U.S. patent number 3,679,738 [Application Number 05/020,051] was granted by the patent office on 1972-07-25 for alkali metal salts of polyacetylenic polyoic acids.
This patent grant is currently assigned to The Battelle Development Corporation. Invention is credited to George E. Cremeans.
United States Patent |
3,679,738 |
Cremeans |
July 25, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
ALKALI METAL SALTS OF POLYACETYLENIC POLYOIC ACIDS
Abstract
Radiant-energy photosensitive crystalline alkali metal salts of
polyacetylenicpolyoic acids and the partial lower alkyl esters of
the acids, which acids contain a minimum of two acetylenic linkages
as a conjugated system; and a preparing of a clear and transparent
body containing polyvinyl alcohol fixedly positioning dispersed
radiant-energy photosensitive crystalline alkali metal salts.
Inventors: |
Cremeans; George E. (Groveport,
OH) |
Assignee: |
The Battelle Development
Corporation (Columbus, OH)
|
Family
ID: |
27486900 |
Appl.
No.: |
05/020,051 |
Filed: |
March 16, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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555229 |
Jun 6, 1966 |
3501297 |
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Current U.S.
Class: |
560/190;
250/475.2; 430/202; 562/595; 430/270.1 |
Current CPC
Class: |
G03F
7/025 (20130101); C07C 69/606 (20130101); C07C
57/24 (20130101); Y10S 430/168 (20130101); Y10S
430/143 (20130101) |
Current International
Class: |
C07C
57/24 (20060101); C07C 57/00 (20060101); C07C
69/00 (20060101); C07C 69/606 (20060101); G03F
7/025 (20060101); C07c 057/24 (); C07c
069/52 () |
Field of
Search: |
;260/485R,537N |
Other References
black et al., J. Chem Soc. (1953), pp. 1,787, 1,790, 1,791 .
Seher, Fette V. Seifen, 55 (1953) p. 95 .
Annalen, 589 (1954) p. 222.
|
Primary Examiner: Weinberger; Lorraine A.
Assistant Examiner: Skelly; E. Jane
Parent Case Text
RELATED APPLICATIONS
This application is a continuation-in-part of my copending
application Ser. No. 555,229, filed June 6, 1966, entitled "Image
Formation, Materials Therefore and Their Preparation," issuing on
Mar. 17, 1970, as U.S. Pat. No. 3,501,297, under the title
"Photographic Process Using Polyacetyleneicdioic Acid Crystals."
Claims
What is claimed is:
1. Radiant-energy photosensitive crystalline alkali metal salts of
polyacetylenicpolyoic acids and the partial lower alkyl esters of
said acids, which salts have the structural formula
YOOC-- (--CH.sub.2 --).sub.m2 (--C.tbd.C--).sub.2
(--CH.sub.2).sub.m2 --COOy
wherein m2 is an integer greater than 4 and less than 14, and each
Y is an alkali metal atom or one Y is an alkali metal atom and the
other Y is an alkyl radical selected from the group consisting of
the methyl, ethyl, and propyl radicals.
2. The alkali metal salt of claim 1 which is methyl potassium
10,12-docosadiynedioate.
3. The alkali metal salt of claim 1 which is dipotassium
7,9-hexadecadiynedioate.
4. The alkali metal salt of claim 1 which is methyl lithium
10,12-docosadiynedioate.
5. The alkali metal salt of claim 1 which is methyl sodium
10,12-docosadiynedioate.
Description
In general this application relates to photosensitive crystalline
polyacetylenic compositions of matter. More particularly it relates
to certain photosensitive crystalline alkali metal salts of
polyacetylenicpolyoic acids and partial lower alkyl esters of these
acids and their preparation, and in particular to alkali metal
salts of polyacetylenicdioic acids and the partial lower
up-to-C.sub.3 -alkyl esters of these acids and to their preparation
and incorporation of these salts in a clear and transparent
body.
In my aforementioned copending application, issuing as U.S. Pat.
