U.S. patent number 3,909,266 [Application Number 05/325,304] was granted by the patent office on 1975-09-30 for recording member of photocolor developing and eliminating material and the recording method.
This patent grant is currently assigned to Canon Kabushiki Kaisha. Invention is credited to Eiichi Inoue, Isamu Shimizu.
United States Patent |
3,909,266 |
Inoue , et al. |
September 30, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Recording member of photocolor developing and eliminating material
and the recording method
Abstract
This invention provides a photocolor developing and eliminating
composition, a recording member of monochrome or multicolor
developing and eliminating composition, method for image forming,
fixing, or restoring which is applicable to said recording members
and usual recording members of photocolor developing and
eliminating material, and method for projecting image on a screen
of photocolor developing and eliminating material. A photocolor
developing and eliminating composition comprises a photocolor
developing and eliminating material and a stabilizer, which is
either electron or proton donating or accepting material or solid
matter, on which surface said material being dispersed and which
inherently possesses acidic, basic, ionic, electric charge
transferring or high surface energy property at the surface, and
the stabilizer stabilizing the color-developed state continuously,
restoring after fixing the color-developed state to the colorless
state by the stimulus of radiation having another range of wave
length and reproducing a stable color-development. The multicolor
developing and eliminating composition comprises a film matter
prepared by incorporating a photocolor developing and eliminating
material to a transparent or translucent dispersion medium or the
film attaching to a support such as paper and the like, and the
recording member is wholly color-developed by irradiating it by a
radiation having at least one range of wave-length such as light,
heat and the like. Particularly, at least one dispersion medium is
used to cover the whole visible light range in the colored state.
And the color image recording method is very useful for the rapid,
simple and much memorizing and recording in information industry
such as communication, measurement, documentation and display.
Inventors: |
Inoue; Eiichi (Tokyo,
JA), Shimizu; Isamu (Fuchu, JA) |
Assignee: |
Canon Kabushiki Kaisha (Tokyo,
JA)
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Family
ID: |
27579109 |
Appl.
No.: |
05/325,304 |
Filed: |
January 22, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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705758 |
Feb 15, 1968 |
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630519 |
Apr 1, 1967 |
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Foreign Application Priority Data
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Apr 14, 1966 [JA] |
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41-23217 |
May 31, 1967 [JA] |
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42-35075 |
Feb 20, 1967 [JA] |
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42-11070 |
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Current U.S.
Class: |
430/335; 430/432;
430/337; 430/962 |
Current CPC
Class: |
G03C
1/73 (20130101); Y10S 430/163 (20130101) |
Current International
Class: |
G03C
1/73 (20060101); G03C 005/32 (); G03C 001/52 () |
Field of
Search: |
;96/9PC,48,45.2 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Goodrow; John L.
Attorney, Agent or Firm: Fitzpatrick, Cella, Harper &
Scinto
Parent Case Text
This is a continuation of U.S. application Ser. No. 705,758, filed
Feb. 15, 1968, now abandoned, which in turn is a
Continuation-In-Part of U.S. application Ser. No. 630,519, filed
Apr. 1, 1967, and now abandoned.
Claims
What is claimed is:
1. A process which comprises irradiating a recording member
including in the photosensitive layer a photochromic material
selected from the group consisting of carbinols, cyanides,
sulfides, spiropyrans, anils, nitrobenzyl pyridines, azobenzenes,
stilbene and bianthrones by at least one radiation through an
original image pattern to form an image on the recording member and
treating the resulting image with a basic material or an anionic
material selected from the group consisting of sodium hydroxide,
potassium hydroxide, ammonia and amino compounds to fix said image
as a permanent image, said photochromic material having a property
that when irradiated by a radiation of a specific absorption
wavelength range, it obtains an absorption wavelength in the
visible light region, thereby being color-developed and the
color-developed state is eliminated when irradiated by a radiation
of a wavelength range different from that of the previously applied
radiation.
2. A process which comprises irradiating a recording member
including in the photosensitive layer a photochromic material
selected from the group consisting of carbinols, cyanides,
sulfides, spiropyrans, anils, nitrobenzyl pyridines, azobenzenes,
stilbene and bianthrones, by at least one radiation through an
original image pattern to form an image on the recording member and
treating the resulting image with a basic material or an anionic
material selected from the group consisting of sodium hydroxide,
potassium hydroxide, ammonia and amino compounds, to fix said image
as a permenent image, and then the image surface of the recording
member is treated by an acidic material or a cationic material
selected from the group consisting of acetic acid, benzoic acid,
hydrochloric acid, nitric acid and solid Lewis acids to restore the
permanent image surface to the color-developed image surface, said
photochromic material having a property that when irradiated by a
radiation of a specific absorption wavelength range, it obtains an
absorption wavelength range in the visible light region, thereby
being color-developed and the color-developed state is eliminated
when irradiated by a radiation of a wavelength range different from
that of the previously applied radiation.
3. A color recording process which comprises applying a blanket
irradiation of ultraviolet ray or heat to a photochromic recording
member having a photosensitive layer containing a photochromic
material having a visible light absorption spectrum peak in the
colored state present at 400-500 .mu., a photochromic material
having a visible light absorption spectrum peak in the colored
state present at 500-600 .mu. and a photochromic material having a
visible light absorption spectrum peak in the colored state present
at 600-700 .mu., color developing all of the photochromic
materials, selectively eliminating the color of the colored
photochromic materials corresponding to each absorption spectrum by
applying color light image thereto, thereby producing a colored
image.
4. The color recording process according to claim 3 wherein each
photochromic material is uniformly dispersed in the photosensitive
layer.
5. The color recording process according to claim 3 wherein each
photochromic material is separately formed in a layer and the
resulting three layers are laminated to form a photosensitive
layer.
6. A color recording process according to claim 3 wherein one or
more of the reagents contains a photochronic compound and a color
control agent which shifts the natural color elimination absorption
peak of the photochromic compound.
7. A color recording process according to claim 6 wherein the color
control agent is a film-forming material in which the photochromic
compound is distributed.
8. A color recording process according to claim 6 wherein the color
control agent is a solvent for the photochromic compound.
9. A color recording process according to claim 6 wherein the
photochromic compound is distributed in a matrix containing a
film-forming material and a solvent for the photochromic compound
miscible with the film-forming material and, if desired, an
additive compound which acts as a color control agent, all such
compounds contributing to the determination of the color
elimination absorption peak of the photochronic compound.
10. A color recording process according to claim 9 containing three
or more photochromic reagents of different color elimination
absorption peaks in a single photosensitive layer, said components
assisting in determining the spread of the resulting color
elimination absorption spectrum of the layer so that it
substantially covers the visible spectrum.
11. A color recording process according to claim 3 wherein the
photosensitive layer comprises three superposed sub-layers each
having a different characteristic color elimination absorption
spectrum and cooperating with the other layers to substantially
cover the visible spectrum.
Description
This invention relates to a recording technique in which a
photocolor developing and eliminating material is used. More
particularly, this invention relates to a novel recording members
of monochrome or multicolor photocolor developing and eliminating
material, methods for color-developing, fixing and restoring which
are applicaable to said recording members and usual recording
members of photocolor developing and eliminating material, and
image projecting methods in which novel screens comprising
photocolor developing and eliminating material are used.
Heretofore, photosensitive materials used in conventional
recording, photographic or copying technique are such that a latent
image is formed on said photosensitive material by exposure,
developed by chemical or physical means and then fixed to form
stable images. In such prior art a number of processes are
necessary to form the image, and a fairly large apparatus and
consumption materials are required. In addition, the treating speed
is disadvantageously slow.
In conventional photographic techniques such as the silver salt
photography, the diazo photography, the thermal photography,
electrophotography and the like, the image formation is carried out
according to the abovementioned processes. Among these processes,
there is seldom a process in which a once formed stable image is
eliminated and the same photosensitive surface is again exposed to
form an image. A conventional recording material by which a
photosensitive surface is exposed to light to form an image thereon
and the image is then eliminated followed by new exposure to form
another image is a photochromic material.
A photochromic material is generally converted to the colored state
by irradiating a radiation having a specified wave length or a
specified energy (including rays of wave length in the range of
infrared or ultraviolet ray etc., hereinafter comprehensively
called "radiation") and the formed color is eliminated by the
stimulus of heat or light having different wave length or radiation
having different energy. When the photochromic material is used as
a material for a recording member, the recording member is exposed
to a radiation having a specified range of wave length to form
colored images and then another radiation having a range of wave
length different from the previous one is applied to eliminate all
of or a part of the colored images. Thus, the recording member is
ready for reexposure. As mentioned above, a recording member
comprising a photochromic material can effectively reproduce
various images repeatedly on the same recording member.
However, the conventional photochromic substances (hereinafter
called "photocolor developing and eliminating material") can not
remain lastingly in the colored state for a long time. Therefore,
when a photochromic material is used as a material of a recording
member, an image which is stable for a long time is not
obtained.
In order to solve such problem, heretofore, a photocolor developing
and eliminating material has been irradiated with a radiation to
develop a color and the colored state thus formed has been simply
stabilized. However, such stabilizing treatment makes the
elimination of the once stabilized image difficult as in case of
the printing-out photography and deteriorates the photocolor
developing and eliminating property. Thus, the repeating recording
by the same recording member is not possible.
The color-developing mechanism of photocolor developing and
eliminating materials is not yet fully understood. However, the
presently known photocolor developing and eliminating materials are
considered to develop the color by a change such as photo-ion
dissociation, photo hydrogen transmission, photo radical
dissociation, photo steric structure change, photooxidation,
photoreduction and the like caused by irradiation of light
(radiation).
