U.S. patent number 3,767,414 [Application Number 05/255,617] was granted by the patent office on 1973-10-23 for thermosensitive copy sheets comprising heavy metal azolates and methods for their use.
This patent grant is currently assigned to Minnesota Mining and Manufacturing Company. Invention is credited to Jacquelyn D. Bush, Brian K. Hill, William A. Huffman, Dean R. Lowrey.
United States Patent |
3,767,414 |
Huffman , et al. |
October 23, 1973 |
THERMOSENSITIVE COPY SHEETS COMPRISING HEAVY METAL AZOLATES AND
METHODS FOR THEIR USE
Abstract
Copy-sheets containing heavy metal azolates, such as silver
imidazolates, are imaged by heating with a reducing agent applied
in image-forming pattern. Colored images are then produced in
base-sensitive copy-sheets by heating the imaged azolate sheet
thereagainst.
Inventors: |
Huffman; William A. (White Bear
Lake, MN), Lowrey; Dean R. (North Oaks, MN), Hill; Brian
K. (Village of Cottage Grove, MN), Bush; Jacquelyn D.
(St. Paul, MN) |
Assignee: |
Minnesota Mining and Manufacturing
Company (St. Paul, MN)
|
Family
ID: |
22969138 |
Appl.
No.: |
05/255,617 |
Filed: |
May 22, 1972 |
Current U.S.
Class: |
430/151; 430/155;
430/203; 430/336; 430/616; 430/618 |
Current CPC
Class: |
G03C
1/52 (20130101); G03C 5/56 (20130101); G03C
1/4989 (20130101); G03C 1/73 (20130101) |
Current International
Class: |
G03C
1/52 (20060101); G03C 5/56 (20060101); G03C
1/498 (20060101); G03C 1/73 (20060101); G03c
001/02 (); G03c 001/72 (); B41n 005/00 () |
Field of
Search: |
;96/114.6,114.1
;117/36.8,36.9 ;250/65T |
Other References
chemical Abstracts, 1964, 733 b,c..
|
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Suro Pico; Alfonso T.
Claims
What is claimed is as follows:
1. Method of imaging comprising subjecting a first sheet material
having a stratum containing a polymeric heavy metal azolate to heat
at least at image areas and in the presence of a reducing agent to
provide on said sheet material a visible image.
2. Method of claim 1 wherein said metal is silver.
3. Method of claim 1 wherein said reducing agent is
photosensitive.
4. Method of claim 3 wherein said reducing agent is supplied from a
second sheet held in face-to-face contact with said first sheet
material.
5. Method of claim 4 wherein said second sheet is first exposed to
a light-image to an extent just sufficient to desensitize all of
said reducing agent in the lighted areas.
6. Method of claim 1 including the further step of heating the
imaged first sheet in face-to-face contact with a base sensitive
print sheet.
7. Method of claim 6 wherein said print sheet contains an acid
stabilized diazo.
8. Method of claim 6 wherein said print sheet contains a
base-reactive acid-base indicator.
9. Method of claim 7 wherein said first sheet material includes at
least in the image areas thereof a layer containing a said reducing
agent which is photosensitive.
10. Method of claim 1 wherein said stratum contains a catalytically
small proportion of silver nitrate.
11. Sheet material including a paper-thin backing carrying an
image-forming stratum comprising a heavy metal azolate.
12. Sheet material of claim 11 wherein said heavy metal is
silver.
13. Sheet material of claim 12 wherein said heavy metal azolate is
silver imidazolate.
14. Sheet material of claim 13 wherein said stratum includes a
hindered phenolic reducing agent for silver ion, and
phthalazinone.
15. Sheet material of claim 12 wherein is included a catalytically
small amount of silver nitrate.
16. Sheet material of claim 15 having over said stratum a
coterminous vapor-transmissive polymeric barrier layer and an outer
layer comprising a volatilizable reducing agent for silver ion.
17. Sheet material of claim 11 wherein said heavy metal azolate is
a copper azolate.
