U.S. patent application number 09/757464 was filed with the patent office on 2002-02-28 for developer for use with carbonless copy paper and photo imaging system.
Invention is credited to Chaloner-Gill, Benjamin, Shackle, Dale R..
Application Number | 20020025909 09/757464 |
Document ID | / |
Family ID | 23116460 |
Filed Date | 2002-02-28 |
United States Patent
Application |
20020025909 |
Kind Code |
A1 |
Shackle, Dale R. ; et
al. |
February 28, 2002 |
Developer for use with carbonless copy paper and photo imaging
system
Abstract
An electron accepting developer useful for producing visible
images by reaction with an electron donor in carbonless paper and
photo- imaging systems, the developer comprising an acid-treated,
water insoluble alkali metal-modified, inorganic oxide or an
acid-treated molecular sieve.
Inventors: |
Shackle, Dale R.; (Morgan
Hill, CA) ; Chaloner-Gill, Benjamin; (San Jose,
CA) |
Correspondence
Address: |
Thompson Hine & Flory LLP
2000 Courthouse Plaza NE
P. O. Box 8801
Dayton
OH
45401-8801
US
|
Family ID: |
23116460 |
Appl. No.: |
09/757464 |
Filed: |
January 10, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09757464 |
Jan 10, 2001 |
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09290538 |
Apr 12, 1999 |
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6242167 |
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Current U.S.
Class: |
503/201 |
Current CPC
Class: |
B41M 5/3338 20130101;
C01B 13/14 20130101 |
Class at
Publication: |
503/201 |
International
Class: |
B41M 005/30 |
Claims
What is claimed is:
1. A developer material useful for reacting with an electron donor
compound and producing a visible image, said developer comprising
an acid-treated, alkali metal-modified water insoluble inorganic
oxide or an acid-treated molecular sieve.
2. The developer of claim 1 wherein said developer is an inorganic
oxide which exhibits the general formula:
L.sub.w.sup.+aM.sub.y.sup.+b(X.sub.pO- .sub.n).sub.z.sup.-c where L
is lithium, sodium, potassium or hydrogen; M is zinc, magnesium or
calcium; X is silicon, boron, phosphorus, aluminum, sulfur,
titanium or tin; O is oxygen; n is 3 to 25, p is 1 to 6; and each
of w, y and z represents a numeral wherein w(a)+y(b)=z(c).
3. The developer of claim 2 wherein X forms condensed oxides
selected from the group consisting of (Si.sub.3O.sub.9).sup.-6,
(Si.sub.4O.sub.12).sup.- -8, (Si.sub.8O.sub.24).sup.-16,
(Si.sub.2O.sub.5).sup.-2, (Si.sub.6O.sub.17).sup.-4,
(B.sub.2O.sub.5).sup.-4, (B.sub.3O.sub.6).sup.-3,
(P.sub.2O.sub.7).sup.-4, (P.sub.3O.sub.10).sup.-- 5,
(P.sub.3O.sub.9).sup.-3, (S.sub.2O.sub.6).sup.-2.
4. The developer material of claim 1 wherein said acid is nitric
acid or a Lewis acid selected from the group consisting of aluminum
halides, zinc halides, transition metal halides, tin halides, boron
halides, borates, sulfur trioxide, and mixtures thereof.
5. The developer of claim 1 wherein said acid is AlCl.sub.3,
ZnCl.sub.2, MgCl.sub.2, SnCl.sub.4, or mixtures thereof.
6. The developer of claim 2 wherein said inorganic oxide is a
lithium zinc silicate.
7. The developer of claim 2 wherein said inorganic oxide is a
lithium magnesium silicate.
8. The developer of claim 2 wherein said inorganic oxide is a
lithium aluminum zinc silicate.
9. The developer of claim 2 wherein said inorganic oxide is a
lithium zinc borosilicate.
10. The developer of claim 2 wherein said inorganic oxide is a
lithium titanium zinc silicate.
11. The developer of claim 2 wherein said inorganic oxide is a
lithium tin zinc silicate.
12. The developer of claim 2 wherein said inorganic oxide is a
lithium zinc silicon boron oxide.
13. The developer of claim 2 wherein said inorganic oxide is a
lithium zinc silicon phosphate.
14. The developer of claim 2 wherein said inorganic oxide is a
lithium zinc silicon sulfate.
15. The developer of claim 2 wherein said inorganic oxide is a
calcium silicate.
16. The developer of claim 2 wherein said inorganic oxide is a
lithium zinc boron silicon oxide.
17. The developer of claim 2 wherein said inorganic oxide is a
lithium zinc boron sulfur silicon oxide.
18. The developer of claim 2 wherein said inorganic oxide is a
lithium zinc sulfur phosphorus silicon oxide.
19. The developer of claim 2 wherein said inorganic oxide is
lithium zinc aluminate.
20. The developer of claim 2 wherein said inorganic oxide is
lithium zinc borate.
21. The developer of claim 2 wherein said inorganic oxide is
lithium tin borate.
22. The developer of claim 2 wherein said inorganic oxide is
lithium zinc phosphate.
23. The developer of claim 2 wherein said inorganic oxide is
lithium zinc sulfate.
24. The developer of claim 2 wherein said inorganic oxide is
lithium hydrogen zinc phosphate.
25. The developer of claim 2 wherein said inorganic oxide is
lithium hydrogen zinc boron phosphate.
26. The developer of claim 2 wherein said inorganic oxide is sodium
zinc silicate.
27. The developer of claim 2 wherein said inorganic oxide is sodium
zinc borosilicate.
28. The developer of claim 2 wherein said inorganic oxide is
potassium zinc borosilicate.
29. The developer of claim 1 wherein said developer is an
acid-treated molecular sieve, said molecular sieve being prepared
in a reaction which comprises reacting a molecular sieve precursor
in the presence of a templating agent and treating said molecular
sieve with an acid.
30. The developer of claim 29 wherein said molecular sieve
precursor is a silicate, aluminosilicate or borosilicate.
31. The developer of claim 29 wherein said molecular sieve is
tetraethylorthosilicate, tetramethylammonium silicate or
tetraethylammonium silicate.
32. The developer of claim 29 wherein said templating agent is
cetyltrimethyl-ammonium chloride/hydroxide in which about 30% of
the chloride ious have been replaced with hydroxide ions.
33. The developer of claim 29 wherein said acid is nitric acid or a
Lewis acid selected from the group consisting of aluminum halides,
zinc halides, transition metal halides, tin halides, boron halides,
alkyl borates, sulfur trioxide, and mixtures thereof.
34. The developer of claim 33 wherein said acid is AlCl.sub.3,
ZnCl.sub.2, MgCl.sub.2, SnCl.sub.4, or mixtures thereof.
Description
BACKGROUND OF INVENTION
[0001] The present invention relates to a color developer
composition which is designed to be used with recording systems
which employ colorless electron donating materials to form
images.
[0002] Recording materials utilizing developer materials to produce
colored images from colorless or substantially colorless electron
donating materials are well-known. Specific examples of such
recording materials include pressure sensitive carbonless copying
paper, heat-sensitive recording paper, electrothermographic
recording paper, Cycolor.RTM. photographic materials and the like.
They are described in more detail in U.S. Pat. Nos. 2,712,507;
2,730,456; 2,730,457; 3,418,250; 3,432,327; 3,981,821; 3,993,831;
3,996,156; 3,996,405 and 4,000,087. These papers include a
developer sheet (also referred to as a CF (coated front) sheet)
comprising a substrate coated with an electron acceptor which
reacts with a leuco dye transferred to the surface of the developer
sheet to form an image thereon.
[0003] Much research has been directed to developing new and
improved developers for use in the aforementioned recording
materials. Representative examples of the developers that have been
used include phenol derivatives and phenolic resins, biphenols,
methylene bisdiphenols, phenol-formaldehyde novolak resins, metal
processed novolak resins, salicylic acid derivatives and salts. See
U.S. Pat. No. 3,934,070 to Kimura teaching salicyclic acid
derivatives; U.S. Pat. No. 3,244,550 to Farnham teaching biphenols,
diphenols, and resinous products containing them, and U.S. Pat. No.
3,244,549 to Farnham teaching phenol derivatives. Representative
examples of phenol-formaldehyde condensates previously used in the
art are described in numerous patents, including U.S. Pat. No.
3,672,935. Among color developers, phenol-formaldehyde condensates
have been widely used because they exhibit excellent color
development, good coating properties (rheology) and good water
resistance. However, phenolic resins are somewhat colored materials
and become even more colored as they are exposed to ambient
conditions. Such discoloration is a very undesirable attribute in
imaging systems where aesthetic appearance is of extreme
importance. Fading of the image when exposed to extreme
temperatures and humidity is also an undesirable trait of the
currently developer materials. Therefore, it is a principal object
of the present invention to provide an improved developer
composition for use with recording materials which employ leuco
dyes such as carbonless copy paper and photo imaging systems which
overcome some of the deficiencies of prior art developers.
SUMMARY OF THE INVENTION
[0004] The invention is based upon the discovery that molecular
sieves and certain alkali metal-containing water insoluble
inorganic oxides, when treated with an acid, can be used as a
developer for color formers in recording materials.
