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Sept. "27, 1949.
Filed March 26, 1946
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BY mfm
Patented Sept. 27, 1949
Franz Urbach, Rochester, N. Y., assignor to East
man Kodak‘Company, Rochester, N. Y., a cor
poration of New Jersey
Application March 26, 194.6, Serial No. 657,136
6 Claims. (Cl. 250-65)
This invention relates to photorecording and
eral this is a photographic layer, but hand tracing
has for its main object the provision of a method
of simple images may be useful in some cases.
of delayed action photorecording.
With the recording layer in place, the phosphor
layer is then uniformly illuminated with stimulat
ing light, preferably red or infrared light to pro
duce on the recording layer by stimulation, an
optica1 image in the wavelength which the phos
phor emits. The illumination may be over one
The term photorecording is here used to refer
to the recording of light, usually photographic,
but in some cases the ?nal step may be actually a
manual one. The process here described should
be compared to that described in my application
Serial Number 657,135 ?led concurrently here
area of the phosphor layer at a time. The wave
with, the two processes having different advan- l1. length emitted is longer than that of the exciting
radiation and when red or infrared is used as the
tages for different purposes. Reference is also
stimulating radiation, the wavelength emitted is
made to my concurrently ?led application Serial
shorter than the stimulating radiation. The
No. 657,137 having to do with a third system
luminous image formed on the recording layer is
of photography, particularly for infrared pho
negative to the image which exhausts the phos
tography, by using in part phosphors of the same
phor layer. In the case where the recording layer
type as used in the present invention. The in
is a photographic one, normal processing will
frared photography case is limited in its utility
to relatively long wavelength infrared light be
produce an image positive with respect to ‘the
cause at shorter wavelengths, photographic emul~
sions can be directly sensitized. However, the
present invention has advantages which make it
exhausting image.
useful in the visible as well as in the infrared
When the exhausting is carried far enough to
reduce the excitation (stimulable brightness) of
the least exhausted areas to 1/3 of the unexposed
value, the later stimulated image will have a rela
tively high gamma approximating 2. It will be
For certain purposes the present invention is
noted that the exhausting exposures are of rea
the most useful of the three. It is particularly
sonably short time when using the highly sensitive
useful for photocopying and, because of the high
phosphors described below.
gamma (approaching 2) inherent in the process,
The following examples are given of the com
it is useful for re?ex copying.
position of infrared sensitive phosphors which
According to the invention, a phosphor of the
type to be described below is uniformly excited 30 are particularly useful in the present invention.
There are others which will work, but perhaps
with short wavelength radiation and then an
not as well as those here listed. As pointed out
image is formed on the phosphor, either by con
in my copending applications relative to the
tact or projection printing using light of non
preparation and composition of phosphors them
tion of the phosphor layer in proportion (not 35 selves, each phosphor mustinclude a base, a ?ux
necessarily linear proportion) to the image in
and at least one activator. The flux is used in
the usual way in small percentages to bond the
tensity. This exhausting may be entirely due
to the stimulating of the phosphorescence or it
materials during ?ring. The concentrations of the
may be due to stimulation combined with the
activators appear in parts per million by Weight
quenching effect which occurs with some phos 40 relative to the whole phosphor after ?ring. The
‘ exciting wavelength in order to exhaust the excita
phors (or even to quenching alone by non-stimu
lating ‘wavelengths but this is quite rare). In
exact value depends on the speci?c details of the
preparation and the quantities may be varied
from those given without materially affecting
either case the phosphor is exhausted where il
luminated by the image and now contains in 45 their use for the present invention. The prepa
ration of these phosphors follows the conven
amounts of excitation, a negative image relative
tional methods used in preparing ordinary phos
to that which was exposed. It will be noted that
phors, it being noted that the sensitivity can be
the phosphor layer could be stored either after
Varied depending on the degree of oxidation of
the excitation or following the image exhaustion,
if any reason for storing occurs. In any case the
the sul?des or selenides.