According to this invention, a photocolor developing and
eliminating material system and a stabilizer co-exist to stabilize
the color-developed state continuously, restore the color-developed
state to the colorless state by the stimulus of radiation having
another range of wave length and reproduce a stable
color-development. The photocolor developing and eliminating
material systems include those which develop color by a change such
as photo-ion dissociation, photo radical dissociation, photo
hydrogen transmission, photo steric structure change,
photooxidation, photoreduction and the like. The stabilizer is a
material system which stabilizes the color-developed state,
eliminates the stabilized state by a stimulus of radiation having
the other range of wave length to restore to the original colorless
state. The stabilizer is a material system having a property of
electron or proton donating or accepting which copes with atoms,
atom groups, free radicals, ions etc. generated by the
color-developing mechanism involved in color-developed state of the
photocolor developing and eliminating material.
The stabilizing mechanism of the stabilizer is not yet clarified,
but it is probably considered that the atoms, atom groups, free
radicals, ions etc. generated as above are stably retained without
causing a reversible reaction by the electron or proton donating or
accepting reaction with the stabilized and as the result the
color-developed state of the photocolor developing and eliminating
material is stabilized. Thus, a novel recording member which can
produce stable colored images is obtained by incorporating the
photocolor developing and eliminating material and the stabilizer
to the photosensitive layer of the recording member.
The photocolor developing and eliminating material and the
stabilizer as mentioned above are homogeneous system materials.
When the stabilizer is dissolved in a dispersion medium together
with the photocolor developing and eliminating material, the
stabilizer is dissolved therein in the molecular state and assumes
a property of electron or proton donating or accepting. The
stabilizer in the molecular state effects the electron or proton
donating or accepting action with the atoms, atom groups, free
radicals, ions or the like produced in the color-developed state of
the photocolor developing and eliminating material. As the result,
the stabilization is effected.
While the above mentioned stabilizer is composed of a material of
homogeneous system, according to an additional aspect of this
invention a heterogeneous material or an intermediate material is
also effectively used as a stabilizer for the photocolor developing
and eliminating material. The stabilizers of a heterogeneous
material or intermediate materials are heterogeneous system
materials, the surface of solid particles of which are acidic,
basic, ionic, of electric charge transferring or of high surface
energy, or the particle surface of which is treated so as to assume
such property as mentioned above. Examples of the stabilizers
include solid acids, solid bases, sizing agents, ionic solid and
the like. The photocolor developing and eliminating material may be
bonded to the solid particle surface of the stabilizer by simply
contacting or using a binder.
In general, the heterogeneous system material is in a form of
particle-like solid at a usual state. Therefore, the heterogeneous
system material can not exist in a molecular state together with
the photocolor developing and eliminating material while the
stabilizer of electron or proton donating or accepting material can
be present in a molecular state. The heterogeneous system material
is not dissolved in a dispersion medium in a molecular state, but
dispersed in the medium in a state of solid particle. Therefore,
the stabilizing mechanism of the heterogeneous system material is
different from that of the homogeneous system material. The solid
particle itself of the heterogeneous system material should have a
stabilization effect. According to the present invention, a
heterogeneous system material, the solid particle surface of which
intrinsically possesses a tendency of stabilizing the photocolor
developing and eliminating material is selected as a stabilizer.
Examples of such material include materials which surface is
acidic, basic, ionic, of electric charge transferring, or of high
surface energy. The photocolor developing and eliminating material
is uniformly bonded to the surface of the solid particle of the
stabilizer by contacting or using a binder to stabilize the
photocolor developing and eliminating material in the color
developed state.
Alternatively, the particle surface of the heterogeneous system
material is subjected to a stabilizing treatment in advance so as
to impart acidic property, basic property, ionic property, electric
charge transferring property or high surface energy thereto, and
then the particle surface thus treated is homogeneously coated with
the photocolor developing and eliminating material by, for example,
contacting or using a binder to produce a novel and stable
photocolor developing and eliminating member having a stable
color-developed state and retaining the photocolor developing and
eliminating property. Particularly, when the photocolor developing
and eliminating material contacted with the particle surface is
impregnated with a stabilizer of a homogeneous system material such
as an electron or proton donating or accepting material as
mentioned above, a remarkably stable photocolor developing and
eliminating material is produced.
In other words, according to the aspect of this invention in which
a heterogeneous system material is employed as a stabilizer, the
surface of the stabilizer particle which has inherently acidic
property, basic property, ionic property, electric charge
transferring property and high surface energy or the surface of the
stabilizer particle which is subjected to the treatment for
imparting to the surface the acidic property, basic property, ionic
property, electric charge transferring property or high surface
energy, is contacted with or coated with the photocolor developing
and eliminating material alone or the photocolor developing and
eliminating material to which an electron or proton donating or
accepting material is incorporated as a stabilizer. Thus, the
color-developed state of the photocolor developing and eliminating
material is continuously stabilized and can be restored to the
colorless state by a stimulus of a radiation having the other range
of wave length.
The stabilization means of the photocolor developing and
eliminating material as mentioned above may be applied to the
fixing and chemical elimination of the color-developed image, the
color image recording member, or the color image recording method
as mentioned later. It is possible to obtain clear contrast,
excellent half tone images as well as line images. The images may
be erased or modified if desired. Further, the recording member and
the recording process may be used in multiple uses. The recording
member in which the photocolor developing and eliminating material
stabilized in accordance with the present invention gives stable
color-developed images, and the fixing and chemical elimination of
the color-developed image as described later is established.
Therefore, the recording member and the recording process of this
invention may find remarkable uses in the fields of calculation,
translation, communication, documentation or the other various
information treating systems for recording, accumulation,
modification, erasing and layout of the information.
It is an object of this invention to provide novel photocolor
developing and eliminating matters in which the unstable
color-developed state of photocolor developing and eliminating
materials is stabilized continuously and the color-developed state
can be eliminated by a radiation having the other range of wave
length, i.e. the reversibility of photocolor developing and
eliminating property is still retained.
It is a further object of this invention to provide novel recording
members which can produce the color-developed images stabilized
continuously.
The above-mentioned various stabilizing means can retain the
color-developed stage of image for from several ten minutes to
several ten hours, but the developed color image is not kept as an
everlasting image.
According to a further aspect of this invention, the color
developed state of the photocolor developing and eliminating
material is retained as an everlasting image, that is, fixed, and
further the lasting image thus produced is restored to the original
state in which the material assumes the photocolor developing and
eliminating property.
Heretofore, a fixing and restoring method has not yet known by
which the color-developed image of the photocolor developing and
eliminating material is fixed as an everlasting image and then the
fixed image is restored to the original stage where the material
prosesses the photocolor developing and eliminating property.
According to conventional methods, when the color-developed image
is once fixed as an everlasting image, for example, in the
printing-out photography, it is not possible to restore the
material to the original state where the photocolor developing and
eliminating property is restored again. According to the method of
this invention, the fixing is carried out by treating the
photocolor developing and eliminating recording member in the
color-developed state with a basic material or an anion. The
color-developed image is converted to a latent image, for example,
when the photocolor developing and eliminating material is a
spiropyran compound, the color-developed image is changed to a
yellow latent image state. The mechanism is not yet fully
understood, but it is considered that the atom, atom group, free
radical or the like produced in the photocolor developing and
eliminating material in the color-developed state is combined with
the basic material to form a certain stable chemical complex which
is everlastingly retained as the yellow latent image.
Further, with respect to the restoring method, the fixed image is
treated with an acidic material (cationic treatment). It is
considered that this treatment neutralizes a certain chemical
complex salt forming a yellow latent image and the basic material
as the fixing agent is eliminated to form a colored image having
photoreversibility.
It is a further object of this invention to provide a process
comprising fixing as an everlasting stable image a color-developed
image of a recording member including singly a photocolor
developing and eliminating material, a recording member including a
photocolor developing and eliminating material to which a
stabilizer is incorporated, or a recording member which is prepared
by contacting or coating the surface of particles of a
heterogeneous system material, which itself has inherently the
stabilizing activity or is subjected to a stabilizing treatment,
with a photocolor developing and eliminating material.
Also, it is a further object of this invention to provide a
restoring process which comprises restoring the fixed image to the
original photocolor developing and eliminating state thereby the
material assuming a photoreversibility.
It is a further object of this invention to develop the application
fields of the recording member by imparting the everlasting
property to the color-developed visible image and, if desired, by
reverting the color-developed image to the original photocolor
developing and eliminating state.
In view of the special properties of the recording member
comprising a photocolor developing and eliminating material and the
stabilization, fixation, and restoration thereof, various novel
reproduction methods are provided.
According to a further aspect of this invention, a normal image or
a reverse image can be optionally formed on the same recording
member by using a recording member comprising a photocolor
developing and eliminating material according to a simple
process.
Heretofore, a reverse image has been produced often by a wet
process of chemical procedure and the stability of procedure has
not been satisfactory, and moreover a fairly large scale apparatus
and a lot of consumption materials are required. In addition, the
treating speed is disadvantageously slow.
According to this invention, the inherent properties of photocolor
developing and eliminating materials are utilized to form a reverse
color-developed image by irradiating a recording member comprising
a photocolor developing and eliminating material through an
original pattern by a radiation having a specific range of wave
length, or to form a normal image by uniformly color-developing the
whole surface of the recording member and irradiating the recording
member by a radiation having the other range of wave length.
Therefore, the method of this invention enables to form simply and
rapidly a desired normal image and a desired reverse image on the
same recording member. With respect to the formation of the reverse
color-developed image on the recording member, a radiation having
wave length ranges corresponding to the characteristic absorption
ranges of a photocolor developing and eliminating material in the
recording member is projected to the recording member through an
original pattern to bring the recording member to a color-developed
state having the range of absorption wave length in visible light
region. If the original pattern is negative in the above case, a
positive color-developed image, i.e. a reverse image, is obtained
since the radiation is projected to the portion of the recording
member corresponding to the image parts of the original pattern. On
the contrary, with respect to the formation of a normal image on
the recording member, a radiation having the ranges of wave length
correspondng to the characteristic absorption wave length region of
the photocolor developing and eliminating material in the recording
member is projected to the recording member to color-develop
uniformly the whole surface of the recording member, and then the
color-developed recording member is irradiated by a radiation
having the other range of wave length through a positive original
pattern to eliminate the portions of the recording member other
than portions corresponding to the original pattern. As the result,
a positive color-developed image is formed. Further, the whole
surface is color-eliminated and irradiated again by a radiation
having the above-mentioned specified range of wave length through a
negative original pattern to form a positive reverse image on the
recording member. As mentioned above, a normal image or reverse
image is optionally obtained by the same recording member. Further,
a repetition is possible which eliminates the recorded image by
light, restores to the original wholly color-developed state, and
records again. Further, a recording member formed by the
combination of spirans may be treated with, for example, aliphatic
amines such as hexylamine, or a strong alkaline solution such as
that of potassium hydroxide to stabilize the image everlastingly in
a stage of yellow latent image, and then treated with organic acids
or inorganic acids to restore the image to the original colored
image.
