DE2058025A1 - Method and apparatus for generating a positive image - Google Patents

Description

EGG. DU PONT DE NEMOURS AND COMPANY 10th and Market Streets, Wilmington, Delaware 19 898, V.St.A

Method and apparatus for generating a positive image

(1) Field of application of the invention

The invention relates to an exposure method and an exposure device for generating positive images, i.e. colored images on a relatively lightfast Background. In particular, the invention relates to a method and an apparatus of this type in those who work with light-sensitive materials that are exposed to light in a range of wavelengths activate for color formation and by irradiating with light of a different wavelength range at the color formation be prevented. The light-sensitive material is exposed in such a way that a positive reproduction of the original can be obtained obtained by exposing the material in a controlled manner to an overall exposure to the color-forming (image-forming) radiation subordinates and it at the same time in a "selected th pattern exposed to the color-preventing radiation. There-

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through is the material in the surfaces of the selected pattern what through the color-forming and color-preventing radiation irradiated together, and the color formation is prevented at these points.

(2) State of the art

U.S. Patents 3,390,996 and 3,390,994 and U.S. Patent Application Serial No. 740 476 of June 27, 1968 are light-activatable, color-forming, photosensitive substances, such as hexaarylbiimidazoles and leuco dyes, described which take on a color when irradiated with ultraviolet light and can be deactivated against the formation of such a color by giving them a light activatable oxidation-reducing agent mixture, for example a mixture of a quinone which can be activated by visible light and a compound which contains cleavable hydrogen, such as an aliphatic polyether or a Hitrilotrifettsäurealkylester _o These mixtures are referred to as "light-sensitive material". The irradiation of such mixtures with ultraviolet light produces a color which corresponds to the dye form of the leuco dye; on the other hand, the color-forming components are deactivated against color formation by irradiation with visible light. The deactivation is based on the formation of a hydroquinone from the ghinone used, and this preferably reduces the photoactivated hexaarylbiimidazole before the same can oxidize the leuco dye to the dye.

Phototropic spiropyran systems are in the United States patents 3,486,899, 3,485,765, 3,022,318, 2,978,462 and 2,953,454, in British Patents 889,186 and 887,902 as well in Dutch laid-open specification 69 03746.

These chromophore unsubstituted spiropyrans are generally almost colorless compounds in which the pyran ring

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is intact, and either reside as crystalline solids before or can also be dissolved in most solvents. These compounds can be converted to a colored state, if desired, with the 2'-1 'bond opened by irradiating them with light in which the blue to ultraviolet wavelengths predominate, and leaving them can be converted back to the uncolored state if desired by irradiating the solution in question with light that consists primarily of wavelengths in the green to infrared range of the spectrum.

Another photochromic substance, namely 2,3-diphenylindenone oxide, was made by E.F. üllman and W.A. Henderson, Jr., | in "Journal of the American Chemical Society", Volume 88 (1966), Page 4942. This compound undergoes reversible photoisomerization to give deep red pyrylium oxides.

The above publications describe photographic imaging and fixing processes using the photoimageable and radiation-deactivatable photosensitive material in two special processing steps subject to the action of two radiations in succession, the first radiation being used for image exposure, and depending on the sequence of exposure, one obtains a negative or a positive of the original.

i In these known systems runs preventing ^ color formation normally much slower than the color formation, and is therefore the limiting factor which determines the speed, can be provided with the light-sensitive objects on the basis of such compositions with a picture and fixed. The time taken to form a positive reproduced image is the sum of the periods of time required for the successive steps of color prevention and color formation. In many cases there is a need to this time up

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to shorten the formation of the end product. There is also a need for direct and quick dry, hard copies from a PiIm showing an image, especially as positive, directly readable enlargements of microfilms.

The invention is therefore based on the object of a simplified exposure method and a simplified exposure device for the production of positive images with the aid of the above-described, known photosensitive To develop compositions of matter, especially a Process for the production of dry, hard, black or white positive copies on paper or film directly of positive or negative films, or for the production of · color slides. This procedure is intended to be used for direct reproduction of microfilms in enlarged form.

Summary definition of the invention

The invention relates to a method for producing a positive image on a layer of one for two different ones Radiation-sensitive material that responds to rays of two different wavelengths in such a way that that when exposed to rays of the first wavelength range it becomes a first colored state and when exposed with rays of the second wavelength range changes into a second colored (or the colorless) state, and that characterized in that it is caused by simultaneous irradiation with rays of both wavelength ranges at the transition into the colored state can be prevented.

The method according to the invention is characterized in that that the named material located on a surface intended for image recording is simultaneous with rays of the exposed to both wavelength ranges, the radiation of the first wavelength range over the whole to be irradiated

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Surface is directed and has such an intensity that it is not struck by both types of radiation Points of the surface cause color formation, at those also hit by the radiation of the second wavelength range However, the surface does not cause any imaging, while the radiation of the second wavelength range in the form a pattern corresponding to the image to be recorded on the surface to be irradiated is directed and such an intensity has that it prevents the formation of color on the areas hit by it on the surface.

According to a preferred embodiment of the invention, use f det is a mixture of photosensitive material

(A) a color-forming component consisting of '!

(1) an organic film former and

(2) a first photoactivatable oxidizing agent capable of, upon irradiation with light, a first Wavelength the color former to a colored connec- ' dung to oxidize, and

(B) a deactivating ingredient consisting of

(1) a second photoactivatable oxidant, which can be activated by light of a second wavelength range, is not Oxidant for the color former, but when activated by light of the second wavelength range, etc. is reducible, and

(2) a reducing agent which is a reducing agent for the second but not for the first oxidizing agent and is capable of reducing the second oxidizing agent upon irradiation with light of the second wavelength range to a second reducing agent which is a reducing agent for the photoactivated first oxidizing agent so that the second reducing agent comparable the color forming reaction between the color former and the first oxidant; prevents · ■

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another "preferred embodiment of the invention the photosensitive material contains a phototropic spiropyran or a phototropic indenone oxide.

The device for carrying out the method according to the invention is characterized by

(1) a device for storing the photosensitive material in the form of an image recording area,

(2) a first source of radiation and a device for the Radiation in a first wavelength in a practically uniform radiation current density on the entire surface to judge the photosensitive material,

(3) a second source of radiation and a device for the Radiation in a second wavelength range in a practically uniform radiation current density over the whole To straighten the surface of the photosensitive material,

(4) one between the surface of the photosensitive material and that emanating from the second radiation source

■ Radiation arranged modulator, which generates a pattern of this radiation on the surface and for the second Radiation has essentially transparent as well as essentially impermeable! Surfaces,

wherein the first and second radiation sources, the means for directing the beams and the modulator with respect to the surface of the photosensitive material and in are arranged with respect to one another that

(a) In the absence of the modulator, both radiations hit the same overall surface to be provided with the image and

(b) the modulator blocks out an image-forming part of the second radiation without the light-sensitive surface shield the mixture of substances from the first radiation.

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Description of the drawings

Fig. I illustrates schematically the simultaneous exposure method according to the invention for generating a non-reversible fixed image. _r :

. Fig. 2 shows a projection Yergrösserungsvorrichtung which according to the characteristics of the invention, Figure 1 makes use _t; and is particularly suitable for enlarging microfilms in the form of hard copies.

Fig. 5 is a top plan view of a projected enlarged one Image created by simultaneous imaging and fixing.

has been developed and fixed according to the invention / |

Fig. 4 shows a novel viewing and copying machine for viewing microfilms and producing enlarged hard copies ^; Copies. This apparatus makes use of the inventive concept illustrated in FIGS. 2 and 3 and enables the image to be copied to be viewed positively in a strong ambient light, as well as the simultaneous viewing and making of hard copies. "■■ '-. ■,

Description of the invention '■:

The term "deactivating" refers to preventing color formation in the photoimageable, photoactivatable material. Deactivation takes place when ^: f the material is exposed to sufficient heat to make the exposed areas relatively insensitive to the color-producing reaction. Of this ER ^*: aimed Entaktivierungsgrad depends on the intensity of the entaktivierenden radiation and the exposure duration starting from "The thus exposed material is" deactivated "or" fixed ", where 'the DEACTIVATED surface-to form the background against which the color area (image area) is to be considered. The resistance of the background to color formation during the subsequent exposure generally depends on the

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intensity of the color-producing light and the exposure time al ». With reference to the preferred materials according to the invention which rely on ultraviolet light (for color generation) and are responsive to visible light (for inactivation), the term "inactivated" means that the material against color formation under the influence of normal room light, daylight and sunlight, which is normally contains ultraviolet components, is practically desensitized.

The term "color formation", sometimes referred to as image formation, refers to the process in which the photosensitive material is subjected to sufficient exposure to oppose the deactivated area to create a visible colored surface.

The term "color preventing" includes (1) photo-deactivation, in which the color-forming material is made practically insensitive to the color-generating radiation, and (2) photographic extinction, in which the color that changes upon exposure to the first (color-forming) radiation has formed, extinguished or is faded.

The method of co-irradiation according to the invention (i.e. the simultaneous irradiation of certain parts of a surface with activating and color-preventing Radiation) provides several new and important results and advantages over that carried out in successive stages Prior art irradiation methods. The time until the finished images and the fixed one are formed Product is significantly shortened, because the deactivating 'and the color-forming exposure are not consecutive, but are carried out simultaneously, and partly because the deactivation is due to joint irradiation

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apparently faster than deactivation by, successive irradiation processes. Furthermore, deactivation can occur if one is exposed to intense deactivating radiation operated in practically the same time as the normally photographically faster Color formation. Surprisingly, the joint produces irradiation also less color in the deactivated areas than the separate, multi-stage irradiation. Hence receives you get a better contrast between the colored and the deactivated areas than you get with the same exposure, but in two successive procedural stages.

In Fig. 1, the method according to the invention is shown schematically f. The figure shows the passage of deactivating, ie visible light radiation 1 through a light modulator 2 generating a pattern, which is shown in the figure as a template with a surface 3 permeable to light radiation 1 and a surface 4 opaque to light radiation 1. The radiation 1 passes through the surface 3 and impinges on the surface 5 of a light image forming performance and photoentaktivierbaren material, as defined above, where it produces a pattern which is represented by the surface 7 is the same color-producing, d _f h ₀ ultraviolet Light radiation 6 directed over the entire surface 5 including the surface 7, whereby color forms in part 8 of the surface 5, while in part 7 (which was hit by the deactivating light radiation 1 at the same time) significantly less or no color forms .

