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Патент USA US3042526

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United States Patent O?iice
1
3,042,516
Patented July 3, 1962
2
of New Jersey
the dark or in light in which the ultraviolet portions
have been eliminated. These and other objects of the
invention will become apparent from the description
which follows.
In a copending application, Serial No. 787,112, ?led
January 16, 1959, an invention was described comprsiing
No Drawing. Filed Sept. 22, 1959, Ser. No. 841,460
12 Claims. (CI. 96-48)
on exposure to light and are capable of being ?xed in
3,042,516
PRINT-OUT CONIPOSITIONS FOR PHOTOGRAPHIC
PURPOSES AND PROCESS OF USING SAME
Eugene Wainer, Cleveland Heights, Ohio, assignor to
Horizons Incorporated, Cleveland, Ohio, a corporation
light sensitive print-out compositions which develop color
stable form by subsequent heating, which compositions
This invention relates to compositions of matter which 10 are composed of arylamines and halogenated hydrocar
are sensitive to light and suitable for photographic and
bons dispersed in a plastic ?lm-forming base, and which
photographic reproduction purposes and to processes for
may also contain minor amounts of basic materials such
using such compositions. More particularly, this inven
as amines or zinc oxide for stabilization of the mixture
tion relates to the production of stable colored print-out
before exposure, and minor amounts of phenol deriva
tives for stabilization of the mixture after developing and
?xing, and particularly in the presence of light, heat and
air. The invention described also comprehended combi
nations of these arylamines to produce speci?c color
effects, and sensitization of the system to the visible by
images produced by exposing dry ?lms formed from such
compositions of matter to light, the compositions com
prising: a base consisting of a plastic binder or ?1m—
forming dispersing medium, originally dissolved in a suit
able solvent; one or more aryl amines; one or more hal~
ogenatcd hydrocarbon compounds selected from the 20 the addition of a yellow to red type color former, ex
group consisting of halogenated hydrocarbon compounds
posure to ultraviolet if this visible range color sensitizer
which are capable of generating free radicals on exposure
is not present, and ?nally disposing such over-all system
to ultraviolet or visible light; and one or more sulfur
compounds which may be either organic or inorganic
on a suitable base such as glass, paper, plastic ?lm, and
the like.
sul?des, and the compositions may also include one or 25
Further, in this copending application, it is pointed out
more additional constituents which affect the stability
that fogging of the unexposed portions develops slowly
and/or sensitivity of the system.
over a period of weeks on exposure to air in the presence
‘In general. the compositions of the present invention
of light or heat or both, and it appears that this reaction
provide a photographic system from which a stable image
requires the presence of air, in that the colors which
may be obtained entirely by dry processing techniques, 30 develop as a result of fogging tend to be ditferent in hue
namely, simply by exposure to ultraviolet light followed
by exposure to air containing signi?cant amounts of mois~
ture. Oxygen may be used in place of the air, in which
than those obtained by the primary halogenating reac
tion. This defect was minimized or eliminated by the
case the ?xing reaction is more rapid.
and by heat ?xing as a further step. Other techniques
Such a system
has utility in the photocopy ?eld of blueprints and tech
nical information, the reproduction of typed and printed
pages, the reproduction of information as exposed
through micro?lm, the recording of information of tran
sient events as on the face of a cathode-ray tube, and
the like.
Principal objects of this invention are to effect a re
action between suitable arylamines, halogenated hydro
addition of minor percentages of certain reducing agents,
' such as overcoating and the like were also utilized.
Further, as described in the same copending applica
tion, some of the halogenated hydrocarbons are so active
that they require stabilization through the addition of
mild bases such as alkyl amines, zinc oxide, and the like
40 in the formation of the active mixture prior to formation
on the ?lm.
The compositions of the present invention constitute
carbon compounds, and sulfur compounds as above de
improvements over those described in the aforesaid ap
scribed so that under the influence of ultraviolet light a
plication. The present compositions eliminate the need
colored derivative is produced as the result of the fore 45 not only for the relatively complicated stabilization sys
going reaction; to develop this color-forming reaction
rapidly enough so that the total time of exposure and
development may be accomplished in a few seconds in
tem for prevention of fogging on storage prior to expo
sure or fogging in the unexposed areas after exposure,
but also eliminate the need for heat ?xing. These com
order to make available a permanent and stable image;
positions make it possible after photographic exposure of
to provide systems in the exposure, development and fix 50 dry ?lm to ultraviolet light to obtain an image which is
ing stages which may be processed by totally dry tech
niques; to provide means of ?xing which permits stabili
zation of the image and the elimination of the sensitivity
to ultraviolet light simply on exposure to air, preferably
self-?xing simply by exposure of the pictorial image to
still air, preferably moist, for a period of 8 to 10 hours,
in which all portions of the ?lm have ready access to
air. If the air is moving, the ?xing is completed within
moist, in the absence of ultraviolet light; to provide
two to three hours.