It is a further object of this invention to provide a novel and
simple process for forming optionally a normal image or a reverse
image rapidly on the same recording member by using a recording
member comprising photocolor developing and eliminating
material.
There are various conventional processes for recording colored
images. For example, in the known silver salt methods, a color
image exposing is carried out and further a color-developing step
involving the reduction of the silver salt is necessary. In
electrolytic electrophotography, an electrolytic color-developing
step is employed, and in diazo methods a coupling color-developing
method is employed. However, these prior arts involve a wet type of
chemical reaction and lack in the stability of procedure. In
addition, the prior arts necessitate a fairly large scale of
apparatus and a lot of consumption materials and further the
treating speed is disadvantageously slow.
According to the present invention, a novel color recording member
based on a novel color recording process is provided. Said
recording member comprises a film like matter itself prepared by
incorporating a photocolor developing and eliminating material to a
transparent or translucent dispersion medium, or said film like
matter attached to a support such as paper, transparent support and
the like. The recording member is wholly color-developed by
irradiating it by a radiation having at least one range of wave
length such as light, heat, a combination of light and heat, and
the like. Particularly, at least one dispersion medium is used to
cover the whole visible light range in the colored state since the
combination of the different absorption wave length ranges caused
by each combination of the photocolor developing and eliminating
material with the different dispersion mediums may cover the whole
visible light range. Alternatively, at least one photocolor
developing and eliminating material is selected in such a manner
that each of the material has each different individual absorption
spectrum in the colored state and the combination of the material
shows the photocolor eliminating property at the visible light
range.
This is explained further in detail below. In general, it is
necessary to construct a color recording member in such a manner
that the color recording member has the absorption region or the
color-developing region over the whole visible light range.
According to this invention, the recording member is constructed so
that it shows the absorption over the whole visible light
range.
1. In general, the photocolor developing and eliminating material
shows the characteristic absorption in ultraviolet wave length
range or infrared wave length range before the photocolor
developing and eliminating material is color-developed. Therefore,
when these materials are irradiated by, for example, a radiation of
wave length of ultraviolet region, it becomes a color-developed
state having the absorption wave length range at the visible light
range. And the color depends on the type of the photocolor
developing and eliminating material. The first type of color
recording member of this invention comprises at least one
photocolor developing and eliminating material which is selected in
such a manner that the material has the absorption wave length
range over the whole visible light range, and the material is mixed
and made into a layer.
2. The absorption wave length range in the color-developed state
can be changed by dissolving the photocolor developing and
eliminating material and changing the dispersion medium in which
the material is dispersed in a matrix state. The second type of
color recording member comprises the photocolor developing and
eliminating material dispersed in at least one dispersion medium in
a matrix state, the photocolor developing and eliminating material
being combined with the dispersion medium in such a manner that the
photocolor developing and eliminating material has the absorption
wave length range over the whole visible light range at the color
developed state and the photocolor developing and eliminating
material combined with the dispersion medium being coated to form a
multiple layer.
In this case, when the additive such as stabilizer as mentioned
above is incorporated to the dispersion medium, the absorption wave
length range of the photocolor developing and eliminating material
in the visible light range can be somewhat changed in the color
developed state. Therefore, when an appropriate dispersion medium
and an additive are used in combination, it is possible that one
and the same photocolor developing and eliminating material has the
absorption wave length range over the whole visible light region in
the color developed state. In other words, the photocolor
developing and eliminating material is appropriately dispersed in a
dispersion medium in which an additive is incorporated, and
different dispersion mediums are employed to form a multiple layer.
Thus, the combinations of the dispersion mediums and the photocolor
developing and eliminating material enable to provide a color
recording members that the absorption range covers the whole
visible light range in the color-developed state.
3. In 1 and 2 above, a combination of two or more photocolor
developing and eliminating materials having each different
absorption wave length ranges at the color developed state can
cover the whole visible light range. Or, the same photocolor
developing and eliminating material is used together with different
dispersion mediums to which an additive may be or not incorporated,
and at least one of them is arranged as a multiple layer to form a
color recording member having the absorption wave length range
covering the whole visible light range.
Further, the combination of 1 and 2 also provides a recording
member. In other words, the absorption wave length range of the
photocolor developing and eliminating material in the
color-developed state can be easily changed by appropriately
selecting the photocolor developing and eliminating material, the
dispersion medium and the additive. Therefore, at least one of them
having each different absorption wave length is combined to provide
a color recording member having the absorption wave length range
covering the whole visible light range.
Therefore, the recording member is irradiated by a radiation having
at least one specific wave length range to color-develop and then a
color original image pattern is projected to the color-developed
recording member by using a radiation having the different wave
length range to eliminate the developed color of the photocolor
developing and eliminating material in the recording member in
accordance with the color pattern of the color original image.
Thus, a positive color referring to the original image is directly
formed and recorded.
Particularly, in the above-mentioned color recording member the
photocolor developing and eliminating material is formed in a layer
state in accordance with the dispersion medium, for example, in
three layers. However, it is not always necessary to form a
multiple layer. Alternatively, it is also possible that each of
photocolor developing and eliminating materials or a mixture of
each of them with a dispersion medium is finely divided and each of
the resulting finely divided photocolor developing and eliminating
is homogeneously mixed and formed in one layer.
Further, a color image formed in the color recording member may be
changed to a yellow latent image and stabilized lastingly by
treating with an alkali or base. If necessary, the stabilized
latent image may be restored to the original color image by an acid
treatment.
The color image recording method of the present invention is very
useful for the rapid, simple and much memorizing and recording in
information industry such as communication, measurement,
calculation, documentation and display. Further, it is also useful
as monitors in color image treating systems.
It is a further object of this invention to provide a method for
producing directly a record of color image by exposing an image
recording member to a color image projection. The purpose of this
invention is to provide a novel color recording member which
utilizes a photocolor developing and eliminating material.
It is a further object of this invention to provide a method which
comprises using one and the same color recording member, forming a
color image directly on the recording member, eliminating the color
image by a radiation having at least one wave length range such as
light, heat and a combination of light and heat, and thus forming a
color image repeatedly on one and the same recording member.
It is a further object of this invention to provide a method which
comprises fixing a color image produced on the novel color
developing member to convert the color image to an everlasting
stable image in a latent image state and, if necessary, restoring
the latent image to the original color image.
It is a further object of this invention to provide a novel image
formation by projection in which a photocolor developing and
eliminating material and a novel reproduction method are
employed.
It is a further object of this invention to provide a novel
projection method which comprises using a novel screen comprising a
photocolor developing and eliminating recording member and forming
optionally a normal image and a reverse image.
In conventional projection methods, a reverse image is prepared in
advance and projected. However, the method for obtaining the
reverse image necessitates often wet type steps of chemical
reactions taking a long time and the procedure stability is low.
Further, the method necessitates a fairly large scale apparatus and
much consumption materials and the procedure is complex. Further,
in the conventional projection method a dark room is necessary to
enchance the contrast of the projected image.
This invention provides a novel method of projecting images which
uses a screen prepared by dispersing a photocolor developing and
eliminating material alone or a photocolor developing and
eliminating material to which the previously mentioned material is
added, if necessary, a binder being added thereto, in a liquid
matrix such as benzene, toluene and the like, or in a high polymer
dispersion medium, and forming a film from the resulting
dispersion. Alternatively, the screen may be prepared by coating
the dispersion of the photocolor developing and eliminating
material on a support such as resin, glass, metal, paper, fiber,
wood, porcelain and the like.
In this method of this invention, a method for forming a normal
image or a reverse image by using one and the same recording member
is applied to an image projecting method such as a slide
projection, a cinema and the like. In the novel image projection
method of this invention, in case that a reverse image projection
is obtained by using a screen comprising a photocolor developing
and eliminating material, the photocolor developing and eliminating
material is usually color-developed by an appropriate exciting
light such as ultraviolet light and the like enabling to form an
absorption range in the visible light region. When the negative
film is irradiated by an appropriate exciting light, the exciting
light does not pass through the dark parts of the negative film and
the corresponding part on the screen hardly color-develops while
the exciting light passes the light part or the transparent part
and the corresponding part on the screen color-develops.
Thus, a positive image is obtained from a negative film.
This image exists only while the exciting light is projected, and
when the exciting light is removed, the image is eliminated.
Therefore, the method as mentioned above can be utilized in the
projection of cine-film as well as the projection of slide-film.
When a screen is made from a material giving an after image, it is
not always necessary to project continuously an exciting light.
Further, it is effective to project a visible light to a screen for
the purpose of accelerating the elimination of the after image or
irradiating the screen.
On the contrary, in order to obtain the normal image projection, an
already color-developed matter in the visible light range or a
matter which has been color-developed by a stimulus of light other
than visible light, a stimulus of heat and the like, is exposed to
a visible light to eliminate the image, and thereby a normal image
projection is obtained.
When the matter is not yet color-developed in a visible light
range, it is necessary to color-develop uniformly the whole surface
in a visible light range by applying a color-developing means
inside of the screen, or from the front or the behind of the
screen. When a visible light is projected through a positive film
to the already color-developed screen or the screen color-developed
by a certain color-developing means, a developed color at a portion
of screen corresponding to a portion of the film which the visible
light passes through, is eliminated to give a positive image
projection.