The light sources are selected so that the deactivating components of the photosensitive material on the Light 1 and its color-forming components respond to light 6. The position of the (not shown) Sources of the radiations 1 and β and the angles at which they hit the surface 5 of the photosensitive material,

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are not decisive, provided that only the deactivating Radiation passes through the modulator 2 before it hits the surface 5 and then the deactivated surface part 7 forms, and provided only the color-producing radiation hits the whole surface 5. The light sources are preferably arranged in such a way that the deactivating and the color-forming Radiation according to the specified patterns. Distributed uniformly over the light-sensitive surface 5 can be.

The intensities of the deactivating radiation 1 (of the second wavelength range) and of the color-forming radiation 6 (des first wavelength range) and the exposure times are selected so that color is generated in the area part 8, while in the plane part 7 exposed on the same side only very much little or no parbe is produced. To increase the speed and the time it takes to train the To shorten the reproduced image, the deactivating radiation can be as intense as it is with the persistence of the materials used is compatible with this radiation. For a given exposure to deactivating light radiation can be the exposure kit of the color-forming light radiation as a function of the relative deactivation and color "formation rates" of the photosensitive materials concerned and varies depending on the desired effect will. The color-forming radiation should of course be so intense that it can be read, i.e., "visible amounts of dye." generated in the desired surface parts 8, but it must not be so intense that they are exposed at the same time in the Surface parts 7 lead to substantial color formation and thereby impair the contrast and legibility. A key feature of the invention is that the intensity of the color-generating radiation changes easily can be controlled so that only very little or no color occurs at the jointly exposed areas, surprisingly

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one obtains by the joint irradiation Images with a better background and, as a result, better contrast than the step process for making positives Images in which the same exposure conditions are applied, but in which first image-wise with deactivating Radiation and then the entire area is exposed to color-forming radiation.

Pig. 1 shows the light modulator 2 and the light-sensitive surface 5 as parallel planes which are spaced apart in order to allow the surface 5 to be flooded with the color-generating radiation 6. If it is possible to expose the surface 5 to the color-generating radiation without interference from the modulator, there is a need between the upper | surface 5- and the modulator 2 to be no gap. ^ emxi for example the! surfaces 3 and 4 »ie the whole modulator 2, for which the color-forming light 6 is permeable, you can see the surface 5 at the same time from the same direction as with contact copying, with the two radiations 1 and 6 through the modulator 2 expose through it so that a fixed image is obtained in a single process step. Another example is the Pail that the photosensitive material is located as a thin coating on a carrier (film, quartz or glass) that is transparent to the wavelengths that produce the color. In this case, the photosensitive material can be arranged between the modulator 2 and the color-generating light source 6. In other words: the deactivating radiation and the color-forming radiation can be applied simultaneously from opposite directions.

Pig. Figures 2 and 3 show a microfilm enlarger in which the main features of the method according to the invention are embodied are. Fig. 2 is a side view of the overall system while Pig. Figure 3 illustrates a top view of the projected image. The system includes lamp 9 (the source for the

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deactivating light 1), an air-cooled filter cell 10, which contains the light filter 11 in a transparent, infrared absorbing medium 12 (e.g. water), the film window 13, the microfilm 14 (which is used as a modulator 2 according to FIG. 1 serves), on which ^ that which is to be enlarged and in the form of a hard copy to be reproduced image is located, the projection lens unit 15 with the lenses 16 for projecting the Image of the film 14 as an enlargement on the screen 18, which is on the surface 5 with the light-sensitive image recording material is coated or serves as a background for a coated film or paper, and the color-generating radiation sources 6 with the reflectors 17 in order to direct a flood of light 6a onto the entire surface 5.

The screen 18, which serves as a screen and as a mechanical support for the coating of the photosensitive material can, which constitutes the image receiving surface 5, is normally arranged so that the image (recording) plane is perpendicular on the directional axis of the inactivating projected image-wise Light 1 is. The light sources 6 with the reflectors 17 are located somewhat outside the path of the deactivating Light 1 and are matched to one another in terms of their size so that the light emanating from the light source 6 6a irradiates the surface 5 uniformly.

The filter cell 10 primarily has the task of the film 14 to protect against overheating (melting) and "useless" Radiation, i.e. radiation other than that which is absorbed by the photosensitive material and in the deactivation process can be recovered to filter out. The cell also serves to store the amount of heat absorbed by the film to be limited to a mini-space. In a preferred embodiment, namely the projection of a microfilm image with relatively intense blue light, a filter is used that allows this blue light to pass through. Furthermore,

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the filter is cooled by immersion in water. Of course you can also use other light filters and suitable heat absorbers, the selection of which depends on the particular, Photo-generating and photo-inactivatable material and the sensitivity of the light modulator to heat. For example, one can use two-tone mirrors as either Use translucent or reflective media instead of or in addition to the filter cell 10.

The Pig's viewing and copying machine. 4 consists of the projector 20 (the components containing 9 to 16 of Pig. 2), the Lampenfeidern 6 with the reflectors 17, the screen 18, the supply roll 21 with a photosensitive ma- \ TERIAL 5 coated paper or coated accordingly PiIm feeds, the feed mechanism 22, the extraction mechanism 23, the housing 24 with viewing slot 25; the slightly visible light from the environment (e.g. positional light or artificial room light) can penetrate into the housing so that the viewer 26 can see the screen 19, and the exit slot 27 for the hard copy 28, i.e. the photo-fixed paper provided with the photograph - or pilmmaterial. The feed mechanism 22 may be provided with a cutter to deliver the copy 28 in the form of individual sheets (enlarged pilm frame) instead of a continuous tape. U

A viewing and copier similar to that of the Pig. 4 can be used with separate viewing and copying stations be formed, and the projected beam 1 can be arranged by inserting, removing or rotating accordingly Mirror can be aimed either at one or at the other station. In such a device, the Copy station must be completely shielded from room light, so that the image receiving paper remains on until exposure. Place and Place on the copy plate can be left. Perner can be viewed on a rear projection screen,

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has the advantage that you can take a closer look at the picture than on a reflective screen.

In the case of the viewing and copier with separate viewing and copy stations one can place a two-tone mirror in the projected light beam, leaving only those Light wavelengths are directed onto the copier station, which cause deactivation, while others are visible Light wavelengths are simultaneously directed onto the viewing screen. With such a device it is possible that To view the image at the same time as copying.

From the above it follows that the combination of the common irradiation method and the above photosensitive materials a consistent "positive" system for the reproduction and enlargement of microfilms represents. Since the joint irradiation produces positive images, i.e. exact reproductions of the original, is obtained, the process can be applied directly to positive ("black-on-white") microfilms and provides positive, visible ones Enlargements are like positive hard copies. With direct It is no longer necessary to copy the film, as with the known method, first of all to copy the original negative into a to convert a positive copy and then copy it onto a negative microfilm.

As already mentioned, the degree of deactivation that can be achieved with a certain material depends on the intensity the deactivating radiation and the exposure time. If you decrease the intensity or the exposure time, a so-called "partial deactivation" can be achieved. In other words, by reducing the amount of inactivating Radiation in the process can create an imaged but partially deactivated layer obtain. Then you can "add" information by moving the partially deactivated surface image by image (information

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Stencil) exposed to imaging radiation.

The photosensitive material

As already mentioned in the general definition of the invention, there is a preferred material for use in the context of Invention of a color-forming and a deactivating component.

The color-forming component in turn consists of a color former and a first photoactivatable oxidizing agent.

The first photoactivatable oxidant is preferably a g 2,2 ', 4,4', 5,5'-hexaarylbiimidazole, which sometimes is also referred to as 2,4,5-Triarylimidazolyldimeres. These compounds are able to dissociate to the corresponding triarylimidazolyl radicals under the influence of light. These hexaarylbiimidazoles absorb a maximum in the range from 255 to 275 ΐπμ and usually also show a certain amount, if auoh. lower absorption in the range from 300 to 375 πιμ. Although the absorption bands usually fade down to wavelengths of about 420 αμ, the compounds require light for their dissociation which is rich in wavelengths in the range from 255 to 375 ΐπμ. The radiation of the first wavelength range used in the method according to the invention therefore consists of ultraviolet Light. f

The hexaarylbiimidazoles correspond to the general formula

ED ED

IL JS

A A

in which A, E and D are identical or different, carbocyclic or heterocyclic aryl groups which are unsubstituted

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may be or have substituents that promote dissociation of the kexaarylbiimidazole to the triarylimidazolyl radical or the Oxidation of the Ieuco dye does not interfere, and each of the dashed Circles "means four delocalized electrons, i.e. two conjugated double bonds that form the yalenes of the Saturate carbon and nitrogen atoms of the imidazolyl ring. Each of the aryl groups E and D can have 0 to 3 substituents and the aryl groups A may have from 0 to 4 substituents.

The aryl groups include mono- and binuclear aryl groups, such as phenyl, biphenyl, naphthyl, pyridyl, puryl and thienyl. Suitable inert (i.e. not interfering with the process described here) substituents on the aryl groups have Hammettsche Sigma (para) values in the range from -0.5 to +0.8 and must not contain any hydroxyl, sulfhydryl, amino, alkylamino or dialkylamino groups be. Representative substituents and their sigma values (based on H = 0.00) as described by Jaffe in "Chem. Rev.", vol. 53 (1953), pages 219-233, are the following: methyl (-0.17), ethyl (-0.15), tert-butyl (-0.20), phenyl (0.01), butoxy (-0.32), phenoxy (-0.03), fluorine (0.06), chlorine (0.23), bromine (0.23) , Iodine (0.28), methylthio (-0.05), nitro (0.78), ethoxycarbonyl (0.52) and cyano (0.63) ο The above substituents are preferred; one can however, also use other substituents, such as trifluoromethyl (0.55), chloromethyl (0.18) ', carboxyl (0.27), cyanomethyl (0.01), 2-carboxyethyl (-0.07) and methylsulfonyl (0.73). The substituents can therefore be halogen atoms, cyano groups, lower hydrocarbon radicals (including alkyl, Haloalkyl, cyanoalkyl, hydroxyalkyl and aryl groups), lower alkoxy, aryloxy, lower alkylthio, arylthio, Sulfo-, alkylsulfonyl-, arylsulfonyl-, nitro- and lower alkyl carbonylr it te be. The above-mentioned alkyl groups preferably have 1 to 6 carbon atoms, while the aryl groups preferably contain 6 to 10 carbon atoms.

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The aryl radicals are preferably carbocyclic radicals, in particular Phenyl radicals, and the substituents preferably have Hammett's sigma values in the range -0.4 to +0.4, and this applies in particular to lower alkyl, lower alkoxy, chlorine, fluorine, bromine and benzo groups.