18. A print sheet useful in a couplet with the sheet material of
claim 15 in forming an image in color and comprising a
base-reactive color-producing stratum and an outer stratum
containing a photosensitive reducing agent for silver ion.
19. Print sheet of claim 18 wherein the color-producing Stratum
comprises an acid-stabilized diazo and an azo coupler component and
said reducing agent is a substituted .alpha.-naphthol.
20. A couplet of the sheet material of claim 16 and in face-to-face
contact therewith a print sheet having a base-reactive
color-producing stratum and an outer stratum containing a
photosensitive reducing agent for silver ion.
Description
This invention relates to the image recording art particularly as
exemplified by the copying or reproduction of documents, designs,
and similar graphic originals in making projection transparencies
as well as hard copies. In one important aspect there are involved
novel compositions and coated sheet materials.
Heat-sensitive copy-sheets containing heavy metal salts, especially
silver salts, of organic acids have been described, for example in
U.S. Pat. No. 2,910,377. The present invention in one aspect
likewise relates to heat-sensitive sheet materials containing
organic silver or other heavy metal salts but employing
specifically different materials and providing unexpected
advantages.
Heat-sensitive copy-sheets containing organic silver salts have
also been employed in conjunction with light-sensitive components,
for example as described in U.S. Pat. No. 3,094,417. In another
aspect the present invention similarly relates to the recording of
light-images, again using novel materials and with advantageous
results.
A particularly important aspect of the present invention relates to
the formation of images in color, using the heavy metal salt
copy-sheet in an intermediate process step.
It has now been found possible to employ heavy metal, particularly
silver, azolates as components of primary copy-sheets having
improved stability against backgrounding and which are further
useful, e.g., in the preparation of secondary copies in color.
The azoles include the dinitrogen, five membered, unsaturated
heterocyclic compounds having the skeletal structure ##SPC1##
In its simplest form the copy-sheet of the present invention
comprises a film or coating containing a silver imidazolate or
pyrazolate dispersed in a polymeric binder. Amounts of the silver
compound equivalent to from one-half to 14 grams of silver per
square meter are useful. Imaging is accomplished by heating the
coating in the presence of a suitable reducing agent, preferably
together with other auxiliary components as will be further
described. The reducing agent may be locally applied to the sheet,
e.g., by inscribing with an ink containing the material or by
transfer from a source sheet, and the entire sheet then heated.
Alternatively, the reducing agent is supplied over the entire
surface of the copy-sheet either as a separate coating or contained
in a second sheet, and imaging is accomplished by localized
heating, accomplished thermographically or with heated stylus or
type, or by localized removal of the reducing agent followed by
over-all heating.
Hindered phenolic reducing agents, e.g., butylated hydroxytoluenes,
are useful but by themselves require undesirably high temperature
for reaction with the silver salt in reasonable time and are
therefore more effectively used in conjunction with at least minor
proportions of more active reducing agents, e.g., non-hindered
phenols such as methyl gallate or methoxyhydroxynaphthalene. In all
cases, reduction of the silver salt occurs, accompanied by a
visible change in the copy-sheet film or coating.
The copy-sheet showing a visible image obtained as just described
is useful as a permanent record, showing substantially no loss of
density at image areas or darkening of non-image areas during
prolonged storage. The sheet is additionally useful in making
further copies of the image areas in color. For the latter use the
imaged sheet is promptly heated while in contact with a further
sheet or stratum containing a base-sensitive color-producing
system. The volatilizable azole compound released during formation
of the silver image is transferred to the base-sensitive layer and
there causes the formation of a colored image. Preferably the
secondary colored image is formed in a separate sheet or film which
is then removed, leaving the primary silver image in the first
sheet. The base-sensitive sheet may itself carry a layer of
reducing agent for reaction with the silver salt, in which event
both images may be formed simultaneously.