No. 3,501,297, there is taught and claimed a process for
photographic formation of a visual positive image through
employment of crystals of an alkali metal salt of a
polyacetylenicdioic acid having a minimum of two acetylenic
linkages as a conjugated system. In other related copending
applications, Ser. NOS. 555,238; 555,230; and 562,125 issuing on
Mar. 17, 1970, as U.S. Pat. Nos. 3,501,303; 3,501,302; and
3,501,308, respectively, there are taught and claimed
photosensitive image-receptive elements, process of formation of a
visual print-out image, process for direct photographic formation
of a visual print-out image, and radiant-energy sensitive
compositions of enhanced photosensitivity and their process of
preparation and their employment in a photographic process for
direct formation of a visual image.
In general, the present invention's alkali metal salts of
polyacetylenicpolyoic acids and the partial lower alkyl esters of
these acids are radiant energy photosensitive in their crystalline
form and are of utility in the elements, composition, and processes
taught in the aforementioned applications. Some of these salts are
useful in the particular process claimed in my aforementioned
copending application and others are useful in various elements,
compositions, and processes of the other aforementioned
applications.
In general, the photosensitive crystalline polyacetylenic
compositions of matter of the invention are alkali metal salts of
polyacetylenicdioic acids, having a minimum of two acetylenic
linkages as a conjugated system, and of the partial lower alkyl
esters of these acids. They preferably are of the following general
structure:
YOOC--(-CH.sub.2 --).sub.ml (-C.tbd.C--).sub.n (-CH.sub.2
--).sub.m2 --COOY
wherein n is an integer of at least 2 and with especial preference
for n is 2, i.e., a diacetylenic compound, and ml and m2 each are
integers, not necessarily the same, but by especial preference the
same, greater than 4 and less than 14, and each Y is an alkali
metal atom (i.e., lithium, sodium, potassium, rubidium, or cesium
atom) or one Y is an alkali metal atom and the other Y is a lower
alkyl radical of up to three carbon atoms and by especial
preference is the methyl radical. The preferred alkali metal salts
are the lithium, potassium, and sodium salts with lithium salts
especially preferred. Included within and illustrative of the
photosensitive crystalline alkali metal salts of the invention
are:
each of the dilithium, disodium, dipotassium, dirubidium, and
dicesium salts of 7,9-hexadecadiynedioic acid,
8,10-octadecadiynedioic acid, 9,11-eicosadecadiynedioic acid,
10,12-docosadiynedioic acid, 11,13-tetracosadiynedioic acid,
12,14-hexacosadiynedioic acid, 13,15 -octacosadiynedioic acid,
14,16-triacontadiynedioic acid, 15,17-dotriacontadiynedioic acid,
15,17-tetratriacontadiynedioic acid, and
16,18-hexatriacontadiynedioic acid; and
each of the monolithium, monosodium, monopotassium, monorubidium,
and monocesium salts of each of the monomethyl, monoethyl, and
monopropyl esters of 7,9-hexadecadiynedioic acid,
8,10-octadecadiynedioic acid, 9,11-eicosadecadiynedioic acid,
10,12-docasadiynedioic acid, 11,13-tetracosadiynedioic acid,
12,14-hexacosadiynedioic acid, 13,15-octacosadiynedioic acid,
14,16-tricontadiynedioic acid, 15,17-dotriacontadienedioic acid,
15,17-tetratriacontadiynedioic acid, and
16,18-hexatriacontadiynedioic acid.
Most conveniently one prepares the alkali metal salts of the
invention from their corresponding polyacetylenicpolyoic acids and
the lower alkyl monoesters of those acids. My aforementioned
copending application includes citations of patents and journal
articles which include exemplary and illustrative teachings of
known methods for preparation of polyacetylenicpolyoic acids and
their lower alkyl monoesters. For examPle, 9,11-eicosadiynedioic
acid and 10,12-docosadiynedioc acid are reported by Black et al, J.
Chem. Soc. (1953), 1,787, 1,790, 1,791, as byproducts of coupling
reactions; 9,11-eicosadiynedioic also is taught by Seher in Fette
u. Seifen, 55 (1953), 95and 10,12-docosadiynedioic acid also is
taught by Sher in Fette u. Seifen, 55 (1953) 95, and in Annalen,
589 (1954), 222. A particularly convenient method of preparation is
an oxidative coupling or dehydrocondensation reaction of terminal
acetylenic compounds whose other terminus is of lower alkyl ester
structure, and depending on whether one couples the same or
different of such terminal acetylenic compounds there is provided
the symmetrical or unsymmetrical lower alkyl polyacetylenicdioate.