In a preferred class of hexaarylbiimidazole, the 2- and 2'-position aryl groups are phenyl rings with an o-substituent which has a Hammett's sigma value in the range from -0.4 to +0.4. The o-substituents are preferably fluorine, chlorine, bromine, methyl and methoxy groups, in particular chlorine atoms. Such biimidazoles have less of a tendency than others to cause the light-sensitive material λ to be applied to the frame and when it is dried at slightly elevated temperatures.
form.

doors, e.g. in the range from 70 to 100 ° 0, to select a color

Most preferably, the 2-phenyl ring carries only the above described o-j pendant group and the 4- and 5-phenyl rings are either unsubstituted or substituted by lower ^alkoxy: substituted groups.

The preferred hexaarylbiimidazoles include 2,2 · -Bis- (ochlorphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5' - (m-methoxyphenyl) -biimidazole.

The representative hexaarylbiimidazoles, which according to the Invention can include:

2,2'-bis- (o-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis- (p-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (p-carboxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2' -.Bis- (o-chlorophenyl) -4,4 ', 5,5 ^f tetrakis - (p-methoxyphenyl) -

biimidazole,

2,2'-bis (o-chlorophenyl) -4,4 ', 5.5 ^! -tetraphenylbiimidazole,. 2 ₁ 2 ^l -Bis- (p-chlorophenyl) -4,4 ', 5,5'-tetrakis- (p-methoxyphenyl) ~

biimidazole,

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2,2'-bis (p-cyanophenyl) -4,4 ', 5,5'-tetrakis- (p-methoxyphenyl) -

biimidazole,

2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2 · -Bis- (2,4-dimethoxyphenyl) -4,4', 5.5 '-tetraphenylbiimidazole, 2,2'-bis (o-ethoxyphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (m-fluorophenyl) -4,4 ', 5.5 * -tetraphenylbiimidazole, 2,2 '-Bis- (o-fluorophenyl) -4,4', 5,5 * -tetraphenylbiimidazole, 2,2 * -Bis- (p-fluorophenyl) -4, 4 ', 5> 5 '-tetraphenylbiimidazole, 2,2'-bis (one-hexyloxyphenyl) -4 | 4 ', 5.5 ^r -tetraplienylbiimidazole, 2.2 »-Bis- (on-liexylphenyl) -4.4 ^f , 5.5', tetrakis- (p-me-fchoxy-

phenyl) - "biimidazole,
2,2'-bis (3,4-methylenedioxyphenyl) -4,4 ', 5,5'-tetraphenylbi-

imidazole,
2,2'-bis (o-chlorophenyl) -4> 4 ', 5,5'-tetrakis- (m-methoxyphenyl) -

biimidazole,
2,2'-bis- (o-chlorophenyl) -4,4 ', 5,5'-tetrakis- / in- (ß-phenoxy-

ethoxyphenyl_) 7-Mii] 3idazole,

2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (p-methoxyphenyl) -4,4'-bis (o-methoxyphenyl) -5,5'-

diphenylbiimidazole,

2,2'-bis (o-nitrophenyl) -4,4 '»5» 5'-tetraphenylbiimidazole, 2,2'-bis (p-phenylsulfonylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,

2,2'-bis (p-sulfamoylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4,6-trimethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,

2,2'-di-4-biphenylyl-4,4 ', 5,5'-tetraphenylbiinidazole, 2,2 · -Di-1-naphthyl-4 »4 ', 5,5'-tetrakis- (p-methoxyphenyl) -bi-

imidazole,
2,2'-Di-9 ~ phenanthryl-4,4 ', 5,5' ~ tetrakis- {p-methoxyphenyl) -

biimidazole,

2,2'-diphenyl-4,4 ', 5,5'-tetra-4-biphenylyllximidazole, 2,2 · -Mphenyl ~ 4,4 ', 5,5' - te tra-2,4 ™ xylylbiimidazole, 2,2 '-Di-3-pyridyl-4,4', "5,5 '-tetraphenylbiimidazole,

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2,2'-Di ~ 3-thienyl-4,4 ', 5,5 * -tetraphenylbiimidazole, 2,2 · -di-o-toluyl-4,4', 5,5'-tetraphenylbiimidazole, 2,2 ' -Di-p-toluyl-4,4-di-o-toluyl-5,5 · -diphenylbiimidazole, 2,2 »-Di-2,4-xylyl-4,4 ', 5,5 * -tetraphenylbiimidazole, 2 , 2 ', 4,4', 5,5 ^f -Hexakis- (p-benzylthiophenyl) -biimidazole, 2,2 ', 4,4', 5,5'-hexa-1-naphthylbiimidazole, 2,2 ', 4,4 ', 5,5'-hexaphenylbiimidazole,

2,2'-3is- (2-nitro-5-methoxyphenyl) -4,4 ', 5,5'-tetraphenyl-

Mimidazole,
2,2 '-Bis- (0-nitroph.enyl) -4,4', 5,5 ^f -tetrakLa- (in-iaet] ioxy-

phenyl) biimidazole "and
2,2'-bis (2-clilor-5-sulfophenyl) -4.4 ^l , SjS'-tetraphenylbi- | imidazole.

The hexaarylbiimidazoles can be prepared by the methods described in British Patent 997,396, by Hayashi et al. Bull. Ohem. Soc. Japan, Vol. 33 (1960), p. 565, and U.S. Patent 3,445,234 are described. The preferred production method is based on the oxidative dimerization of the corresponding iriarylimidazole with perricyanide in alkali and generally gives the 1,2'-hexaarylbiimidazoles; However, sometimes obtained in Geraisch with the 1,2'-isomer, the 1,1'-, 1 »4'-, 2,2'-, 2,4'- and 4,4 ^f -Hexaarylbiimidazole. Pur purposes of the invention, it is immaterial which isomer is used, so-M far as it is only able to dissociate under the influence of light to Triarylimidazolylrest.

The color former is preferably a leuco dye. Under a "leuco dye" is the colorless (doh. reduced) Form a dye compound to adjust, which is through oxidizing the triarylimidazolyl radical to the colored form.

The leuco dyes, which differ from the according to the invention The compounds used oxidize triarylimidazolyl residues with color formation, include amino

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triaryliDethanes, aminoxanthenes, aminothioxanthenes, amino-9,10-dihydroacridines, Aminophenoxazines, aminophenothazines, aminodihydrophenazines, Aminodiphenyimethane, leucoindamines, aminohydrocinnamic acids (Gyanethanes, leucomethanes), hydrazines, leukoindigoids Dyes, amino-2,3-dihydroanthraquinones, tetrahalogen-p, ρ'-biphenols, 2- (p-hydroxyphenyl) -4,5-diphenylimidazole, Phenethylanilines and the like. These classes of leuco dyes are detailed in United States patents 3,445,234, 3,423,427, 3,449,379, 3,395,018, and 3,390,997 ".

The preferred leuco dyes are the aminotriaryl methanes. It is preferred to use aminotriarylmethanes in which at least two of the aryl groups have phenyl groups

(A) one in the p-position to the bond to the methane carbon atom-en R-RgN substituents, in which R and R ₂ hydrogen atoms, Cj- to G ^ -alkyl radicals, 2-hydroxyethyl, 2-cyanoethyl , Benzyl or phenyl radicals, and

(b) a lower alkyl, lower alkoxy, fluorine, chlorine, bromine or butadienyl radical which is in the o-position to the bond to the methane carbon atom and which, when bonded with the phenyl group, forms a naphthalene ring with it, and the third aryl group, if different from the first two, is thienyl, furyl, oxazylyl, pyridyl, thiazolyl, indolyl, indolinyl, benzoxazolyl, quinolyl, benzothiazolyl, phenyl, naphthyl or one of the radicals mentioned substituted by lower alkyl, lower alkoxy, methylenedioxy, fluorine, chlorine, bromine, amino, lower alkylamino, lower dialkylamino, lower alkylthio, hydroxy, carboxy, carbonamido -, lower carbalkoxy, lower alkylsulphonyl, lower alkylsulphonamido, Cg to C ₁₀ arylsulphonamido, nitro or benzylthio groups. Preferably the third aryl group is the same as the other two.

- 20 -

1Ö9823 / 2040

OR-500-A y

Particularly preferred aminotriarylmethanes correspond to the general one formula

YY ¹ -1 H 1 -.

R ₄ R ₃ N- / V c - ^^ VnR ₃ R ₄

in the

R, and R ₄ lower alkyl radicals (preferably ethyl groups)

or benzyl residues,

Y and Y ¹ are lower alkyl groups (preferably methyl groups) and X is a p-methoxyphenyl, 2-thienyl, phenyl, 1-naphthyl, 2,3-dimethoxyphenyl, 3,4-methylenedi ä oxyphenyl-, p- Benzylthiophenyl radical or a radical of the composition

mean, wherein Y, R ₃ and R _{4 have} the above meanings.

X is preferably a phenyl, 1-naphthyl, p-benzylthiophenyl radical or a remainder of the composition

These triaryl methanes are used as salts of strong acids, e.g. of mineral acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid and phosphoric acid, of organic acids such as acetic acid, oxalic acid, p-toluenesulfonic acid, Trichloroacetic acid, trifluoroacetic acid or perfluoroheptanoic acid, or from Lewis acids, such as zinc chloride, Zinc bromide and ferric chloride, the proportion of acid usually being varies in the range from 1 to 20 moles, preferably from 4 to 10 moles, per mole of leuco dye. The phrase "strong

- 21 -

109823/2040

OR-5OOO-A

Acid "here means an acid having an anilino-amino group forms a salt.