The silver salt of imidazole is a preferred constituent of these
novel copy-sheet materials. Various substituted imidazoles may also
be used, benzimidazole being particularly useful. Mixtures of
azolates may be used, a mixture of a major proportion of silver
imidazolate and a minor proportion of silver benzimidazolate being
particularly advantageous. Pyrazole forms a silver salt with which
visible but weak primary images may be prepared. Azolates of heavy
metals other than silver are somewhat less desirable for producing
dense primary images but are frequently more useful in other ways.
The copper salts, for example, produce low visual density primary
images but which are electrically conductive, and whose
conductivity may be enhanced by electroless plating in the
preparation of printed circuit boards or for other purposes.
Heavy metal salts of various azoles have been reported in chemical
literature. For example, Bauman and Wang, at page 370 of Inorganic
Chemistry, Volume 3, (1964), describe the preparation of silver,
zinc, copper, nickel and cadmium salts, (by them referred to as
"complexes") of imidazole and N-methylimidazole, and the titration
of silver imidazolate with sodium hydroxide. The silver salt of
imidazole is represented by these authors as corresponding on
ultimate analysis to the formula Ag(C.sub.3 H.sub.3 N.sub.2).
However the compound has now been further found to have a molecular
weight of the order of 20,000 and to have very low solubility, and
is therefore to be considered as polymeric in nature, a conclusion
which is further supported by the results of infra-red
analysis.
The methods of preparation of the metal azolates described in the
publication by Bauman and Wang result in products which in many
cases produce only marginally operable copy-sheets. Modifications
of these processes which result in materials of much smaller
particle size are believed to be well within the skill of the art
and involve changes in temperature of reaction mixture, rate of
addition of reactants, concentration of reactants, extent of
agitation, and the like; and reduction in particle size of the
azolates is found to give greatly increased efficiency in copy
sheet applications. In a typical laboratory scale example,
following the general procedure described by Bauman and Wang,
silver nitrate solution is diluted to 1/4 molar and the mixture is
maintained at 2.degree.-5.degree. C. with vigorous agitation during
addition of imidazole. 0.75 Molar sodium hydroxide solution is
added dropwise to a final pH of 10.50, and vigorous agitation is
continued for an additional half hour prior to filtration. The
particle size of the white powdery product obtained after washing
and drying the precipitate is from about 3 microns to substantially
less than 1 micron as determined with a "Quantimet 720" particle
size analyzer using a scanning light beam. Weight loss on heating
in hydrogen is 38.3 - 39.3 percent; theoretical for silver
imidazolate is 38.3 percent.
For coating purposes the metal salt is well dispersed in a liquid
vehicle, together with other components as desired, the degree of
dispersion being sufficient to provide a uniform coating with good
optical properties. For such purposes milling in a ball mill and in
presence of an inert polymeric binder is effective. Vinyl resins,
cellulosic derivatives and various other polymers are all useful;
polyvinyl butyral resin is presently preferred.
Incorporation of hindered phenolic reducing agents in the coating
containing the azolate lessens the amount of reducing agent which
must be supplied at image areas and is usually desirable.
Phthalazinone is a known toner for silver images and is found
useful in the present compositions for such purposes. Pigments are
sometimes used, e.g., to provide opacity or to lighten the
background color and provide improved contrast; zinc oxide is one
example. Plasticizers are sometimes helpful particularly where less
flexible polymeric binders are to be used. It has been discovered
also that catalytically small amounts of silver nitrate are
particularly useful when added to the silver azolate coatings,
which are thereby rendered more sensitive, and require less
reducing agent and toner to provide a given image density.
Commercial diazo paper or film is one example of a secondary image
sheet on which images in color may be formed by heating in contact
with the imaged silver azolate sheet. Such papers contain an
acid-stabilized diazonium salt in conjunction with an azo coupler.
Transfer of imidazole, liberated at image areas from silver
imidazolate, to the diazo sheet results in a coupling reaction
between the diazonium compound and the coupler, with formation of
an azo dye image. Proper selection of diazo and coupler components
makes possible a variety of image colors.