[0005] The developer material of the present invention may be used
in any recording system in which a color precursor is reacted with
a Lewis acid or electron accepting color developer. Such recording
systems include pressure sensitive recording materials like
carbonless paper, thermal recording systems and photosensitive
systems like the Cycolor.RTM. imaging system described in U.S. Pat.
No. 4,399,209 and related patents. It may be used in a
self-contained system in which the color precursor and developer
are in the same or different layers but present on the same support
or it may be used in a transfer system containing a donor or
imaging sheet and a developer sheet wherein the donor or imaging
sheet contains an image-forming agent capable of reacting with the
developer material to form an image. To produce a visible image,
the donor or imaging sheet is assembled with the developer sheet
and pressure is applied to the sheets to cause transfer of the
image-forming agent to the developer sheet. It is particularly
envisioned that the developer material of the present invention be
coated on a substrate sheet to provide a developer sheet which is
then used in association with an imaging sheet containing
photosensitive microcapsules containing an image-forming agent. The
developer material may also be utilized in a self-contained imaging
format.
DETAILED DESCRIPTION
[0006] In accordance with the present invention, a new color
developer has been discovered which overcomes many of the drawbacks
of the currently used developers.
[0007] In one embodiment of the invention, the developer is an
acid-treated, alkali metal-modified, inorganic oxide such as
silicate, aluminate, borate, borosilicate, phosphate, sulfate,
silicon oxide, etc. A typical example of these developers are
compounds of the general formula:
L.sub.w.sup.+aM.sub.y.sup.+b(X.sub.pO.sub.n).sub.z.sup.-c
[0008] where L is lithium, sodium, potassium or hydrogen; M is
zinc, magnesium or calcium; X is silicon, boron, phosphorus,
aluminum, sulfur, titanium or tin; O is oxygen; n is 3 to 25 and p
is 1 to 6; and each of w, y and z represents a numeral wherein
w(a)+y(b)=z(c) such that the compound is electronically neutral.
The general formula is a simplified definition of the compounds.
More complex materials are possible because of the tendency of some
of the anion forming atoms X to create condensed oxides. Examples
of oxide anion structures include (Si.sub.3O.sub.9).sup.-6,
(Si.sub.4O.sub.12).sup.-8, (Si.sub.8O.sub.24).sup.-16,
(Si.sub.2O.sub.5).sup.-2, (Si.sub.6O.sub.17).sup.-4,
(B.sub.2O.sub.5).sup.-4, (B.sub.3O.sub.6).sup.-3,
(P.sub.2O.sub.7).sup.-4, (P.sub.3O.sub.10).sup.-- 5,
(P.sub.3O.sub.9).sup.-3, (S.sub.2O.sub.6).sup.-2 etc.
[0009] In another embodiment of the invention, the developer is an
acid-treated molecular sieve. Molecular sieves typically comprise a
variety of compositions such as silicates, aluminosilicates,
aluminophosphates, transitional aluminates, and the like. The
inorganic oxide and molecular siene should be essentially water
insoluble, i.e., less than 1% soluble in water.
[0010] The alkali metal-modified inorganic oxides can be prepared
by a process which typically consists of heating the reactants
together in air in a temperature range of about 200 to 1200.degree.
C. for several hours, the temperature used being dependent on the
nature of the reactants. After this reaction is complete an acid
treatment as discussed later is performed on the reaction
product.
[0011] A hydrothermal crystallization process is used for preparing
the molecular sieves.
[0012] This process typically involves of mixing the reactants in a
solvent, usually water, and then heating the mixture in a closed
reactor at 100 to 300.degree. C. for several hours. This reaction
is typically carried out in the presence of a templating agent,
which provides a specific structure. Following the completion of
this reaction, the product is treated with acid. This treatment is
followed by a calcining operation. A variety of templates have been
used to synthesize molecular sieves from molecular sieve precursors
such as the silicate, aluminosilicate, and borosilicate family.
Preferably, the molecular sieve precursor is a silicate such as
tetraethylorthosilicate (TEOS), tetramethylammonium silicate,
tetraethylammonium silicate, etc. Molecular sieves are prepared by
crystallization in an aqueous reaction mixture containing an
inorganic templating agent such as a nitrogen-containing
organo-cation. By varying the synthesis conditions and the
composition of the reaction mixture, different zeolites can be
formed. The role of templating agents in the preparation of
molecular sieves is well known. The positive charge of the
organocation templating species is believed to interact with the
negatively charged silicate subunits, resulting in the
crystallization of the resultant molecular sieve. The organic
cation also greatly affects the characteristics of the gel. These
effects can range from modifying the gel pH to altering the
interactions of the various components via changes in hydration
(and thus solubilities of reagents) and other physical properties
of the gel.
[0013] It has been observed that many of the organocations which
have been used as templates for zeolite synthesis are
conformationally flexible. These molecules can adopt many
conformations in aqueous solution, therefore several templates can
give rise to a particular crystalline product. Rollmann and
Valyocsik, Zeolites 5, 123 (1985) describe how varying the chain
length for a series of alpha, omega-linear diamines resulted in
different intermediate-pore products. It has also been reported by
M. D. Shannon et al., Nature 353, 417-420 (1991) that three
different products which have related framework topologies, can be
formed from three linear bis-quaternary ammonium templates of
varying chain lengths. Altering the structure of a conformationally
rigid organic molecule can also lead to a change in the zeolite
obtained, presumably due to the differing steric demands of each
template. S. I. Zones, Zeolites 9, 458.467 (1989) reported that in
switching from 1,3-dimethylimidazolium hydroxide to
1,3-diisopropylimidazolium hydroxide as template, using the same
starting gel (SiO.sub.2/Al.sub.2O.sub.3=100), the former directs
toward formation of ZSM-22 whereas the latter affords ZSM-23.
[0014] Crystalline zeolitic molecular sieves prepared by
hydrothermal crystallization from reaction mixtures containing
organic templating agents can, in general, be prepared in forms
more highly siliceous than those which are synthesized in the
absence of the organic reagents. It has been proposed that the
crystallization mechanisms are different. In the case of the
low-silica species, the mechanism involves the formation of
stabilized metal cation aluminosilicate complexes and is controlled
largely by the aluminate and aluminosilicate solution chemistry. In
the case of the highly siliceous molecular sieves, a true
templating or clathration mechanism is involved in which the
organic reagent, typically an alkylammonium cation, forms complexes
with silica via hydrogen bonding interactions. These complexes
template or cause replication of the structure via stereo-specific
hydrogen bonding interaction of the quaternary ammonium cation with
the framework oxygens. Whatever the synthesis mechanism, the
templated crystal structures in many instances can be directly
synthesized over a very wide range of silica alumina
(SiO.sub.2/Al.sub.2O.sub.3) ratios. At the extreme upper end of the
range, the compositions are essentially silica polymorphs
containing no AlO.sub.2 tetrahedra in their framework structure.
Those highly siliceous molecular sieves, particularly those having
SiO.sub.2/Al.sub.2O.sub.3 molar ratios of 200 or greater, are
highly hydrophobic and strongly organophilic. As such, they have
found extensive use in molecular sieve separations involving
organic substrates, particularly those in which water vapor cannot
be entirely excluded from contacting the adsorbent.
[0015] In accordance with the invention, the water insoluble alkali
metal-modified inorganic oxides and the molecular sieves are
treated with a Lewis acid. The acid enhances the developing ability
of the molecular sieve or inorganic oxide. Preferably, the acid is
a Lewis acid such as aluminum halides, zinc halides, transition
metal halides, tin halides, boron halides, borates, sulfur
trioxide, etc. Mixtures of the above Lewis acids are also useful in
treating the alkali metal-modified inorganic oxide and molecular
sieve materials. The preferred Lewis acids include AlCl.sub.3,
ZnCl.sub.2, MgCl.sub.2, SnCl.sub.4 and mixtures thereof. Other
acids such as HNO.sub.3 have been used successfully to treat the
developer materials of the present invention.
[0016] The mechanism whereby the acid enhances the developing
ability of the inorganic oxide or molecular sieve is not entirely
clear. The Lewis acid cation may substitute for other cations in
the oxide or sieve, or the Lewis acid may simply be physically
absorbed within the oxide or molecular sieve. The treatment of the
inorganic oxide or sieve is carried out by mixing the inorganic
oxide or sieve with a solution containing about 10 to 20% by weight
of the Lewis acid, allowing the mixture to stand for a suitable
period of time, e.g., 1 to 2 hours, decanting the water, and drying
in the case of the oxide or drying and calcining in the case of the
sieve. Depending upon the nature of the oxide and the Lewis acid,
the mixture may gel in which case there may not be water to decant.
The concentration of the Lewis acid solution and the time the
inorganic oxide or sieve stand in the acid can be adjusted to
control the acidity of the acid treated product such that the
product provides the desired reactivity with the color former and
yields an image with good color density.
[0017] The developer materials of the present invention can be used
alone, combined with each other, or in combination with other
developer materials conventionally employed in carbonless paper.