This coupling reaction will be more readily understood from a
typical and illustrative preparation, which follows, of the
dimethyl ester of 10,12 -docosadiyne dioic acid. These diesters
through known hydrolysis and/or ester interchange methods then are
converted to their corresponding diacid and lower alkyl monoester.
Conversion of a dimethyl ester of a diynedioic acid to its
corresponding monomethyl ester will be more readily understood from
a typical and illustrative preparation, which follows, of the
monomethyl ester of 10,12-docosadiynedioic acid.
ILLUSTRATIVE PREPARATION OF DIMETHYL ESTER OF
10,12-docosadiynedioic ACID
200 grams of a commercially available 10-undecynoic acid is heated
in 600 ml. of boron trichloride-methanol solution (10 percent w/v)
to 60.degree.C. 10 minutes after the solution becomes clear it is
poured into liter of ice water and extracted with three 400 ml.
portions of petroleum ether (b.p. 30.degree.- 60.degree.C.). The
combined petroleum ether extracts are washed with two 200 ml.
portions of water and dried over magnesium sulfate. Filtration and
removal of the petroleum ether under reduced pressure yields 213
grams of the colorless liquid, methyl 10-undecynoate, b.p.
106.degree.-7.degree.C. at 2.5 mm. Hg.
Into a 5 liter, three-neck flask are placed 20 grams of cuprous
chloride, 24 grams N,N,N', N'-tetramethylethylenediamine (TMEDA),
2,400 ml. of methanol and the 213 grams of the aforeprepared methyl
10-undecynoate. The reaction mixture is stirred vigorously while
oxygen is bubbled therethrough. The temperature of the reaction
mixture is maintained below 45.degree.C. by occasional cooling with
an ice-bath during the first hour of the reaction. After
approximately 12 hours, the stirring and oxygen flow are
discontinued and the methanol removed using a rotary evaporator and
reduced pressure. The residue is extracted with four 300 ml.
portions of petroleum ether (b.r. 30.degree.-60.degree.C.) and the
resulting bluish solution washed with five 100 ml. portions of an
aqueous 4 percent hydrochloric acid solution and followed by
washing with two 200 ml. portions of water. The resulting colorless
petroleum ether solution is dried over magnesium sulfate. The
magnesium sulfate is removed by filtration and the filtrate
concentrated to about 800 ml. and cooled. The resulting white
crystalline product is collected by filtration and dried, yielding
185 grams of dimethylester of 10,12-docosadiynedioic acid, m.p.
41.degree.-42.degree.C., ##SPC1##
(in this example and other examples, which follow, the nuclear
magnetic resonance (N.M.R.) spectra are obtained on a Varian
Associates HR-60 spectrometer in deuteriochloroform solution.
Chemical shifts are reported in cycles per second downfield from
the internal standard tetramethyl silane at 60 Mc./sec. The number
in parenthesis is the relative area of the resonance.)
ILLUSTRATIVE PREPARATION OF MONOMETHYL ESTER OF
10,12-docosadiynedioic ACID
2 liters of methanol are poured into a 5-liter flask followed by
185 grams of the dimethyl ester of 10,12-docosadiynedioic acid. The
mixture is stirred until the diester dissolves. To the resulting
solution are added 509 ml. of 0.928 N. barium hydroxide-methanol
solution. The reaction mixture is stirred at room temperature for
24 hours. The precipitated barium salt is removed by filtration and
washed with methanol. The methanol filtrates are concentrated and
filtered until no further barium salt can be obtained. The barium
salt is triturated under 500 ml. of 1 N. HCl and the resulting
mixture extracted with three 300 ml. portions of ether. The
combined ether extracts are washed with 200 ml. of water and dried
over magnesium sulfate. After removal of the magnesium sulfate by
filtration and the ether by reduced pressure distillation, the
resulting solid is recrystallized from petroleum ether (b. r.
