JPS5950972B2 - energy ray recorder - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an energy ray recording material which is improved as a non-silver salt sensitive material for energy rays such as alternating beams and electron beams so that color tones other than blue or green can be obtained by photosensitization. be.

There are various types of non-silver salt recording materials that are sensitive to energy rays such as light and electron beams, among which free radical sensitive materials are one of the most sensitive.

However, this sensitive material mainly consists of an activator such as polyhalogen, which generates free radicals upon incidence of energy rays, and a color former, such as allylamine, which reacts with the activator.
In response to energy rays, it produces a chain reaction unique to free radicals, resulting in high sensitivity, and since it develops color upon energy input, it is non-developable, and fixing requires only heating. The sensitivity is still lower than that of silver salt sensitive materials.For example, when used for electronic vino recording, the amount of incident electricity required to start recording is 1 of that of silver salt.
It is about 10'' coulombs/cm2 compared to 0''0 to 100 coulombs/cm2, and it is necessary to increase the sensitivity by 100 to 1000 times. On the other hand, some types of free radical sensitive materials can be effectively made highly sensitive by increasing their density by subjecting them to so-called photosensitization treatment after irradiation with energy rays.

For example, using carbon tetrabromide as a polyhalogen as an energy-sensitive activator and leucomalachite green as a coloring agent,
When coated with a suitable binder resin such as polystyrene to a thickness of several microns on a substrate such as glass or film, it develops a green color when irradiated with energy rays, and has a wavelength of 630 mμ.
This produces an absorption band centered on . Next, the photosensitive material is 90-1
When the entire surface of the image is irradiated with red light while being heated to 00° C., the image area with an absorption band absorbs energy, causing unreacted molecules to react, producing a dye, and increasing the density. In this case, since red light has no spectral sensitivity to unreacted non-image areas, the effective sensitivity increases by about 100 times, reaching a sensitivity equivalent to that of silver halide film for electron beams, and television recording. Real-time recording is possible even at speeds of As described above, although this photosensitization is extremely effective, it also has some drawbacks. The biggest problem is that the color development is limited to blue to green tones that can absorb red light. In other words, blue to green images are not very pleasant to the senses, and the light for reproducing and reading these images is limited to the area centered around the red light, so they are not suitable for use in, for example, television recording film. Red light such as He-Ne laser has no problem in reproducing and reading when
) cannot be applied because blue light without afterglow is used. In another example, as described in Japanese Patent Publication No. 49-20213, an organic halogen compound is used as an activator, N-vinyl carbazole is used as a coloring agent, and a small amount is added as a sensitizer auxiliary agent. A recording material containing a symmetrical fluoran compound is known, but since it requires a medium-strong exposure for the initial exposure in negative-positive type, and the coloring agent is N-vinyl carbazole, it is impossible to obtain a high-quality recording material. Has sensitizing properties,
In addition, it was not possible to satisfy the demand for recording images with a variety of color tones.

Generally, in order to read out an image with light of any wavelength, it is necessary to develop other colors, such as reddish-purple, orange-yellow, or black.

However, when using color formers that form these orange-yellow to reddish-purple pigments, the absorption bands of these tones are on the short wavelength side, so even if the same photosensitization as described above is possible, light in the short wavelength band When irradiated with light in this band, the polyhalogen of the activator is exposed to light, and a reaction occurs not only in the image area but also in the non-image area, resulting in an increase in density in both the image and non-image area. This results in fogging and does not increase only the image density. Therefore, conventionally, photosensitization is only possible for blue to green colors, and photosensitization is not possible for other colors.
This was the biggest difficulty. Another difficulty, although not essential, is that photosensitization in these blue to green tones tends to amplify faint fog that has occurred in non-image areas.

Another drawback is that the slope of the characteristic curve (i.e., the gamma value) of the density characteristic (irradiation energy vs. color density characteristic) obtained as a result of photosensitization tends to become small, making it unsuitable for recording that requires contrast. There is.

The object of the present invention is to eliminate the above-mentioned conventional drawbacks, and to use polyhalogen as an energy-sensitive activator, which develops a color other than blue or green, preferably black, and which can be made highly sensitive by photosensitization. Another object of the present invention is to provide a non-silver salt energy ray recorder using an asymmetric fluoran derivative as a coloring agent.