It is a further object of this invention to provide a projected
image forming process such as a process for obtaining a clear
positive projected image directly from a negative film, a process
for obtaining a clear negative projected image from a negative film
by applying a color-eliminating means to a color-developed
projection surface, a process for effecting a reverse projection
and a normal projection to one and the same projection surface, and
a process by which any dark room is not necessary to form a
color-developed image. With respect to "color-developed image" of
the photocolor developing and eliminating material, many of the
photocolor developing and eliminating materials are usually
colorless before color-developing, but some of the photocolor
developing and eliminating materials are colored. For example, when
a colorless photocolor developing and eliminating material is
irradiated by a radiation having the characteristic absorption
range, the colorless material is colorized to form a colored image
while a colored photocolor developing and eliminating material
becomes colorless or the color is changed to a different color.
Therefore, the term color-developed image in this invention means
an image formed by irradiating a colorless or colored photocolor
developing and eliminating material by a radiation.
Other object of this invention will be clarified from the detailed
explanations in accordance with the attached diagrams. In the
following paragraphs, the attached diagrams are briefly
explained.
FIG. 1 is the respective absorption spectrum curves of the three
kinds of photosensitive components which are used for the color
image recording material of this invention;
FIG. 2 is the absorption spectrum of the photosensitive matter
composed of the three kinds of photosensitive components;
FIG. 3 is the diagram showing the spectrum distribution of the
positive color slide which is the original image;
FIG. 4 is a diagram showing the spectrum distribution of the color
image obtained by exposing the positive color slide of FIG. 3;
and
FIG. 5 is a diagram showing the absorption spectrum curve of the
state of color development of the respective kinds of photocolor
developing materials used in this invention.
FIG. 6 through FIG. 8 show the embodiments of the method of the
production of a projected image of this invention, and FIG. 6 shows
the light path for forming the projected image by irradiating a
negative film onto a screen made of the photocolor developing and
eliminating material with ultraviolet light; FIG. 7 shows the light
path of the case when the image of the negative film is projected
on a screen with a tungsten lamp, and the screen is irradiated with
ultraviolet ray; FIG. 8 shows the light path of the case when the
visible light, ultraviolet ray or the mixed light thereof is used
as the light source.
Generally speaking, a photocolor developing and eliminating
material develops color from the colorless state by exposure, i.e.,
by the irradiation the radiation of a specific range of wave
length, or a photocolor developing eliminating material can change
color from the colored state, and can be reduced into the original
state by the irradiation of the radiation of other range of wave
length. For example spiropyran compound is known to be changed into
the state having new absorption in the visible range, i.e., in the
photocolor developing state.
However, the color-developed state can be retained for a certain
period of time (such as several minutes in polystyrene film at a
room temperature) but it is reduced to the original state
(colorless state).
As mentioned above, in accordance with this invention, a new
photocolor developing and eliminating material whose
color-developing state can be stabilized for a long time by taking
into consideration the developing and eliminating mechanism through
the photocolor developing and eliminating mechanism of the
photocolor developing and eliminating material, and the new
photocolor developing and eliminating material is used as the
recording material.
It is considered that the conventional photocolor developing and
eliminating materials which develop colors by the photo-ion
dissociation, photo-radical dissociation, photo hydrogen
transmission, photosteric structure change, photo-oxidation or the
photoreduction or such like changes.
Examples of the compounds which photocolor-develop and eliminate
according to such mechanisms include:
1. Photo-ion dissociating materials
a-1. carbinols such as
malachite green carbinol, crystal violet carbinol, phenolphthalene
carbinol and the like.
a-2. cyanides such as
orlamine cyanide, brilliant green cyanide, malachite green cyanide,
pararose aniline cyanide, phenol phthalene cyanide and the
like,
a-3. sulfides such as
crystal violet sulfide, malachite green sulfite, methyl violet
sulfite, para-rose aniline hydrosulfite, rose-aniline sulfite and
the like,
b. spiropyrans such as
1,3,3-trimethyl-indolino-benzopyryl spiran and the derivatives
thereof,
bispiro-2,2'-(5,6-benzopyran)
5,6-benzopyran-2-spiro-2' .beta.-naphthopyran,
3,3'-dimethyl-bispiro-2,2'-(.beta.-naphthopyran and the like,
2. Photo-radical dissociating materials such as
a. tetrachloro-1 (4H) + phthalenone, tetrachloro-1(2) + phthalenone
and the like,
b. hexaphenyl bi-imidazolyl, tetra phenyl pyrole dimer and the
like
3. Photo-hydrogen transmitting materials
a. Anils such as
salicylidene aniline, salicylidene meta toluidine, salicylidene
orthochloroaniline, salicylidene metaphenylene diamine, 5-bromo
salicylidene .alpha.-naphthyl amine and the like,
b. Aromatic nitro compounds such as
2-(2',4'-dinitrobenzyl pyridine,
4-(2',4'-dinitrobenzyl) pyridine
4. Photo steric structure changing materials
a. Cis-trans transmission materials such as
4,4-dimethyl amino azobenzene, 4-nitro-4-amino-azobenzene,
4,4-diamino stilbene-2,2'-disulfonic acid, diformyl-4,4'-diamino
stilbene-2,2'-disulfonic acid and the like.
b. Bianthrones such as
xanthylidine anthrone, bianthrone and the like
5. Photo-oxidizing or photo-reducing materials such as
methylene blue and the iron salts, thionine and the iron-salts.
In accordance with this invention, the material having electron or
proton donating or accepting properties is added as the color
developed state stabilizer to the photocolor developing and
eliminating materials, and the color developed state is stabilized
by giving and receiving of electron or proton.
The effect of the stabilizer depends on the combination of the
photocolor developing and eliminating substance and the stabilizer,
concentration, temperature and the properties of the binder to be
added for preparing the photosensitive layer or the properties of
matrix in which dispersing the photocolor developing and
eliminating materials is dispersed when the photocolor developing
and eliminating materials are contained in the recording member.
Therefore, the specific substances cannot be specified, but the
following materials are effective.
As electron donating materials the following can be given.
1. .pi.-electron donating materials such as
a. benzene and alkyl derivatives such as benzene, toluene, xylene
and the like.
b. polycyclic aromatic compounds such as naphthalene, anthracene,
pyrene, tetracene, perylene and the like
2. n-electron donating materials
a. aliphatic amines such as ethyl amine, propyl amine, butyl amine,
octylamine, and the like
b. aromatic amines such as aniline, dimethylaniline, paraphenylene
diamines, and the like
As electron accepting materials the following can be given.
1. quinones such as
tetracyano quinodimethane (TCNQ) chloroanil, bromo anil,
paraquinone, .alpha.-naphthoquinone, .beta.-naphthoquinone, and the
like
2. Nitro compounds such as
2,4-dinitro benzene, 1,3,5-tri-nitrobenzene or the like
As proton accepting materials, the following compounds can be
given,
Acrydine, quinoline, benzylamine, pyridine, diphenylamine, methyl
ethyl ether, azobenzene, chlorobenzene, or the like
As the proton donating materials the following compounds can be
given.
Phenol, aniline, acetic acid, butyalcohol, crotonic butylalcohol,
benzoic acid or the like
The above given compounds are effective as the stabilizers, and
when combined with the photocolor developing and eliminating
materials, the mixture is coated on the supporters such as metal,
paper, plastic or the like, or is coated by dispersing the mixture
in an appropriate matrix materials to prepare the photosensitive
layer of the recording material, and the mixture dispersed in the
matrix is formed in the state of film, and the obtained film is
used.
Thus obtained recording material can perform color development and
color elimination by the irradiation of X-ray, ultraviolet ray,
visible ray, infrared ray and various kinds of radiations.
It is not specified which of photocolor developing wave length or
photocolor elimination is on the side of long wave length.
As mentioned above, in accordance with the method of this
invention, when a stabilizer is contained in photocolor developing
and eliminating materials, it is possible to retain lastingly the
stable color developing state when the radiation of a specific wave
range is given to the materials.
Therefore, when such new materials are used as the main component
of the recording material, it is apparent that a recording material
which can be widely used is obtained.
For example, phototyping materials, materials for making master
sheets for printing, and the recording materials for
telecommunication machines and electronic computers or other
recording materials.
For example, when mis-typing is made by the erroneous operation is
phototyping, or a part of the phototyped copy is changed because of
the correction of the original, the photosensitive surface is
eliminated, or the separately corrected typing is replaced for the
mistyped portion or the portion to be corrected by eliminating the
photosensitive surface or phototyping is done anew, when the
conventional photosensitive material is used, and therefore the
phototyping technique has been remarkably retarded, as is known to
those skilled in the art. However, when this invention is employed,
such correcting operation can be easily done with a short time by
erasing the image by irradiating the radiation for erasing the
color of the portion which is to be corrected, and by exposing the
corrected image with the radiation for color-development.
Japan this invention is very convenient in phototyping system in
Japen where the people use a great number or characters and various
kinds of letters. In other applications of this invention, most of
the correcting operations which require remarkable experiences can
be quickly carried out by making use of the reproduction of the
image by means of reexposure, and the erasing through the radiation
stimulus. The following are the examples to further illustrate the
recording materials to which the stabilizing method of this
invention is applied.
EXAMPLE 1
34.4 mg of malachite green cyanide, 20.4mg. of
tetracyanoquinodimethane, and 10 g. of ethylcellulose were
dissolved into 100 g. of alcohol, and the obtained mixture was
coated on a transparent glass plate and the coated mixture solution
was dried. Thus prepared photosensitive layer developed bluish
green at the quantum yield of 1 when irradiated with 313 m.mu.. of
mercury lamp ray and the photosensitive layer could be kept in a
stable color developing state and then when 365 m.mu.. of mercury
lamp ray was irradiated thereto the color thereof was eliminated.
The process of color development and color elimination could be
repeated over and over again.
EXAMPLE 2
10 g. of salicylidene anil, 9 g. of acrydine were uniformly mixed,
and thermally melted, and then cooled off. Thus obtained crystal
was crushed, and was finely dispersed into resin, and a film was
prepared. Thus prepared recording material developed yellowish
orange by the irradiation of 365 m.mu.. of mercury lamp ray, and
the color developing state can be stably retained, and then a
tungsten lamp was used as the light source, and the erasing of
color could be carried out by irradiating the light rays above 420
m.mu.. by using a filter and tungsten lamp as the light source. The
process of color development and color elimination could be carried
out repeatedly.