30.degree.-60.degree.C.). The crystalline product is collected by
filtration, washed with cold petroleum ether and dried. A
conversion to 118 grams of monomethyl ester of
10,12-docosadiynedioic acid, m.p. 61.degree.-62.degree.C., is
obtained. N.M.R. spectrum; ##SPC2##
In addition, 18 grams of unsaponified dimethyl ester and 8 grams of
the diacid are isolated and recovered.
The infrared spectra (Perkin-Elmer 521 spectrometer) of the diyne
diester and half-ester products of the preceding examples are
consistent with the expected absorption bands. All obtained UV
spectra (Carey Model 14M) show the uniquely characteristic
absorption of the diyne group (--C.tbd.C--C.tbd.C--) with maxima at
215, 225, 240 (.epsilon..apprxeq.380) and
254.mu.(.epsilon..apprxeq.230).
In general, to provide the alkali metal salts of the invention one
conveniently converts the corresponding polyacetylenicopolyoic acid
or its lower alkyl monoester. In preparation of the preferred
alkali meal salts of the invention one appropriately converts a
partial lower alkyl ester of the formula
ROOC--(--CH.sub.2 --).sub.m1 (--C.tbd.C--).sub.2
(--CH.sub.2).sub.m2 --COOH
wherein m1 and m2 each are integers, not necessarily the same, but
by special preference the same, greater than 4 and less than 14,
and R is an alkyl radical selected from the group consisting of
methyl, ethyl, and propyl radicals, or one converts its
corresponding diacid, or converts a mixture of the partial lower
alkyl ester and its corresponding diacid.
In one conversion method, an appropriate amount of an alkali metal
hydroxide, oxide, acetate carbonate, or like reactant known for
preparation of alkali metal salts of organic acids from the
corresponding organic acids, is reacted therewith in a suitable
solvent to provide the particularly desired mono- or di-alkali
metal salt. Alternatively the lower alkyl di- and mono-esters of
the polyacetylenicpolyoic acid are saponified in whole or part, as
desired, by the action of the requisite amount of an alkali metal
hydroxide or like reactant to provide the particular mono- or
di-alkali metal salt as desired. Preparation techniques and methods
are well known in the art for such conversions of organic acids and
their esters, with it only necessary when applying a particular
method to polyacetylenicpolyoic compounds that care be used in its
selection and application so as not to be destructive of the
polyacetylenic structural portion of the polyoic acid being thus
treated.
In utilization of photosensitive crystalline polyacetylenic
compounds, including the alkali metal salts of this invention, in
the various applications taught in my aforementioned copending
applications, there are employed useful photosensitive
image-receptive elements comprised of the alkali metal salt and a
carrier means which serves to fixedly position the photosensitive
crystalline alkali metal salts of the invention. My aforementioned
copending application, Ser. No. 555,229, maturing into U.S. Pat.
No. 3,501,297, includes considerable teachings and description
therein as to nature and identity of the carrier means, preparation
of various useful image-receptive element, various image-forming
applications, and the like, and by this reference hereto, that
description is incorporated in this application to further teach
useful embodiments and applications employing the alkali metal
salts of the invention.
In some image-forming applications, an image-receptive element,
comprised of the alkali metal salts of the invention fixedly
positioned by the carrier means, should be clear and transparent.
In these applications the unexposed element serves as a camera film
or the like and the exposed element serves as a negative for
subsequent transmission exposure in reproduction of positive copies
of the image thereon. In these embodiments, it is requisite that
the element be clear and transparent, and especially in its
background areas. With many photosensitive crystals of various
photosensitive crystalline polyacetylenic compounds, a requisite
and desirable clarity and transparency is not readily obtained. In
the present invention, however, it advantageously has been found
that the alkali metal salts of the invention can prepared as a
suspension of very fine crystals in the order of micron and
submicron size suspended in resinous binder solutions and upon
removal of the solvent therefrom will provide a clear and
transparent body, such as a free-formed film and/or a clear and
transparent coating on a clear and transparent suitable substrate
to provide useful image-receptive elements.
The description herein of the invention now will be amplified by
the following specific examples of various illustrative embodiments
of the invention.