means of stabilization of the preexposed surfaces so that
condition whereby not only will the unexposed portion
the desired color reactions take place only on exposure
to radiation of speci?c nature; to provide means of sta
bilization of the developed image so that once formed,
it is sufficiently permanent for practical purposes; to pro
vide means of stabilization of unexposed portions of the
of the ?lm no longer fog on standing, but also a condi
ultraviolet light. A further feature of this improvement
resides in the fact that the solutions prior to deposition
image so that on continued exposure to light after the
on a suitable base are inde?nitely stable when placed in
By the term “?xing" is means a
tion wherein the exposed portions of the ?lm are no
longer sensitive to development of color on exposure to
?rst images are formed, color and fogging does not de
velop; to provide print-out systems which are sensitive
a bottle in which the air has been substantially replaced
with solvent fumes. If the bottle is brown colored and
65
to visible light: to provide a range of colored images
kept tightly covered, an inde?nite stability is available.
with respect to hue and tint: and, it is a further object
Further, the prepared plate after spreading the composi
of the invention to establish systems in which the de
tion and drying the same is also inde?nitely stable on
sired color is developed by exposure to light and the
storage providing it is placed in a container which is
facility for producing such color as a result of continued
sealed against the intrusion of air. The adverse elfects
exposure to light of a similar wavelength is destroyed by 70 of the intrusion of air may still further be minimized by
exposure of the system (after the image has been once
the deliberate addition of crystals of some of the agents
developed) to moist air in a state of motion either in
which are present in the raw photosensitive mix. Still
3,042,516
another important bene?t is the elimination of the heat
ing step for ?xing purposes.
Finally, in the referred to copending application, it is
4
There appears to be no real distinction between the
various types of plastic materials which might be utilized
as a base. The main requirements are that they be essen
noted that certain of the halogenated hydrocarbons re
tially neutral, that is, not exhibit distinctly acid or basic
quired prestabilization in order to reduce their activity,
and such prestabilization involved the deliberate addition
resin systems may be dispersed on any substrate such as
of weak alkalies to the mixture. It is a further advan
tage of the present invention that the need for such pre
characteristics, and that they be non-hygroscopic. These
glass, paper, plastic ?lms, and the like.
The second essential constituent of my composition is
a halogenated hydrocarbon. The halogenated hydrocar
stabilization additives has been obviated.
Describing my invention ?rst in general terms, I have 10 bons useful for the purposes of my invention are those
organic halogen compounds which when exposed to light
found that certain secondary and tertiary amines and to
of suitable wavelength are decomposed photochemically
a very much lesser extent, primary amines, separately or
to produce free radicals. As described in my earlier ?led
in combination, when mixed with certain organic halo
application Serial No. 787,112, the activation energy of
gen compounds which may be alkyl or aryl derivatives
formation of the halogen free-radical is the important de
or mixtures thereof, plus an addition of certain sulfur
termining factor and it appears that in order for the halo
compounds which may be organic or inorganic in nature
genated hydrocarbon to be effective in the present process
will, depending on the nature of the amine, the organic
halogen compound in question and the sulfur compound,
produce brilliantly colored products on exposure to light
it must have an energy of dissociation or in other words
an energy of formation of the free halogen radical of
Each of
The images obtained may be 20 not less than 40 kilogram calories per mole.
in times of a few seconds.
either in the form of line copy or continuous tone by use
of techniques as described later. In general the basic
sensitivity of the system is in the ultraviolet becoming
substantial at 4000 A. and less, the photographic speed
increasing as shorter and shorter wavelength ultraviolet
the halogen compounds hereinafter indicated as preferred,
it will be noted, is a halogenated hydrocarbon in which
at least one active halogen (cl, Br or I) is attached to a
carbon atom having not more than one hydrogen atom
attached thereto. The preferred halogenated hydrocar
bons are carbon tetrabromide, iodoform, and tetrachloro
is used as the exposing energy. Sensitivity to the visible
tetrahydronaphthalene. Other halogenated hydrocarbons
may be incorporated through the addition of certain
which are effective but less useful either for reasons of
azo-aniline type compounds which exhibit a yellow color
solubility, volatility, or slow speed of development are
in solution.
