U.S. patent number 3,870,435 [Application Number 05/290,353] was granted by the patent office on 1975-03-11 for visual recording method and means.
This patent grant is currently assigned to Pilot Man-Nev-Hitsu Kabushiki Kaisha. Invention is credited to Yasuzo Murata, Akio Watanabe.
United States Patent |
3,870,435 |
Watanabe , et al. |
March 11, 1975 |
VISUAL RECORDING METHOD AND MEANS
Abstract
An almost colorless aqueous ink containing a color coupler is
used to inscribe a record on a recording sheet having a coated
layer containing a fine white powder and a color developer which
reacts with the color coupler to form a visual record of vivid
color of highly durable nature.
Inventors: |
Watanabe; Akio (Hiratsuka,
JA), Murata; Yasuzo (Hiratsuka, JA) |
Assignee: |
Pilot Man-Nev-Hitsu Kabushiki
Kaisha (Tokyo-to, JA)
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Family
ID: |
12969594 |
Appl.
No.: |
05/290,353 |
Filed: |
September 19, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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53054 |
Jul 7, 1970 |
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Foreign Application Priority Data
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Jul 9, 1969 [JA] |
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44-54399 |
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Current U.S.
Class: |
427/261; 346/20;
428/144; 503/219; 347/98; 346/96; 347/96; 347/100; 427/145;
427/150; 503/211; 503/225 |
Current CPC
Class: |
B41M
1/36 (20130101); Y10T 428/2438 (20150115) |
Current International
Class: |
B41M
1/36 (20060101); B41M 1/26 (20060101); B41c
001/06 () |
Field of
Search: |
;117/36.2,36.8,36.9,5,1.7 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Herbert, Jr.; Thomas J.
Attorney, Agent or Firm: Burns; Robert E. Lobato; Emmanuel
J. Adams; Bruce L.
Parent Case Text
This is a continuation-in-part application of our copending U.S.
Pat. application Ser. No. 53,054, filed July 7, 1970 and now
abandoned.
Claims
What we claim and desire to protect by Letters Patent is:
1. A visual recording method which comprises inscribing a record
with an aqueous ink containing a color coupler having a chromatic
appearance in the range of from colorless to lightly colored which
is selected from the group consisting of ammonium metavanadate,
sodium metavanadate, and vanadium pentoxide on a recording
structure comprising a base structure provided over a surface
thereof with a coated layer containing at least a dispersion of a
fine white powder selected from the group consisting of calcium
carbonate, silicon dioxide, talc, titanium dioxide, aluminum oxide
and clay and a color developer which is at most only slightly
soluble in water and is selected from the group consisting of
lauryl gallate, stearyl dihydroxybenzoate, calcium
dihydroxynaphthalenesulfonate, and 2-ethylhexylammonium
dihydroxynapthalenesulfonate, which developer thereby reacts with
said color coupler to form a visual record of strong color.
2. A visual recording combination comprising a recording structure
comprising a base structure supporting over a surface thereof a
coated layer containing at least a white powder selected from the
group consisting of calcium carbonate, silicon dioxide, talc,
titanium dioxide, aluminum oxide and clay and a color developer
which is at most only slightly soluble in water and is selected
from the group consisting of lauryl gallate, stearyl
dihydroxybenzoate, calcium dihydroxynaphthalenesulfonate, and
2-ethylhexylammonium dihydroxynaphthalenesulfonate and an aqueous
ink having a chromatic appearance in the range of from colorless to
lightly colored and containing a water soluble color coupler which
is a compound selected from the group consisting of ammonium
metavanadate, sodium metavanadate, and vanadium pentoxide, said
coupler being capable of reacting with said color developer to form
a visual record of strong color on said recording structure when a
record is inscribed thereon with said ink.
3. A visual recording combination as claimed in claim 2, in which
said base structure is a sheet material.
4. A visual recording combination as claimed in claim 3, which is
used in a writing machine.
5. A visual recording combination as claimed in claim 3 which is
used in a printing press.
6. A visual recording combination as claimed in claim 3 in which
said ink is used in a stamp pad, and said visual record is formed
on said recording sheet material by being transferred thereto from
said stamp pad by a stamp.
7. A process for producing a visual recording combination
comprising a recording structure and an ink for inscribing visual
records thereon, which process comprises
dissolving at least a water soluble color coupler which selected
from the group consisting of ammonium metavanadate, sodium
metavandate, and vanadium pentoxide in water to prepare said ink of
a chromatic appearance in the range from colorless to
lightly-colored,
combining a color developer which is at most only slightly soluble
in water and is selected from the group consisting of lauryl
gallate, stearyl dihydroxybenzoate, calcium
dihydroxynaphthalenesulfonate, and 2-ethylhexylammonium
dihydroxynaphthalenesulfonate, a fine white powder selected from
the group consisting of calcium carbonate, silicon dioxide, talc,
titanium dioxide, aluminum oxide and clay and a solvent to form a
coating dispersion,
applying said dispersion as a uniform coating on a surface of a
base structure, and
drying said coating thereby to prepare a recording structure, said
color coupler and color developer being capable of reacting with
each other to form a visual record of strong color on said
recording structure when a record is inscribed thereon with said
ink.
Description
BACKGROUND OF THE INVENTION
This invention relates generally to visual recording methods and
means and more particularly to a new method and means for
inscribing with colorless or light-colored inks records on
recording structures. The invention also concerns a process for
producing the visual recording means.