That is, the energy ray recording material of the present invention has the general formula RCX3 as an energy-sensitive activator, in which R is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, and x is a halogen atom of the same or different types. A sensitive layer having a polyhalogen (a) expressed as above and a 3-7-substituted fluoran derivative (b) as a color former at a mutual weight ratio (a/b) of 0.5 to 2 is provided on a substrate. It is characterized by being able to form a latent image using weak incident energy and then sensitize it by irradiating the entire surface with red light to form an image in the entire hue range. be. As is well known, the 6-2 position substituted form is equivalent to the above-mentioned 3-7 position substituted form, and can be similarly suitable.

The present invention will be explained in detail below with reference to the drawings.

The present invention overcomes the conventional difficulties by making it possible to photosensitize color formers in non-silver salt energy sensitive materials that exhibit tones other than blue to green, such as yellow to reddish-purple, or all tones including blue to green. This was possible due to the following photosensitization method and the structure of the photosensitive material that can realize this method.

The photosensitization method according to the present invention is as shown below.

(1) Initial Image The faint image or latent image produced by energy beam irradiation always includes blue to green or other color tones.

(2) In the subsequent photosensitization, the entire surface is irradiated with red light which is absorbed by the above-mentioned blue to green image areas but is not absorbed by the unreacted sensitizer in the non-image areas and becomes inactive.

(3) The energy of the red light irradiated onto the surface is absorbed by blue to green pigments, and then causes energy transfer to nearby unreacted sensitizer molecules or their bodies, promoting a pigment-forming reaction. vinegar.

(4) The pigments that are newly proliferated by the subsequent absorption of a large amount of red light energy are: 1. Only blue to green pigment molecules 2. Only yellow to red-purple pigment molecules 3. Both of the above pigment molecules coexist to promote proliferation. thing? It has a structure in which absorption energy levels exhibiting yellow to reddish purple and blue to green coexist in one molecule, and the blue to green pigments produced also play the role of absorbing red light energy.

(5) Among the generated pigments, those exhibiting blue to green colors are converted into structures exhibiting yellow to reddish-purple colors by further continuing irradiation with red light.

In that case, the sensitizing effect due to energy absorption continues until the blue to green pigment is exhausted. (6) If yellow to reddish-purple and blue to green pigments coexist and grow from the beginning,
Not necessarily blue or green. →There is no need for a yellow to reddish-purple conversion to take place.

In the above-mentioned photosensitization method, it is necessary to raise the temperature of the photosensitive material in order to increase the reaction rate.
Next, we will develop this invention to realize the above-mentioned photosensitization method. The structure of the energy sensitive material according to Akira is shown below.

The energy-sensitive material according to the present invention includes an activator that generates free radicals upon incidence of energy rays, a coloring agent that reacts with the activator to form a pigment that determines the color tone of a recorded image, and a film-forming process by dispersing these. The main component is a binder. To produce a photosensitive material with such a structure,
These main components are dissolved in a suitable solvent and applied to a plate-like or film-like substrate to form a sensitive material layer with a thickness of several microns to more than ten microns. Next, the composition and manufacturing method of each of the above-mentioned main components will be described.

[1] Activator Engineering A polyhalogen represented by the above general formula RCX is used as an activator that generates free radicals upon incidence of energy beams.

Particularly effective activators include carbon tetrabromide, iodoform, bromoform, carbon tetrachloride, bromotrichloromethane, iodotribromomethane, iodotrichlorobutane,
There are α, α, α-tribromotoluene, and many other equivalent compounds.

[2] Color forming agent As the color forming agent which reacts with the activator to form a variety of pigments, an asymmetric fluoran derivative substituted at the 3-7 positions represented by the following general formula is used.

Ull where R,,R'': hydrogen atom and lower alkyl group, and
A phenyl group and a benzyl group R whose hydrogen atoms may be substituted with a halogen atom or a lower alkyl group.

: Hydrogen atom, halogen atom, lower alkyl group, and
Phenyl group R'': hydrogen atom and lower alkyl group R.