Examples of conventional developers with which the developer of the
invention may be combined are clay minerals, e.g., acid clay,
active clay, attapulgite, etc.; organic acids such as tannic acid,
gallic acid, propyl gallate, etc.; acid polymers such as
phenol-formaldehyde resins, phenol acetylene condensation resins,
condensates between an organic carboxylic acid having at least one
hydroxy group and formaldehyde, etc.; metal salts or aromatic
carboxylic acids such as zinc salicylate, tin salicylate, zinc
2-hydroxy naphthoate, zinc 3,5 di-tert butyl salicylate, oil
soluble metal salts of phenol-formaldehyde novolak resins (e.g.,
see U.S. Pat. Nos. 3,672,935; 3,732,120 and 3,737,410) such as zinc
modified, oil soluble phenol-formaldehyde resin as disclosed in
U.S. Pat. No. 3,732,120), zinc carbonate etc. and mixtures
thereof
[0018] To produce a developer sheet using the developer material of
the present invention, the developer material, typically ground to
a particle size of about 2 to about 10 microns, is dispersed in a
coating liquid, for example water containing a small amount of a
binder, and coated onto a support. The developer coating liquid is
applied to the surface of the support using methods known in the
art. For example, the developer layer may be formed by applying a
coating composition on a support by air-knife coating, pure blade
coating, rod blade coating, short dwell coating, curtain coating or
die coating. As the support, there may be used paper, plastic film,
synthetic paper, non-woven fabric and the like. The amount of the
coating composition is not particularly limited, but is generally
within the range of about 1 to 20 g/m.sup.2 and, preferably about 2
to 10 g/m.sup.c dry weight. Due to the low viscosity of the coating
formulation, high levels of solids may be added to the dispersion
coating solvent. Levels of solids ranging between about 40 to about
70% may be achieved in accordance with the present invention.
[0019] A small amount of a binder is usually used to bind the color
developer to a support such as paper or PET film. The binder
employed may be a natural binder, a synthetic binder or a
combination thereof. Illustrative examples of such binders include
water-soluble polymers such as starches, e.g., oxidized starch,
enzyme-modified starch, cation-modified starch, esterified starch
and etherified starch; cellulose derivatives, e.g., methyl
cellulose, ethyl cellulose, carboxymethyl cellulose, methoxy
cellulose and hydroxyethyl cellulose; polyvinyl alcohols, e.g.,
completely or partially saponified polyvinyl alcohol,
carboxy-modified polyvinyl alcohol, silicon-modified polyvinyl
alcohol and acetoacetyl-modified polyvinyl alcohol; sodium salt of
polyacrylic acid; polyacrylamide; polyvinylpyrrolidone; acrylic
acid amide-acrylic ester copolymer; acrylic acid amide-acrylic
ester-methacrylic acid copolymer; alkali salt of styrene-maleic
anhydride copolymer; alkali salt of styrene-acrylic acid copolymer;
alkali salt of ethylene-acrylic acid copolymer; alkali salt of
isobutylene-maleic anhydride copolymer; sodium alginate; gelatin;
casein; gum arabic; urea resins and melamine resin; and latexes
such as polyvinylacetate latex, polyurethane latex, polyacrylic
acid latex, polyacrylic ester latex, polybutymethacrylate latex,
styrene-butadiene copolymer latex, vinyl chloride-vinyl acetate
copolymer latex, etylene-vinyl acetate copolymer latex and
styrene-butadiene-acrylate latex, butadiene copolymers, vinylidene
chloride copolymers, carboxylated styrene-alkylalcohol copolymers,
latex, maleic anhydride-styrene copolymer, etc. It is to be
understood that all binders well known as film-forming materials
can be used in this capacity. Typically, the binder is used in an
amount of about 2 to 15% by weight and preferably about 5 to 10% by
weight. Other conventional additives such as surfactants,
ultraviolet absorbers, antioxidants, plasticizers, hardeners, etc.
may be employed in carrying out the invention.
[0020] Further, for the purpose of increasing color developing
ability and light resistance, an inorganic pigment may be added to
the color developer. The inorganic pigment comprises aluminum
silicate, zinc silicate, lead silicate, tin silicate, colloidal
hydrated aluminum silicate, zeolite, bentonite, kaolinite active
clay, acid clay, talc and the like. The amount of inorganic pigment
employed is not critical, for example, more than 1 party by weight,
preferably 10 to 1000 parts by weight per 100 parts by weight of
the metal salt of polymer may be used.
[0021] As indicated above, the developer of the present invention
can be used in association with any transfer image-forming system.
For example, the present invention is particularly useful for
preparing a carbonless manifold form. Carbonless paper is widely
used in the forms industry. A typical carbonless form is made up of
one sheet, known as a CB sheet, which is the first page of the
form, and a second sheet, known as a CF sheet, which is the back
page of the form. Where a form having more than two sheets is
desired, as in the case where more than one copy is required, one
or more sheets known as CFB sheets may be placed between the CF and
the CB sheet. A CB sheet consists of a sheet of paper having a
layer of microcapsules containing a color former coated on its back
side, hence the designation CB or "coated back." A CF sheet
consists of a sheet of paper carrying a layer of a developer
material on its front side or "coated front" which reacts with the
color former to produce a colored mark. A CFB sheet is coated on
its front and back sides. The front is coated with developer and
the back is coated with microcapsules. The manifold carbonless
forms will usually comprise from about 2 to about 10 individual
sheets and preferably from about 2 to about 4 individual sheets per
form. To produce a visible image using the developer sheet of the
present invention, the developer is brought into contact with an
electron donating chromogenic color-forming agent. The
color-forming agent is typically maintained in pressure rupturable
microcapsules in a manner well known in the art.
[0022] Preferably the developer material of the present invention
is used in the photosensitive imaging system described in U.S. Pat.
No. 4,399,209 and others.
[0023] The invention is illustrated in more detail by the following
non-limiting Example.
EXAMPLE 1
[0024] Molecular Sieve
[0025] A 25% water solution of cetyltrimethylammonium chloride
C.sub.16H.sub.33(CH.sub.3).sub.3NCl (Aldrich Chemical Co.) was
batch-exchanged through the hydroxide form of an IRA-400 ion
exchange resin(Rohm and Haas) to produce a solution
(C.sub.16H.sub.33(CH.sub.3).su- b.3NCl/OH) in which approximately
30% of the chloride ions have been replaced by hydroxide ions.
[0026] 30.0 g of the C.sub.16H.sub.33(CH.sub.3).sub.3NCl/OH
solution was mixed with 6.0 g of tertaethylorthosilicate (TEOS) in
a polypropylene bottle and stirred for 1 hour at room temperature.
The bottle (loose cap) was then placed in a 100.degree. C. steam
box for 48 hours. The sample was then dried at room temperature.
The dry sample was then placed in a tube furnace and heated under
N.sub.2 flow at 540 .degree. C. for one hour. The gas flow was then
switched to air and the heating was continued for and addition 6
hours. A white solid resulted. The white solid was then reacted
with a 10% HNO.sub.3 solution for 16 hours. The mixture was
filtered and washed with water. The white solid was dried at
120.degree. C. in air. The material was tested using a spot test
method in which a sample of the powdered material is contacted with
TMPTA solutions of three different color precursors, cyan, magenta
and yellow. Color was developed with all three precursors in the
spot test.
EXAMPLE 2
[0027] Molecular Sieve
[0028] 20.0 g of a C.sub.16H.sub.33(CH.sub.3).sub.3NCl/OH solution
(prepared as in Example #1) was mixed with 0.42 g of NaAlO.sub.2.
Then 10.0 g of a 25% tetramethylammoniumsilicate solution (Aldrich)
was added to the mixture. This addition was followed by 2.5 g of
fumed silica (Aldrich). The resulting mixture was placed in a 125
mL closed Parr Reactor and heated for 24 hours at 120.degree. C.
The mixture was then filtered and washed with water. The solid was
dried at 120 .degree. C. The dried solid was then treated with a
10% HNO.sub.3 solution over night. Following the acid treatment the
sample was filtered and washed with water and dried at 120.degree.
C. A heat treatment of the material was then carried out by heating
the sample in a tube furnace under N.sub.2 flow at 450.degree. C.
followed by heating in air for 3 hours. The sample was then
transferred to an oven and was heated at 500.degree. C. in air for
8 hrs. The sample was tested via the spot method and exhibited
color development.
EXAMPLE 3
[0029] Molecular Sieve
[0030] 20.0 g of a C16H.sub.33(CH.sub.3).sub.3NCl/OH solution
(prepared as in Example #1) was mixed with 0.68 g of ZnCl.sub.2,
10.0 g of a 25% tetramethylammoniumsilicate solution (Aldrich), 2.5
g of fumed silica (Aldrich) and 0.42 g LiOH.H.sub.2O. This mixture
was then placed in a closed 125 ml Parr reactor and heated at
120.degree. C. for 24 hours. The mixture was filtered and the white
solid obtained was washed with water and ethanol. The product was
then dried at 120.degree. C. The sample was then added to 100 ml of
a 10% HNO.sub.3 solution and stirred at room temperature over
night. The mixture was filtered and the solid washed with water.