EXAMPLE 1
Methyl Potassium 10,11-docosadiynedioate
To monoethyl ester of 10,12-doscadiynedioic acid of an acid number
of 150 to 160, which had been prepared from its corresponding
diester by a hydrolysis technique, there is added aqueous potassium
hydroxide in the amount calculated to neutralize the half-ester
constituent. The resulting clean solution is filtered. The filtered
solution now containing methyl potassium 10,12-docosadiynedioate,
is evaporated to substantial dryness on a paper. Upon drying,
crystalline methyl potassium 10,12-docosadiynedioate is
precipitated onto the surface of the paper and this crystalline
methyl potassium 10,12-docosadiynediote undergoes a visible color
change upon exposure to ultraviolet radiation of a wavelength of
2,537 A.
EXAMPLE 2
There is added dropwise about 0.45 gram of aqueous 50 percent
potassium hydroxide to a mixture of about 4 grams of water and
about 1 gram of monomethyl ester of 10,12-docosadiynedioic acid
product of an acid number of about 166. The resulting solution is
filtered and 1 gram of the filtered solution added with stirring to
0.86 gram of aqueous 20 percent polyvinylpyrrolidone (such as a
medium viscosity grade of commercially available
polyvinylpyrrolidone). The resulting solution of about 20 percent
solids is applied to coat the surface of glass microscope slides
and dried. The resulting elements comprise a glass substrate having
adhered thereto a dry solid coating comprised of about 47 percent
of polyvinylpyrrolidone binder containing dispersed therein about
53 percent of fine crystalline methyl potassium
10,12-docosadiynedioate.
These elements are useful as image-recording elements in electron
microscopy to provide a visible blue-colored image of an electron
microscopic specimen.
EXAMPLE 3
Dipotassium 7,9-Hexadecadiynedioate
To an aqueous dispersion of 7,9-hexadecadiynedioic acid there is
added aqueous 50 percent potassium hydroxide in an amount
sufficient to dissolve the polyyne and to give an aqueous solution
of dipotassium 7,9-hexadecadiynedioate. This aqueous solution of
the dipotassium salt is mixed with aqueous polyvinyl alcohol and
coated onto a glass surface as described in preceding examples. The
resulting element comprises a glass surface having adhered thereto
a dried film of polyvinyl alcohol containing dispersed crystals of
the dipotassium salt.
A screen is laid over the elements coating and exposure made to
ultraviolet radiation. No visible image is observed after this
exposure. The exposed element then is immersed in concentrated
hydrochloric acid for about 10 seconds and dried at about
50.degree.C. A faint image now is observed and upon exposure of
this acid-treated element completely overall to ultraviolet
radiation there results a blue-colored positive image of the
screen.
In place of hydrochloric acid other strong mineral acids, such as
sulfuric acid and the like may be used, and in place of immersion
an acid vapor treatment is useful.
EXAMPLE 4
A monomethyl ester of 10,12-docosadiynedioic acid product of acid
number of about 155-160 (theoretical acid number of this monoester
is about 149 with this product being prepared from its diacid so as
to contain both monoester and diacid in an amount providing the
product with acid number 155-160) is mixed with its corresponding
diacid, 10,12-docosadiynedioic acid in an amount to provide a
polyyne product mixture of acid number of about 170. To this
mixture in water there is added dilute aqueous potassium hydroxide
in an amount between 100 to 120 percent of the amount calculates
equivalent to neutralize all carboxyl groups present in the diacid
and monoester contained in the mixture. This amount of dilute
aqueous potassium hydroxide dissolves the major portion of the
acetylenic compounds. The resulting neutralized water solution of
the potassium salt is filtered and the filtrate is mixed with about
12 percent by weight of an aqueous polyvinyl alcohol that is about
88 to 90 percent hydrolyzed polyvinyl acetate, such as commercially
available Elvanol 51-05. It then is applied as a coating to a glass
plate and air dried at about 45.degree.C. The dispersed potassium
salt in the dried film approximates particles about 0.5 to 1.5
microns in size. The ratio of potassium salt to polyvinyl alcohol
in the applied dispersion is such that the dried coating consists
essentially of about 60 percent polyyne potassium salt crystals and
40 percent polyvinyl alcohol. A second coating application of the
dispersion is applied and air dried. Thereafter, the resulting
image-receptive element consists essentially of the glass plate
substrate material and adhered thereto dried clear and transparent
coatings approximating 0.1 gram per square inch, of polyvinyl
alcohol binder containing dispersed therein crystals of methyl
potassium 10,12-docosadiynedioate.