While the color forming reaction may be effected by 30 bromoform, chloroform, carbon tetrachloride, tetrabrom
butane, hexachlorethane, hexachlorbenzene, dichlorben
exposure of solutions containing the above combination
acne, and the like. It appears that these compounds
of reactants to ultraviolet radiation, it has been found
decompose under the in?uence of light and particularly
preferable to deposit the several reactants in the form
ultraviolet light through the formation of two free radi
of a thin ?lm wherein they are dispersed in a suitable
cals, one of which is a free radical halogen and a second
base or hinder. In this way, a dry system is presented
is a free radical residue. Thus, for example, the free
for exposure, development and processing, with outstand
radicals obtained as a result of photodecomposition of
ing advantages noted above.
carbon tetrabromide would be the bromine free radical
All of the various ingredients of the light sensitive
and the carbon tribrornide free radical. In the reactions
in a suitable binder. More uniform results are obtained 40 to be described, it is not known which portion of the
compositions of this invention are dispersed or dissolved
if at least a portion and preferably all of the ingredients
are soluble in the binder. The primary exception to this
requirement is where insoluble pigments are utilized
both for the development of continuous tone and as an
active sul?ding agent. In addition to the solvents and
residue is the active agent.
The nature of the halogenated hydrocarbon has a some
what speci?c effect on the nature of the color which forms.
For example, carbon tetrabromide used as the photohalo
genator for diphenylamine will on very short exposures
plastic materials, plasticizing agents such as high boiling
point liquids may also be utilized to improve the ?exi
produce a blue, and as the exposure continues to be ex
ers have been chosen with two requirements as the foun~
ing application.
tended, the color becomes almost black. lodoform in
the same degree of molecular equivalence ?rst produces
bility of the ?lm and to still further improve the degree
a greenish-yellow and the color on lengthy exposure is
of solution of the active agents.
The types of binders and recommended solvents for 50 green. The use and effectiveness of these halogenated
hydrocarbons has been described in the aforesaid copend
these binders are listed in Table 1. Solvents for the bind
The third essential constituent of the color-forming sys
tems of this invention is an aryl amine. Typical amines
useful in the systems of present invention are listed below
by way of example in Table 2. All of the amines listed
are aryl amnies, and it is a requirement that the simple
solvent is to insure as good solubility for other reagents
or substituted amine grouping be a side chain attached
as possible.
to an aryl nucleus. Furthermore it has been found that
TABLE 1
60 the color-producing action is more effective from the
Plastic Bases (10% Solutions)
standpoint of depth of color and speed on exposure to
[All parts are by weight]
light when the amine is substituted with complex sub
stituents. Generally speaking, in the type of compositions
Number
‘Blnder
Solvent
which are being described, secondary amines appear to
65 be the most effective with respect to speed of develop
1 ........ ._ cellnlosi-ncetute _______ __ 30 methylene dichloride-{~70
acetone.
ment of color. Tertiary amines are very slightly slower
2..
.. . cellulose nitrate _______ _. 30 ethyl aleohol+70 ethyl other.
dation for the choice. The ?rst is the ability to produce
a relatively low viscosity solution of the polymeric mate
rial in question for concentrations of plastic in the range
of 5 to 15%, and the second requirement imposed on the
it ________ _.
ehlerinatetlrnbb
4 ________ _.
t-thyleellulose
.
70t0lucne+30 act-tone.
.
.6 ________ _.
polyethylene
It ........ _.
polynlethylmetllucry-
_.
3t)
acetone-+40
methyl alcohol.
toluene+30
00to1uene+10aeetone
70acetone-Hi0ethylaeteate.
to those obtained by use of secondary amines.
late.
7 ________ __
. .
\.l.___.
tn.
.,
.
polystyrene . . . _ . _ . _ _ . . _.
00tolnene+l0 acetone.
IllllIv'VlllYltlt't'ttllt‘.
40 methyl alcohol+~1tl acetone-l
.
‘.10 toluene.
|mlyvlnylehlortdt-_....._ 80 tetrahydroluran—l~20 acetone.
[mlyvinylldtne chloride 80 tetrahytlrolm-nn+20 acetone.
t-npolynler.
in this respect and single primary amines are exceptionally
slow. Signi?cantly, however, mixtures of primary amines
yield unexpected results with speeds that are comparable
For ex
ample, in the compositions of the invention aniline used
alone usually produces a very faint grayish color, whereas
para-toluidine will produce a faint yellow. In both cases,
75 the photoreactions are relatively slow.
If a mixture of
3,042,518
6
aniline, para-toluidine, and ortho-toluidine is employed in
TABLE 4
the system, a very rapid photoreaction is available and
deep red colors develop out.