The following are the explanations about the embodiments in which
the substance of heterogeneous system belonging to another type, or
the intermediate substances between the homogeneous system and
heterogeneous system were used as the stabilizers.
When the heterogeneous system materials or the intermediate
substances between a heterogeneous system material and a
homogeneous system material were used as the stabilizers, as
explained in detail, the materials having stabilizing properties,
such as acidic, basic, ionic, electric charge transmitting
properties or high surface energy, should be selected as the
surface of the solid particles of said materials, or the surface of
said material should be treated so as to give the above mentioned
properties to the surface thereof.
In the following, examples of the photocolor developing and
eliminating material systems, heterogeneous system material
stabilizers having inherently a stabilizing surface, the
intermediate substances thereof, heterogeneous system material
stabilizers subjected to a stabilizing treatment, intermediate
substances thereof, and concrete examples where the above-mentioned
materials and stabilizers are employed, are shown.
Representative and preferable photocolor developing and eliminating
materials in this invention are as follows:
A. spirans such as
1,3,3-trimethylindolino 6'-nitrobenzo pyrylspiran
6'-nitro-8'-methoxy-1,3,3-trimethyl
indolino-6'-nitrobenzopyrylspiran
6'-nitro-8'-fluoro-1,3,3-trimethylindolino-6'-nitrobenzopyrylspiran
6'-8'-dibromo-1,3,3-trimethylindolino-6'-nitrobenzopyrylspiran
and the combinations of spiropyran compounds
and hydrogen donors, i.e., proton donating substances such as
phenols, organic carboxylic acids, weak inorganic acids and the
like.
B. anils such as
salicylidene-aniline, salicylidene-m-toluidine,
salicylidene-p-toluidine, salicylidene-orchloraniline,
salicylidene-p-bromoaniline, salicylindene-m-bromoaniline,
salicylidene-p-bromoaniline, salicylidene-m-phenylene-diamine,
salicylidene-o-anisidine, salicylidene-p-anisidine,
salicylidene-m-aminobenzoic acid,
salicylidene-p-aminobenzoic acid,
and the combination of anil compounds and proton accepting
materials such as acrydine, quinoline and the like,
C. semicarbazones such as
cinnamic aldehyde semicarbazone, m-methoxy cinnamic aldehyde
semi-carbazone, o-methoxy cinnamic aldehyde semi-carbazone,
o-methoxy cinnamic aldehyde phenyl semicarbazone, and the like.
As the examples of the heterogeneous system material having the
surface for stabilizing the specific state of photocolor developing
and eliminating materials, the following can be given
1. As solid materials, organic and inorganic compounds having
acidic surfaces, basic surfaces, ionic solid, electric charge
transmitting properties, or high surface energy, and paper, fiber,
wood, porcelain, metal, glass, synthetic fiber, resin film or the
like.
2. As gel form materials, for example, substances as shown below or
inorganic sol form substances and organic gel form substances
containing the below given individual materials or the like.
The inventors of this invention have found out the fact that it is
more effective in some cases to treat the surface by using the
substances having acidic, basic, ionic, electric charge
transmitting, or having high surface energy.
In the following examples of the substances are shown below.
1. As high polymers:
nitrocellulose
cellulose acetate
ethyl cellulose
polyethylene
polystyrene
polyvinyl acetate
polyvinyl alcohol
polyvinyl chloride
polyacrylonitrile
polymethylmethacrylate
gelatin
2. As the solid acid, Lewis solid acid is used, and the example of
Lewis solid acid are as follows.
natural clay minerals
acidic terra abla,
clarite
bentonite
kaolin
fuller's earth
montmorilonite
fluoridine
solidified acids such as those obtained by adhering sulfuric acid,
phosphoric acid onto silica gel or alumina
phosphoric acid obtained by using quatz sands as carrier
the calcined compounds of diatomaceous earth and phosphoric
acid
cation exchange resin
silica-alumina, silica-magnesia, silica-boria
inorganic chemicals
ZnO, Al.sub.2 O.sub.3, TiO.sub.2, CeO.sub.2, As.sub.2 O.sub.3,
V.sub.2 O.sub.5, SiO.sub.2, Sb.sub.2 O.sub.5, CaSO.sub.4,
MnSo.sub.4, CuSO.sub.4, NiSO.sub.4, CoSO.sub.4, CdSO.sub.4,
SrSO.sub.4, MgSO.sub.4, FeSO.sub.4, BaSO.sub.4, KHSO.sub.4, K.sub.2
SO.sub.4, (NH.sub.4).sub.2 SO.sub.4, Al.sub.2 (SO.sub.4).sub.3,
Fe.sub.2 (SO.sub.4).sub.3, Cr.sub.2 (SO.sub.4).sub.2,
Ca(NO.sub.3).sub.2 --4H.sub.2 O, Bi(NO.sub.3).sub.3 --5H.sub.2 O,
Zn(NO.sub.3).sub.3 --6H.sub.2 O, Fe(NO.sub.3).sub.3 --9H.sub.2 O,
CaCO.sub.3, Zr phosphate, Ti phosphate, AlPo.sub.4, PbCl.sub.2,
HgCl.sub.2, CuCl.sub.2, AlCl.sub.3, SnCl.sub.2, CaCl.sub.2, AgCl,
H.sub.2 WO.sub.4, AgClO.sub.4, ZnS, CaS, Mg(ClO.sub.4).sub.2
3. lewis solid base is generally used as the solid base and the
examples of the Lewis solid base are as follows,
Inorganic chemicals such as
CaO, MgO, BeO, SiO.sub.2, ZnO, Na.sub.2 CO.sub.3, K.sub.2 CO.sub.3,
KHCO.sub.3, (NH.sub.4).sub.2 CO.sub.3, BaCO.sub.3, KNaCO.sub.3,
Na.sub.2 WO.sub.4 --2H.sub.2 O, KCN
Those prepared by adhering caustic soda to silica gel, and those
prepared by adhering potassium hydroxide
anion exchange resins
nitrous oxide activated carbon, ammonia activated carbon
4. As the sizing agents, rosin, emulsified wax, reinforced sizing
agent, bitumen emulsifier, latex, silicon and the like.
5. As the examples of ionic solids, the following can be given.
sodium chloride,
potassium chloride,
magnesium chloride, or those having above 50 percent of
ion-crystalinity
As the means for contacting photocolor developing and eliminating
materials above or the mixture thereof with electron or proton
donating or accepting stabilizers to the above mentioned surface,
the following can be given.
1. As the liquid matrix, such as
benzene,
toluene,
xylene,
cyclohexane,
normal hexane,
butylalcohol,
ethyl alcohol,
isopropyl alcohol
dimethylformamide
acetone
methyl alcohol
ethyl acetate
ethyl ether
pyridine
trichlene and the like, or the homologues thereof.
2. As the solid matrix, the following examples can be given.
Condensate type polymers such as
polyamide type resin,
N-alkyl polyamide,
polyimide,
polypeptide,
polyester type resin,
polycarbonate resin,
polyacid anhydride resin,
polyether type resin, and the like.
As polymerized type polymers, the following examples can be
given.
aliphatic hydrocarbon type vinyl resin,
aromatic hydrocarbon type vinyl resin (polystyrene type)
vinyl alcohol type resin,
nitrile type resin,
acryl type resin,
methacryl type resin and the like
As the examples of such high polymer substances as above the
following can be given.
nitrocellulose,
cellulose acetate,
ethyl cellulose,
polyethylene,
polystyrene,
polyvinyl acetate,
polyvinyl alcohol,
polyvinyl chloride,
polyacrylonitrile,
vinyl chloride,
polymethyl metacrylate,
and gelatine and the like.
In addition to the above, oligomer and other single molecular
organic substances having excellent adherability can be used.
It is also possible to use synthetic photo-color developing
materials obtained by chemically bonding photocolor developing
materials to high polymer or oligomer.
The following are the concrete examples to further illustrate this
invention.
However, a great number of modifications within the technical scope
of this invention may be carried out as a matter of course.
EXAMPLE 3
20 mg. of 6'-nitro-1,3,3-trimethylindolinobenzopyrylspiran was
dissolved into 10 ml. of toluene, and thus obtained mixture
solution was coated uniformly on the art-treated surface of one
sided art paper whose thickness is about 80 .mu.. in such a manner
that the coating could become from 1 to 2 .mu.. to prepare the
photocolor developing and eliminating recording material.
EXAMPLE 4
20 mg. of 6'-nitro-1,3,3-trimethylindolinobenzopyrylspiran was
dissolved into 10 ml. of toluene, and thus obtained mixture was
coated on an aluminum plate whose thickness is about 100 .mu.. in
such a manner that the thickness of the coating could become from 1
to 2 .mu.. to prepare a photocolor developing and eliminating
recording material.
EXAMPLE 5
5 g. of ethyl cellulose was mixed along with 500 mg. of ethyl
alcohol and the mixture was sufficiently stirred, and after
dissolving the same sufficiently the mixture was coated on an art
paper, and the coating was dried.
Thereafter, 20 mg. of
6'-nitro-1,3,3-trimethylindolinobenzopyrylspiran was dissolved into
10 ml. of toluene, and the mixture was coated on the art paper
having been coated with the above prepared ethyl cellulose in such
a manner that the thickness of the coating became as thick as 0.5
to 1 .mu.. to prepare a photocolor developing and eliminating
recording matter.
EXAMPLE 6
20 mg. of 6'-nitro-1,3,3-trimethylindolinobenzopyrylspiran was
dissolved into 10 ml. of toluene, and the obtained mixture was
coated on a polystyrene film whose thickness is 100 .mu.. to
prepare a photocolor developing and eliminating recording
matter.
In the above given examples from 3 through 6, the photocolor
developing and eliminating recording material is subjected to
exposure and fixation before or after drying treatment as is
described in the following paragraphs.