Drying at 120.degree. C. was the next process step. Finally the
sample was heated under N.sub.2 flow in a tube furnace at
500.degree. C. for one hour, followed by heating in air at
500.degree. C. for 10 hours. The sample was tested via the spot
method and exhibited color development.
EXAMPLE 4
[0031] Molecular Sieve
[0032] 60.0 g of a C.sub.16H.sub.33(CH.sub.3).sub.3NCl/OH solution
(prepared as in Example #1) was mixed with 3.30 g
Na.sub.2SnO.sub.3, 30.0 g of a 25% tetramethylammoniumsilicate
solution (Aldrich) and 7.5 g of fumed silica (Aldrich). The mixture
was placed in a closed 300 mL Parr reactor and heated at
120.degree. C. for 39 hours. The resulting mixture was filtered and
the solid was washed with water and ethanol. The solid was dried at
120.degree. C. and then treated with 400ml of a 20% HNO.sub.3
solution for 20 hours. The mixture was filtered and the solid was
washed with water and ethanol. The sample was dried at 120.degree.
C. A heat treatment consisting of heating under N.sub.2 at
500.degree. C. for 3 hours followed by heating in air at
500.degree. C. for 14 hours completed the material preparation. The
sample was tested via the spot method and exhibited color
development.
EXAMPLE 5
[0033] Molecular Sieve
[0034] 60.0 g of a C.sub.16H.sub.33(CH.sub.3).sub.3NCl/OH solution
(prepared as in Example #1) was mixed with 1.26 g NaAlO.sub.2 and
30.0 g of a 25% tetramethylammoniumsilicate solution (Aldrich).
Then 7.50 g of fumed silica (Aldrich) was added to the mixture. The
resulting mixture was placed in a closed 300 mL Parr reactor and
heated at 120.degree. C. for 24 hours. The white reaction product
was collected on a filter and washed with water. The product was
then heated in air with the following schedule, 3 hours 200.degree.
C., 1 hour 300.degree., 1 hour 400.degree., and 8 hours at
500.degree. C. This material developed color very well in a spot
test. The material was coated onto a plastic sheet using a three
per cent PVA binder. It was then imaged using a commercial
carbonless CB sheet. A black image was produced.
[0035] One half of the product was treated with 200 ml of a 25%
ZnCl.sub.2 for 2 days. The mixture was then filtered and the solid
washed with water. The sample was dried at 125.degree. C. The
sample was tested via the spot method and exhibited color
development. The material was also tested in a carbonless system
and a black image was obtained.
EXAMPLE 6
[0036] Lithium Zinc Silicate, Li.sub.xZn.sub.y(SiO.sub.4).sub.4
[0037] In the amounts shown in the table below, lithium carbonate
(Aldrich Chemical Co.), zinc oxide (Aldrich Chemical Co.) and
silica (Davison Chemical, Grace Division, Grade 22 60 .ANG.,
60.times.200 mesh) were ground in a mortar and then placed in an
alumina crucible and heated to 1100.degree. C. in air for 16 hours.
Once cooled, the materials were treated with a 10% HNO.sub.3
solution (5 g/25-30 mL solution) for a period of 8-16 hours. The
material was filtered, washed with distilled water, and dried at
110.degree. C. for 3-6 hours.
1 Sample 6A x = 14, y = 1 4.30 g Li.sub.2CO.sub.3 0.68 g ZnO 2.00 g
SiO.sub.2 6B x = 12, y = 2 3.69 g Li.sub.2CO.sub.3 1.35 g ZnO 2.00
g SiO.sub.2 6C x = 10, y = 3 3.07 g Li.sub.2CO.sub.3 2.03 g ZnO
2.00 g SiO.sub.2 6D x = 8, y = 4 2.46 g Li.sub.2CO.sub.3 2.71 g ZnO
2.00 g SiO.sub.2 6E x = 6, y = 5 1.84 g Li.sub.2CO.sub.3 3.39 g ZnO
2.00 g SiO.sub.2 6F x = 4, y = 6 1.23 g Li.sub.2CO.sub.3 4.06 g ZnO
2.00 g SiO.sub.2 6G x = 2, y = 7 0.61 g Li.sub.2CO.sub.3 4.74 g ZnO
2.00 g SiO.sub.2
[0038] All of the above samples were tested via the spot method and
exhibited color development.
EXAMPLE 7
[0039] Lithium Magnesium Silicate,
Li.sub.xMg.sub.y(SiO.sub.4).sub.4
[0040] In the shown in the table below, lithium carbonate (Aldrich
Chemical Co.), magnesium oxide (Aldrich Chemical Co.) and silica
(Davison Chemical, Grace Division, Grade 22 60 .ANG., 60.times.200
mesh) were ground in a mortar and then placed in an alumina
crucible and heated to 1100.degree. C. in air for 16 hours. Once
cooled, the materials were treated with a 10% HNO.sub.3 solution (5
g/25-30 mL solution) for a period of 8-16 hours. The material was
filtered, washed with distilled water, and dried at 110.degree. C.
for 3-6 hours.
2 7A x = 14, y = 1 4.30 g Li.sub.2CO.sub.3 0.34 g MgO 2.00 g
SiO.sub.2 7B x = 12, y = 2 3.69 g Li.sub.2CO.sub.3 0.67 g MgO 2.00
g SiO.sub.2 7C x = 10, y = 3 3.07 g Li.sub.2CO.sub.3 1.01 g MgO
2.00 g SiO.sub.2 7D x = 8, y = 4 2.46 g Li.sub.2CO.sub.3 1.34 g MgO
2.00 g SiO.sub.2 7E x = 6, y = 5 1.84 g Li.sub.2CO.sub.3 1.68 g MgO
2.00 g SiO.sub.2 7F x = 4, y = 6 1.23 g Li.sub.2CO.sub.3 2.01 g MgO
2.00 g SiO.sub.2 7G x = 2, y = 7 0.61 g Li.sub.2CO.sub.3 2.35 g MgO
2.00 g SiO.sub.2
[0041] The above samples were tested via the spot method and
exhibited color development.
EXAMPLE 8
[0042] Lithium Zinc Silicate, Li.sub.4Zn.sub.3Si.sub.2O.sub.9
[0043] In the amounts shown in the table below, lithium carbonate
(Aldrich Chemical Co.), zinc oxide (Aldrich Chemical Co.) and
silica (see chart for silica type) were ground in a mortar. Samples
12E-I were mixed with minimal water to form a paste prior to
heating. The paste was placed in an alumina crucible and heated to
100.degree. C. for 4 hours followed by 1100.degree. C. in air for
10-13 hours. Samples 12A, 12C-D did not receive the 4 hour heating
at 100.degree. C. Sample 12B had the following heating regime:
950.degree. C. for 16 hours, followed by 1100.degree. C. for 4
hours. Once cooled, the materials were treated with a 20% HNO.sub.3
solution (5 g/25-30 mL solution) for a period of 8-16 hours. The
material was filtered, washed with distilled water, and dried at
110.degree. C. for 3-6 hours.
3 8A 24.60 g Li.sub.2CO.sub.3 40.63 g ZnO 20.00 g SiO.sub.2 Davison
Chemical, Grace Division, Grade 22 60 .ANG., 60 .times. 200 mesh 8B
3.69 g Li.sub.2CO.sub.3 6.09 g ZnO 3.00 g SiO.sub.2 Davison
Chemical, Grace Division, Grade 22 60 .ANG., 60 .times. 200 mesh 8C
1.23 g Li.sub.2CO.sub.3 4.06 g ZnO 2.00 g SiO.sub.2 Davison
Chemical, Grace Division, Grade 22 60 .ANG., 60 .times. 200 mesh 8D
6.15 g Li.sub.2CO.sub.3 20.3 g ZnO 10.00 g SiO.sub.2 Davison
Chemical, Grace Division, Grade 22 60 .ANG., 60 .times. 200 mesh 8E
6.15 g Li.sub.2CO.sub.3 20.30 g ZnO 10.00 g SiO.sub.2 Davison
Chemical, Grace Division, Grade 22 60 .ANG., 60 .times. 200 mesh 8F
6.15 g Li.sub.2CO.sub.3 20.30 g ZnO 10.00 g SiO.sub.2 Synthetic
Amorphous Precipitated Silica (Sipernat-22), Degussa Corp. 8G 6.15
g Li.sub.2CO.sub.3 20.30 g ZnO 10.00 g SiO.sub.2 Amorphous
Precipitated Silica, FK-310, Degussa Corp. 8H 18.45 g
Li.sub.2CO.sub.3 60.90 g ZnO 30.00 g SiO.sub.2 Synthetic Amorphous
Precipitated Silica (Sipernat-22), Degussa Corp. 8I 18.45 g
Li.sub.2CO.sub.3 60.90 g ZnO 30.00 g SiO.sub.2 Synthetic Amorphous
Precipitated Silica (Sipernat-22), Degussa Corp.
[0044] The above samples were tested via the spot method and
exhibited color development.