,R. : Hydrogen atom, lower alkyl group, halogen atom, phenyl group, benzyl group, naphthylmethyl group and diphenylmethyl group which may be substituted with a lower alkyl group or lower acyl group, and -N at the 7th position piperidino group)
\.

- Substituted with N [ ] H2 Z: hydrogen atom, halogen atom, lower alkyl group, lower alkoxy group, and nitro group, and amino group whose hydrogen atom may be substituted with a lower alkyl group m: 1 to 4 Integer A: benzene nucleus or naphthalene nucleus bonded at the 5th and 6th positions B: benzene nucleus or naphthalene nucleus bonded at the 4'' and 5'' positions.

In addition, the fluoran derivatives mentioned here are disclosed in, for example, Japanese Patent Publication No. 46-4616, 1982-2966.
No. 3, No. 48-4052, No. 16202-16202, No. 33207-33207, No. 48-43298, No. 49-Sho.
No. 17490, No. 51-1165, No. 51-1167
No., No. 51-2009, No. 51-2010, Japanese Unexamined Patent Publication No. 48-60719, No. 64016, British Patent Specification BP-126901, etc. Many of them belong to the pressure pigment type coloring agents, and these develop color when they come into contact with acid clay, bentonite, phenolic resin, etc. as a color developer in a solution state.

In the present invention, the fluoran derivative is combined as a coloring agent with the polyhalogen of the activator, which reacts by generating free radicals upon incidence of energy ray images such as light and electrons. This enabled recording of images and photosensitization over a multicolor gamut.

Among the above-mentioned fluoran derivatives, representative examples of those that have coloring properties not only from blue to green but also from yellow to reddish-purple color range and can achieve the object of the present invention are as follows. It will look like Table 1.

However, the fluoran derivatives used in the recording medium of the present invention are not limited to these exemplified compounds. [3]
Binders and Solvents Binders as film-forming agents that disperse the above-mentioned activators and color formers include polystyrene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, styrene-butadiene copolymers, Synthetic or semi-synthetic resins such as polyvinylidene chloride, vinylidene chloride acrylonitrile copolymer, polyvinyl methacrylate, methacryl ethyl acrylate copolymer, polyvinyl butyral, polyvinyl alcohol, ethyl cellulose, and nitrocellulose, gelatin, casein, etc. It is preferable to use a natural polymeric material of .

Depending on the composition of the sensitive material, examples of solvents for dissolving and dispersing these components and coating them on the substrate include benzene, toluene, methanol, ethanol, butanol, trichloroethylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, Carbon tetrachloride, methyl cellosolve, tetrahydrofuran, dioxane, dimethylformamide,
And water and others are used alone or in combination.

Next, the substrate used in the recording medium of the present invention and the method for manufacturing the above-mentioned sensitive material will be explained.

As the substrate of the sensitive material layer according to the present invention, glass, porcelain,
Polyester, triacetate, paper, etc. are made into plate shapes as appropriate.
It is used in the form of a film or sheet, but especially in the case of electron beam sensitive materials, it is necessary to form a thin layer of transparent conductor on the substrate by metal vapor deposition or Nesa coating. .

In addition, as for the conductivity obtained in this case, it is preferable that the specific resistance is at least 10 7 Ω/Cm 2 or less. In addition, the proportions of the above-mentioned sensitive material are as follows: polyhalogen 2-27% fluorane derivative 2-27% binder
65-90% other additives
This should be done appropriately within a range of several percent or less.

A particularly important point regarding this mixing ratio is the ratio of the polyhalogen to the 3-7-substituted fluoran derivative, which is closely related to the optical density of the recording medium after optical amplification. For example, when the total weight of polyhalogen and fluoran derivative is 100% and the weight percent of polyhalogen is increased from zero, the optical density begins to increase rapidly from about 20%, as shown in Example 8 described later. Approximately 33%
In other words, it reaches a practical level at a weight ratio of 0.5, and as described below, it peaks at about 40 to 50% and then gradually decreases, but it remains in a practical level up to about 66%, or a weight ratio of 2. It's getting old. Therefore, as can be seen from Examples 1 to 10 described later, sufficient effects can be obtained when the blending ratio of polyhalogen and 3-7 position substituted fluoran derivative is in the range of 0.5 to 2 weight ratio. The preferred proportion of the main component is polyhalogen.
15% fluorane derivative
15% binder 70%
It is desirable to set the value to a certain degree.