Another form of color image sheet may be identified as containing
in acid form an acid-base indicator which undergoes a visible
change when exposed to the basic azole liberated at the primary
image areas.
The following Examples, in which all proportions are in parts by
weight unless otherwise indicated, will serve further to illustrate
but not to limit the invention.
EXAMPLE 1
Silver imidazolate of minimal particle size is prepared as
described hereinabove. The dry powder (4.5 parts) is mixed into a
12 percent solution of polyvinyl butyral in methylethyl ketone (30
parts) by prolonged milling in a ball mill. The resulting
suspension is coated on both paper and film backing sheets using a
coating bar held at an orifice of four mils (0.1 mm.) and the
coatings are air dried, to provide primary copy-sheets.
A desensitizable intermediate transfer sheet, prepared as described
in U.S. Pat. No. 3,094,417 and containing dye-sensitized
substituted .alpha.-naphthol, is exposed to a light-image to an
extent just sufficient to cause complete desensitization of the
sheet at non-image areas, leaving the .alpha.-naphthol reducing
agent only at the image areas. It is then placed in face-to-face
contact with the primary copy-sheet and the couplet is heated by
passing around a metal roller maintained at 260.degree. F. Upon
separation of the sheets, a visible record of the light-image is
observed on the copy-sheet in the form of brown images on a white
background.
The light-sensitive intermediate transfer sheet may be replaced by
a transfer sheet coated with methyl gallate as used in U.S. Pat.
No. 2,910,377. The transfer sheet is held in face-to-face contact
with the copy-sheet and the couplet is held in heat-conductive
contact against a printed original which is then briefly exposed to
intense infra-red radiation. A copy of the printed image is formed
on the copy-sheet.
The copy formed in the latter instance is placed in face-to-face
contact with a commercial "Ozalid" diazo sheet and the couplet is
held for one-half minute between metal platens maintained at
120.degree.-125.degree. C. A copy of the image areas appears in
color on the surface of the diazo sheet.
EXAMPLE 2
The procedures of Example 1 are duplicated except that silver
benzimidazolate is substituted for the silver imidazolate.
Substantially identical results in terms of image formation and
appearance are obtained, along with improved stability of
background against darkening during prolonged storage in an office
file cabinet.
EXAMPLE 3
Silver imidazolate 4.5 12% Polyvinyl butyral in MEK 30
Phthalazinone 1.25 Reducing agent 0.3 Silver nitrate 0.045
The reducing agent, a hindered phenol consisting of butylated
hydroxytoluene available under the trademark designation "CAO-3,"
is added to the ball milled mixture of the several other components
under brief mixing and the composition is promptly coated on paper
and film backings, and dried. The resulting primary copy sheets are
imaged as described under Example 1 except that in the second
procedure the coating of methyl gallate is applied directly to the
unprinted surface of the printed original instead of on a separate
source sheet. Dense black images are obtained on the primary
copy-sheet in all cases. The sheet both before and after imaging
has high thermal stability.
A secondary sheet is prepared by coating a transparent film backing
with a solution of
4% solution of nitrocellulose in 1:3 alcohol:ether 30.0
1-diazo-2,5-dibutoxy-4-morpholino- benzene sulfate 0.75
3-hydroxy-2-naphthol-phenetide 0.25 3-hydroxy-2-naphthol-toluidide
0.25
applied at a wet thickness of about 3 mils, and dried, in absence
of light. The film backing is a polyester film which has first been
subbed with "duPont 49,000," a soluble polyester of glycols,
phthalic acids and sebacic acid, applied from solution in
trichloroethane, or alternatively has been subjected to a surface
treatment by corona discharge. A freshly imaged primary copysheet
is placed in face-to-face contact with the secondary sheet and the
couplet is heated at 260.degree. F. A faintly yellowish projection
transparency is produced which when used with an overhead projector
rapidly bleaches to a water-white appearance in the non-image areas
and projects a blue image on a white background.
EXAMPLE 4
Polyester film base is coated with a 4 mil layer of a solution of
0.01 part of o-cresolphthalein and ten parts of polyvinyl butyral
in 90 parts of acetone and the coating is dried.