The above prepared photosensitive recording material is subjected
to the exposure by using the ultra violet ray obtained by using the
light from a 500 W high pressure mercury lamp and the glass filter
(UV-D25) at a distance of 10 cm from the light source for about 15
seconds in the Examples from 3 to 5, and for about one minute in
Example 4, and for about 30 seconds in Example 6 and the
photosensitive recording material developed reddish purple and
retained stable clear color for more than 20 minutes.
When a negative image is placed between the photosensitive member
and the light source, the corresponding positive photocolor image
could be obtained.
When thus colorized photosensitive member was subjected to the
irradiation of the visible ray obtained by using a glass filter
(UV-39) against the light from the light source for 30 seconds, and
the colorizing state was perfectly eliminated. The color developing
and eliminating process could be repeated over and over again.
The photosensitive member in the colorized state was treated with 1
percent caustic soda aqueous solution, the developed color could be
fixed.
When thus fixed color image was treated with 5% hydrochloric acid
alcohol aqueous solution, and the above mentioned treatment with
visible light was carried out, and the fixed state was turned back
to the photocolor developing and eliminating state.
EXAMPLE 7
5 g. of kaolin, and 15 ml. of ethylalcohol were sufficiently mixed
by using an ultrasonic wave stirer for about 5 minutes, and the
mixture was coated on a one sided art paper whose thickness is 80
.mu.. in such a manner that the thickness of coating could become
about 10 .mu.. thick.
EXAMPLE 8
5 g. of acidic terra abla, and 15 ml. of ethylalcohol were
sufficiently mixed for about 5 minutes by using an ultrasonic wave
stirer, and the obtained mixture was coated on two sided art paper
(whose thickness is 80 .mu..) in such a manner that the thickness
of the coating could become as thick as about 10 .mu..
EXAMPLE 9
5 g. of kaolin, 0.02 g. of ethyl cellulose, 15 ml. of dioxane were
sufficiently mixed for about 10 minutes by using an ultrasonic wave
stirer, and the obtained mixture was coated on two sided art paper
whose thickness is about 100 .mu.. in such a manner that the
thickness of the coating could become about 15 .mu..
EXAMPLE 10
5 g. of bentonite, and 15 ml. of ethyl alcohol, were sufficiently
mixed for about 5 minutes by using an ultrasonic wave stirer, and
the obtained mixture was coated on an aluminum plate of 100 .mu..
thick in such a manner that the thickness of the coating could
become about 10 .mu..
Photocolor developing and eliminating material was coated on the
surface prepared in Example 7 through 10 in the same manner as in
Example 3 through 6, and photocolor developing and eliminating
recording member can be obtained.
EXAMPLE 11
5 g. of kaolin, 20 ml. of ethyl alcohol, and 20 mg. of
6'-nitro-1,3,3-trimethylindolinobenzopyrylspiran were sufficiently
mixed for about 5 minutes by using an ultrasonic wave stirer, and
then the obtained mixture was coated on an art paper, aluminum
plate or a glass in such a manner that the coatings could become as
thick as about 10 .mu..
As described so far in the preceding paragraphs, the resulting
stabilized color developed image on the recording material was
fixed as a permanent image, and the fixed image is turned back to
the original image, and the following is an explanation about the
method therefor.
In accordance with this invention, as described above, the
colorized image is retained as a permanent latent image by the
treatment by basic material or anion as the stabilizer, and then
the fixed image is turned back to the photoreversible colorized
image by treating the fixed image with acidic material or cation as
a restoring agent.
As the examples of the fixing agents for fixing the colorized
image, the following can be given, inorganic base such as sodium
hydroxide, potassium hydroxide and the like, and ammonia, and amino
compounds such as ethylamine, propyl amine, butyl amine and the
like, and potassium cyanide, sodium cyanide, or such like salts or
a weak acid and a strong base, Bronsted base and the salts thereof
may be used.
As the restoring agents, for example, organic acids such as acetic
acid, benzoic acid and the like, and inorganic acids such as
hydrochloric acid, nitric acid and the like, Lewis solid acid and
such like acids may be used.
The recording material is treated with these in liquid state of
gaseous state.
The following is an explanation about the examples of the fixing of
the photosensitive material and the method for restoring the
photocolor development and elimination property, but it is a matter
of course that a great number of modifications can be done within
the scope of this invention.
EXAMPLE 12
68 mg. of 6'-nitro-1,3,3-trimethylindolinobenzopyrylspiran, 36 mg.
of p-nitrophenol, 10 g. of polystyrene were dissolved in 60 g. of
xylene, and the mixture was coated on a transparent glass plate and
dried to prepare a recording material.
Thus obtained photosensitive layer was developed into red color by
irradiating ultraviolet ray by using a 250 W ultra high pressure
mercury lamp, and Toshiba Filter UVD-25 at a distance of 10 cm from
the light source for 30 seconds, and it was kept in a stable
colorized state for about 60 hours.
Next, by using a Toshiba Filter UV-39, visible light was irradiated
thereto for 30 seconds at the same distance from the light source,
and the colorized state was perfectly eliminated, and the color
developing and eliminating process could be carried out
repeatedly.
The recording material in the colorized state was treated with 10%
ammonia alcohol aqueous solution (3 parts by volume of ethyl
alcohol, and 7 parts by volume of water), and the developed color
could be fixed.
Thus fixed color was treated with 5% hydrochloric acid alcohol
aqueous solution and the fixed state was restored to the original
photocolor developing and eliminating state.
EXAMPLE 13
59 mg. of 6'-nitro-1,3,3-trimethylindolinobenzopyrylspiran and 10
g. of ethyl cellulose were dissolved into ethyl alcohol aqueous
solution (containing 9 parts by volume of ethyl alcohol and one
part by volume of water), and the obtained mixture was coated on a
glass plate, and dried, and thereafter the coating was peeled off,
and a transparent film was obtained.
Thus obtained film was subjected to color development into purplish
color by the irradiation of ultraviolet ray obtained by the
combination of a 250 W ultra high pressure mercury lamp and Toshiba
glass Filter UV D-25 at a distance of 10 cm from the light source,
and the colorized state was retained at a room temperature for more
than 20 minutes in a dark place, and when it was irradiated with
visible light, it was eliminated right away.
Thus obtained colorized state was fixed as yellow color developed
state by the treatment of 5% sodium hydroxide alcohol aqueous
solution.
The fixed colorized state was treated with 10% acetic acid alcohol
aqueous solution, and it was stabilized in yellowish orange color
developed state, but when visible light was irradiated thereto by
using the same light source and Toshiba Filter UV-39 at the same
distance, it was eliminated and turned back to the original
state.
It is possible to carry out the process of color
development-fixation-stabilization-elimination can be repeated
substantially without any fatigue.
The following is an explanation about the embodiment of of a color
recording member in which the new photocolor developing and
eliminating material for forming a color image directly on the
recording material is used.
The photocolor developing and eliminating materials used for the
color recording member of this invention are preferably spiropyran
compounds as given above, or the mixture of the above given
compounds and the hydrogen donating materials i.e. proton donating
materials, such as phenols, as the stabilizers, anils or the
mixture of anils and proton accepting materials such as quinoline,
and semicarbazones.
Such photocolor developing and eliminating materials have
respectively the specific absorption wave length ranges.
This is explained in accordance with FIG. 5. In FIG. 5, the
horizontal axis represents wave length of the radiation to be
irradiated onto the photocolor developing and eliminating material,
and the vertical axis represents the ratio of absorption. For
example, cinnamic aldehyde semicarbazone in FIG. 5 a) has the
absorption spectrum range (shown by the solid line in FIG. 5) in
such a wave length range that is shorter than 400 m.mu. i.e., in
ultraviolet ray portion.
When ultraviolet ray is irradiated onto this compound, the
absorption range is generated in the visible range (the curve shown
by the dotted line in FIG. 5).
In FIG. 5 almost blue absorption is shown, and therefore said
material develops the complementary color of blue color.
In the same manner as is apparent from the diagrams from FIG. 5 b -
d, N-salicylidene-m-toluidine, N-4'-methylsalicylidene aniline,
N-salicylidene aniline and the like have the respective specific
absorption wave length ranges in ultraviolet ray portions, and
absorb the light of said wave length ranges, and come to have the
specific absorption wave length ranges in the respective visible
ranges, and the respective complementary colors are developed.
The color recording member of this invention can be prepared by
dispersing at least one kind of the above mentioned photocolor
developing and eliminating materials therein in the form of matrix,
and as the high polymers as the dispersing agents, the following
materials can be given.
1. As the examples of condensate type high polymers;
polyamide type resin,
N-alkylpolyamide,
polyimide,
polypeptide,
polyester type resin
polycarbonate resin,
polyacid anhydride resin,
polyether type resin
2. As polymer type high polymers;
aliphatic hydrocarbon type vinyl resin,
aromatic hydrocarbon type vinyl resin (polystyrene type),
vinyl alcohol type resin,
nitrile type resin,
acryl type resin,
methacryl type resin,
As the examples of such high polymer materials as given above, the
following can be given;
nitrocellulose
cellulose acetate
ethyl cellulose
polyethylene
polystyrene
polyvinyl acetate
polyvinyl alcohol
polyvinyl chloride
polyacrylonitrile
polyvinyl chloride
polymethylmethacrylate
gelatin and the like
In addition to the above, oligomer or other monomer organic
substances having excellent bonding property may be used.
It is also possible to use synthetic photocolor developing
materials prepared by chemically bonding photocolor developing
materials to high polymers or oligomers.
The examples of liquid dispersing agents include benzene, toluene,
xylene, cyclohexane, normal hexane, butyl alcohol, ethyl alcohol,
methyl alcohol, isopropyl alcohol, dimethyl formamide, acetone,
ethyl ether, ethyl acetate and the homologues.
When photocolor developing and eliminating materials are dispersed
into a dispersing agent in the form of matrix, the absorption wave
length ranges in visible light range at the color developed state
depend on kinds of the dispersing medium.