Preferred Composition Ranges of Ingredients Per 100
TABLE 2
Parts by Weight of Resin or Plastic Base
5
Number
Active Amines 1
N um her
Name
1 ______ __
Formula
10
l ______ __
tliphcnylaminc_...__.
tlilwnlylmulne...
it
_._
N-N’~dlvtl1ylanilinn“,
(‘?ll5N(c2II5)2
Call-.Nt?lla);
t7 _
[HY-ninthylttnohlstN-
(Cl11:)2NC5ll4CHzCiilI4N(Clls)g
T .
p-p’—ln-uzylidlnchls-
HClIIO?NCBTiA‘IQLilicnlls
hunt.
__ p-|1'-p"-Inotltylidint-~
is
tristN-N’tltmnthyla
4 ______ __
PrOlCl'X‘t'tl ratio of orgat
mixture lltllllllt‘
p-toluidine
. _ _ . _ __
._
_
l’roforrt'd ratio of
_
2 to 1.
l to 30.
1‘
Between 1 to 1 and 30
to l.
garlic suliur compound.
S ______ __
10 to ‘200.
Between 0.5 to 1 and
7.._._ -_ Preferred ratio olaryl amino to lnor-
15
500 to 1,000.
10 to 100.
.
game sulfur compound.
Between 10 to 1 and 3
to l.
Phatoscusitlzvr t/o rlsible l__________
0.1 to 1.0.
ll_.______
Plastlrlzer I _____________ _.
It] to 1m.
10 _____ __
Ultraviolet. absorber I _____________ __
0.1 to 1.0.
[(CXI3)2NCOII|]3CII
1 If present.
ulliuu).
0..
Organic halogen compound._
Aryl amino. ___________ __
6 ______ __
N-Nhdimvthylnnilinn.
N'alimctltylaniline).
tN-N'-tlilnvtl|yluui
Solvent ___________________________ __
compound to :try] amino
Sulfur (‘Oil’lpOlllltL
((lqlhhN
__
_
Range)
2 ______ __
tCttllmNll
,__,
fl
Parts by Weight
3 ______ __
tCttlM‘llmNll
triplu'nylnmiuv .
Reagent
p-CllsCalhNllz
CallsNH-z
Once the combination of reagents and solvent has been
disposed on a suitable base, the solvent allowed to evap
orate so that a dry ?lm is present and the surface ex
posed to light so as to produce an image, ?xing is readily
o-toluidiue.__ o-(JllsCslhNllz
l 'l‘hv amines are listed to (lt'l'lOlLt‘ the base structures which are active.
it Hit‘ amine is t'oltlplt‘xt'tl and still retains the same base structure it is
25 obtained by permitting the ?lm to be exposed to moving
nlso active.
air or oxygen containing moisture. The combination of
air and moisture or oxygen and moisture appears to be
a requirement.
Another type of amine may be utilized in addition to
the arylamine in order to extend the sensitivity of the
over-all photoreaction to the visible. Compounds which
Plasticizers may be advantageously added to the sys
are most suitable for the purpose are yellow azo com- 30 tem in amounts of between 25% and 100% of the weight
pounds such as N,N’-dimethylphenylazoaniline and 4
phcnylazodiphenylamine. These may be utilized in ex
?exibility of the dried ?lm and in certain cases to im
ceptionally small percentages to impart sensitivity to the
prove the solubility of agents whose solution is required
of the resin present (dry basis) in order to improve the
visible, generally as high up in the spectral range as green.
in order for them to be effective. Suitable plasticizers
The novel additions which distinguish the present in- 35 include: dioctylphthalate, tricresylphosphate, polyethyl
vention from that described in Serial No. 787,112 and
ene glycol, di(2 - ethylhexyl)maleate, di(2 — ethylhexyl)
which make it possible for such systems to be self-?xing
tetrahydrophthalate and tri(2-ethylhexyl)phosphate.
on exposure to moist air and still retain stability on stor
Further, and signi?cantly, true continuous tone effects
age are sulfur compounds. Sulfur compounds which
may be obtained through use of speci?c groups of the
have been found to be effective for the purpose are listed
sulfur compounds which have been mentioned previous
m Table 3 and it is noted that these are both organic and
ly. These are not only part of the active chemical sys
inorganic in nature. In general, these comprise sulfur
tem, but as the result of the reaction, ?nely divided in
compounds taken from the class of thiols, organic disul
soluble particles are retained in the ?lm so that develop
?des. thioureas. thioacetamides, and the like. Invariably
ment of color in depth may be obtained as a function of
these are sulfur compounds in which the sulfur is attached 5 the degree of exposure, thus leading to continuous tone.
directly to a carbon atom. The inorganic sul?des which
The usual improvements in photographic speed as a
have been found to be effective are light colored or white
result of exposure to ultraviolet light may also be obtained
sul?des which are readily soluble in dilute acids and may
by adding ultraviolet absorbers as is common in the
.