The main component sensitizer having such a composition is dissolved in an appropriate solvent, and this is applied as a coating liquid onto a substrate by spinner coating, knife coating, bar coating, or other conventional coating methods, and the sensitizer is dried by natural drying or the like. The thickness of the layer is adjusted to about 2 to 20 microns, preferably about 2 to 10 microns.

Next, a method of recording and sensitizing a one-line energy image of a photosensitive material according to the present invention will be explained. Recording of energy ray images on the recording medium of the present invention is carried out in the following manner.

A light or radiation image is irradiated onto the sensitive material in air, and an electron beam image is irradiated onto the sensitive material in vacuum as a two-dimensional image or a time-series scanning line image.

When the irradiation dose of energy rays is large, a clear image with high density is recorded, but the recording material of the present invention can be used as a highly sensitive sensitive material and is particularly effective when the irradiation dose is small. In other words, when the amount of energy ray irradiation is small, only a latent image or a faint image is recorded on the recording material of the present invention, and the color tone of the image is within the yellow to green color gamut. However, it generally contains many blue to green components. However, in the recording medium of the present invention, photosensitization can be performed by significantly increasing the density of this initial image, which ultimately leads to an increase in sensitivity, and changing the color tone from yellow to purple. . A method of photosensitization accompanied by a change in color tone as described above will be described below.

In order to sensitize the recording medium of the present invention, the recording medium on which a latent image or a faint image has been generated by the initial irradiation with an energy beam image is heated and irradiated with red light.

That is, the recording medium after being irradiated with energy rays is heated to 80 to 110°C in the dark or under red safety light in an appropriate heating plate or heating tank with hot air flow, and at the same time, the entire surface of the recording medium is heated, including the image area. Even non-image areas are irradiated with red light. Light sources for such irradiation include helium neon,
Although laser light or the like may be used, for example, a tungsten bulb or a halogen bulb may be used, and a heat ray absorption filter 1 and a red color filter 1 may be combined with this, and a portion of the filter etc. may be exposed by keeping an appropriate distance from the light source. Irradiation can be carried out appropriately after cooling. Note that red light for photosensitization is generally desirable to have a wavelength of 590 to 680 mμ, but even if it contains heat rays in a longer wavelength range, it may cause a temperature rise above the appropriate temperature and cause performance deterioration of the recording medium. There is no problem as long as there is no.

Further, it is desirable that the heating tank be well ventilated to appropriately exhaust gas generated by the reaction. By continuously applying red light irradiation and heating as described above, the density of only the image portion of the recording medium of the present invention increases with time, but the density of the non-image portion does not change at all.

Furthermore, the color tone of the image area in the recording medium of the present invention is such that the initial blue to green components generally increase in density once, but then gradually decrease; on the other hand, the yellow to reddish-purple components further increase in density. This continues to increase, resulting in a tendency for the absorption wavelength of the image portion as a whole to shift to a shorter wavelength band of 590 mμ or less.

Note that in photosensitization by red light irradiation, blue to green components may not decrease, but the blue to green pigment acts as a window for red light energy absorption and transfers that energy to surrounding unreacted molecules. It is thought that the movement promotes the production of yellow to reddish-purple pigments.

Further, the time required for the above sensitization process is from several tens of seconds to several tens of minutes, and varies depending on the temperature, red light intensity, type of sensitive material, etc.

As described above, the density value or absorbance of the initial latent image or faint image can be increased to values of 1 to 1.5 or more.

That is, compared to the initial energy ray irradiation amount, 100~
Since an image with a density value comparable to that obtained with an irradiation dose of 1000 times or more is obtained, the sensitivity of the photosensitive material is amplified by 100 to 1000 times or more, and the blue to This makes it possible to increase color tones other than green. Next, the fixing process for the recording medium of the present invention is achieved by evaporating the unreacted polyhalogen, and this fixing process is simultaneously achieved by heating during the photosensitization process.