Particular examples of aminotriarylmethanes which can be used according to the invention are the following:

Bis- (4-amino-2-butylphenyl) - (p-diraethylaminophenyl) methane,

Bi3- (4-amino-2-chlorophenyl) - (p-aminοphenyl) methane, Bis- (4-amino-3-chlorophenyl) - (o-chlorophenyl) methane, Bis- (4-amino-3-chlorophenyl) -pheny! Methane, bis- (4-amino-3,5-diethylphenyl) - (o-chlorophenyl.) - methane, Bis (4-amino-3,5-diethylphenyl) - (o-ethoxyphenyl) methane, Bis (4-amino-3,5-diethylphenyl) - (p-methoxyphenyl) methane, Bis (4-amino-3,5-diethylphenyl) - (phenylmethane, Bis (4-amino-3-ethylphenyl) - (o-chlorophenyl) methane, Bis- (p-aminophenyl) - (4-amino-m-toluyl) methane, Bis - ('p-aminophenyl) - (o-chlorophenyl) -methane, bis- (p-aminophenyl) - (p-chlorophenyl) -methane, Bis (p-aminophenyl) - (2,4-dichlorophenyl) methane, Bis (p-aminophenyl) - (2,5-dichlorophenyl) methane, Bis (p-aminophenyl) - (2,6-dichlorophenyl) methane, Bis (p-aminophenyl) -phenylmethane,

Bis- (4-amino-o-toluyl) - (p-chlorophenyl) methane, Bis (4 ~ amino-o-toluyl) - (2,4-dichlorophenyl) methane, Bis- (p-anilinophenyl) - (4-amino-m-toluyl) methane, Bis (4-benzylamino-2-cyanophenyl) - (p-aminophenyl) methane, Bis (p-benzylethylaminophenyl) - (p-chlorophenyl) methane,

Bis- (p-benzyläthylaainophenyl) - (p-diethylaminophenyl) -methane, Bis (p-benzylethylaminophenyl) - (p-dimethylaminophenyl) methane, bis (4-benzylethylamino-o-toluyl) - (p-methoxyphenyl) methane,

Bis (p-benzylethylaminophenyl) -phenylmethane, Bis (4-benzylethylamino-o-toluyl) - (o-chlorophenyl) methane, Bis- (4-benzylethylamino-o-toluyl) - (p-diet / laminophenyl) -

methane,
Bis- (4-benzyläthylamino_-o-toluyl) - (4-diethylainino-o-toluyl) -

methane,

- 22 -

109823/2040

OR-5OOO-A

Bis (4-benzylethylamino-o-toluyl) - (p-dimethylaminophenyl) -ηethane,

Bi s ~ /? - clilor-4- (2-diethylaminoethyl) -äthylaminophenyl / - (° ~ chlorophenyl) methane,

Bis- ^ p-t> is- (2-cyanoethyl) -aminophenyl7-phenylinethane,

Bis- / p- (2-cyanoethyl) ethylamino-o-toluyl7- (p-dimethylaminophenyl) methane,

Bis- / p- (2-cyanoethyl) -me-fchylaminophenyl7- (p-diethylaminopheny1) -m e than,

Bis- (p-dil3utylaminophenyl) - ^ p- (2-cyanoethyl) -methylaminoph eny l7-ni e than,

Bis (p-dibutylaminophenyl) - (p-diethylaminophenyl) methane,

Bis- (4-diethylamino-2-butoxyphenyl) - (p-diethylaiJquinophenyl) methane,

Bis (4-diethylamino-2-fluorophenyl) -o-toluylmethane, Bis- (p-diethylaminophenyl) - (p-aminophenyl) -idethane,

Bis (p-diethylaminophenyl) - (4-anilino-1-naphthyl) methane,

Bis- (p-diethylaminophenylJ-Cm-butoxyphenyl) methane, Bis-Cp-diethylaminophenyli-Co-chlorophenylJ-methane, Bis (p-diethylaminophenyl) - (p-cyanophenyl) methane, Bis (p-diethylaminophenyl) - (2,4-dichlorophenyl) methane,

Bis (p-diethylaminophenyl) - (4-diethylamino-1-naphthyl) methane, Bis (p-diethylaminophenyl) - (p-dimethylaminophenyl) methane, Bis (p-diethylaminophenyl) - (4-ethylamino-1-naphthyl) methane,

Bis- (p-diethylaminophenyl) -2-naphthylmethane, bis- (p-diethylaminophenyl) - (p-nitrophenyl) methane, Bis (p-diethylaminophenyl) -2-pyridylmethane,

Bis (p-diethylamino-m-toluyl) - (p-diethylaminophenyl) methane,

Bis (4-diethylamino-o-toluyl) - (o-chlorophenyl) methane,

Bis (4-diethylaraino-o-toltiyl) - (p-diethylaminophenyl) methane, Bis- (4-diethylamino-o-toluyl) - (p-diphenylaminophenyl) methane,

Bis> - (4-diethylamino-o-toluyl) -phenylmethane, Bis- (4-dimethylamino-2- "broiDphenyl) -pheny im ethane,

Bis (p-dimethylaminophenyl) - (4-anilino-1-naphthyl) methane,

Bis- (p-dimethylaminophenyl) - (p- "butylaminophenyl) methane,

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109823/2040

JR-5OOO-A 2!

Bis- (p-dimethylaminophenyl) - (p-sec. Butylethylaminophenyl) -

methane,

Bis (p-dimethylaminoplienyl) - (p-ch.lorph.enyl) methane, Bis-Cp-dimethylaminophenylJ-Cp-diethylaiüinophenylJ-inethan, Bis- (p-dim ethylamino phenyl) - (4-ä.ime thylamino-1-naphthyl) -

methane, bis (p-dimethylaminophenyl) - (6-dimethylamino-m-toluyl) -

raethane, bis (p-dimethylaminophenyl) - (4-dimethylamino-o-toluyl) methane,

Bis (p-dimethylaminophenyl) - (4-ethylamino-i-naphthyl) methane, Bis-Cp-dimethylaminophenylJ-Cp-hexyloxyphenylJ-methane, Bis- (p-dimethylamino phenyl) - (p-m e thoxyphenyl) -m e than, Bis (p-dimethylaminophenyl) - (5-methyl-2-pyridyl) methane, Bis- (p-dimethylaminophenyl) -2-quinolylmethane, Bis- (p-dimethylaminophenyl) -o-toluylmethane, Bis- (p-dimethylaminophenyl) - (1,3,3-trimethyl-2-indolinylidene-

rn e thy 1) -m e than,

Bis-C ^ dimethylamino-o-toluylJ-Cp-aminophenyli-methane, Bis- (4-dimethylamino-o-toluyl) - (o-'bromophenyl) methane, Bis (4-dimethylamino-o-toluyl) - (o-cyanophenyl) methane, Bis (4-dimethylamino-o-toluyl) - (o-fluorophenyl) methane, Bis- (4-dimethylamino-o-toluyl) -1-naphthylmethane, Bis- (4-dimethylamino-o-toluyl) -phenylmethane, Bis (p-ethylaminophenyl) - (o-chlorophenyl) methane, bis (4-ethylamino-m-toluyl) - (o-methoxyphen, vl) methane, Bis (4-ethylamino-m-toluyl) - (p-methoxyphenyl) methane, Bis (4-ethylamino-m-toluyl) - (p-dimethylaminophenyl) methane, bis (4-ethylamino-m-toluyl) - (p-hydroxyphenyl) methane, Bis- / 4-ethyl- (2-hydroxyethyl) -amino-m-toluyl7- (p-diethyl-

aminophenyl) methane,

Bis- / p "-2-hydroxyethyl) aminophenyl7- (o-chlorophenyl) methane, Bis- / p-bis- (2-hydroxyethyl) -aminophenyl / - (4-diethylamino-o-

toluyl) methane, Bi s- / p- (2 -m e thoxy ethyl) -aminophenylT'-phenylmethane,

- 24 -

109823/2040

Bis (p-methylaminophenyl) - (o-hydroxyphenyl) methane, Bis-Cp-propylaminophenylJ-Cm-bromphenylJ-methane, Tris ^ (4-ajnino-o-toluyl) methane, Tris (4-anilino-o-toluyl) methane, Tris (p-benzylaminophenyl) methane, Tris- / T-bis (2-cyanoethyl) -amino-o-toluyl7-methane, Tris- / p- (2-cyanoethyl) -ethylaminophenyl / '- iB ethane, . Iris (p-dibutylarainophenyl) methane, Iris- (p-di-n-butylaminophenyl) methane, Tris (4-diethylamino-2-chlorophenyl) methane, Tris (p-diethylaminophenyl) methane,

Tris (4-diethylamino-o-toluyl) methane, λ

Tris (p-dihexylamino-o-toluyl) methane, Tris (4-dirnethylamino-o-toluyl) methane, Tris- (p-hexylaminophenyl) -methane, Tris- ^ p-bis- (2-hydroxyethyl) -aminophenyl7-methane, Tris- (p-methylaminophenyl) -methane, Tris-Cp-dioctadecylaminophenylJ-methane, Tris (4-diethylamino-2-fluorophenyl) methane, Tris (4-dimethylamino-2-fluorophenyl) methane, Bis (2-l) rom-4-diethylaminophenyl) -phenylmethane, Bis- (2- "butoxy-4-diethylaminophenyl) -phenylmethane, Bis (4-diethylamino-o-toluyl) - (p-methoxyphenyl) methane, Bis (4-diethylamino-2-methoxyphenyl) - (p-nitrophenyl) methane, Bis (4-diethylamino-1-naphthyl) - (4-diethylamino-OTtoluyl) -

methane,. "

Bis- (4-diethylamino-o-toluyl) -1-naphthy! Methane, Bis- (4-diethylamino-o-toluyl) -phenylmethane, Iris- (4-dimethylamino-2-chlorophenyl) -methane, bis- (4-dimethylamino-2,5 ~ dimethylphenyl) -phenylmethane, Bis- (4-dimethylamino-o-toluyl) - (o-bromophenyl) methane, Bis (4-ethylbenzylamino-o-toluyl) - (p-methoxyphenyl) methane, Tris (p-diootylamino-o-toluyl) methane, bis ~ (4-diethylamino-o-toluyl) - (4-methoxy-1-naphthyl) methane, Bis-C 4-diethylamino-o-toluyl) -C 3 »4,5-trimethoxyphenyl) methane,

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109823/2040

uxi-5000-A ty

ty

Bis- (4-dläthylamino-o-toluyl) - (p-hydroxyphenyl) -raetlian, 5- / Ms- (4-diethylamino-o-toluyl) -methyl7-2,3-cresotinic acid, 4- / l3is- (4-diethylamino-o-toluyl) -methy2j7-phenol, 4- ^ is- (4-diethylamino-o-toluyl) -methyl7-acetanilide, 4 -, / bis (4-diethylamino-o-toluyl) -methyl / - phenylace tat, 4- ^ bis (4-diethylamino-o-toluyl) -methyl7-benzoic acid, 4- / bis-C4-diethylamino-o-toluyl) -niethyl7-diphenylsulfone, 4- / bis (4-diethylamino-o-toluyl) -methyl7-phenylmethylsulfone, 4- ^ bis (4-diethylamino-o-toluyl) -methyl7-methylsulfonanilide, 4- / bis- (4-diethylamino-o-to ^ yl) -methyl7-p-toluylsuirone-

anilide,

Bis (4-diethylamino-o-toluyl) - (p-nitrophenyl) methane, Bis (4-diethylanjino-o-toluyl) - (2-diethylamino-4-methyl-

5-thiazolyl) methane,
Bis (4-diethylamino-o-toluyl) - (2-diethylamino-5-methy1-

6-benzoxazolyl) methane,
Bis- (4 ~ diethylamino-o-toluyl) - (2-diethylamino-5-methyl-