.
.
.
40
he used alone or in mixture. either with themselves or
art.
Such ultraviolet absorbers are benzil. stilbene de‘
with the organic sulfur compounds indicated in the table. 50 rivatives, phenylsalicylate. and the like. Usually amounts
The organic sulfur compounds also may be used in
of the order of one-tenth of a percent or less are suf
mixture.
?cient for the purpose.
The coating solution prior to deposition is inde?nitely
TABLE 3
stable when stored in a tightly closed brown bottle in
Stabilizer Sulfur Compounds
55 which all air has been displaced with solvent fumes. Aft
er the coating composition is spread on a suitable sub
strate and allowed to dry, the sensitive ?lm thus obtained
Number
Name
Formula
is inde?nitely stable if stored in the dark in the absence
of air. One of the means for accomplishing this is to
_ o-tuninolmnrr'ui-thiol ...... ..
Nrncnnstr
60 place the ?lm in a polyethylene bag and replace the air
llisltlimi-tlrrllliiwarlmmyll- [(L‘llglgNCSlgSg
with nitrogen, and then heat seal the polyethylene. Sta
tlisult‘nlv.
bility for a period of months may also be obtained with
Y l~ullyl-2-thiollrt-u._.._______. l‘llxt‘llCllzNlH‘SNllg
out the use of nitrogen, by using a rather thin gauge, poly
lJt-tlit‘lhH-ltlilourci
____ _- (‘Ell5NlI(‘SN[l(‘2ll5
lllitlll?‘ll
.
._
,
.
.
_____.__
Nllgf‘h‘Nllg
tlollm'tutt'tltiol . r _ , s
_ _ _ _ _.
ClhH‘llglnSll
llliltllt‘t‘tzllllitlt‘
____ _.
(‘IMF-“N11;
lhiotlt'ctltnilitlo..
____ _.
(‘llgCSNllCgllb
tltiolwm'
____ __
(‘ellg?b‘NlK‘slls
Ililtlt‘
l\tiot‘ul‘lmltilitlt‘ .
ethylene bag material and wrapping the sensitive plates
65
tightly so as to squeeze out as much of the air as possible
NtnCsNuNm
before heat sealing. Each time a plate is removed from
the bag for use, this squeezing out of the air followed by
ZnS-(lrlS
heat scaling is a requirement.
(‘?llbNllf‘sNllcalls
Z118
gas21193
111183
A still simpler techique is
to store the sensitive plates in an air-tight container which
70 may be a box or a plastic bag in which a few crystals of
carbon tetrabromide have been placed in the bottom of
the bag. The extremely low but signi?cant volatility of
the material gradually develops an atmosphere of carbon
which these various ingredients may be mixed to produce
the desired results.
75 tetrabromide, which apparently prevents the small amount
in Table 4 are given the ranges of proportions in
3,042,510
7
8
of residual air from being clfcctive as a destroyer of the
\inlct light indicated the permanency of ?xing, since no
sensitivity of the plate.
further coloration developed on such an exposure.
A system has now been described comprising a plastic
base or hinder, an aryl amine. a free radical producing
organic halogen compound. a sulfur compound, with or
without the addition of plasticizers, ultraviolet absorbers.
and sensitizers to the visible. Such a system is dissolved
or dispersed in a suitable solvent or mixture of solvents
EXAMPLE :3
To the composition of Example 1 there was added
005 gram of N-N’-dimethylphenylazoaniline, 5 grams
of dioetylphthalate, and 0.1 gram of phenylsalicylate.
The resulting mixture was spread on a glass plate and
allowed to dry, the spreading thickness being such that
and is deposited on a suitable base such as glass, plastic.
a ?nished dried thickness after all solvents have been
paper. and the like or it may be prepared in the form 10
eliminated was of the order of one mil. It was then ex
of a self supporting ?lm. After the solvent has been
posed to a No. 2 re?ector photo?ood lamp at a distance
eliminated by evaporation, the dry ?lm is then exposed
of 10 inches for a period of 5 seconds and the dense
to ultraviolet or visible light and such exposure will gen
blue-black color obtained as in Example 1 was developed
crally be in the range of l to 30 seconds. After exposure.
out with a faintly yellow background. After exposure,
the image is ?xed simply by permitting the exposed ?lm
the image was ?xed by blowing air across the ?lm for
to be exposed to moving ordinary air containing the mois
a period of two hours.
ture it normally contains in the range of 40 to 75% rela
EXAMPLE 4
tive humidity for a period of 8 to 10 hours, preferably
in the dark, though ordinary light containing no ultra
violet may also be used if sensitizers to the visible are
absent.