[0045] After cooling, Example 8A was divided into two samples and
treated with a 10% SnCl.sub.4 and a 10% ZnCl.sub.2 solution for 16
hours, respectively. The materials were washed with distilled water
and dried at 110.degree. C. for 3-6 hours. Both samples were tested
via the spot method and exhibited color development.
EXAMPLE 9
[0046] Lithium Aluminum Zinc Silicate,
Li.sub.4Al.sub.xZn.sub.3Si.sub.2-xO- .sub.9-0.5x
[0047] In the amounts shown in the table below, lithium carbonate
(Aldrich Chemical Co.), zinc oxide (Aldrich Chemical Co.), aluminum
hydroxide (Alfa-Aesar) and silica (see chart for silica type) were
ground in a mortar. Samples 13E-13H were mixed with minimal water
to form a paste prior to heating. All samples were heated in an
alumina crucible. Samples 13A-13B were heated to 950.degree. C. in
air for 16 hours, followed by heating at 1100.degree. C. for 4
hours, whereas samples 13C-13H were heated at 1100.degree. C. for
10-16 hours. Once cooled, the materials
4 9A x = 0.5 3.69 g Li.sub.2CO.sub.3 6.09 g ZnO 1.24 g Al(OH).sub.3
2.25 g SiO.sub.2 Davison Chemical, Grace Division, Grade 22 60
.ANG., 60 .times. 200 mesh 9B x = 1.0 3.69 g Li.sub.2CO.sub.3 6.09
g ZnO 2.48 g Al(OH).sub.3 1.50 g SiO.sub.2 Davison Chemical, Grace
Division, Grade 22 60 .ANG., 60 .times. 200 mesh 9C x = 0.1 1.51 g
Li.sub.2CO.sub.3 5.00 g ZnO 0.20 g Al(OH).sub.3 2.34 g SiO.sub.2
Davison Chemical, Grace Division, Grade 22 60 .ANG., 60 .times. 200
mesh 9D x = 0.1 1.23 g Li.sub.2CO.sub.3 4.06 g ZnO 0.165 g
Al(OH).sub.3 1.90 g fumed SiO.sub.2 Aldrich Chemical Co., 0.014
.mu..mu. particle size 9E x = 0.1 6.15 g Li.sub.2CO.sub.3 20.30 g
ZnO 0.825 g Al(OH).sub.3 9.50 g SiO.sub.2 Davison Chemical, Grace
Division, Grade 22 60 .ANG., 60 .times. 200 mesh 9F x = 0.1 6.15 g
Li.sub.2CO.sub.3 20.30 g ZnO 0.825 g Al(OH).sub.3 9.50 g fumed
SiO.sub.2 Aldrich Chemical Co., 0.014 .mu..mu.particle size 9G x =
0.1 6.15 g Li.sub.2CO.sub.3 20.30 g ZnO 0.825 g Al(OH).sub.3 9.50 g
SiO.sub.2 Synthetic Amorphous Precipitated Silica (Sipernat-22),
Degussa Corp. 9H x = 0.1 6.15 g Li.sub.2CO.sub.3 20.30 g ZnO 0.825
g Al(OH).sub.3 9.50 g SiO.sub.2 Amorphous Precipitated Silica,
FK-310, Degussa Corp.
[0048] The above samples were tested via the spot method and
exhibited color development.
EXAMPLE 10
[0049] Lithium Zinc Borosilicate,
Li.sub.4B.sub.xZn.sub.3Si.sub.2-xO.sub.9- -0.5x
[0050] In the amounts shown in the table below, lithium carbonate
(Aldrich Chemical Co.), zinc oxide (Aldrich Chemical Co.), boric
acid (Aldrich Chemical Co.) and silica (see chart for silica type)
were ground in a mortar. Samples 16D- 16G, 16I were mixed with
water to form a paste prior to heating. The powder or paste was
then placed in an alumina crucible and heated to 950.degree. C. in
air for 16 hours, followed by heating at 1100.degree. C. for 4
hours for samples 14A-B whereas samples 14C-14I were heated to
1100.degree. C. in air for 10-12 hours. Once cooled, the materials
were treated with a 10% HNO.sub.3 solution (5 g/25-30 mL solution)
for a period of 8-16 hours. The samples were filtered, washed with
distilled water, and dried at 110.degree. C. for 3-6 hours.
5 10A x = 0.5 3.69 g Li.sub.2CO.sub.3 6.09 g ZnO 0.77 g
H.sub.3BO.sub.3 2.25 g SiO.sub.2 Davison Chemical, Grace Division,
Grade 22 60 .ANG., 60 .times. 200 mesh 10B x = 1.0 3.69 g
Li.sub.2CO.sub.3 6.09 g ZnO 1.54 g H.sub.3BO.sub.3 1.50 g SiO.sub.2
Davison Chemical, Grace Division, Grade 22 60 .ANG., 60 .times. 200
mesh 10C x = 0.1 1.51 g Li.sub.2CO.sub.3 5.00 g ZnO 0.13 g
H.sub.3BO.sub.3 2.34 g fumed SiO.sub.2 Aldrich Chemical Co., 0.014
.mu..mu. particle size 10D x = 0.1 6.15 g Li.sub.2CO.sub.3 20.30 g
ZnO 0.51 g H.sub.3BO.sub.3 9.50 g SiO.sub.2 Davison Chemical, Grace
Division, Grade 22 60 .ANG., 60 .times. 200 mesh 10B x = 0.1 6.15 g
Li.sub.2CO.sub.3 20.30 g ZnO 0.51 g H.sub.3BO.sub.3 9.50 g fumed
SiO.sub.2 Aldrich Chemical Co., 0.014 .mu..mu. particle size 10F x
= 0.1 6.15 g Li.sub.2CO.sub.3 20.30 g ZnO 0.51 g H.sub.3BO.sub.3
9.50 g SiO.sub.2 Synthetic Amorphous Precipitated Silica
(Sipernat-22), Degussa Corp. 10G x = 0.1 6.15 g Li.sub.2CO.sub.3
20.30 g ZnO 0.51 g H.sub.3BO.sub.3 9.50 g SiO.sub.2 Amorphous
Precipitated Silica, FK-310, Degussa Corp. 10H x = 0.1 18.16 g
Li.sub.2CO.sub.3 60.00 g ZnO 1.52 g H.sub.3BO.sub.3 28.06 g
SiO.sub.2 Davison Chemical, Grace Division, Grade 22 60 .ANG., 60
.times. 200 mesh 10I x = 0.1 18.16 g Li.sub.2CO.sub.3 60.00 g ZnO
1.52 g H.sub.3BO.sub.3 28.06 g fumed SiO.sub.2 Aldrich Chemical
Co., 0.014 .mu..mu. particle size 10J x = 0.1 18.16 g
Li.sub.2CO.sub.3 60.00 g ZnO 1.52 g H.sub.3BO.sub.3 28.06 g
SiO.sub.2 Synthetic Amorphous Precipitated Silica (Sipernat-22),
Degussa Corp.
[0051] The above samples were tested via the spot method and
exhibited color development.
EXAMPLE 11
[0052] Lithium Titanium Zinc Silicate,
Li.sub.4Zn.sub.6(Si.sub.1.9Ti.sub.0- .1O.sub.4).sub.4
[0053] In a mortar, 1.51 g of lithium carbonate (Aldrich Chemical
Co.), 5.00 g of zinc oxide (Aldrich Chemical Co.), 2.34 g of silica
(Davison Chemical, Grace Division, Grade 22 60 .ANG., 60.times.200
mesh) and 0.16 g of titanium dioxide (Aldrich Chemical Co.) were
ground and placed in an alumina crucible and heated to 1100.degree.
C. in air for 16 hours. Once cooled, the materials were treated
with a 10% HNO.sub.3 solution (5 g/25-30 mL solution) for a period
of 8-16 hours. The sample was filtered, washed with distilled
water, and dried at 110.degree. C. for 3-6 hours. The above sample
was tested via the spot method and exhibited color development.
EXAMPLE 12
[0054] Lithium Tin Zinc Silicate,
Li.sub.4Zn.sub.6(Si.sub.1.9Sn.sub.0.1O.s- ub.4).sub.4
[0055] In a mortar, 1.51 g of lithium carbonate (Aldrich Chemical
Co.), 5.00 g of zinc oxide (Aldrich Chemical Co.), 2.34 g of silica
(Davison Chemical, Grace Division, Grade 22 60 .ANG., 60.times.200
mesh) and 0.31 g of tin dioxide (Aldrich Chemical Co.) were ground
and placed in an alumina crucible and heated to 1100.degree. C. in
air for 16 hours. Once cooled, the materials were treated with a
10% HNO.sub.3 solution (5 g/25-30 mL solution) for a period of 8-16
hours. The sample was filtered, washed with distilled water, and
dried at 110.degree. C. for 3-6 hours. The above sample was tested
via the spot method and exhibited color development.