6-benzothiazolyl) methane,
Bis- (4-diethylamino-o-toluyl) - (1-ethyl-2-methyl-3-indolyl) -

methane,
Bis (4-diethylamino-o-toluyl) - (1-l3enzyl-2-methyl-3-indolyl) -

methane,
Bis (4-diethylamino-o-toluyl) - (1-ethyl ^ -methyl-S-methoxy-

3-indolyl) methane,

Bis- (1-o-xylyl-2-methyl-3-indolyl) - (4-diethylamino-otoluyl ) -methane,

Bis- (4-diethylamino-o-toluyl) - (i-ethyl-5-indolinyl) -methane, bis- (i-isobutyl-6-methyl-5-indolinyl) - (4-diethylamino-otoluyl) -methane,
Bis (4-diethylamino-o-toluyl) - (8-methyl-9-oleolindinyl) -

methane,
Bis (4-diethylamino-2-aoetamidophenyl) - (4-diethylamino-o-

t οluyl) -me than.
4- / B "is- (4-diethylamino-o-toluyl) -methyl7-N-ethylacetanilide,

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109823/2040

UR-5OOO-A f $

Bis- ₍ ^ - (1-phenyl-2,3-dimer; hyl-5-pyrazolinyl _i } 7- (4-diet] iyl-

amino-o-toluyl) methane,

Bis- (4-diethylamino-o-toluyl) - (7-diethylamino ~ 4-methyl ^ - coumar inyl) -me than,

Bis (4-diethylamino-o-toluyl) - (4-aerylamidophenyl) methane, Bis (4-diethylamino-o-toluyl) - (p- "benzylthiophenyl) methane, Bis (4-diethylamino-o-toluyl) - (4-isopropylthio-3-methyl-

phenyl) methane,
Bis- (4-diethylamino-o-toluyl) - (4-chloridenzyl thiophenyl) -

methane,

Bis (4-diethylamino-o-toluyl) - (2-furyl) methane. Bis- (4-diethylamino-o-toluyl) - (3,4-methylenedioxyphenyl) - |

methane,

Bis, - (4-diethylamino-o-toluyl) - (3,4-dimethoxyphenyl) methane, Bis (4-diethylamino-o-toluyl) - (3-methyl-2-thienyl) methane, Bis (4-diethylamino-o-toluyl) - (2,4-dimethoxyphenyl) methane, Bis - ^ / 4-C2-cyanoethyl) - (2-hydroxyethyl) -amino-o-toluyl7 ~

(p-benzylthiophenyl) methane, Bis- / 4- (2-cyanoethyl) - (2-hydroxyethyl) -amino-o-toluyl7-2-thienylmethane, -

Bis (4-dibutylamino-o-toluyl) -2-thienylmethane, Bis (4-diethylamino-2-ethylphenyl) - (3,4-methylenedioxy-

phenyl) ~ methane,
Bis (4-diethylamino-2-fluorophenyl) - (p-benzylthiophenyl) - j

methane, '™

Bis (4-diethylamino-2-fluorophenyl) - (3 _f 4-methylenedioxyphenyl) -m e than,

Bis (4-diethylamino-o-toluyl) - (p-methylthiophenyl) methane, Bis- (4-diethylamino-o-toluyl) -2-thienylmethane, Bis- (4-dimethylamino-2-hexylphenyl) - (p-butylthiophenyl) -

methane, bis- / 4- (H-ethylanilino) -o-toluylT- (3,4-dibutoxyphenyl) methane,

/ 4-Ms- (2-hydroxyethyl) -amino-2-fluorophenyl7- (p-benzyl-

thiophenyl) methane, ■

- 27 - "109823 / 2Q40

Bis- (4-dläthylamino-o-toluyl) - (p-chlorophenyl) methane, Bis (4-diethylamino-o-toluyl) - (p-bromophenyl) methane, Bis- (4-diethylamino-o-toluyl) - (ρ-fluorophenyl) methane, Bis- (4-diethylamino-o-toluyl) -p-toluylmethyl,

Bis (4-diethylamino-o-toluyl) - (4-methoxy-1-naphthyl) methane, Bis (4-diethylamino-o-toluyl) - (3,4,5-trimethoxyphenyl) methane,

Bis- (4-diethylamino-o-toluyl) - (p-hydroxyphenyl) methane, Bis (4-diethylamino-o-toluyl) - (3-methylthienyl) methane.

The deactivating component of the photosensitive material consists of a second photoactivatable oxidizing agent and a reducing agent. The deactivating component is sometimes referred to as a "redox couple". The second photoactivatable oxidizing agent is preferably a quinone, e.g. Pyrenquinone or phenanthrenequinone, and the reducing agent is a polyether or a compound of the general formula N ^ CCH ₂ ) COOR / ,, in which η is 1 or and R is a lower alkyl radical. The oxidizing agent is preferably a polynuclear quinone, which is mainly in the range from 430 to 550 Ίημ. absorbed, such as 1,6-pyrenquinone, 1,8> -pyrenquinone, 9,10-phenanthrenequinone or mixtures of these quinones, in particular 9> 10-phenanthrenequinone, while the reducing agent is preferably a C - to C, -alkyl ester of nitrilotriacetic acid or the 3 »3 ', 3" -nitrilotripropionic acid, in particular trimethyl nitrilotripropionate.

These deactivating components respond to visible light and preferably light that is rich in wavelengths is between 380 and 460 πιμ.

Compounds which can be used according to the invention in this sense are described in US Pat. No. 3,390,996. Particularly The material described in column 3, line 68 to column 4, line 2 of this patent specification is preferred in which the color former is an aminotriarylmethane with at least two

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109823/2040

p-dialkylamino-substituted phenyl groups which are substituted in the o-position to the methane carbon atom by an alkyl, alkoxy group or a halogen atom, the first photoactivatable oxidizing agent a 2 _t 2 ¹ - {o-aubB-t ± -tVLievtes phenyl) -4, 4 ', 5,5'-tetraphenylbiiiaidazole, the second photoactivatable oxidant of the redox couple (the oxidant of the patent mentioned) is a quinone and the reducing agent (of the redox couple according to the patent) is a polyether. The o-substituents on the 2- and 2'-phenyl groups are preferably F, Cl, Br, alkyl, alkoxy or benzo groups. These * preferred materials and components thereof are in the cited patent in column 4, line 56 to column 5, line 4J, column 8, lines 34-56; Column 11, lines 11-19 and column 12, lines 21-23.

The materials used according to the invention also include those according to US Pat. No. 3,390,994. In particular Reference is made here to those in column 2, lines 51-64, of this patent specification Embodiment described referred to. This embodiment consists of an intimate mixture of

(a) a salt of an acid with the leuco form of an iriphenylmethane dye, in the case of at least two of the phenyl rings in the p-position to the methane carbon atom by a Cj to C dialkylamino group are substituted, (b) a 2,2 ', 4,4S SfS'-hexaaryrbiimidazole, whose aryl groups are identical or different can be and preferably as o-substituents in the 2- and 2'-aryl groups a chlorine, bromine, fluorine atom, a have lower alkoxy, methyl or benzo groups, and

(c) a redox couple consisting of (1) a pyrenquinone or phenanthrenequinone as oxidizing agent and (2) a compound of the general formula N / CcHoLCOORTz, in which η denotes

&. χι j

Has the value 1 or 2 and R is a straight-chain lower alkyl radical . Means as a reducing agent. The components (a) and

(b) represent the color former of the light-sensitive material, while component (c) represents the deactivating constituent

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109823/2040

0R-5Q00-A '

forms part of the material. Typical components for one Material can be found in the cited patent in column 3, line 21 to column 5, line 37.

The deactivating component of the material described in the preceding paragraph can be obtained by a mixture of 1,6- and 1,8-pyrenquinone (in amounts of 0.04 to 0.4 mol per mol of triimidazole), either 9-10 phenanthrenequinone, perinaphthenone or 4-methoxy ~ 1,2-naphthioquinone (in amounts of 0.04 to 2 moles per mole of triimidazole) and an ether containing at least one oxymethylene group in which the methylene radical bears at least one hydrogen atom, e.g.

(CH ₂ ) _n R RO- (CH ₂ CH-O) _1n -R,

where η has the value 0 or 1, m has a value from 1 to 15, R a hydrogen atom or an alkyl, phenyl, alkylphenyl, biphenylyl or acyl radical, R ¹ for η = 0 a hydrogen atom and for η = 1 represents a hydrogen atom, an OH group or a radical R.

A preferred photoimageable and photoactivatable Material contains:

(A) as color-forming (image-forming) ingredients

(1) a salt of a leukotriaryl methane with a salt-forming one Acid and

(2) a hexaarylbiimidazole which absorbs mainly in the ultraviolet and a photooxidant is for the salt of leukotriaryl methane, and

(B) as a deactivating (image-fixing) component

(3) a second photo-oxidizing agent (preferably a polynuclear quinone) which can be activated at longer wavelengths, for example by visible light, than those required to activate the biimidazole, not the leuco dye as the dye

30 -

1Q9823 / 2Q4Q

OR-5QOO-A G (

'Photo-oxidized and reduce to a second reducing agent in its photo-activated state lets, and

(4) a first reducing agent (preferably an ether with removable hydrogen, an ester with removable hydrogen, a lower alkyl nitrilotriacetate or a lower 3> 3 ', 3 ^ll -nitrilotripropionic acid alkyl ester), which is a reducing agent for the photoactivated second oxidant, but not for the is photoactivated biimidazole, wherein the first reducing agent reduces the photoactivated second oxidizing agent to the second reducing agent, the latter being a reducing agent for the activated biimidazole, whereby it prevents the color-forming reaction between the activated biimidazole and the leuco dye.

The pick-up ratio of the biimidazole used as a photo-oxidizing agent to the aminotriarylmethane serving as color former can vary in the range from about 0.1: 1 to about 10: 1. Of the the preferred range is from 1 ti to 2: 1.

The quinone of the redox couple can be used in relation to the biimidazole in molar ratios of 0.01: 1 to 2: 1, with Molar ratios from 0.2: 1 to 0.5: 1 are preferred. The reducing component (e.g. the 3,3 ', 3 "-liitrilotripropion-" acid trimethyl ester) of the redox couple (the deactivating Component) is used in molar ratios of about 1: 1 to 40: 1, based on the quinone.

The photosensitive materials can contain polymeric binders in order to thicken them or to adhere to supports bring to. Binders can also serve as an embedding compound for the material, and the mixture can be poured, extruded or otherwise shaped into self-supporting photographic pilms. translucent and film-like

- 31 -

109823/2040

OR-500-A / 38.