The action is greatly accelerated if the air is
moved rapidly across the surface in which case the ?x
ing takes place in 2 to 3 hours. If moist oxygen is used,
?xing takes place in 30 to 60 minutes. After such treat
ment. the exposed portions are insensitive to visible and
A composition was formulated by adding 2.0 grams
of para-para'-benzylidinebis(dimethylaniline), 5 grams
of tetrachlorotetrahydronaphthalene, 0.5 gram of thi
ourea, and 3.0 grams of tri(2~ethylhexyl) phosphate to
100 ccs. of a 10% solution of polystyrene in a mixture
of toluene and acetone 90:10. After spreading the re
sulting composition on a glass plate and permitting the
ultraviolet light even on long exposure.
The light sotlrce utilized for exposure purposes in this
solvent to evaporate completely, a ?lm thickness of 1.5
speci?cation is the General Electric re?ector type sun
lamp of 275 watts using a glass envelope. At a distance
sunlamp at a distance of 10 inches for three seconds,
of It) inches. exposure times of 1 to 30 seconds are ob
taincd.
Having described my invention, the following examples
are indicative of specific methods of practice and are to
be construed as illustrative rather than as limiting.
EXA RIFLE 1
One hundred (100) ccs. of a solution containing 10
grams of a low molecular weight polyvinyl chloride in
mils was obtained. This was exposed to a GB. 275 watt
after which a rich deep green color was obtained in the
This was allowed to stand in the dark
box with ready access of air for a period of 10 hours to
30 light struck areas.
complete the ?xing operation.
EXA MI‘LE 5
One hundred (l00) ccs. of a solution of polyvinyl ace
tate in a mixture of methyl alcohol, acetone and toluene
(40:40:20) was mixed with 2.0 grams of para-para’
para"-methylidynetris(N-N’-dimethylaniline), 8.0 grams
of carbon tetrabromide, 2.0 grams of thioacetamide,
an 80:20 mixture of tetrahydrofuran and acetone was
10.0 grams of dioctylphthalate, 20 ccs. acetone, and
mixed with It) grams of diphcnylamine, 15 grams of car 40 stirred vigorously until the solution of the ingredients
bon tetrabromide, 2 grams of bis(dimcthylthi0car
was complete. The resulting solution was spread on a
bamylldisul?dc, and finally 20 ccs. of acetone. The mix
paper base and a measurable thickness of 0.8 mil was
ture was stirred until all of the ingredients were dis
obtained. This was exposed to a GB. 275 watt sunlamp
solved, after which the composition was spread on a
glass plate so that a dried thickness of approximately 1
mil was obtained.
After all solvent has evaporated. the sensitive surface
at a distance of 10 inches for a period of 2 seconds on
which exposure a deep royal blue developed out in the
exposed areas.
Air from a small fan was blown across
the image for a period of 2 hours, after which reex
was exposed to a 275 watt GE. sunlamp at a distance
posure to ultraviolet light for a period of 2 minutes in
of 10 inches for a period of 5 seconds, after which time 50 dicated no fogging.
a dense bluc~black image was obtained. The exposed
EXAMPLE 6
film was then placed in a dark cabinet fitted with means
to permit the entry of air and therein retained for 10
hours. Subsequent exposure to ultraviolet light pro
vided no noticeable effect even though the ultraviolet
exposure comparable to the intensity indicated original
ly extended for a period of 5 minutes.
EXA M I‘LE 2
One hundred (100) ccs. of a solution containing 10
grams of a low molecular weight polyvinyl chloride dis
solved in an 80:20 mixture of tetrahydrofuran and ace
tone was mixed with 4 grams of diphenylamine, 6 grams
of carbon tetrabromide, 2.0 grams of dodecanethiol and
?nally 20 ccs. of acetone. The mixture was stirred until
all the ingredients were dissolved, after which the com
position was spread on glass with a doctor knife so that
a dried thickness of 1 mil was obtained.
One hundred (100) ccs. of a solution containing 10
grams of polystyrene dissolved in a 90: 10 toluene-acetone
mixture was mixed with a solution of 2 grams of aniline,
4 grams of para-toluidine, and 4 grams of ortho-toluidine
dissolved in 90 grams of toluene. To the resulting solu
tion was added 10.0 grams of carbon tetrabromide, t.0
grams of thiosemicarbizide, 5.0 grams of tricresylphos
phate, 0.1 gram of N-N’-dimethylphenylazoaniline, and
30 ccs. of acetone.
The solution was stirred until all of
the ingredients were completely dissolved and was then
spread on a glass plate and a ?lm thickness of 1.2 mils
was obtained. This was exposed for a period of 5 seconds
and ?xed by storing in a dark cabinet in the presence of
air for 12 hours.