This is explained in accordance with the diagrams FIG. 5 e, f, g,
h.
For example, when
8'-carboxy-1,3,3-trimethylindolinobenzopyrylspiran is used as the
photocolor developing and eliminating material, and acetone
solution, methyl alcohol solution, and propyl alcohol solution are
used as the dispersing medium as is shown in the diagrams FIG. 5
(e-1) through (e-3), the absorption wave length of the visible
range comes to be different in the color developed state. In other
words, in the solution of an acetone dispersing agent the
absorption wave length range is present in about green color
portion (see the diagram (e-1)), and in methyl alcohol dispersing
agent, the absorption wave length range is present in about blue
portion (see the diagram (e-2)).
The color recording member of this invention may be prepared in the
following manner.
1. One or more than one layer of photosensitive component or one or
more than one kind of photosensitive component (i.e., photocolor
developing and eliminating material or the mixture of the same and
the stabilizers) is uniformly coated on the transparent or
non-transparent supporter.
2. One or more than one layer of photosensitive component or one or
more than one kind of photosensitive component is uniformly
dispersed into the dispersing medium without a support to prepare
the photosensitive material.
The following is an explanation about the process for recording the
images.
1. When photocolor developing and eliminating materials containing
photochromic substances are used: when spiropyran compounds or the
mixture of spiropyran compounds and stabilizers, are used, the
recording material is, in advance, wholly exposed to photocolor
developing light such as ultraviolet ray to make it sensible to the
light of the whole visible range, and the resulting recording
material is subjected to the color image exposure, and the
recording is carried out by using a photocolor eliminating process.
It is possible to repeat a step of erasing the recorded image by
light, a step of restoreing the same to the original totally
colorized state, and a step of recording again.
By treating the photosensitive materials which are prepared by the
combination of spirans by an aliphatic amine such as hexyl amine or
a strong alkali such as caustic potassium, the image thereon is
permanently stabilized in the form of yellow latent image, and when
it is treated with an organic acid and an inorganic acid, it may be
turned back to the original color image.
2. The case in which a thermal color developing and photocolor
eliminating materials containing photochromic substances:
1. The combinations of the above given spirans with phenols,
organic carboxylic acids, and strong acids (mineral acids)
2. 1,3,3-trimethylindolino-8'-carboxybenzopyrylspiran and
semi-carbazones (refer to item C above)
When the group of materials in 1) and 2) above is used, ultraviolet
ray and heat are used in advance to the effect that the color is
developed so as to make the recording member sensible to the whole
visible range, and then a color image exposure is carried out, and
the elimination is carried out in accordance with the exposed
portion, and a positive color image is recorded.
Thus obtained recorded image can be turned back to the original
totally colorized state by means of heat and ultraviolet ray
irradiation to the effect that the image can be erased, and this
operation can be carried out repeatedly.
When the photosensitive materials obtained by the combination of
spirans, are used, the yellow latent image can be permanently
stabilized by treating the same with amine such as hexyl amine or a
potassium hydroxide solution. When it is further treated with an
acid, it can be turned back to the original color image.
The following are the concrete examples of this invention. It is a
matter of course that a great number of other modifications within
the scope of the technical idea of this invention can be carried
out.
First, the following Example 14 refers to an example of a color
recording member having the absorption range covering the whole
visible light range prepared by selecting appropriately the
dispersion medium and the additive into which one and the same
photocolor developing and eliminating material is dispersed and
incorporating them to the photosensitive layer.
EXAMPLE 14
1,3,3-trimethylindolino-6'-nitrobenzo pyrylspiran 60 mg.
polystyrene 10 g. A xylene 50 cc.
1,3,3-trimethylindolino-6'-nitrobenzopyryl spiran 60 mg.
p-nitrophenol 40 mg. B polystyrene 10 g xylene 50 cc.
1,3,3-trimethylindolino-6'-nitrobenzopyrylspiran 60 mg. malonic
acid 40 mg. polystyrene 10 g. C benzene 50 cc.
The respective mixtures A, B and C were coated sequentially on
glass plates uniformly and the resulting coating was dried, and a
three layer transparent film was prepared and thus prepared
transparent film was used as the photosensitive material.
Or, the mixtures A, B, and C were separately sprayed on a supporter
such as polyester transparent support or a paper to prepare a
photosensitive material.
The color image recording was carried out in such a manner that the
above prepared photosensitive materials were placed at a distance
of about 50 cm from the light source and by using a 500 W mercury
lamp as the light source and a visible light cut filter (Toshiba
glass Filter UV-D 25) the total exposure was carried out for 10
seconds to have the photosensitive material sensitized in the whole
visible light range, and then, the color image was exposed from the
distance of 50 cm for 10 seconds by using a 250 W tungsten lamp,
the color developing material was eliminated of the colors
corresponding to the color developing material, and a positive
color image could be obtained.
Next, when the positive color image was dipped in a 10 percent
aqueous solution of potassium hydroxide, the color image was
changed into yellow latent image and is stabilized permanently.
When it was again dipped in the solution of acetic acid, it could
be again changed into color image.
FIG. 1 shows the absorption spectra of the respective
photosensitive materials A, B, and C of the above example (the
horizontal axis showing the wave length .lambda. by m.mu.) and FIG.
2 shows the absorption spectrum of the photosensitive material
composed of the three layers A, B and C as mentioned above.
When the positive color slide of the spectrum distribution shown in
FIG. 3 was exposed in the same manner as above, the positive color
image of FIG. 4 could be obtained.
The following Example 15 refers to an example of a color recording
member comprising a photosensitive layer including more than one of
photocolor developing and eliminating materials uniformly mixed and
made into one layer.
EXAMPLE 15
N-salicylidene aniline 10 g A acrylidine 10 g.
8'-carboxy-1,3,3-trimethylindolinobenzo- pyrylspiran 60 mg. B
ethylcellulose 10 g 6'-nitro-8'-methoxy-1,3,3-trimethylindolino-
benzopyrylspiran 60 mg. C polystyrene 10 g
The following is an explanation about the method for preparing the
A, B, and C.
a: 10 g. of N-salicylidene aniline and 10 g of acrylidine are
thermally melted at 100.degree.C, and the hot mixture is abruptly
cooled off, and then finely crushed.
B: 60 mg. of 8'-carboxy-1,3,3-trimethylindolinobenzopyrylspiran and
10 g. of ethyl cellulose are dissolved into 50 cc. of alcohol and
then the mixture solution is finely crushed after having dried the
same.
C: 60 mg. of
6'-nitro-8'-methoxy-1,3,3-trimethylindolinobenzopyrylspiran and 10
g. of polystyrene and dissolved into 50 cc. of xylene, and the
powders A and B are dispersed thereinto and the obtained mixture is
coated on a paper support and the coating is thermally dried to
prepare a photosensitive material.
The color image recording material was totally irradiated for 10
seconds with ultraviolet ray by using a 500 W mercury lamp and
thermal color-development was carried out for about one minute at a
temperature ranging from 50.degree.C to 60.degree.C by using a
heater or heat ray so that the whole visible range could be
sensitized.
Next, the color image was exposed for 10 seconds at a distance of
50 cm by using a positive color slide and a 250 W tungsten lamp,
and the color elimination was carried out in accordance with the
sensitized portion, and a positive color image could be
recorded.
Thus obtained recorded image can be erased by turning the same into
the original colorized state by heat and the irradiation of
ultraviolet ray, and this operation can be effected repeatedly.
As described so far, the structure of the color recording material
of this invention is that a photosensitive material is dispersed
into a transparent or semi-transparent dispersing material, and the
photosensitive material is used in the form of film or plate, or
the photosensitive material is made into a single layer or
multi-layer, and is adhered on a plane support such as film, paper,
metal, or glass.
In addition to the above, photosensitive material is used in the
form of thin layer on the support without using the dispersing
agent, and a transparent high polymer film is coated on said thin
film to make the color recording material of this invention.
In the color recording member of the following Example 15A, more
than one of photocolor developing and eliminating materials are
used and each of them has each individual absorption range in the
color-developed state, and further the dispersion medium and the
additive are appropriately selected and incorporated to a
photosensitive layer in such a manner that the absorption range
covers the whole visible light range.
EXAMPLE 15A
1,3,3-trimethylindolino-6'-nitro- benzopyrylspiran 60 mg. Malonic
acid 40 mg. A Polystyrene 10 g. Benzene 50 cc.
8'-carboxy-1,3,3-trimethylindolino- benzopyrylspiran 60 mg. B
Ethylcellulose 10 g. 6'-nitro-8'-methoxy-1,3,3-trimethyl-
indolinobenzopyrylspiran 60 mg. C Polystyrene 10 g.
A, B, and C above are sequentially coated on a glass plate
uniformly and dried to form a three-layer transparent film which is
used as a photosensitive material. Or, A, B and C are separately
scattered on a support such as a polyester transparent support or
paper to form a photosensitive material. Color image recording is
carried out by using the resulting photosensitive material in a
recording member. The whole surface of the recording member is
exposed to a ultraviolet light obtained by passing a light from a
500 W mercury lamp through a visible light cut filter (Toshiba
Glass Filter UV-D25) for 10 seconds at a distance of about 50 cm.
from the light source to sensitize the recording member for the
whole visible light range. The recording member is then exposed to
a color image of a positive color slide by using a tungsten lamp
(250 W) at a distance of 50 cm. for 10 seconds and the
color-developed member corresponding to each color is eliminated to
form the positive color image. Further, the recording member thus
treated is soaked in a 10 percent solution of potassium hydroxide
to change the color image to a yellow latent image which is
everlastingly stabilized. When the latent image is treated with an
acetic acid solution to produce the color image again.
The following is an explanation about the concrete examples of a
new method for optionally forming normal image and a reversal
image, in accordance with the demand, by using a recording material
in which photocolor developing and eliminating materials are
used.
In regard to the photocolor developing and eliminating materials,
stabilizers, dispersing mediums and such like recording materials
which were used in the following examples, those which have already
been given in the preceding paragraphs were used in the following
examples.