The end polymers are "preferred. Examples of these are Ethyl cellulose, polyvinyl alcohol, polyvinyl chloride, polystyrene, polyvinyl acetate, polymethacrylic acid methyl ester, cellulose acetate, Cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, chlorinated rubber, copolymers of the above-mentioned vinyl monomers and gelatin. The amounts of the binder and the potting compound vary from about 0.5 part by weight to about 200 parts by weight per part of the total weight s amount of leuco dye and hexaarylbiimidazole. in the in general, 0.5 to 10 parts by weight are used as an adhesive or thickener, while self-supporting ones are used for production Films in larger quantities can be used. In the case of certain polymers, it is useful to add a plasticizer to to give flexibility to the PiIm or coating. The plasticizers include polyethylene glycols, as they are commercially available under the term "Carbowax" and related substances such as substituted phenol-ethylene oxide adducts, e.g. those from o-, m- and p-cresol, o-, m- and p-phenylphenol as well as p-Nonylphenol available polyethers including the commercially available Substances such as the alkylphenoxypolyoxyethylene ethanol (Igepal). Other plasticizers are the acetic acid, Propionic acid, butyric acid esters and other carboxylic acid esters of ethylene glycol, diethylene glycol, glycerine, pentaerythritol and other polyhydric alcohols and the phthalic acid and phosphoric acid alkyl esters, such as phthalic acid dimethyl ester, Phthalic acid diethyl ester, phthalic acid dioctyl ester, phosphoric acid tributyl ester, Trihexyl phosphoric acid, trioctyl phosphoric acid, triphenyl phosphoric acid, tricresyl phosphoric acid and cresyldiphenyl phosphoric acid.

Other photochromic compounds

Other photochromic compounds can also be used according to the invention. The main requirement that these connections must be satisfied by the following reversible equation:

- 32 -

109823/2040

OR-5QOO-A 33

colorless - ^ colored state. visible light state

Compounds that meet this condition are known per se; their value in the case of joint irradiation according to the However, the invention was not yet known. Examples of suitable compounds are the following:

(A) a photochromic compound of the general formula

R R

in which X, Y and Z can be identical or different and monovalent radicals, namely hydrogen atoms, carboxyl groups (-COOH), "alkoxy, nitro, hydroxyl, alkoxycarbonyl, cyano, halogen, amino, amido, Alkylsulfone, arylsulfone, acyl or acylamido groups, and wherein the hydrocarbon groups bonded to functional radicals have not more than 8 carbon atoms and are preferably alkyl radicals with 1 to 4 carbon atoms, at least one of the substituents X, Y and Z is not a hydrogen atom and As shown, the substituent Z can be in one of the 4 ^f - to 7 ^f positions, while the substituents X and Y can be in any of the positions No. 5 to S, and

R is a hydrocarbon radical, such as an alkyl, cycloalkyl, alkenyl, aryl, alkaryl or aralkyl radical with no more than 20 carbon atoms and preferably an alkyl radical with 1 to 8 carbon atoms} See U.S. Patent 3,485,765.

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109823/2040

0E-50Q0-A

2Ü58025

Representative photochromic spirobenzopyranindolines according to the invention can be used are in the named patent in column 3, line 4 to column 4, Line 10, listed. The preferred phototropic compounds are those in which Z is hydrogen or an alkoxycarbonyl radical, while X and Y. Nitro groups or a nitro group in combination with a hydrogen atom, a methoxy group or a halogen atom, or mean halogen atoms.

(B) 3-alkyl-3'-methyl-spiro / benzoxazole-2,2 '- (2 ^l H-1'-benzopyrans of ^the general formula

Alkyl _nn

and the derivatives of these compounds which are substituted in the benzene ring according to British patent specification 889 186.

(C) 3-Alkyl-3 ^t -methyl-spiro- _< / benzothiazole-2.2 ^t - (2 ^I H-1'-benzopyran) 7 of the general formula

Alkyl

and the derivatives of these compounds substituted in the benzene ring according to British patent specification 887 902.

(D) derivatives of 3'-methyl-spiro- (2H-1-ß-naphthopyran-2,2 - -1'-benzopyran /) of the general formula

109823 / 2Q4Ö

0R-5000-A

according to US Pat. No. 2,978,462 and derivatives of Compound 3-phenyl-spiro- (2H-1-benzopyran-2,2 '- ^' H-1- "benzopyran /) the general formula

Hi, 4th

according to the USA patent specification 3,022,318 and (E) 2,3-diphenylindenone oxide

described in "Journal of the American Chemical Society", Volume 88 (1966), pages 494-2.

The medium in which the photochromic compound is dissolved can be liquid or solid. Liquid media that used are generally inert diluents and especially solvents such as hydrocarbons, halo-

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109823/2040

gene hydrocarbons, alcohols, esters, ketones, ethers and the like. For the purposes of the invention, however, the photochromic compound is preferably used in solution in a solid Substance, especially in the form of a solution in a thermoplastic Resin. The concentration in which the photochromic compound is used in the materials according to the invention can vary within wide limits and is best determined according to the desired application, because the photochromic properties of a material are not only determined by the respective photochromic compound, but also by the medium in question and the concentration of the photochromic compound can be influenced. Generally one uses but the photochromic compounds in relatively dilute solutions, and concentrations ranging from 0.001 to 10 percent by weight, based on the dilution medium, is satisfactory for most purposes.

As already mentioned, the photochromic compound is preferably incorporated into plastic compounds. Suitable thermoplastic Resins are cellulose esters, such as cellulose acetate butyrate, Polyolefins such as polyethylene, polypropylene and mixed. polymers of ethylene with vinyl esters or acrylic acid esters, Polyvinyl halides, such as polyvinyl chloride and polyvinylidene chloride, polystyrene and copolymers of styrene and butadiene and / or acrylonitrile, acrylic resins such as methyl polymethacrylate, polyvinyl acetals such as polyvinyl butyral, Polyvinyl alcohol, polyvinyl esters such as polyvinyl acetate, and polyesters such as polyethylene terephthalate. Particularly preferred thermoplastic resins are plasticized and non-plasticized cellulose ester resins.

Various methods, which have already been used to mix additives into the thermoplastic resins, can can also be used for the phototropic compounds according to the invention. These methods include dissolving the resin and the phototropic compound in a common solution

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109823/2040

205802 *

OR-5 0.00-A

solvent, subsequent mixing and evaporation of the solvent, although one preferably heats the resin above its softening point to a liquid state and then the photochromic compound admixed directly. These mixing processes can use rubber rollers, Banbury mixers, and screw extrusions be used. Of course, care must be taken that the temperatures used do not lead to Decomposition of the constituents of the mixture lead · You can use the above-indicated diluents, solvents, thermoplastic Resins or thermoplastic resins and solvents also add several photochromic compounds.

Modifying agents such as those described in U.S. Pat ft 3 485 765 described modifiers, sensitizers, as described in US Pat. No. 3,486,899, and means to treat the images

to make permanent with sulfur dioxide, or other chemical i Add funds, or under certain circumstances you can by simple

The solvent-containing capsules are subjected to pressure in the case of substance |

Mash mixtures that require the presence of a solvent.

require means so that the two light-triggered reac-;

before you go. Even those in the Dutch open;

Legungsschrift 69 03746 described means for generating ^: a stable colored state can be used.

Carrier ■!

To produce images according to the invention, supports can be coated or impregnated with the materials by known methods. The supports customary in graphic art and for decorative purposes can be used as supports ^; like paper (from tissue paper to thick cardboard), pollen from | Plastic or polymers such as regenerated cellulose, cellulose acetate, cellulose nitrate, the polyester made from "glycol and terephthalic acid, vinyl polymers and copolymers, polyethylene, polyvinyl acetate, polymethacrylic acid methyl

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10 ^ 423/2040

OR-5QOO-A.

esters, polyvinyl chloride, textiles, glass, wood and metals. The photosensitive material can, usually as a solution in a solvent, sprayed onto the surface of the support, brushed on, by Yialzen application or dip coating be applied, or it can be applied to the support in some other way by dipping or spraying, whereupon the solvent is allowed to evaporate. In general, solvents are used which are at normal pressures evaporate. Examples are amides such as N, N-dimethylformamide and Ν, Ν-dimethylacetainide, alcohols and ether alcohols, such as methanol, ethanol, propanol-1, propanol-2, buta-

fc nol and ethylene glycol, esters such as methyl acetate and ethyl acetate, aromatic hydrocarbons such as benzene, o-dichlorobenzene and toluene, ketones such as acetone, methyl ethyl ketone and 3-pentanone, aliphatic ^ halogenated hydrocarbons, such as methylene chloride, chloroform, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane and 1,1,2-trichlorethylene, various others Solvents such as dimethyl sulfoxide, pyridine, tetrahydrofuran, Dioxane, dicyanoyclobutane and 1-methyl-2-oxohexamethyleneimine, as well as mixtures of these solvents in various proportions, as they may be required to produce solutions. It is often beneficial to have a small amount of solvent residue remains in the dried mass, so that the desired degree of image generation can be achieved in the subsequent

™ can achieve the following exposure. Ordinary drying,

as is customary in papermaking or the casting of films, leads to the retention of copious amounts Solvent to obtain a mass with good photosensitivity. The masses obtained in this way feel dry and can be kept at room temperature. Many of the masses absorb moisture from the air, especially those that do an acid salt of an aminoleuco form of a dye on a: Have cellulosic carriers, and in this case the water acts as a suitable solvent.

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109823/2040

0R-5000-A $ 3

example 1

The photosensitive paper used below is made as follows manufactured:

A coating agent is prepared from the following ingredients:

acetone
Propanol-2

2,2'-bis-co-chlorophenyl) -4, '4 ·, 5,5'-tetrakis- (m-raethoxyphenyl) -biimidazole
(5.36 χ 10 * "* mole)

Tris (4-diethylamino-o-toluyl) methane

(1.8 10-5 mol)
p-Toluenesulfonic acid monohydrate

(2.1 χ 10 " ⁵ moles)
3.3 ', 3 "-Nitrilotripropionic acid trimethyl ester 1.0 ml

(4.2 10-5 moles)
9,10-phenanthrenequinone (2.6 x 10 " ⁴ " · moles) 0.054 g

Cellulose acetate butyrate 6.0 g

(thermoplastic binder; "Eastman EAB-171-40»)

Polyethylene oxide adduct. of o-phenylphenol, 3.0 g prepared from 2.25 moles of ethylene oxide per mole of the phenol; average composition C ₆ H ₅ -C ₆ H ₄ O (CHCHO) H

54 ml 6th ml ο * 4180 β ο, 0900 G ο, 400 G

Calendered, bleached sulphite pulp paper of high resistance is coated with the above compound. The paper is dried in a stream of hot air until it has a non-sticky surface.

The Magnifying Device, the Pig. 1 to 3 of the drawings corresponds, has a 35mm projector, an ordinary one Screen and a blue fluorescent lamp (ultraviolet from low intensity). The color temperature of the projection lamp is 3200 ° K at the radiation source and delivers white Light from 244 m candles lighting on the screen at a distance from lampshade to lamp, the magnification of a tenfold

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1Q9823 / 2040

2Ü58025

0R-5000-A w /%

35 mm slides (silver on polyester film base) result. Me ultraviolet lamp is outside of the projected Lamp light beam and irradiates the screen over the entire area hit by the light from the projection lamp with a radiation density of 0.2 milliwatts / cm at the Screen surface.