EXAMPLE 7
A coating composition was formulated consisting of
The dry sensitive surface was exposed for 8 seconds
100 ccs. of a 10% solution of cellulose nitrate dissolved
to the 275 wait (til. sunlamp at a distance of l0 inches
giving an exposure color of deep blue-black. The ex
in a mixture of ethyl alcohol and ethyl ether (30:70),
powtl tilni was lixcd by exposing it to moist moving oxy
_:~cu passed over at a rate of about 1 liter per minute for
to which there was added 5.0 grams of zinc sul?de, 10
grams of carbon tetrabromide, 5.0 grams of diphenyl
amine, 0.05 gram of phenylsalicylate, 0.02 gram of N
N-dimethylphenylazoaniline, and 5 grams of dioctyl
~15 minutes. The moisture was obtained by bubbling the
oxygen tluough water. Subsequent treatment with ultra_ 75 phthalate. After thorough mixing and grinding to disperse
3,042,510
10
4. The ?lm of claim 3 wherein the amount of said azo
the zinc sul?de as completely as possible. the mixture
was spread on a glass plate in sut?cicnt thickness to pro~
vide a dried ?lm after all solvent was eliminated approxi
mately 1.5 mils in thickness. This was exposed to a gray
step scale negative for a period of 20 seconds and the
image was in a blue-black color.
compound is from 0.001 to 0.02 part by weight per part
of plastic.
It was ?xed by re
taining the exposed ?lm in a dark box in the presence
of air for 12 hours. Of the thirty steps of gray on the
negative, twenty were recorded on the photosensitive sur
face.
10
EXAMPLE 8
7. The ?lm of claim 1 in which the arylamine is se
lected from the group consisting of secondary amines,
tertiary amines and mixtures of at least two primary
amines.
Twelve 4 x 5 glass plates were coated with the disper<
sions of Example l. Separately another twelve plates
were coated with the dispersions of Example 7. Six of
the plates prepared in accordance with Example I and
six of the plates prepared in accordance with Example
8. The ?lm of claim 1 containing in addition ?nely di
vided insoluble pigment, dispersed in said plastic.
9. The ?lm of claim I in the form of a self-sustaining
translucent ?lm.
H]. A print-out member consisting of the ?lm of claim
24 on a support selected from the group consisting of glass,
paper and plastic.
ll. in a method of ?xing brilliantly colored images
7 were separately stored as follows: plates were stacked
one on top of each other and clear glass plates were
placed on the top plate. The packages were inserted
in a polyethylene bag which was molded around the plate
so as to squeeze out as much of the air as possible and
produced in a photosensitive layer comprising an arylamine
and an organic halogcnvcontaining compound by exposure
the bag was then heat sealed. One month later, one of
the plates was removed from the bag and exposed to
of said layer to ultraviolet light, said exposure being un
der such conditions that a free radical is produced by
ultraviolet light in accordance with the teachings of the
previous examples for a period of 6 seconds and a full
density image obtained.
5. The ?lm of claim 1 containing in addition up to
about 0.1% by weight of an ultraviolet absorber, dispersed
in said ?lm-forming plastic.
6. The ?lm of claim 1 containing in addition between
about 0.01 and l part by weight of a plasticizer per part by
weight of plastic, dispersed in said plastic.
decomposition of said halogen-containing organic com
Repeating the same experi
pound. said halogen~containing compound being selected
ment after sealing the bag but with a three month lapse
from the group consisting of halogenated hydrocarbons
of time produced substantially the same results. In a
having an energy of formation of the free halogen radical
second series, six plates each were stored in separate
and sealed polyethylene bags in which approximately one 30 of not less than about 40 kilogram calories per mol and is
reacted with said arylamine to produce a brilliantly col
gram of carbon tctrabromide was placed in the corner
ored reaction product in the exposed portions of the layer;
of the bag. These bags were opened six months later
and again one of the plates was exposed as taught in
the previous examples for a period of 5 seconds and
again a full density image was obtained. Simultaneously
the improvements which comprise: providing at least one
sul?de selected from the group consisting of organic sul
?des in which the sulfur is attached directly to a carbon
atom and inorganic sul?des in which the sulfur is at
with the original preparation of these materials, plates
prepared in accordance with Example l and Example 6
tached directly to a metal atom as an additional constituent
in said photosensitive layer and ?xing the image compris
ing said colored reaction product by exposing the surface
after solvent elimination were stored in a dark cabinet
with ready access of air for a period of 12 hours and
of said sul?de-containing layer to a moist oxygen-cow
after exposure to ultraviolet light, no noticeable image 40 raining gas, thereby stabilizing the brilliantly colored im
was obtained.
age against fading.
