The dye suspension consists of a magenta colored dye, 3,10-dibeiisoyl.amiiio-2,9-diiosopropoxy-6,13-dichloro-triphenodioxazine; .a C, yan dye: a polychloride substituted Eupfei'phthalocyanin, C. I. lir. 74260, from Imperial Color and .. Ghemieal Company; and a yellow dye, Indofast Yellow Toner, Flavan thron, G. I. ITr, 706OO, by Harmon Golors, This Tri-Hiche is exposed to a multicolored image and gives a ■ full color image with good density and color separation.

.-. ^; - ■■■;: ■. Example XX -.

The dye suspension consists of a magenta dye: 2 -, 9-dibensoyl-6,13 - dichloro-triphenodioxazine; a cyan '■ ^; dye, Ifenolite Fast Blue G .. S ,, the alpha form of metal ^; free Phthalöcj'-arain, C, I. Hr. 74100, by Arnold Hoffcann Oom-: pany; and gelbera dye, 1-Gyan-2,3 - (. 3 ^r -ni1: rO) - ph-t'ho, lpyl-7., - 8-benzopyrroeolin, manufactured according to the method from the American patent application Serial Έο , 445 235 from 2 "4" 1965. Mesc l'ri-Kisch is exposed to a multicolored .OiId and results in full-colored images with a thick density and good color tones.

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Example XXI '

The dye suspension consists of a magenta dye, 2.9 difuroyl-6,15-CIiCIiIor-triphenodioxazine; a cyan dye V Cyan Blue XR, the alpha form of eupferphthaloeyanine, from Collway Colors; and a yellow dye, 2,4-di ~ (1'-anthraquinonyl-ainino) -6- (i ^u -p3n2enyl) -s-triaciii, prepared as described in the application R 42 99 ° 1Xa / 57e. This tri-blend is exposed to a multicolored image xind gives full color images of good density and color separation,.

The compounds according to the above general formula can can be used for xerographic imaging processes. You can in these processes in the same way as the compounds from application R 42 328 are used.

As far as the invention relates to xerographic imaging processes. it is described in the following using the examples, the detailed various preferred embodiments describe the invention. Relate parts, proportions and percentages unless otherwise stated, based on weight.

The xerographic plates used in the following examples are treated as follows. Mixtures of special dyes and a resin binder are made by grinding the dye or a solution of a binder and one or more solvents _; Treated in a ball mill. This is done by adding the desired dye content to the dyes

SQ9840 / T325

He receives the desired proportions of the resin solution in a mixture. A quantity of steel balls (size one-eighth) is added and the container is rotated for about half an hour to obtain a homogeneous dispersion. The cooled slurry is spread on an aluminum support and dried in the oven for about 3 minutes at about 100 ° C. The coated plate is stored in the dark for about 1 hour and then checked .. ·

In the examples, the panels are tested as follows. The plate is charged with a corona charger to about -400 T and exposed with a light-dark image. The plate will according to that given by Iv'alkup in US Pat. No. 2,518,551: Cascade method developed. The powder created on the plate * image corresponds to the projected image, the developed image can; either melted on the plate or electrostatically on a Transfer sheet to be transferred and melted there. T / will that If the image is transferred, the plate is then cleaned of the remaining image powder and can be used again for the above process be used.

Example ΧΣΙΙ:

To treat the xerographic plate, first about 2 parts of lucite 2Q42 "an ethyl methaerylate polymer from S * I. DuPont de liemours and Co." - "about 18 parts of benzene and about 1 part 2 ^ 9 - dibenzoyl-öjri'-diclilor- triphenodiQxazin mixed, This mixture; is in a thickness of about S. micron on :, an aluminum carrier :. . the panel is painted and hardened; ¹ daiin ^: charged, with-

ORKSfNALlMSPECTEp

With the help of a Simmons Omega Ό3 enlarger, the one Tungsten light source with an earbtera door of 2950 ° K "has, for 4-5 seconds with. exposed to a light-bunkel image (the lighting E "' strength: on the plate is 30 lux, measured with a Weston Light meter model Er. 756) and developed as above described. The resulting 3ild v / irä directly on the plate heat melted.