To illustrate the method according to the invention, becomes a sheet of the photosensitive paper described above with the projection and fluorescent lamps switched off placed on the screen. Then both lamps are switched on simultaneously for 30 seconds and then switched off. The so exposed Paper shows a blue image with an optical reflectance density of 0.37 against a pale yellow background with an optical reflectance density of 0.15 «The contrast between the colored areas and the background areas is judged to be good. The pale yellow background that is resistant to color formation caused by ambient light and its yellowness owes to the presence of phenanthrenequinone in the light-sensitive material, bleaches in the event of further exposure to room light, daylight or sunlight gradually turned to white color.

If, for comparison purposes, one uses the same (unexposed) paper with the same rays, but one after the other, namely first 30 seconds with the projector lamp and then another 30 seconds over the entire surface with the ultraviolet When light is irradiated, the resulting image has an optical density of 0.32 (slightly lower) ·, the optical density of Background is 0.19 (which is considerably higher), and the contrast is only moderate (which means worse).

Example 2

Example 1 is used using a 16-minute microfilm projector with a flat 6 lens of one focal length

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109823/2040

0R-5000-A

58.1-mm and a General Electric 200-watt EJL lamp as well two 6.55 mm thick sheets of heat-absorbing glass. The illuminance of the through the transparent places of the visible light passing through microfilm is 215 m candles at the image plane of the screen, which corresponds to the distance a 21x magnification. The two blue fluorescent lamps are located immediately outside of the visible light beam projected image-wise and are directed in such a way that they cover the whole image plane with a radiation density at the

Image area of 0.28 milliwatts / cm with ultraviolet lic: - * irradiate.

Samples of the photosensitive paper described in Example 1 were "-11" for the different ones indicated below Irradiated periods of time with both radiations. The results are as optical reflectance densities the blue image area (which has only been exposed to ultraviolet light) and the background area (the one of both Types of radiation have been taken and therefore deactivated).

Simultaneous exposure to produce copies at 21x magnification

0.28 mW / cm ² ultraviolet light, 215 m candles visible light

Time,
Sec. Optical density,
image Optical density,
background difference
in the opti
cal densities . 5 0.12 0.08 0.04 10 0.20 0.09 0.11 15th 0.29 0.09 0.20 20th 0.54 0.10 0.24 25th 0.41 0.11 0.50 50 0.47 0.15 0.54 40 0.56 0.15 0/45 50 . 0.65 0.15 0.48 60 0.68 0.16 0.52 120 0.85 . 0.19
- 41 - 0.64

109823/2040

OR-50OO-A (Λ

The results show that the optical density of the “blue image increases with increasing exposure time, the optical density increases However, the density of the area irradiated with both types of radiation increases to a much lesser extent the optical densities of the background show only an insignificant or takes place in the presence of visible light no color formation at all due to blue dye takes place.

That the simultaneously irradiated papers described above practically largely prevent color formation when exposed to ultraviolet rays Scattered radiation can be deactivated by prolonged exposure to room light, daylight and sunlight demonstrate.

Example 3

A fixed hard copy of high quality is also kept under the above-described irradiation conditions with a photosensitive paper according to Example 1, but with the following modification:

The amount of 2,2'-bis (o-chlorophenyl) -4,4 ', 5.5 ^t -tetrakis- (mmethoxyphenyl) -biimidazole is reduced to 0.334 g (by 20 fo) and that of the 9,10- Phenanthrenequinones increased to 0.065 g (by 20 #).

When using this material, there is even less color formation in the exposure to both types of rays background surfaces hit at the same time.

Example 4

A microfilm enlarger according to FIGS. 2, 3 and 4 has a 16 mnt micr © film projector, which is connected to a near the Ultraviolet and 300 watt arc lamps emitting in the visible regions of the spectrum

- 42 -

103823 / 2G4Ü

and-a Corning GS 5-57 filter (a bandpass filter that allows light to pass through in the wavelength range from 360 to 500 ταμ with a maximum at 420 ΐημ), which is immersed in a water-filled cell and placed between the lamp and the Mim window is. The projector is set to a 21.3-fold magnification on an almost white screen arranged at a corresponding distance. When projected with the filtered light, the silver image on the polyester film appears black on the screen on a light blue surface with a photochromic illumination reading of approximately 150 to 180 m candles, has a pleasing appearance and is clearly recognizable in normal room lighting. On opposite sides of the screen, immediately outside of the produced light beam are located in a waste d was 12.7 cm from the screen two rows of blue fluorescent tubes with reflectors (4 tubes in each row), which are directed so that they have the surface of the lamp light produced overlap completely with ultraviolet light, the total radiation density of the ultraviolet light being approximately

1 milliwatt / cm.

With the projector switched off and the fluorescent lamps switched off, a sheet of light-sensitive paper according to Example 1 is placed on the projection surface of the screen. The projection lamp and the fluorescent lamps turn on at the same time and turn off after 10 seconds. The exposed paper now has a 21.3 times magnification of the | Microfilm image in the form of a clear blue image (the colored area 8 in Fig. 1 and 3 corresponds to) on a pale yellow, the deactivated background on (which is the common loading. \ Exposed surface 7 according to FIGS. 1 and 3 corresponds).

If one exposes another sample of the same photosensitive paper one after the other and fixes it by first one Irradiated with the light of the projection lamp for 10 seconds to create a "latent" image, and then one

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109823/2040

OE-5OOO-A to

Overall exposure to the ultraviolet light of those described above Fluorescent lamps do to develop the image to the same optical density, you get one though clearly legible image; however, the deactivated background is noticeably more colored (bluish), and the contrast between the colored and the deactivated areas is less.

example 5

Using the apparatus and method of Example 4, the photosensitive paper described in Example 1 is made irradiated with both types of radiation at the same time. The exposure conditions and results are in the following table contrasted with those of the two-stage irradiation process.

109823/2040

Simultaneous irradiation to produce a hard copy enlarged 21 times

Visible light: 180 m candles
Ultraviolet light: see below
Exposure time: see below

I. _# Attempt .
No. Type of
Irradiation UV, mW / cm Time,
Sec. Optical density difference ■ Ρ *
VJl 1 simultaneously
after another 2.0
2.0 10
10 image Behind
reason in the opti
cal densities 10! I. 2 simultaneously
after another 1.5
1.5 5
5 0.84
0.85 0.40
0.58 0.44
0.27 ma
to 3 simultaneously
after another 1.5
1.5 10
10 0.34
0.31 0.02
0.01 0.32
0.30 δ / ε 4th simultaneously
after another 1.5
1.5 15th
15th 0.64
0.64 0.11
0.30 0.53
0.34 ο
* · »
O 5 simultaneously'
after another 1.25
1.25 10
10 0.77
0.78 0.12
0.41 0.65
0.37 6th simultaneously
after another 0.76
0.76 20th
20th 0.64
0.63 0.06
0.22 0.58
0.41 7th simultaneously
after another 0.76
0.76 30th
30th 0.61
0.60 0.03
0.05 0.58
0.55 8th" simultaneously
after another 0.76
0.76 40
40 0.71
0.71 0.01
0.18 0.70
0.53 0.80
0.78 0.02
0.28 0.78
0.50

Cn OO CD

205802b

OR-5OOO-A M

The results show that with simultaneous irradiation, less background color with better contrast (greater un- ' difference in the optical densities) than with two-stage irradiation, and that the time until the formation of a narten copy is significantly increased by simultaneous irradiation with the color-producing and the deactivating rays shorten (practically halve).

Example 6

Work according to Example 5 with the photosensitive paper described below under the specified exposure conditions:

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109823/2040

Type of
Irradiation UV, mW / cm ² Time,
Sec. Optical density difference
in the opti
cal densities - 1
\ Ii η ι ■ · simultaneously 0.75 10 image Behind
reason 0.27 O
ψ
\ n
O
O
> ■ fr » 1 attempt
No. after another 0.75 10 0.47 0.20 0.23 1 simultaneously '0.50 10 0.43 0.20 0.23 after another 0.50 10 0.27 0.04 0.16 OJ simultaneously 0.50 30th 0.21 0.05 0.51 after another 0.50 30th 0.61 0.10 ' 0.47 3 simultaneously 0.57 60 0.68 0.21 0.60 after another 0.57 60 0.85 0.25 0.50 4th 0.87 0.37

OK-5O.OO-A '

The photosensitive paper was made from the following coating composition manufactured:

Components

acetone

Cellulose acetate butyrate ("Eastman EAB-171-40")

p-Nonylphenol-ethylene oxide adduct: G ₉ H ₁₉ C ₆ HO (CC

Tris (p-diethylaminoethyl-ot0luy1) methane

p-Toluenesulfonic acid monohydrate

2,2 * -bis- (o-chlorophenyl) -

4,4 ', 5.5'-tetrakis- (m-methoxyhl -biimidazole

Gewients
place Molars
Shares 92 46.0
6.0 - 0.75 4.0 2.25
1.00 0.300 0.2 .0.344
0.624 0.4 0.0371 0.0664

1,6- and 1,8-pyrenequinone. (equal amounts of weight)

9,1O-phenanthrenequinone

The solution is applied to bleached sulfite pulp roll paper and the acetone is allowed to evaporate. You get a 0.01 mm thick coating.

Example 7

About the variability of the method according to the invention and the one in Pig. 4 illustrated viewing and copier, the exposure and described above Pixie machine modified to have a 12.7 cm wide roll of photosensitive paper, a device for conveying.

of the roll paper over the surface of the screen, a device for cutting the paper into square sheets of 12.7 cm on a side, and an arrangement for ejecting the co-irradiated paper (the hard copy) from the device.

109123/2040

ΟΕ-5ΟΟΟ-Δ (ι ft

When the paper feed to the projection surface of the The projection lamp is switched on on the screen, so d'ass it throws a 21.3-fold enlarged black image on a light blue background on the screen. This looking before Copying enables the observer to determine the quality and position of the image to be copied and any necessary Make settings before copying. The fluorescent lamps are switched on to produce the hard copy, and at the same time, the photosensitive roll paper is started to be conveyed at a feeding speed of 30.5 cm / sec. and places a sheet of paper between the screen and the projected one within about 1 second Lamper oht. After 10 seconds of exposure, this will be Sheet al & hard copy taken out. It shows a sharp blue image on a clear, deactivated background,

Example 8

A legible hard copy of good consistency - twenty-one times Enlargement of a black B: ldes on a pale yellow background - is also obtained if, according to Example 4, with a photosensitive paper works, its photosensitive Layer contains the same ingredients as in Example 1, with the difference that the 0.0900 g of tris- (4 ^ diethylamino-o-toluyl) methane by 0.1706 g of bis (4-diethylamino-otoluyl) -3,4-dimethoxyphenylmethane be replaced.