This list is not as long as in my other case,
next essential step of the invention is to place the
excited phosphor layer containing the latent ex
haustion image in printing relation (contact or
projection printing) to a layer of material on
which a permanent record can be made. In gen
only the ones most useful for the present inven
tion being here included, but of course anypof
them could be used. The phosphors most easily
. exhausted are preferable in the present case.
tion image is then placed in contact with a photo
graphic layer 40 and printed by ?ooding with
infra red light from a lamp 35. The ?ooding
Eu 100 Sm 100
Go 100 S111 40
Cu 100 Sin 20
illumination may be either from below as shown
5 or through the photographic layer 40 as from
lamp 42 shown in broken lines. Successive prints
may be made as shown by moving the phosphor
Ce 100 S11 10,000
Cu 100 Bi 100
Pb 100
M11 200'Ou l
Pb 40,000 On 1
Pb 40,000 Cu 20
Eu 100 Sm 100
Eu 100 Bi 100
layer intovcontact with- another- photographic
.layer‘ 4|. Preferablytheintensity of- the lamp
10 35 is increased for successive printings in order
to keep the brightness of the phosphorescent
image at a high level. I have found that a
"plurality of prints may be made from a single
xphosphorescentimage in this manner.
In my copending application Serial; Number‘ 15 .—-Because‘ of the high gamma obtained with
657,137, item No. 6 was recommended'for use at
{this method it is" quite possible to make the ex
Dry Ice temperatures, but for the present inven
. posure to the original image 33 by re?ex printing
tion, it is quite useful at room temperature since
as illustrated in'Fig. 5. That is, infra red light
it is easily exhausted.
,rfromflthe lamp 45 passes through the phosphor
Some of these particular phosphors were de 20 layer 32 and is re?ected from the printed page
veloped by me as is indicated by my oopending
.133. The phosphor is uniformly exhausted .by the
applications referred to.above.
slight. directly from the lamp 45 but modifier
The manner in which the present inventiorrmay
entially exhausted by the light re?ected from-.the
be performed will be fully understood from the
printed-page. The-over -all flooding tends to
following. description when. read in connection 25 reduce ‘the contrast, of course, but..the..pr0cess
with the accompanying drawings in which:
has adequate contrast to allow .for this.
Figs- 1, 2,.and 3 constitute a .flow chart illus
Having thus described thepreferred: embodi~
trating one embodiment of. the invention.
’ merits
my invention I Wishto pointvoutthat it
Fig. 4 similarly illustrates another embodiment
is not limited to these structures but-.ds'of. the
of. the invention.
30 scope of‘the appended claims.
' Fig. 5 shows anarrangement. alternative to one
. of ‘the steps illustrated in Fig.4.
. In Fig. 1 light from an .ultraviolet lamp. l l uni
\I claim:
1. The method of delayedactionphotorecord
' ing of - a long wavelength image which comprises
.formly excites a phosphor I0, which eitherim
(a) substantially uniformly. exoitingwithshort
mediately. or_ after. sui?cient relaxationtime to 35 wavelength radiation .a layenotaphosphorrof
,allow the. spontaneous afterglow.v to 'die down, is
.the type-whichstores the excitation energyand
..moved_as indicated by the arrow‘ I 2 into printing
"releases at leastipartof it,.in.trigger fashion-when
relation with anobject. It, a pictureof which. is
.- stimulated by.’ longer -wavelength .light,v the re
desired. The object is illuminated. by yellow, red
leased energy being‘ light .of.-wavelength. inter
.and infra red light by lamps: I1 and‘ light‘from u'iJ.mediate-between: the excitingaand stimulating
the object is brought .to‘focus by a lens. 15 on the
=radiation‘wavelength, (b) formingiran imagedn
phosphor ID as shown in Fig.2. ‘This is allowed
saidi-longere wavelength lighton the-phosphor
to continue long enough to. exhaust the excitation
layer to exhaust the excitation of the phosphor
‘inthe phosphor Impreferably bystimulation
._ 2 layer in proportion to the imageintensity atileast
alone since the best‘ phosphors are those which 'i') :partly .by stimulating then (0) --placing the. ex~
‘ have a high stimulation e?ect, butthe exhaustion
- citeds-phosphor layer containing the latent ex~
may be at least partly by a, quenching e?ect. ‘The
layer A I 0 containing ‘ the, latent negative‘ image
. in degrees of exhaustion may be- stored or maybe
moved directly as indicated by the arrow 20 into '
, printing relation v.with. a . permanent, recording
‘layer 23. The layer. Ill, is then uniformlyJilh1m~
inated with infra red light from lamps 2i and the
negativeimage'. therein is photographed'by lens
haustion' image therein in printing relationto a
layer of material on-whichajx-permanent vrecord
canbemade; ~(d) illuminating the phosphor layer
with said-longer wavelength ‘light to produce on
therecording- layer by‘ stimulation an optical
. image insaid intermediate wavelength light.nega
tive to said 'longerwavelength imageand (e) pro
H .zducing ' a permanent record» ,in- : accordance‘ with
' 22 of a camera 24 onto the photographic ?lm‘ 23. ‘)0- the {negative image on the recording layer.