EXAMPLE 13
[0056] Lithium Aluminum Zinc Silicate,
Li.sub.4Zn.sub.6(Si.sub.1-nAl.sub.n- O.sub.(4-0.5n)).sub.4
[0057] In the amounts shown in the table below, aluminum hydroxide
(Alfa-Aesar), silica (Davison Chemical, Grace Division, Grade 22 60
.ANG., 60.times.200 mesh), lithium carbonate (Aldrich Chemical Co.)
and zinc oxide (Aldrich Chemical Co.), were ground in a mortar and
then placed in an alumina crucible and heated to 110.degree. C. for
12 hours. Once cooled, the materials were treated with a 10%
HNO.sub.3 solution (5 g/25-30 mL solution) for a period of 8-16
hours. The samples were filtered, washed with distilled water, and
dried at 110.degree. C. for 3-6 hours.
6 13A, n = 0 0.00 g 2.00 g SiO.sub.2 1.23 g Li.sub.2CO.sub.3 4.06 g
ZnO Al(OH).sub.3 13B, n = 0.01 0.033 g 1.98 g SiO.sub.2 1.23 g
Li.sub.2CO.sub.3 4.06 g ZnO Al(OH).sub.3 13C, n = 0.03 0.099 g 1.94
g SiO.sub.2 1.23 g Li.sub.2CO.sub.3 4.06 g ZnO Al(OH).sub.3 13D, n
= 0.05 0.165 g 1.90 g SiO.sub.2 1.23 g Li.sub.2CO.sub.3 4.06 g ZnO
Al(OH).sub.3 13E, n = 0.07 0.231 g 1.86 g SiO.sub.2 1.23 g
Li.sub.2CO.sub.3 4.06 g ZnO Al(OH).sub.3 13F, n = 0.09 0.298 g 1.82
g SiO.sub.2 1.23 g Li.sub.2CO.sub.3 4.06 g ZnO Al(OH).sub.3 13G, n
= 0.11 0.364 g 1.78 g SiO.sub.2 1.23 g Li.sub.2CO.sub.3 4.06 g ZnO
Al(OH).sub.3 13H, n = 0.13 0.430 g 1.74 g SiO.sub.2 1.23 g
Li.sub.2CO.sub.3 4.06 g ZnO Al(OH).sub.3 13I, n = 0.15 0.496 g 1.70
g SiO.sub.2 1.23 g Li.sub.2CO.sub.3 4.06 g ZnO Al(OH).sub.3
[0058] The above samples were tested via the spot method and
exhibited color development.
EXAMPLE 14
[0059] Lithium Zinc Silicate, Li.sub.4Zn.sub.3Si.sub.2O.sub.9
[0060] In the amounts shown in the table below, lithium carbonate
(Aldrich Chemical Co.), zinc oxide (Aldrich Chemical Co.) and fumed
silica (Aldrich Chemical Co., 0.014 .mu..mu. particle size) were
ground in a mortar and placed in an alumina crucible and heated in
air at 110.degree. C. for 10-12 hours. Once cooled, the materials
were treated with a 20% HNO.sub.3 solution (5 g/25-30 mL solution)
for a period of 8-16 hours. The samples were filtered, washed with
distilled water, and dried at 110.degree. C. for 3-6 hours.
7 14A 2.00 g SiO.sub.2 1.23 g Li.sub.2CO.sub.3 4.06 g ZnO 14B 10.00
g SiO.sub.2 6.15 g Li.sub.2CO.sub.3 20.3 g ZnO
[0061] The above samples were tested via the spot method and
exhibited color development.
EXAMPLE 15
[0062] Lithium Zinc Aluminate
[0063] In a mortar, 0.13 g of lithium carbonate (Aldrich Chemical
Co.), 0.578 g of zinc oxide (Aldrich Chemical Co.), and 20.00 g
aluminum hydroxide (Alfa-Aesar) were ground and placed in an
alumina crucible and heated to 1000.degree. C. in air for 12-16
hours. Once cooled, the materials were treated with a 10% HNO.sub.3
solution (5 g/25-30 mL solution) for a period of 8-16 hours. The
material was filtered, washed with distilled water, and dried at
110.degree. C. for 3-6 hours. The above sample was tested via the
spot method and exhibited color development.
EXAMPLE 16
[0064] Lithium Zinc Borate
[0065] In the amounts shown in the table below, a lithium source
(Aldrich Chemical Co.), zinc oxide (Aldrich Chemical Co.) and boric
acid (Aldrich Chemical Co.) were ground in a mortar and placed in
an alumina crucible and heated in air at 425.degree. C. for 12-16
hours. Once cooled, the materials were treated with a 10% or a 20%
HNO.sub.3 solution (5 g/25-30 mL solution) for a period of 8-16
hours. The material was filtered, washed with distilled water, and
dried at 110.degree. C. for 3-6 hours.
8 16A 0.18 g LiOH 0.70 g ZnO 15.00 g H.sub.3BO.sub.3 16B 0.71 g
Li.sub.2CO.sub.3 2.80 g ZnO 60.00 g H.sub.3BO.sub.3 16C 0.18 g
Li.sub.2CO.sub.3 1.40 g ZnO 15.00 g H.sub.3BO.sub.3 16D 0.38 g LiOH
1.46 g ZnO 15.00 g H.sub.3BO.sub.3 16E 0.60 g LiOH 2.32 g ZnO 15.00
g H.sub.3BO.sub.3 16F 0.85 g LiOH 3.29 g ZnO 15.00 g
H.sub.3BO.sub.3 16G 1.13 g LiOH 4.39 g ZnO 15.00 g H.sub.3BO.sub.3
16H 1.45 g LiOH 5.64 g ZnO 15.00 g H.sub.3BO.sub.3
[0066] The above samples were tested via the spot method and
exhibited color development.
EXAMPLE 17
[0067] Lithium Tin Borate
[0068] In the amounts shown in the table below, lithium hydroxide
monohydrate (Aldrich Chemical Co.), tin dioxide (Aldrich Chemical
Co.) and boric acid (Aldrich Chemical Co.) were ground in a mortar
and placed in an alumina crucible and heated in air at 425.degree.
C. for 12-16 hours. Once cooled, the materials were treated with a
10% or a 20% HNO.sub.3 solution (5 g/25-30 mL solution) for a
period of 8-16 hours. The sample was filtered, washed with
distilled water, and dried at 110.degree. C. for 3-6 hours.
9 17A 0.38 g LiOH 2.70 g SnO.sub.2 15.00 g H.sub.3BO.sub.3 17B 0.60
g LiOH 4.30 g SnO.sub.2 15.00 g H.sub.3BO.sub.3 17C 0.85 g LiOH
6.09 g SnO.sub.2 15.00 g H.sub.3BO.sub.3 17D 1.13 g LiOH 8.13 g
SnO.sub.2 15.00 g H.sub.3BO.sub.3 17E 1.45 g LiOH 10.44 g SnO.sub.2
15.00 g H.sub.3BO.sub.3
[0069] The above samples were tested via the spot method and
exhibited color development.
EXAMPLE 18
[0070] Lithium Zinc Silicon Boron Oxide
[0071] In the amounts shown in the table below, lithium hydroxide
monohydrate (Aldrich Chemical Co.), zinc oxide (Aldrich Chemical
Co.), boric acid (Aldrich Chemical Co.) and silicic acid (Aldrich
Chemical Co.) were ground in a mortar and placed in an alumina
crucible. Samples 22A-C were heated in air at 450.degree. C. for
12-16 hours. Samples 22B-C received an additional heating at
500.degree. C. in air for 8 hours. Samples 22D-Q were heated in air
at 500.degree. C. for 12 hours. Once cooled, the materials were
treated with a 10% or a 20% HNO.sub.3 solution (5 g/25-30 mL
solution) for a period of 8-16 hours. The samples were filtered,
washed with distilled water, and dried at 110.degree. C. for 3-6
hours.
10 18A 0.38 g LiOH 1.46 g ZnO 10.00 g H.sub.3BO.sub.3 6.32 g
H.sub.2SiO.sub.3 18B 0.38 g LiOH 1.46 g ZnO 10.00 g H.sub.3BO.sub.3
3.61 g H.sub.2SiO.sub.3 18C 0.38 g LiOH 1.46 g ZnO 10.00 g
H.sub.3BO.sub.3 4.54 g H.sub.2SiO.sub.3 18D 0.38 g LiOH 1.46 g ZnO
10.00 g H.sub.3BO.sub.3 6.32 g H.sub.2SiO.sub.3 18E 0.38 g LiOH
1.46 g ZnO 10.00 g H.sub.3BO.sub.3 2.00 g H.sub.2SiO.sub.3 18F 0.38
g LiOH 1.46 g ZnO 10.00 g H.sub.3BO.sub.3 1.00 g H.sub.2SiO.sub.3
18G 0.38 g LiOH 1.46 g ZnO 10.00 g H.sub.3BO.sub.3 8.10 g
H.sub.2SiO.sub.3 18H 0.38 g LiOH 1.46 g ZnO 10.00 g H.sub.3BO.sub.3
10.00 g H.sub.2SiO.sub.3 18I 0.38 g LiOH 1.00 g ZnO 10.00 g
H.sub.3BO.sub.3 3.6l g H.sub.2SiO.sub.3 18J 0.26 g LiOH 1.00 g ZnO
10.00 g H.sub.3BO.sub.3 3.61 g H.sub.2SiO.sub.3 18K 0.38 g LiOH
2.00 g ZnO 10.00 g H.sub.3BO.sub.3 3.6l g H.sub.2SiO.sub.3 18L 0.52
g LiOH 2.00 g ZnO 10.00 g H.sub.3BO.sub.3 3.6l g H.sub.2SiO.sub.3
18M 0.38 g LiOH 3.00 g ZnO 10.00 g H.sub.3BO.sub.3 3.61 g
H.sub.2SiO.sub.3 18N 0.78 g LiOH 3.00 g ZnO 10.00 g H.sub.3BO.sub.3
3.6l g H.sub.2SiO.sub.3 18O 0.38 g LiOH 4.00 g ZnO 10.00 g
H.sub.3BO.sub.3 3.6l g H.sub.2SiO.sub.3 18P 1.04 g LiOH 4.00 g ZnO
10.00 g H.sub.3BO.sub.3 3.6l g H.sub.2SiO.sub.3 18Q 3.04 g LiOH
32.00 g ZnO 80.00 g H.sub.3BO.sub.3 28.80 g H.sub.2SiO.sub.3
[0072] The above samples were tested via the spot method and
exhibited color development.