However, heating for fixing treatment takes 10 minutes or more at a temperature of 80°C, for example, so depending on the conditions of the photosensitization treatment, heating may be performed for 10 minutes or more at a temperature of 80 to 110°C after the sensitization treatment. It is sufficient to apply it for 1 minute to 1 minute. As described above, by using the recording medium having the structure according to the present invention and the sensitization treatment, it is possible to perform photosensitization for tones other than blue to green, which could not be done conventionally, such as yellow to reddish-purple. It has now become possible to achieve increased sensitivity.

Next, examples of recording bodies and sensitization processing according to the present invention will be described.

Example 1 2 grams of carbon tetrabromide as an activator, 2 grams of 3-diethylamino-J-diben-dylaminofluorane as a color former, 8 grams of polystyrene as a binder, 8 grams of a mixed solvent of 7 volumes of toluene and 3 volumes of acetone as a solvent.
Preparation, dissolution, and dispersion of 2 cc were performed.

This mixed solution was coated at 3000 r with a spinner coater.
It was coated on borosilicate glass which had been subjected to a transparent conductive treatment (Nesa coating) by rotation at pm for 30 seconds, dried, and a 7 micron thick sensitive material layer was deposited to form a recording medium.

When this recording medium was irradiated for 10 seconds at an accelerating voltage of 30 Kv and a beam current density of 10-°A/Cm in a vacuum, as shown in Fig.
An absorption spectrum showing slight absorption near 0 mμ was produced, and a pale dark blue-green color was produced.

Then, the recording medium was subjected to the following photosensitization treatment. Red light irradiation was carried out using a 1 Kw halogen bulb as a light source, and a device that combined this with a heat ray absorption filter and a red filter.

The distance between the light source and the recording medium was 35 cm, and the irradiation energy beam on the sensitive material surface was 15 mW/Cm. The recording medium was heated by placing the sensitive material on a temperature-controlled hot plate, and the temperature of the surface of the sensitive material was maintained at 90°C. When red light irradiation is continued as described above, as shown in Figure 1, the image density increases in the absorption band of the two filters mentioned above at first, but as the processing time progresses, the absorption in the long wavelength region increases. The absorbance decreased, and absorption with high absorbance gradually showed a tendency to move to a shorter wavelength region, eventually showing a dark reddish-purple-orange color. It is recognized that the above sensitization treatment amplified the density of yellow to reddish purple having an absorption range in the short wavelength band.

Example 2 When electron beam irradiation was performed on a recording medium with the same sensitive material composition as in Example 1, the density characteristics of color development, that is, the sensitivity characteristics with respect to changes in the amount of electron beam irradiation, were compared with those at the initial stage before photosensitization. FIG. 2 shows a comparison of the characteristics and changes in characteristics as the sensitization process progresses when photosensitization is performed.

Since a blue filter is used to measure the density, the characteristics shown in the figure indicate the sensitization characteristics for short wavelength tones, but the second
As is clear from the figure, the density increases even in the low irradiation dose area where no color density was initially observed, and the sensitivity characteristic curve shows a tendency to shift toward the lower beam irradiation dose.
As a result, the sensitivity has increased, meaning that it has been amplified nearly 1000 times. Further, the slope of the density characteristic curve, that is, the gamma value, is a large value without lowering the gamma unlike conventional leucomalachite green, and there is almost no increase in fog. FIG. 3 shows a comparison of the density characteristics of a conventional recording medium and a recording medium of the present invention.

Example 3 A recording medium having the same composition as in Example 1 was manufactured, and it was heated in vacuum at a beam current density of 10-8 coulombs/Cln and 10
The sample was irradiated with an electron beam of -J/N/d to develop a faint color and then heated to a temperature of 90° C. in the dark, but as shown in FIG. 4, the concentration did not increase much after 20 minutes.

However, when red light irradiation was then performed in the same manner as in Example 1 while in this heated state, as shown in the figure,
The image density increases rapidly, and after 10 minutes, the image density reaches 1.
Reached 4. Therefore, it is recognized that the photosensitization of the photosensitive material according to the present invention is essentially different and effective from the sensitization effect caused by mere heating. Example 4 A recording medium having the same composition as in Example 1 was manufactured and irradiated with light using a 500 W ultra-high pressure mercury lamp.