A freshly imaged primary copy sheet prepared and processed as
described under Example 3 is heated for one-half minute at
120.degree. C. in contact with the coated film. A red image is
formed, corresponding to the image of the printed original when
viewed through the transparent film.
Incorporation of zinc oxide in the film coating produces a
white-appearing film on which the red image appears with good
contrast.
EXAMPLE 5
Component A B silver imidazolate 0.5 2.0 reducing agent of Example
3 0.5 0.5 phthalazinone 0.5 0.5 binder (polyvinyl butyral) 2.0 0.5
solvent (MEK) 18.0 10.0
mixtures A and B are separately prepared and coated on paper
substrates, and the dried primary copy-sheets are imaged by heating
in contact with a reflex exposed light-sensitive intermediate
transfer sheet as described under Example 1 and under identical
conditions. Sheet A produces a dense visible image on a
substantially unchanged background; sheet B produces an image of
still greater density but with some background darkening.
EXAMPLE 6
A receptor sheet is prepared by coating polyester film at a coater
bar setting of four mils, with a solution containing
vinyl chloride-acetate copolymer 40
N-(bis(4-dimethylaminophenyl)methyl)pyrrolidine 1 salicylic acid
0.2 methylethyl ketone 160
The dried sheet is a dense cyan color. It is placed against a
freshly imaged primary copy-sheet prepared and processed as
described under Example 3. The couplet is heated briefly. The color
is discharged at image areas, forming a substantially colorless
clear image against a cyan background. On an overhead projector the
thus imaged sheet projects a white image on a blue-green
background.
EXAMPLE 7
Copper (I) imidazolate is prepared by mixing cupric chloride in
0.05 molar solution with an excess of imidazole, adding ascorbic
acid and sodium sulfite to reduce the copper (II) to copper (I) as
shown by conversion from blue to straw color, adding molar sodium
hydroxide solution to cause precipitation, filtering, and washing
and drying the resultant white powder.
A mixture of 10 parts of the powder with 100 parts of 10 percent
solution of polyvinyl butyral in a mixture of methylethyl ketone
and toluene is applied at 6 mils to a polyester film and dried. A
printed sheet having on the reverse surface a coating of methyl
gallate is placed against the coated film in face-to-face contact
and the printed surface is briefly exposed to intense infra-red
radiation, causing heating of the imaged areas and the formation of
a corresponding copper image on the coated film. The copper image
is intensified by dipping the film in an electroless copper plating
solution. The image areas are found to be electrically
conductive.
EXAMPLE 8
A primary copy-sheet prepared as described under Example 3 is first
overcoated with a minimal continuous barrier coating of vinyl
chloride-vinyl acetate copolymer and then with a photo-sensitive
overcoat of dye-sensitized 4-methoxy-1-naphthol. The resulting
integral sheet is first exposed to a light-image to densensitize
the photosensitive layer at the light-struck areas and is then
heated to cause an image-forming reaction at the unexposed areas,
the substituted naphthol diffusing through the very thin separating
layer for reaction with the silver imidazolate.
EXAMPLE 9
A commercial "Ozalid" diazo sheet as used in Example 1 is first
overcoated with a photosensitive layer of dye-sensitized
substituted .alpha.-naphthol as also employed in Example 1. The
sheet is exposed to a light-image sufficient to desensitize the
coating at the light-exposed areas. It is then placed in
face-to-face contact with a primary copy-sheet prepared as
described in Example 3 and the composite is heated. A dense black
image forms on the primary copy-sheet; a colored reverse image
appears on the diazo print sheet. There is involved first a
transfer of the residual .alpha.-naphthol from the diazo sheet to
the copy-sheet where it reacts with the silver salt to form a
silver image, followed by transfer of the liberated imidazole from
the copy-sheet to the diazo sheet where it neutralizes the acid
stabilizer component and permits the diazo and coupler components
to unite with formation of an azo dye image.
* * * * *