In the preceding Example 4, diacid is added to bring the monoester
product to an acid number approximating 170 in order to produce a
substantially clear and transparent dried coating. At lower acid
numbers and those approaching theoretical for the monoester, the
photosensitive potassium salt prepared therefrom results in a
polyvinyl alcohol coating which is not clear but is translucent. At
acid numbers greater than 170 or those wherein the diacid content
exceeds about 7-1/2 percent and more of the polyyne mixture, the
photosensitive potassium salt in the resulting dried coating is not
as photosensitive to electron beam irradiation as that derived from
a lower than 170 acid number monoester product.
In the resulting elements of dried photosensitive films on the
glass plate, the polyyne potassium salt loadings can range up to
about 75 percent by weight. At higher loadings, insufficient
polyvinyl alcohol binder is present to firmly adhere all
crystalline particles to the glass plate and some crystals brush
off relatively easy. In films of less than one-half mil dry
thickness, polyyne potassium salt loadings of the dried film lower
than about 40 percent by weight are not desirable in that
sufficient photosensitive material is not present to produce an
image of suitable density upon a short duration exposure to an
electron beam.
EXAMPLE 5
Methyl Lithium 10,12-Docosadiynedioate
There slowly is added 0.84 gram of finely ground LiOH.sup.. H.sub.2
O to a stirred filtered solution of 7.8 grams of the monomethyl
ester of 10,12-docosadiynedioic acid dissolved in 40 ml. methyl
alcohol. A fine white crystalline precipitate of methyl lithium
10,12-dicosadiynedioate appears. The resulting solution with some
precipitate formed therein then is cooled by permitting to stand
overnight in about 40.degree.F. refrigerator to permit additional
crystalline precipitate to form. When the resulting crystalline
precipitate is filtered off through collection on a filter paper in
a Buchner filter and then air dried, it appears to be fine particle
crystals somewhat gelatinous in appearance. Yield is about 6.2
grams. A small sample of this precipitate, now having a slight
bluish cast, on a hot-block melting-point bar changes to a pink
color at about 96.degree.C., from a pink to an orange color at
about 120.degree.C., becomes transparent at about 165.degree.C.,
and apparently melts within the range of 184.degree.-192.degree.C.
In contrast, the monomethyl ester of 10,12-docosadiynedioic acid on
the same hot-block melting-point bar melts at about
57.degree.C.
A small portion of the above-prepared methyl lithium
10,12-dicosadiynediote is slurried in distilled water to provide a
suspension thereof in water and quickly flowed onto a paper
substrate and permitted to air dry thereon. The resulting product
is an image-receptive element comprised of a paper support means
having fine crystalline photosensitive methyl lithium
10,12-docosadiynedioate relatively fixedly positioned and physical
adhered thereto. This element is useful for direct photographic
formation of a visual print-out image through exposure to
ultraviolet 2,537 A. radiation.
EXAMPLE 6
There is added 0.21 gram of fine LiOH.sup.. H.sub.2 0 to a stirred
filtered solution of 1.8 grams of the monomethyl ester of
10,12-docosadiynedioic acid dissolved in 20 ml. of methyl alcohol.
A light pasty mass of methyl lithium 10,12-dicosadiynedioate forms
quickly, is centrifuged therefrom, and the clear liquid thereover
removed. The resulting pasty precipitate is mixed with and
dispersed in 20 ml. of acetone, and then in centrifuged therefrom
and the acetone thereover removed. This lithium salt, still
containing a minute amount of acetone, is washed with water and the
water filtered therefrom. Whereupon the lithium salt, still damp
from the water, is mixed with and readily dispersed in an aqueous
10 percent by weight polyvinyl alcohol solution and flowed to
provide a thin coating thereof on thin film of a polyethylene
terephthalate polymer. This coating then is permitted to air dry.