This light irradiation was performed using a heat absorption filter with an illumination intensity of 55 mW/Em2 at a distance of 20 cm from the light source.
After irradiation for seconds, the image density of blue-green color was 0.1
was gotten. When the recording medium was heated to 90°C and photosensitized for 7 minutes at a red light illuminance of 15 mW/Cm2, the image changed to a blackish reddish-purple color and the image density increased to 1.3. A significant photosensitizing effect was observed.

Example 5 2 gr of carbon tetrabromide was used as an activator, 2 gr of 3-diethylaminol-aniline fluorane was used as a coloring agent, 8 gr of polystyrene was used as a binder, and 40 cc of a mixed solvent of 3 volumes of ethyl alcohol and 7 volumes of toluene was used as a solvent. A recording medium was prepared by manually coating a solution in which the above-mentioned components were dissolved in this solvent on a triacetate film by a bar coating method to deposit a light-sensitive material layer with a thickness of about 10 microns.

The illuminance of this recording medium using an ultra-high pressure mercury lamp as a light source was 55mW/
When irradiated with light of Cm for 10 seconds, the absorption wavelength λMa
It exhibited a dark green color with x at 470 mμ and 610 mμ.

This was placed on a hot plate and heated to 90°C, and irradiated with red light in the same manner as in Example 1.
In 7 minutes, the absorption in the long wavelength region shifts from λMax58Omμ to the shorter wavelength side, the blue-green component decreases, the whole changes to black tone, the absorbance becomes 1.0 to 1.5, and the image density increases significantly. did. Example 6 1g of carbon tetrabromide was used as an activator, 1gr of 3-diethylamino-6-methyl-dimethyl)anilino-fluorane was used as a color former, and 7gr of toluene was used as a binder with 4gr of polystyrene. 1 volume, 3 volumes of acetone, 1 volume of solvent
The solution was dissolved in 6 cc and applied to borosilicate glass imparted with conductivity using a spinner applicator to form a photosensitive material layer with a thickness of 8 microns.

When this was irradiated with an electron beam in a vacuum at an accelerating voltage of 30 kV and a current density of 10 -8 coulombs/♂, it developed a light black edge color. When this was heated and irradiated with red light in the same manner as in Example 1, the color tone became blackish after 10 minutes and the density was amplified to 1.0 to 1.5. Example 7 2 grams of carbon tetrabromide was used as an activator, and 2 grams of 3-diethylamino-J[di-para-chlorobenzylamino-fluorane] was used as a coloring agent.
Using polystyrene 10gr' as a binder, these components were dissolved in 45cc of a mixed solvent of 7 volumes of toluene and 3 volumes of acetone, and coated on a triacetate film by the bar coating method to form a photosensitive material layer with a thickness of about 12 microns. did.

This was carried out using an ultra-high pressure mercury lamp at an illuminance of 55 mW/Cnlt.
When irradiated for a second, a faint blue-green color could be observed.

When this was heated and irradiated with red light in the same manner as in Example 1, after 7 minutes, the once increased blue-green color decreased and the color changed to a black tone with a slightly higher reddish-purple content, with an absorbance of 1. It was amplified to more than 0. Example 8 2 gr of α,α,α-trichlorotoluene as an activator, 1 gr of 3-ethylparatolylamino-6-methyl-J-anilinofluoran as a coloring agent, 1 gr of vinyl chloride-vinyl acetate copolymer (vinyl chloride 87 %, vinyl acetate 13
%) was dissolved in 24 cc of a mixed solvent of equal amounts of toluene and methyl ethyl ketone.

This was coated on a conductive glass substrate using a spinner coater to obtain a 10 micron thick photosensitive material layer. When this was irradiated with an electron beam at a current density of 10<-8 >Coulombs/Cnl<2> in a vacuum in the same manner as in Example 1, a light black edge color was developed.

When this was heated and irradiated with red light in the same manner as in Example 1, the green component decreased after 10 minutes, and a black tone image with high density was obtained as a whole. Example 9 2 gr of iodoform as an activator, 2 gr of 4-diethylamino-6-methyl-J-anilinofluorane as a coloring agent,
10 grams of a copolymer of methyl methacrylate (95%) and ethyl acrylate (5%) was added to the binder, and 50 cc of a mixed solution of equal amounts of toluene, acetone, and ethyl acetate was added as a solvent and dissolved therein.