; 'Example XXIII

^: . : ■■ A

Zur- treatment of xero graphically en plate v / ground first, a binder and a solvent as described in Example XXII with about -1 ₁ part of 2-9 I3imethOxy - mixed for 6, 13-dichloro-triphenodioxaziii. This mixture is painted to a thickness of about G Iilcron on an aluminum support and cured. The plate is then: charged, with the help of a Simmons OmoQa Ό3 enlarger, which: a 'tolfram light source with a 3? Color temperature of /

l £ has imagesetter for 45 seconds with light-eineia Dunlcel ^image: tet (the illuminance on the disk is 30 lux measured with "INEM Weston Beleuehtungsmeßgerät model ITr 756th) and ent- (

/; ^: -: .- Example XXIY

To treat the xerographic plate, about 3 ; I! Eile lucite 2042 ra.it etv / a 100 parts benzene and about 10 parts 3, .- 1; O ^ Iiii> ensoylaTniiio-2,9-diethoxy-6,1 '^ -riiacirlamino-triphenodioxa ziii get-iincht. Sierae Finchuiig is about 8 Mi

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• Crown painted on an aluminum support and cured. The plate is then charged, with the help of a Simmons Omega D3 enlarger, which has a wolf light source with a color temperature of 2950 ° IC, for 45 seconds, with a bright and dark image exposed (the illuminance on the plate is... 30 lux, measured with a Weston light meter model STr. 756) and developed * The image is heat-melted on the plate. . ^: ■ - ■ ".- -

Example XSC? '

To treat the xerographic plate, approx Parts Lucite 2042. with about 90 parts benzene and about 10 parts 3,10-dibenzoylamine-2,9-diisopropoxy-6,13-dichloro-trihenodiOXacine mixed. This mixture comes in a strength of about 10 Micron painted on an aluminum support and cured. the

j plate is then loaded by a Pilmpοsitiv for about 30 seconds

J exposed '\ customer using a strong ,, long-wave ultraviolet light (1680 microwatts / _cm: eni of 3660 · A radiation at a distance of 45) and developed * Developed on the disk; Schaffert Patent US ■ in the process .2 576 .047-specified electrostatically onto a recording - transfer sheet _and; powder image is after νon. would be melted. The picture on the recording sheet, corresponds to the bertfied original, the plate v.drd cleaned of '". . Veise to be "refused" again * The. Picture on the Aü'fnalimeblatt, .- corresponds.-deia original. _: .

Example XXVI.

To treat the xerographic plate, first about 10 parts of Lucite 2042 are mixed with about 90 parts of benzene and about 2 parts of triphenodioxazine. This mixture is spread on an aluminum support to a thickness of about 10 microns and cured. The disc is then loaded, through a positive film for about 30 seconds using a strong, long-wave ultraviolet lamp exposed (1680 microwatts / cm "of 3660 A radiation at a distance of 45 cm) and developed. This corresponds M wrapped image electrostatically exceed a _{Aufnahmeblabt:} wear and v / ärmegeschmolzen the image on the Aufnahmehlatt corresponds to the original the plate is cleaned of residual powder image and can in the described "manner reused will...

Although in the examples about electrophoretic and xerographic Imaging process special compositions and ratios have been described, other suitable .3-substances with, similar results can be used, and the ITarb- | st of f compositions or the dye-resin compositions other substances are added to improve their properties, to strengthen or to influence differently. The coloring ■ and / or dye-resin compositions can if desired / be color sensitive or can be combined with other photoconductors, organic or inorganic, mixed or otherwise combined. . .

Other modifications and variations of the invention are possible.

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Claims (6)

Claims T 52271 7 r.J Imaging process in which an image is captured with the help of electrical photosensitive particles is produced, especially electrophoretic or xerographic imaging process, thereby characterized in that the particles contain substituted or unsubstituted triphenodioxasine. 2. Imaging method according to claim 1, characterized in that the particles are a 2,9 or 3,10-dialkoyl or diaryloyl triphenodioxazine contain, 3. Imaging method na, ch claim 1, characterized ^ ekemizsichnet that the particles contain 2,9-ibenzoyl triphenodioxazine. 4. Imaging method according to claim. 1, characterized in that the particles contain 2,9-diacetayl triphenodioxazine ... _r 5. Imaging method according to one of the preceding claims, characterized in that a layer of a suspension of said particles is an electric field between at least. zi-rei electrodes is exposed and. that the suspension is simultaneously an image -au ^ eöctzt, whereby at least one of the electrodes a fabric image is generated from migrated particles. 6. mapping method according to one of claims 1 to 4 »characterized in that leave the particles with an organic binder mixed and then to an electrostatically charged and with a pattern of activating electromagnetic radiation; exposed xerography marriage. Plate is brought to c. On this one Generate latent electrostatic image. '' 909840/1325 SAD ORIGINAL