EXAMPLE 19
[0073] Lithium Zinc Phosphate, Li.sub.3Zn.sub.xPO.sub.x+4
[0074] In the amounts shown in the table below, lithium phosphate,
tribasic (Aldrich Chemical Co.) and zinc oxide (Aldrich Chemical
Co.) were ground in a mortar and placed in an alumina crucible and
heated in air at 800.degree. C. for 12-16 hours. Once cooled, the
materials were treated with a 10% HNO.sub.3 solution (5 g/25-30 mL
solution) for a period of 8-16 hours. The samples were filtered,
washed with distilled water, and dried at 110.degree. C. for 3-6
hours.
11 19A x = 1 11.58 g Li.sub.3PO.sub.4 8.14 g ZnO 19B x = 2 11.58 g
Li.sub.3PO.sub.4 16.28 g ZnO 19C x = 3 5.79 g Li.sub.3PO.sub.4
16.28 g ZnO
[0075] The above samples were tested via the spot method and
exhibited color development.
EXAMPLE 20
[0076] Lithium Zinc Silicon Phosphate
[0077] In amounts shown in the table below, lithium phosphate,
tribasic (Aldrich Chemical Co.), zinc oxide (Aldrich Chemical Co.)
and silicic acid (Aldrich Chemical Co.) were ground in a mortar and
placed in an alumina crucible and heated to 800.degree. C. in air
for 16 hours. Once cooled, the materials were treated with a 10%
HNO.sub.3 solution (5 g/25-30 mL solution) for a period of 8-16
hours. The samples were filtered, washed with distilled water, and
dried at 110.degree. C. for 3-6 hours.
12 20A 11.58 g Li.sub.3PO.sub.4 6.76 g ZnO 1.20 g H.sub.2SiO.sub.3
20B 8.90 g Li.sub.3PO.sub.4 1.88 g ZnO 4.20 g H.sub.2SiO.sub.3 20C
8.90 g Li.sub.3PO.sub.4 3.13 g ZnO 3.00 g H.sub.2SiO.sub.3 20D 8.90
g Li.sub.3PO.sub.4 4.38 g ZnO 1.80 g H.sub.2SiO.sub.3
[0078] The above samples were tested via the spot method and
exhibited color development.
EXAMPLE 21
[0079] Lithium Zinc Sulfate, Li.sub.2Zn.sub.4SO.sub.x+4
[0080] In the amounts shown in the table below, anhydrous lithium
sulfate (Alfa-Aesar) and zinc oxide (Aldrich Chemical Co.) were
ground in a mortar and placed in an alumina crucible and heated in
air at 800.degree. C. for 12-16 hours. Once cooled, the materials
were treated with a 10% HNO.sub.3 solution (5 g/25-30 mL solution)
for a period of 8-16 hours. The material was filtered, washed with
distilled water, and dried at 110.degree. C. for 3-6 hours.
13 21A x = 1 10.99 g Li.sub.2SO.sub.4 8.14 g ZnO 21B x = 2 5.50 g
Li.sub.2SO.sub.4 8.14 g ZnO 21C x = 3 2.75 g Li.sub.2SO.sub.4 8.14
g ZnO
[0081] The above samples were tested via the spot method and
exhibited color development.
EXAMPLE 22
[0082] Lithium Zinc Silicon Sulfate
[0083] In the amounts shown in the table below, anhydrous lithium
sulfate (Alfa-Aesar), zinc oxide (Aldrich Chemical Co.) and silicic
acid (Aldrich Chemical Co.) were ground in a mortar and placed in
an alumina crucible and heated to 800.degree. C. in air for 16
hours. Once cooled, the materials were treated with a 10% HNO.sub.3
solution (5 g/25-30 mL solution) for a period of 8-16 hours. The
samples were filtered, washed with distilled water, and dried at
110.degree. C. for 3-6 hours.
14 22A 10.99 g Li.sub.2SO.sub.4 6.76 g ZnO 1.20 g H.sub.2SiO.sub.3
22B 8.45 g Li.sub.2SO.sub.4 1.88 g ZnO 4.20 g H.sub.2SiO.sub.3 22C
8.45 g Li.sub.2SO.sub.4 3.13 g ZnO 3.00 g H.sub.2SiO.sub.3 22D 8.45
g Li.sub.2SO.sub.4 4.38 g ZnO 1.80 g H.sub.2SiO.sub.3
[0084] The above samples were tested via the spot method and
exhibited color development.
EXAMPLE 23
[0085] Lithium Hydrogen Zinc Phosphate,
Li.sub.2H.sub.3ZnPO.sub.4
[0086] In a mortar, 8.39 g of lithium hydroxide monohydrate
(Aldrich Chemical Co.), 8.14 g of zinc oxide (Aldrich Chemical
Co.), and 13.21 g of ammonium phosphate, dibasic (EM Science) were
ground and placed in an alumina crucible and heated to 500.degree.
C. in air for 16 hours. Once cooled, the materials were treated
with a 25% ZnCl.sub.2 solution (5 g/25-30 mL solution) for a period
of 8-16 hours. The sample was filtered, washed with distilled
water, and dried at 110.degree. C. for 3-6 hours. The sample was
tested via the spot method and exhibited color development.
EXAMPLE 24
[0087] Lithium Hydrogen Zinc Boron Phosphate
[0088] In a mortar, 8.39 g of lithium hydroxide monohydrate
(Aldrich Chemical Co.), 6.76 g of zinc oxide (Aldrich Chemical
Co.), 1.24 g of boric acid (Aldrich Chemical Co.) and 13.21 g of
ammonium phosphate, dibasic (EM Science) were ground and placed in
an alumina crucible and heated to 500.degree. C. in air for 16
hours. Once cooled, the materials were treated with a 25%
ZnCl.sub.2 solution (5 g/25-30 mL solution) for a period of 8-16
hours. The sample was filtered, washed with distilled water, and
dried at 110.degree. C. for 3-6 hours. The sample was tested via
the spot method and exhibited color development.
EXAMPLE 25
[0089] Lithium Calcium Silicate,
Li.sub.2Ca.sub.6(SiO.sub.4).sub.4
[0090] In a mortar, 1.23 g of lithium carbonate (Aldrich Chemical
Co.), 5.00 g of calcium carbonate (Aldrich Chemical Co.) and 2.00 g
silica (Synthetic Amorphous Precipitated Silica (Sipernat-22),
Degussa Corp.) were ground and placed in an alumina crucible and
heated in air at 1100.degree. C. for 12 hours. Once cooled, the
materials were treated with a 10% HNO.sub.3 solution (5 g/25-30 mL
solution) for a period of 8-16 hours. The sample was filtered,
washed with distilled water, and dried at 110.degree. C. for 3-6
hours. The above sample was tested via the spot method and
exhibited color development.
EXAMPLE 26
[0091] Lithium Zinc Boron Silicon Oxide
[0092] In the amounts shown in the table below, a lithium boron
source (Alfa-Aesar), zinc oxide (Aldrich Chemical Co.) and silicic
acid (Aldrich Chemical Co.) were ground in a mortar and placed in
an alumina crucible and heated to 800.degree. C. C in air for 16
hours. Once cooled, the materials were treated with a 10% HNO.sub.3
solution (5 g/25-30 mL solution) for a period of 8-16 hours. The
samples were filtered, washed with distilled water, and dried at
110.degree. C. for 3-6 hours.
15 26A 3.82 g LiBO.sub.2 1.88 g ZnO 4.20 g H.sub.2SiO.sub.3 26B
3.52 g LiBO.sub.2 3.13 g ZnO 3.00 g H.sub.2SiO.sub.3 26C 3.52 g
LiBO.sub.2 4.38 g ZnO 1.80 g H.sub.2SiO.sub.3 26D 3.82 g
Li.sub.2B.sub.4O.sub.7 1.88 g ZnO 4.20 g H.sub.2SiO.sub.3 26B 3.82
g Li.sub.2B.sub.4O.sub.7 3.13 g ZnO 3.00 g H.sub.2SiO.sub.3
[0093] The above samples were tested via the spot method and
exhibited color development.