This was applied to a triacetate film to a thickness of about 10 microns by a bar coating method. This Q-sensitive material was treated with an ultra-high pressure mercury lamp at an illuminance of 55 mW5/CIT in the same manner as in Example 4.
When irradiated with l2 for 10 seconds, a pale dark green color developed.

When this was heated and irradiated with red light in the same manner as in Example 1, the color was amplified to a higher density color with a stronger black tone after 7 minutes. Example 10 1 gr of carbon tetrabromide was used as an activator, 1 gr of 3-diethylamino-6-methyl-J-anilino-4''/5'' benzofluorane was used as a coloring agent, 4 gr of polystyrene was used as a binder, 7 volumes of toluene, 3 g of acetone. The solution was dissolved in 16 cc of a mixed solvent, and applied to a conductive glass substrate to a thickness of 7 microns using a spinner applicator.

This was heated in vacuum with an electron beam in the same manner as in Example 1 for 10
When irradiated with a current density of -8 coulombs/Cm2, a pale dark green color developed.

When this was also subjected to photosensitization treatment in the same manner as in Example 1, the density was amplified to a black tone of 1.0 to 1.3 after 10 minutes. As is clear from the above description, according to the present invention, the following remarkable effects can be obtained.

(1) Conventionally, by photosensitizing a so-called free radical sensitive material, a non-silver salt sensitive material could barely reach the sensitivity range of silver salt, but the color tone was limited to blue-green.

On the other hand, according to the present invention, it is possible to perform photosensitization ranging from a wide range of yellow to reddish-purple color tones, and furthermore, black tone recording is also possible. (2) When the recording medium of the present invention is in the form of a projection film, only red light can be used for the projection light used for reproducing and reading recorded images, whereas in conventional non-silver halide recording materials, only red light can be used. However, it becomes possible to use a wide range of light from blue to red.

Therefore, it can be used, for example, as a recording film for use in a CTR-FSS flying spot type reproducing apparatus using blue scanning light. (3) In the color development density characteristic curve, that is, the sensitivity characteristic curve, with respect to the irradiation amount of energy rays, there is no risk that the gamma will be lowered and γ is less than 1 when photosensitized as with conventional leucotriphenylmethane dyes. Since a characteristic of gamma 1 or more, that is, γ≧1, can be obtained, it is possible to record images with high contrast.

(4) Due to the photosensitization process, the tendency of amplifying fog in the background portion of the recorded screen as in the conventional method is reduced, and a recorded image with good image quality can be obtained.

(5) Since the dye formed from the fluoran derivative used in the present invention has high stability against sunlight and heat, there is extremely little risk of fading and deterioration of the image after recording.

(6) The energy ray-sensitive material according to the present invention is a non-silver salt organic dye-based molecular dispersion, so it has high resolution, and all treatments such as energy ray image irradiation, light amplification and constant deposition are performed by light irradiation and heating. This can be carried out by a non-development dry process consisting only of the following.

[Brief explanation of the drawing]

FIG. 1 is a characteristic curve diagram showing changes in absorption spectrum due to optical amplification of the energy beam recording material of the present invention, FIG. 2 is a characteristic curve diagram showing changes in sensitivity characteristics due to photosensitization of the recording material of the present invention,
FIG. 3 is a characteristic curve diagram comparing and showing changes in sensitivity characteristics due to photosensitization between the recording material of the present invention and a conventional recording material. FIG. FIG. 3 is a characteristic curve diagram showing a comparison of effects.

Claims (1)

[Claims] 1. As an energy-sensitive activator, R is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, and X is a halogen atom of the same or different types.
Polyhalogen represented by the general formula CX_3 (
By depositing on a substrate a sensitive layer having a) and a 3-7-substituted fluoran derivative (b) as a color former at a mutual weight ratio (a/b) of 0.5 to 2. An energy beam recording material, characterized in that a latent image is formed by weak incident energy and then sensitized by irradiation of the entire surface with red light to form an image in the entire hue range.