I claim:
12. A method of developing stable brilliantly colored
images which comprises preparing a composition consist<
ing essentially of (ll a ?lm-forming plastic base material
1. A dry photographic ?lm producing a visible print
out image by exposure to light of a suitable wave length
and rendered insensitive to light by exposure to a moist
oxygen-containing gas selected from the group consist
selected from the group consisting of cellulose deriva
tives and polymers of vinylidcne monomers. (2) at least
one arylaminc. (3) at least one halogenated hydrocarbon
compound having an energy of formation of the free
least one arylamine; (2) at least one halogenated hydro
halogen radical of not less than about 40 kilogram cal
50
carbon compound having an energy of formation of the
ories per mol. selected from the group consisting of com
free halogen radical of not less than about 40 kilogram
pounds which produce free radicals upon exposure to light
calories per mol, selected from the group consisting of
of a suitable wave length and (4) at least one sulfur
ing of oxygen and air, said ?lm consisting essentially of
a ?lm-forming plastic having dispersed therein (1) at
halogenated hydrocarbon compounds which produce free
containing compound selected from the group consisting
of organic sul?des in which the sulfur is attached directly
and (3) at least one sulfur-containing compound selected 55 to a carbon atom and inorganic sul?des in which the sul
from the group consisting of organic sulfides in which
fur is attached directly to a metal atom; there being pres
the sulfur is attached directly to a carbon atom and in
ent in said ?lm between 0.l and 10 part of arylamine by
organic sul?des in which the sulfur is attached directly
weight, per part of ?lm-forming plastic. between 0.] and
to a metal atom; there being present in said ?lm between
0.1 and 1.0 part of arylamine by weight. per part of ?lm 60 2.0 parts of halogenated hydrocarbon compound by
weight. per part of ?lm—forming plastic and between 0.01
forming plastic. betweccn 0.] and 2.0 parts of halogenated
and 0.3 part by weight of sulfur compound by weight. per
hydrocarbon compound by weight. per part of ?lm-form
part of ?lm-forming plastic: said composition being pre
ing plastic and between 0.0l and 0.3 part by weight of
pared in a solvent for the ?lm—forming plastic; depositing
sul?de by weight. per part of ?lm-forming plastic. said
radicals upon exposure to light of a suitable wave length;
?lm-forming plastic being selected from the group con
65 said composition on a support; evaporating said solvent.
leaving a photosensitive ?lm wherein the arylamine. halo
sisting of cellulose derivatives and polymers of vinylidenc
genated hydrocarbon and sulfur-containing compounds
monomers.
are dispersed in said ?lm-forming plastic base material on
2. The lilm of claim I containing in addition an azo
compound dispersed in said ?lm-forming plastic base ma<
tcrial, to enhance the pholt'isensitivity of said ?lm to visible
said support; exposing selected portions of the resulting
70 article to ultraviolet light; and thereafter ?xing the result
ing brilliantly colored image by exposing the surface of
light.
said image bearing article to a moist oxygen-containing
3. The ?lm of claim 2 wherein the said azo compound
is selected from the group consisting of azoanilines and
axodiphcnylamincs,
gas.
75
(References on following page)
3,042,510
12
11
References Cited in the file of this patent
UNITED STATES PATENTS
1,574,357
1,587,272
1.587273
2,097,119
Beebe et al.
Beebe et a1.
Beebe et a1.
Eggert et a1.
__________ __ Feb. 23,
__________ __ June 1,
__________ __ June 1,
__________ __ Oct. 26,
1926
1926
1926
1937
2.673.151
2,789.053
2905,556
Gcrhart ____________ -_ Mar. 23, 1954
Elliott ______________ __ Apr. 16, 1957
Fuchsman el al _______ __ Sept. 22, 1959
FOREIGN PATENTS
633,715
Germany ____________ __ July 16, 1936
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3,042,516
July 3' 1962
Eugene Wainer
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below .
Column 2
I inc 4 l ‘
line 6, for "comprsiing" read —— comprising -—;
for "on" read —— of —-;
meant ——; same column 2,
line 23,
line 55,
for "means" read —“
line 6'1’u strike out "the"; column 4,
for "cl" read —— Cl —-;
line 57,
for "amnies" read —
amines —~; column 8, line 58, for "grams", first occurrence,
read —-- gram ~—; column lOI
numeral
"24"
read
—~—
1
line 19, for the claim reference
——
Signed and sealed this 13th day of November 1962.
(SEAL)
Allest:
EFNEST w. SWIDER
DAVID L- LADD
Aucsting Officer
Commissioner of Patents
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