The resulting product is an image-receptive element comprised of
the polymer film having fine crystalline photosensitive methyl
lithium 10,12-docosadiynedioate fixedly positioned and adhered
thereto by means of the polyvinyl acetate. This element is useful
for direct photographic formation of a visual print-out image
through exposure to ultraviolet 2,537 A. radiation.
EXAMPLE 7
Example 6 is repeated except that in place of the aqueous polyvinyl
alcohol solution there is employed 15 ml. of a 10 percent by weight
N-type ethyl cellulose dissolved in an 80:20 parts by weight
toluene:ethanol solvent. There again results a useful
image-receptive element of utility for direct photographic
formation of a visual print-out image.
Example 8
Example 6 is repeated up to the adding of the lithium salt to the
aqueous 10 percent polyvinyl alcohol solution, then it is heated to
about 60.degree.C. to provide an apparently clear solution. This
clear solution then is permitted to cool to about 25.degree.C.
whereat the lithium salt precipitate reappears to provide an
overall pasty appearing mass. A portion of this pasty appearing
mass is spread as a thin coating on a glass slide and dried in a
forced air oven at about 50.degree.C. The resulting element is very
sensitive to ultraviolet 2,537 A. radiation and useful for direct
photographic formation of a visual print-out image. The image
formed upon such radiation is a dark blue. An exposed element,
having this dark blue image thereon, then is placed on a hot plate
and heated. As the temperature of the element increases the blue
color of the image changes to an orange color, apparently at or
within a temperature range of about 95.degree.-120.degree.C. Upon
removal of the element from the hot plate and cooling of the same,
a reverse color change occurs with the orange colored image going
back to its original dark blue color. In contrast a similar imaged
element containing therein the monomethyl ester of
10,12-docosadiynedioate upon suitable heating irreversibly changes
its image color from a dark blue or purple to an orange to red
color and upon cooling continues to retain its orange to red
coloration.
EXAMPLE 9
Lithium acetate is prepared by suspending 0.42 gram of LiOH.sup..
H.sub.2 O in 5 ml. of methyl alcohol and adding minute drops,
dropwise, of glacial acetic acid thereto until a pH of about 6.0
results. This appeared to require about 1 ml. of the glacial acetic
acid. The above-prepared lithium acetate in methanol then is added
to a 15 ml. methanol solution of 3.8 grams of the monomethyl ester
of 10,12-docosadiynedioate. Upon addition a reaction is observed,
and within several minutes small crystals form and separate. The
crystals are centrifuged therefrom, washed with acetone,
reseparated by centrifuging again, and then washed with distilled
water. The water then is filtered from the crystals and an aqueous
15 percent polyvinyl alcohol solution added thereto and thoroughly
mixed therewith to disperse the fine crystals therein. Coatings of
this polyvinyl alcohol solution containing the fine crystals
dispersed therein then are placed on thin films of polyethylene
terephthalate polymer and are air dried. The resulting element is
useful for direct photographic formation of a visual print-out
image through exposure to ultraviolet 2,537 A. Radiation.
EXAMPLE 10
Methyl Sodium 10,12-Docosadiynedioate
To an aqueous dispersion of a small amount of the monomethyl ester
of 10,12-docosadiynedioic acid in distilled water, there are added,
dropwise, drops of an aqueous 10 percent sodium hydroxide solution
until a pH of about 9 is reached and a clear solution results. This
aqueous solution, now containing methyl sodium
10,12-dicosadiynedioate dissolved therein, is evaporated to
substantial dryness on a paper to provide a deposit of crystalline
methyl sodium 10,12-dicosadiynedioate within and on the paper. Upon
exposure to ultraviolet 2,537 A. radiation, exposed crystals of the
sodium salt slowly, and within less than 5 minutes, undergo a color
change to a light purple color.
In view of the foregoing description and presented illustrative
specific examples of the invention, it will be apparent readily to
one skilled in the art that the invention within its true scope
includes more than that illustrated by specific examples and that
the invention is to be limited only to the extent as set forth in
the appended claims which follow.
* * * * *