EXAMPLE 16
68 mg. of 6'-nitro-1,3,3trimethylindolinobenzopyrylspiran, 36 mg.
of p-nitrophenol, and 10 g. of polystyrene were dissolved into 50
g. of xylene, and the obtained mixture was coated on a transparent
glass plate, and the coating was dried, and peeled off to obtain a
transparent film, and this transparent film was used as the
recording material.
Thus obtained photosensitive layer was subjected to the irradiation
of ultraviolet ray for 30 seconds by using a 250 W ultra-high
pressure mercury lamp and a Toshiba Glass Filter UVD-25 at a
distance of 10 cm from the light source, and thus the
photosensitive layer presented red color, and the photosensitive
layer was kept at the stable colorized state for about 60
hours.
Next, visible light was irradiated for 30 seconds at the same
distance from the light source by using a Toshiba Glass Filter UV
-39, and the colorized state was perfectly eliminated. The process
of color development and elimination can be effected
repeatedly.
The recording material which was in the above mentioned colorized
state was treated with 10% ammonia alcohol aqueous solution
(containing 3 parts by volume of ethyl alcohol and 7 parts by
volume of water), thereby the developed color could be fixed.
When thus obtained fixed color image was treated with 5%
hydrochloric acid alcohol aqueous solution, the fixed state was
turned back to the original photocolor developing and eliminating
state.
The ultraviolet ray obtained by passing the light of a 250 W
ultra-high pressure mercury lamp through a Toshiba Glass Filter
UVD-25 was irradiated for about 30 seconds at a distance of about
10 cm from the light source through the same filter as above, and
thermal color development was carried out by a heater or heat ray
at a temperature from 50.degree.C to 60.degree.C for one minute to
that the whole visible range was sensitized.
Next, a positive image was exposed for 10 seconds at a distance of
30 cm to the light source composed of a 250 W tungsten lamp, and
color eliminated positive image was formed in accordance with the
exposed portion.
Thus obtained recorded image was turned back to the original
totally colorized state by heat and the irradiation of ultraviolet
ray to the effect that the image could be erased, and this
operation could be carried out repeatedly.
When the photosensitive material obtained by the combination of
spirans is treated with amines such as hexylamine or a solution of
potassium hydroxide, thereby the permanent stabilization of yellow
latent image could be attained.
Thus obtained latent image could be turned back to the original
image by treating the same with acid.
EXAMPLE 17
1,3,3-trimethylindolino-6'-nitrobenzopyryl- spiran 60 mg.
polystyrene 10 g. A xylene 50 cc.
1,3,3-trimethylindolino-6'-nitrobenzopyryl- spiran 60 mg. B
p-nitrophenol 40 mg. polystyrene 10 g. xylene 50 cc.
1,3,3-trimethylindolino-6'-nitro- benzopyrylspiran 60 mg. Malonic
acid 40 mg. C polystyrene 10 g. benzene 50 cc.
A, B, and C were respectively coated uniformly on a glass plate,
and then the coating was dried, and a three layer transparent film
was prepared. Thus prepared transparent film was used as the
photosensitive material.
Or, A, B, and C were separately coated on a polyester transparent
support, or paper or such like support by spraying the same to
prepare the photosensitive materials.
The color image recording was carried out in such a manner that the
above prepared photosensitive materials were subjected to the total
exposure for 10 seconds with ultraviolet ray obtained by using a
500 W mercury lamp and a visible light cut filter (a Toshiba Glass
Filter UV-D25) at a distance of about 50 cm from the light source,
so that the whole visible range was sensitized, and then a color
image was exposed thereonto for 10 seconds at a distance of 50 cm
from the light source of a 250 W tungsten lamp, and the color
developed materials corresponding to the respective colors were
eliminated of the colors, and a positive color image could be
obtained. The positive color image was dipped in a 10% aq. solution
of potassium hydroxide and then was changed to a yellow latent
image and thereby permanently stabilized. Thus stabilized image was
changed into a color image by dipping the same in a solution of
acetic acid.
EXAMPLE 18
N-salicylidene aniline 10 g. A acrylidine 10 g.
8'-carboxyl-1,3,3-trimethyl-indolino- benzopyrylspiran 60 mg. B
ethylcellulose 10 g. 6'-nitro-8'-methoxy-1,3,3-tri-
methylindolinobenzopyrylspiran 60 mg. C polystyrene 10 g.
An explanation about the method for preparing the A, B, and C is
described below.
A: 10 g. of N-salicylidene aniline, 10 g. of acrylidine are
thermally melted, rapidly cooled, and then finely crushed.
B: 60 mg. of 8'-carboxy-1,3,3-trimethylindolinobenzopyrylspiran and
10 g. of ethylcellulose were dissolved into 50 cc. of alcohol, and
then the mixture solution was dried into powder.
C: 60 mg. of
6'-nitro-8'-methoxy-1,3,3-trimethylindolinobenzopyrylspiran and 10
g. of polystyrene were dissolved into 50 cc. of xylene, and then
the powders A and B were dispersed therein, and the mixture was
coated on a paper support, and then the coating was dried by
heating and the photosensitive material was prepared.
The color image recording was carried out in such a manner that the
whole surface was subjected to the irradiation of ultraviolet ray
for 10 seconds by using a 500 W mercury lamp, and the thermal
color-development was carried out at a temperature from 50.degree.C
to 60.degree.C for one minute by using a heater or heat ray, and
the whole visible range was sensitized. Next, a color image was
exposed for 10 seconds by using a 250 W tungsten lamp at a distance
of 50 cm from the light source, and the color was eliminated in
accordance with the exposed portion, and a positive color image was
recorded. Thus obtained positive color image could be turned back
to the totally colorized state by heat and the irradiation of
ultraviolet ray to the effect that the image could be erased, and
this operation could be carried out repeatedly.
Next, the following is an explanation in accordance with the
attached diagrams about the concrete examples of the new image
forming method in which a screen prepared from the photocolor
developing and eliminating material is used.
First, the following are the examples for forming the screen of the
photocolor developing and eliminating materials applied to the
method of this invention.
a. 60 mg. of 1,3,3-trimethylindolino-6'-nitro-benzopyrylspiran is
dissolved into 50 ml. of toluene, and thus obtained mixture is
uniformly coated on a high quality art paper and a screen was
obtained.
b. 60 mg. of 1,3,3-trimethylindolino-6'-nitro-benzopyrylspiran and
2 g. of polystyrene are dissolved into 50 ml. of toluene, and thus
obtained mixture is uniformly coated on a cotton cloth to form a
screen.
The following is an explanation in accordance with the diagrams
from FIG. 6 through FIG. 8 about the concrete examples in which the
above prepared screens were used.
EXAMPLE 19 (FIG. 6)
The screen 16 prepared by using the photocolor developing and
eliminating material prepared in accordance with a) or b) above,
was used.
The ultraviolet ray obtained by passing the light form the light
source 11 (500 W ultra-high pressure mercury lamp) through a
visible light cut filter 12, was projected to a negative slide or
negative cine film 13, and the light having passed therethrough was
condensed by the condenser lens 14, and was sent to the projector
lens 15, and the image was projected on the screen 16.
Light passed through the bright portion or the transparent portion
of the negative film 13 and the color was developed at the portion
corresponding to the screen surface 16 and the reversal projected
image was obtained on the negative film. In particular, in carrying
out a slide projection, it is effective to apply visible light from
the light source 11 when the image is changed in order to quicken
the elimination of the after image as the image to be projected is
exchanged.
In carrying out the slide projection, when the degree of the
projection on the screen surface 16 arrives at a certain degree,
the projected image can be retained even when the excited light is
not applied further, and therefore it is not necessary to carry out
continuous exposure.
EXAMPLE 20 (FIG. 7)
The ultraviolet ray obtained by passing the light from the two
light sources 27 (respectively two 250 W ultra-high pressure
mercury lamps) through the visible light cut filter 28, was
projected from the front side onto the screen 26 prepared in
accordance with a) or b) above, and the color was developed on the
whole surface of the screen 26.
The visible light obtained from a 250 W tungsten lamp 21 was
projected onto a positive slide or positive cine film 23, and the
light having passed therethrough was condensed by a condenser lens
24, and was sent to the projector lens 25, and the image was
projected onto the screen 26.
The portion of the screen where the visible light had arrived was
eliminated of the color, and the positive image corresponding to
the positive film was obtained.
In erasing the image, only ultra-violet ray alone excluding visible
light was irradiated, it was reverted to the totally colorized
state.
EXAMPLE 21 (FIG. 7)
The ultraviolet ray light sources 27.sub.1 and 28.sub.1 for totally
coloring the whole surface of the screen in Example 20, were placed
behind the screen as is shown by the dotted line of FIG. 7, and the
irradiation was carried out from behind. The positive image
projection was carried out in the same manner as in Example 20.
EXAMPLE 22 (FIG. 8)
Preparation of screen:
60 mg. of 1,3,3-trimethyl-indolino-8'-carboxy-benzopyrylspiran was
dissolved into 10 ml. of water, and the resuting solution was added
to the solution obtained by dissolving 10 g. of polyvinyl alcohol
into 40 ml. of water, and the whole mixture was sufficiently
stirred.
Thus obtained mixture was uniformly coated and extended on a cotton
cloth, and the surface of the film was colored in red brown color
in the normal state, and thus obtained screen 36 was used, and in
the same manner as in the embodiment of FIG. 8, the projection was
carried out.
The light source as the means for eliminating the color can be
visible light, ultraviolet ray or the mixture of visible light and
ultraviolet ray.
The ultraviolet ray obtained by passing the light from a 250 W
tungsten lamp 31 or a 500 W ultra-high pressure mercury lamp 31
through a visible light cut filter 32, was projected to a positive
slide or positive cine-film 33, and the light having passed
therethrough was condensed by the condenser lens 34, and the
condensed light was sent into the projector lens 35, and was
projected onto the screen 36.
The portion on the surface of the screen where the light has
arrived, was eliminated of the color, and the positive projected
image corresponding to the positive film, was obtained.
* * * * *