Example 9

Readable enlarged hard copies are also available under the Exposure and pixelation conditions of Example 5 with a photosensitive paper made by coating paper with the solution described below and allowing it to evaporate. of the solvent has been prepared:

OR-5OOO-A

Components parts by weight

Acetone 41.4

Propane Oil-2 4.6

Cellulose acetate butyrate

("Eastman EAB-171-40") 6.0

PO ₉ H ₁₉ -C ₆ H ₄ -O (CH ₂ CH ₂ O) ₁ ^ ₅ H 4.0

(as a plasticizer, made by condensing p-nonylphenyl with 1.5 moles of ethylene oxide)

Tris (4-diethylamine-o-toluyl) methane 0.30

2,2'-bis (o-chlorophenyl) -4.4 ^t > 5.5 '~

tetrakis (ra-methoxyphenyl) biimidazole 0.62

p-toluenesulfonic acid monohydrate 0.34

Mixture of approximately equal parts by weight

of 1,6- and 1,8-pyrenequinone 0.37

Example 10

Legible, hard copies are obtained according to Example 4 with a photosensitive paper made by coating paper with the following solution and allowing the solvent to evaporate has been produced:

Components parts by weight

Acetone.

Cellulose acetate butyrate

("Eastman ΞΑΒ-531-1")

0-C ₆ H ₅ -C ₆ H ₄ -O (CH ₂ CH ₂ O) _2, H 5.5

(produced by condensing o-phenylphenol with 2.3 mol of ethylene oxide)

Bis (p-diethylamino-o-toluyl) -3,4-dimethoxyphenylmethane

Bis (p-diethylamino-o-toluyl) phenylmethane

2,2 · -Bis- (o-chlorophenyl) -4,4 ', 5,5'-tetrakis- (m-methoxyphenyl) -biimidazole

p-Toluenesulfonic acid monohydrate 9,10-Phenanthrenohino'n

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109823/2040

OR-5QOO-A '· 0

Example 11

Similar results are obtained when the example is carried out 1 with the light-sensitive material described there on a polyester film as a carrier,

Example 12

The photosensitive paper used in this example is made as follows:

The coating agent is made from the following components:

Acetone 60 ml,

1 ', 3', 3'-trimethyl-6-nitrospiro- (2H-1-benzo- 0.1 g " pyran-2,2'-indoline), produced according to the U.S. Patent 3,485,765,

Cellulose acetate butyrate ("Eastman EAB-381-20") 6.0g

N-ethyl-p-toluenesulfonamide ("Santicizer-3" 2.0g Monsanto Chemical Company)

Calendered, bleached sulphite pulp paper of high resistance is coated with the above compound. The paper is dried in a stream of hot air until its surface is no longer sticky. After drying, a light pink colored paper is obtained, which is reflected in the visible light of the Can easily fade the environment.

Readable hard copies (positive images) obtained with the above-% photosensitive paper according to Example 4 described; a purple image emerges from a pink background.

Example 13

Results similar to those of Example 12 are obtained if the spirane used in Example 12 is passed through an equimolecular Amount of 2,3-diphenyl-1-indenone oxide, prepared by

- 51 -

188823 / 20AO

OR-5ODO-A St

that of Ullman in "Journal of the American Chemical Society", Volume 88 (1966), ■ page 4942, described method replaced. When normal enlargement conditions were used following the procedure of Example 4, a purple-red image was obtained a pink background.

The same results as those described in the above examples are obtained when modified of the examples within the scope of the general disclosure of the above description.

16Ö823 / 2CUQ

Claims (1)

Claims Method for generating a positive image on a layer of one for two different radiations Sensitive material based on two different rays Responds to wavelength ranges in such a way that it is exposed to radiation of the first wavelength range into a first colored state and upon exposure to rays of the second wavelength range in a second colored state, and that is characterized by the fact that it is caused by simultaneous irradiation with rays both wavelength ranges can be prevented from transitioning into the colored state, characterized in that the said material located on a surface intended for image recording is simultaneous with rays of the two wavelength ranges exposed, wherein the radiation of the first wavelength range is directed over the entire surface to be irradiated and has such an intensity that it is at the points on the surface that are not hit by both types of radiation Causes color formation at the points on the surface that are also hit by the radiation of the second wavelength range but does not cause color formation, while the radiation of the second wavelength range in the form of a pattern corresponding to the image to be recorded 109823/2040 is directed to the "to be irradiated surface and a has such an intensity that it causes the dye to form on the Prevented areas of the surface hit by it. 2 · The method according to claim 1, characterized in that: one as a photosensitive material, a mixture of (A) a color-forming ingredient consisting of (1) an organic film former and (2) a first photoactivatable oxidant capable of to oxidize the color former to a colored compound when irradiated with light of a first wavelength, and (B) a deactivating component used, consisting of (1) a second photoactivatable oxidizing agent which can be activated by light of a second wavelength range, is not an oxidizing agent for the color former, but "can be reduced when activated by light of the second wavelength range, and (2) a reducing agent that is a reducing agent for the
second but not for the first oxidizer
and is capable of the second oxidizing agent upon irradiation with light of the second wavelength range to reduce a second reducing agent, which is a reducing agent for the photoactivated first oxidizing agent, so that the second reducing agent causes the color-forming reaction between the
Color former and the first reducing agent prevented. 3. The method according to claim 1, characterized in that · a photosensitive material is used, which as
Color former contains a phototropic spiropyran or a phototropic indenone oxide. 4. The method according to claim 2, characterized in that a photosensitive material is used in which the 54 - 109823/2040 Color former is a leuco dye, the first oxidizing agent is 2,2 ', 4,4', 5,5 ^f -hexaarylbiimidazole, the second oxidizing agent is a quinone and the reducing agent is a polyether or a compound of the general formula N ^ CH _2. ) _N COOH7 ₃ in which η has the value 1 or 2 and R is a lower alkyl radical. 5. The method according to claim 4, characterized in that the light of the first wavelength and ultraviolet light visible light is used as light of the second wavelength range. 6. The method according to claim 2, characterized in that a photosensitive material is used in which f the color former is a salt of a salt-forming acid and a leuco-triarylmethane, in which at least two of the aryl groups are phenyl groups which (a) have an R-RgN substituent in the p-position for bonding to the methane carbon atom, Taei the R and R ₂ Hydrogen atoms, Cj to Cj ₀ alkyl radicals, 2-hydroxyethyl, 2-cyanoethyl, benzyl or phenyl radicals, and the (b) in the o-position to the bond to the methane carbon atom by a lower alkyl, lower alkoxy, fluorine, Chlorine, bromine or butadienyl radical which, when joined together with the phenyl group, forms a naphthalene ring with the latter, are substituted, while the third aryl group, if it differs from the other two, is an ihienyl, furyl , Oxazolyl, pyridyl, thiazolyl, indolyl, indolinyl, benzoxazolyl, quinolyl, benzothiazolyl, phenyl or naphthyl radical, which is in each case replaced by lower alkyl, lower alkoxy, methylenedioxy, fluorine, Chlorine, bromine, amino, lower alk ylamino, lower dialkylamino, lower alkylthio, hydroxy, carboxy, carbonamido, lower carbalkoxy, lower alkylsulphonyl, lower alkylsulphonamido, Cg to C ^ arylsulphonamido, nitro or - 55 - 104823/2040 OR-5OPO-A - * Benzylthio groups can be substituted, the first oxidizing agent a 2,2 ', 4,4', SjS'-hexaphenyrbiimidazole, in which the 2- and the 2'-phenyl group in the o-positions by fluorine, chlorine, bromine atoms, methyl or Methoxy groups are substituted, and in which the 4-, 4'-, 5- and 5'-phenyl groups either unsubstituted or through a lower alkoxy group are substituted, the second oxidizing agent 1,6-pyrenequinone, 1,8-pyrenequinone and / or 9 »1O-phenanthrenequinone, and the reducing agent is a compound of the general formula N ^ TCHp) _n COOR /, in which η and R. have the meanings according to claim 4. 7. The method according to claim 6, characterized in that the light of the first wavelength is used that consists primarily of wavelengths between about 255 and 575 ταμ , and that the light of the second wavelength range is used that is predominantly composed of wavelengths between consists of about 380 and 460 ΐημ. 8. The method according to claim 1, characterized in that: one the pattern of the light of the second wavelength range thereby obtained by letting the light fall through a Mim showing a positive or a negative image. 9. The method according to claim 8, characterized in that the pattern of the light of the second wavelength range is applied projected an image recording surface. 10. The method according to claim 8, characterized in that when using one for the light of the first wavelength range transparent film showing an image, the image recording surface with both types of rays at the same time irradiated by allowing the light of the first and second wavelength ranges to pass through the film. - 56 - 109823/2040 OR-5OOO-A ζΗ 11. Device for performing the method according to claim 1, characterized by (1) a device (18) for storing the photosensitive material in the form of an image recording surface (5), (2) a first radiation source (6) and a device (17) to the radiation in a first wavelength (6a) in a practically uniform radiation current density to direct on the whole surface (5) of the photosensitive material, (3) a second radiation source (9) and a device (10, 15) to generate the radiation in a second wavelength range (1) in a practically uniform radiation current density on the entire surface (5) of the to direct photosensitive material, (4) one between the surface (5) of the photosensitive material and that of the second radiation source (9) outgoing radiation (1) arranged modulator (2), which on the surface (5) a pattern (7) of this Radiation generated and for the second radiation (1) essentially transparent (3) and essentially has impermeable (4) surfaces, wherein the first and second radiation sources, the means for aligning the rays and the modulator with respect to the surface of the photosensitive material and are arranged with respect to one another so that (a) Both radiations, in the absence of the modulator, have the same total surface to be provided with the image meet and (b) the modulator forms an imaging part of the second Fades out radiation without shielding the light-sensitive surface of the mixture of substances from the first radiation. - 57 - 109823/2040 OR-5OOO-A 12. The device according to claim 11, characterized in that the first radiation source (6) is an ultraviolet Radiation source whose ultraviolet light can be used by the light-sensitive material for color formation Contains wavelengths, the second radiation source (9) a source of visible light, which from the contains light-sensitive material for the deactivation exploitable wavelengths, the modulator (2) a Image-bearing film, a template or an electronically or magnetically controlled light modulator for generation optical sign and that is between the source (9) of visible light and the modulator (2) an optical filter (11) which suppresses wavelengths other than those that can be used in the process, and a means (12) for absorbing the infrared radiation from the visible light is located to a sufficient extent to to prevent thermal destruction of the modulator. - 58 - 108823/2040 S3 Blank page