.The ?lm“23 is then‘developed directly to an‘ image
2. .Themethod according‘. to claim 1- in which
positive with respect to .‘the object‘ l5.of Fig.2.
\the-perrnanent recording material ‘is a photo
As in my copending application‘serial No; 657,135
5 graphic ¢material -‘ and the record -is = produced
referred to above this permanent recording. may,
= therein by-direct processing to a~positive relative
in the-case of simple line images, be‘traced 60
- .to.~said. longer wavelength: image.
manually rather than photographically. The
:3. The method according to claim 1 in-which
photographic embodiment is ‘the most important
‘.the'imagewforming is done lay-placing a picture
in ‘this case however and‘ is therefore'ithe one
iltoxbe recorded in-contact with’ the phosphor layer
- ‘illustrated here.
‘A particularly useful embodiment offthe :in-. 65 :~and--exposing the layerv through the-‘picture by
said longer. wavelength light.
‘ vention is‘ illustrated-'in'Figall. 'In this case:>ul
{4. The method according to claim‘ 1 in-Whi'ch
- traviolet or short ‘wavelength visible-light: from
-. the image forming is done by, ‘placing-a3 picture
lamp - 30 uniformly‘ excites :a, phosphors; 3 hwhich
~is-moved to the position-32~inicontact= with a
to be recorded in contact with the phosphor layer
positive record 33 which may-bea printed ‘page 70v and then re?exexposing the layer by said ‘longer
- or the like. The printed page is then .?oodlighted
“wavelength light through the layer to thepicture
with infra red. from a lamp: 34..which stimulates
and thus exhausts the excitationin the ‘phosphor
~ and re?ected therefrom,’ the exhausting oi - the
.excitation ‘being carried to they point where’ the
.-least exhausted area has=dropped to less than-one
The phosphor 32 containing thelatent exhaus- ~ 75 ~ third of its-original excitation. value-whereby the
later stimulated image will have a relatively high
phosphor of the type which stores the excitation
energy and releases at least part of it, in trigger
5. The method of delayed action photorecord
fashion, when stimulated by longer wave length
ing of a radiant image which comprises (a) sub
light, the released energy being visible light of
stantially uniformly exciting with radiation of a 5 wave length intermediate between the exciting
given wavelength a layer of a phosphor of the type
and stimulating radiation wave length, forming
which stores the excitation energy and releases at
an image in said longer wave length light on the
least part of it, in trigger fashion, when stimulat
phosphor layer to exhaust the excitation thereof
ed by a different wavelength light, the released
in proportion to the image intensity and then
energy being light of wavelength longer than said
later illuminating the phosphor layer with said
given wavelength (b) forming an image in a
longer wave length light to produce by stimula
wavelength different from said given wavelength
tion an optical image in said visible intermediate
on the phosphor layer to exhaust the excitation
wave length light negative to said longer wave
therein in proportion to the image intensity, then
length image.
, (c) placing the excited phosphor layer containing
the latent exhaustion image therein in printing
relation to a layer of photosensitive material, (d)
illuminating the phosphor layer uniformly with
light of stimulating wavelength to produce an
optical image which exposes the photosensitive :
The following references are of record in the
?le of this patent:
layer and (6) processing the photosensitive layer
to a record positive relative to said di?erent wave
length image.
6. The method of delayed action formation of
a visible image from a long wave length image
which comprises substantially uniformly exciting
with short wave length radiation, a layer of a
Christensen ______ __ Dec. 15, 1925
Parker ___________ __ Nov. 8, 1927
Kunz et al ________ __. Mar. 16, 1937
Geisen ___________ __ Aug. 13, 1929
Schroter _________ __ Apr. 2, 1935
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