EXAMPLE 27
[0094] Lithium Zinc Boron Sulfur Silicon Oxide
[0095] In the amounts shown in the table below, anhydrous lithium
sulfate (Alfa-Aesar), a lithium boron source (Alfa-Aesar), zinc
oxide (Aldrich Chemical Co.) and silicic acid (Aldrich Chemical
Co.) were ground in a mortar and placed in an alumina crucible and
heated to 750.degree. C. in air for 16 hours. Once cooled, the
materials were treated with a 10% HNO.sub.3 solution (5 g/25-30 mL
solution) for a period of 8-16 hours. The samples were filtered,
washed with distilled water, and dried at 110.degree. C. for 3-6
hours.
16 27A 8.84 g Li.sub.2SO.sub.4 4.00 g LiBO.sub.2 3.93 g ZnO 8.79 g
H.sub.2SiO.sub.3 27B 8.84 g Li.sub.2SO.sub.4 4.00 g LiBO.sub.2 6.54
g ZnO 6.28 g H.sub.2SiO.sub.3 27C 8.84 g Li.sub.2SO.sub.4 4.00 g
LiBO.sub.2 9.16 g ZnO 3.77 g H.sub.2SiO.sub.3 27D 4.42 g
Li.sub.2SO.sub.4 6.80 g Li.sub.2B.sub.4O.sub.7 1.97 g ZnO 4.40 g
H.sub.2SiO.sub.3 27E 4.42 g Li.sub.2SO.sub.4 6.80 g
Li.sub.2B.sub.4O.sub.7 3.27 g ZnO 3.14 g H.sub.2SiO.sub.3 27F 4.42
g Li.sub.2SO.sub.4 6.80 g Li.sub.2B.sub.4O.sub.7 4.58 g ZnO 1.89 g
H.sub.2SiO.sub.3
[0096] The above samples were tested via the spot method and
exhibited color development.
EXAMPLE 28
[0097] Lithium Zinc Sulfur Phosphorus Silicon Oxide
[0098] In the amounts shown in the table below, anhydrous lithium
sulfate (Alfa-Aesar), lithium phosphate tribasic (Aldrich Chemical
Co.), zinc oxide (Aldrich Chemical Co.) and silicic acid (Aldrich
Chemical Co.) were ground in a mortar and placed in an alumina
crucible and heated to 800.degree. C. in air for 16 hours. Once
cooled, the materials were treated with a 5% HNO.sub.3 solution (5
g/25-30 mL solution) for a period of 8-16 hours. The samples were
filtered, washed with distilled water, and dried at 110.degree. C.
for 3-6 hours.
17 28A 7.61 g Li.sub.2SO.sub.4 0.89 g Li.sub.3PO.sub.4 4.38 g ZnO
1.80 g H.sub.2SiO.sub.3 28B 6.76 g Li.sub.2SO.sub.4 1.78 g
Li.sub.3PO.sub.4 4.38 g ZnO 1.80 g H.sub.2SiO.sub.3
[0099] The above samples were tested via the spot method and
exhibited color development.
[0100] In the following examples, the inorganic oxide was treated
with a Lewis acid rather than HNO.sub.3.
EXAMPLE 29
[0101] Lithium Zinc Borosilicate
Li.sub.4B.sub.xZn.sub.3Si.sub.z-mO.sub.9-- 0.5x
[0102] Using a ratio of 1.31 moles of lithium zinc borosilicate to
1 mole of AlCl.sub.3*6 H.sub.2O, about 480 grams of lithium zinc
borosilicate were stirred in 3.5L of distilled water with a
mechanical stirrer. While stirring, the aluminum chloride was
added. The solution was stirred until it coagulated. The gel was
allowed to sit for 1-2 hours before filtration. The majority of the
water was filtered off, but not taken to dryness. The wet powder
was dried in air at 80-100.degree. C. until the powder was dry. The
sample was tested via the spot method and exhibited color
development.
EXAMPLE 30
[0103] Lithium Zinc Borosilicate
Li.sub.4B.sub.xZn.sub.3Si.sub.z-mO.sub.9-- 0.5x
[0104] The procedure of Example 29 was repeated using 1.68 moles
MgCl.sub.2 as the Lewis acid per mole of the borosilicate. The
sample was tested via the spot method and exhibited color
development.
EXAMPLE 31
[0105] Lithium Zinc Borosilicate
Li.sub.4B.sub.xZn.sub.3Si.sub.z-mO.sub.9-- 0.5x
[0106] The procedure of Example 29 was repeated using 1.22 moles
SnCl.sub.4 as the Lewis acid per mole of the borosilicate. The
sample was tested via the spot method and exhibited color
development.
EXAMPLE 32
[0107] Lithium Zinc Borosilicate
Li.sub.4B.sub.xZn.sub.3Si.sub.z-mO.sub.9-- 0.5x
[0108] The procedure of Example 29 was repeated using ZnCl.sub.2 as
the Lewis acid. The sample was tested via the spot method and
exhibited color development.
EXAMPLE 33
[0109] Lithium Zinc Borosilicate
Li.sub.4B.sub.xZn.sub.3Si.sub.z-mO.sub.9-- 0.5x
[0110] The procedure of Example 29 was repeated using a mixture of
AlCl.sub.3 and MgCl.sub.2 as the Lewis acid. The sample was tested
via the spot method and exhibited color.
EXAMPLE 34
[0111] Lithium Zinc Borosilicate
Li.sub.4B.sub.xZn.sub.3Si.sub.z-mO.sub.9-- 0.5x
[0112] The procedure of Example 29 was repeated using a mixture of
0.65 moles AlCl.sub.3 and 0.65 moles SnCl.sub.4 as the Lewis acid
per mole of the borosilicate. The sample was tested via the spot
method and exhibited color.
EXAMPLE 35
[0113] Lithium Zinc Borosilicate
Li.sub.4B.sub.xZn.sub.3Si.sub.z-mO.sub.9-- 0.5x
[0114] The procedure of Example 29 was repeated using a mixture of
0.68 moles AlCl.sub.3 and 0.68 moles ZnCl.sub.2 as the Lewis acid
per mole of the borosilicate. The sample was tested via the spot
method and exhibited color.
EXAMPLE 36
[0115] Sodium Zinc Silicate, Na.sub.xZn.sub.y(SiO.sub.4).sub.4
[0116] In a mortar, 5.30 g (0.05 mol) of Na.sub.2CO.sub.3, 6.0 g
(0.10 mol) of SiO.sub.2 (SIP-22) and 12.21 g (0.15 mol) of zinc
oxide were mixed with a minimal of water to make a paste. Once the
paste was mixed thoroughly, it was placed in an alumina crucible
and placed in an oven. The material was heated at 125.degree. C.
for 4 hours followed by a 16 hour treatment at 850.degree. C. After
cooling, the mixture was ground and treated with 1.3 moles aluminum
chloride per mole of borosilicate. The sample was tested via the
spot method and exhibited color.
EXAMPLE 37
[0117] Sodium Zinc Borosilicate,
Na.sub.4B.sub.3Bi.sub.z-xO.sub.9-0.5x
[0118] In a mortar, 5.30 g (0.05 mol) of Na.sub.2CO.sub.3, 5.71 g
(0.095 mol) of SiO.sub.2 (SIP-22), 0.31 g (0.005 mol) of boric acid
and 12.21 g (0.15 mol) of zinc oxide were mixed with a minimal of
water to make a paste. Once the paste was mixed thoroughly, it was
placed in an alumina crucible and placed in an oven. The material
was heated at 125.degree. C. for 4 hours followed by a 16 hour
treatment at 850.degree. C. After cooling, the mixture was ground
and treated with 1.3 moles aluminum chloride per mole of
borosilicate. The sample was tested via the spot method and
exhibited color.
EXAMPLE 38
[0119] Potassium Zinc Borosilicate,
K.sub.4B.sub.xZn.sub.3Si.sub.z-xO.sub.- 9-05x
[0120] In a mortar, 10.00 g (0.072 mol) of K.sub.2CO.sub.3, 8.26 g
(0.137 mol) of SiO.sub.2 (SIP-22), 0.45 g (0.0073 mol) of boric
acid and 17.66 g (0.217 mol) of zinc oxide were mixed with a
minimal of water to make a paste. Once the paste was mixed
thoroughly, it was placed in an alumina crucible and placed in an
oven. The material was heated at 125.degree. C. for 4 hours
followed by a 16 hour treatment at 1050 - 1100.degree. C. After
cooling, the mixture was ground and treated with 1.3 moles aluminum
chloride per mole of borosilicate. The sample was tested via the
spot method and exhibited color.
[0121] Having described the invention in detail and by reference to
preferred aspects thereof, it will be apparent that modifications
and variations are possible without departing from the scope of the
invention defined in the appended claims.
* * * * *