Examples of aqueous inks known heretofore are inks formed by
dissolving in water dyes such as ink blue and eosin, pigments such
as carbon black, permeation-proofing agents such as dextrin and
arabic gum, and wetting agents such as glycerine and ethylene
glycol. These aqueous inks are advantageous in that they can be
readily used for writing and recording on almost any kind of paper
or like material.
However, since these inks contain dyes and pigments, they are
colored and therefore are accompanied by the undesirable
possibility of contamination or discoloration of the recording
paper, hands, clothing, and nearby articles and facilities during
handling thereof or during their use in recording. When such
articles become thus discolored, it is not easy to wash off the
adhering color or to decolor the same.
Furthermore, since an aqueous ink of the above-stated character
contains a dye or pigment, the ink feed flow tends to be retarded
when the writing tip of a writing instrument using the ink becomes
dry, whereby grazing or abrasive scratching tends to occur. In some
severe cases, the instrument becomes incapable of writing. This
undesirable phenomenon is particularly observable in the case of
black ink and at present is becoming a problem demanding an
effective solution as the use of black ink, which is particularly
effective for making photocopies, becomes increasingly
advantageous.
These difficulties are serious drawbacks particularly in inks for
recording, with pen-writing oscillographs, data produced by
industrial instruments, medical treatment instruments, and various
other measuring instruments.
Heretofore, pen-writing type recording in measuring instruments and
like equipment has been accomplished in each case by feeding an ink
comprising a dye, a permeation-proofing agent, a wetting agent, and
other additives through a tubular writing member having a
small-diameter hole at the writing end thereof, causing this end to
contact lightly a recording substrate medium, such as a paper for
measurements and paper for recording, and causing the substrate
medium to travel at a constant speed. Frequently, there are
instances wherein, when an instrument for such operation is placed
in the operational state for measuring and recording, the ink drips
from the writing member and adheres to the operator's hands,
clothing and other objects from which the ink cannot be easily
washed off. In some instances, the measuring and recording
instrument becomes contaminated by the ink.
Furthermore, the ink in such instruments flows through and out of
an extremely small hole of a diameter of the order of from 0.2 to
0.5 mm., which is normally open and exposed to the atmosphere.
Consequently, the ink dries easily and once the ink dries, it is
not redissolved by the ink subsequently flowing out because of the
dye. Moreover, the ink viscosity tends to rise substantially,
thereby disturbing uniform ink flow, whereby necessary data cannot
be clearly and accurately recorded in some cases.
These undesirable characteristics are particularly pronounced when
black ink is used. Accordingly, at present, red ink is widely used
since these disadvantages are somewhat reduced therein. Records in
red ink, however, cannot be reproduced by photosensitive means with
full clarity and then fully satisfactory copies cannot be
obtained.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a recording
method wherein the above-described difficulties are overcome.
Specific objects and features of the invention will become apparent
as the following disclosure proceeds.
According to the present invention, briefly summarized, there is
provided a method for making visual recordings in which a record is
inscribed on a recording structure comprising a base structure and
a coated layer supported on the base structure and containing at
least a fine white powder and a color developer with an aqueous
colorless or light-colored ink containing a coupler for reacting
with the color developer in the recording structure to form a
visual record of strong color.
According to the present invention, there is further provided a
visual recording combination comprising the above-stated ink and
recording structure.
According to the present invention, there is additionally provided
a process for producing a visual recording combination as stated
above.
The nature, principle, details and utility of the invention will be
more clearly apparent from the following detailed description
beginning with general considerations and concluding with specific
examples of practicce illustrating preferred embodiments of the
invention and results.
DETAILED DESCRIPTION
A feature of the present invention is that it provides a method of
recording and reproductive printing through the use of an ink
comprising a colorless or light-colored solution containing a color
coupler which, upon reacting instantaneously and at room
temperature with a color developer contained in a coated layer of a
recording substrate medium (hereinafter referred to as a "sheet"),
forms a colored compound of strong color and high stability without
discoloration.
This ink according to the invention, differing from conventional
inks containing dyes and pigments, is not colored and, therefore,
does not have the disadvantageous possibility of soiling equipment,
clothing, hands and other objects. The ink used in accordance with
the invention generates a color only when it comes into contact
with the color developer which is the cooperative counterpart agent
contained in the coated layer of the recording sheet. With only the
ccolor coupler therein, the ink is colorless or of light color and
is stable. This is particularly advantageous in that it cannot
generate colors upon contacting ordinary papers, hands, clothes and
equipment.
The viscosity of a conventional colored ink in which a dye of
non-crystalline macromolecular substances is used rises remarkably
when the ink at the writing tip of the writing tool beccomes dry,
and a viscous dye separates out to obstruct the outward flow of the
ink, whereby in severe cases an accurate recording cannot be
attained.
In contrast, the color coupler used in the ink of the invention has
a remarkably high solubility in water, and the rise in viscosity is
small even when the ink becomes dry at the writing tip of the
writing tool. Furthermore, ink thus dried is easily redissolved in
the liquid ink. Accordingly, there is no tendency whatsoever of
retardation of the outward flow of the ink through the tip of the
writing tool, and a visual record which is consistently uniform can
be obtained. Even when the writing is temporarily stopped during
the recording operation and then resumed, the writing tool can
immediately begin writing. Thus there is no possibility of broken
or interrupted traced inscriptions.
Since the ink used according to the invention is colorless or of
light color, it cannot be used for recording on any and all kinds
of recording sheets; it is necessary to select sheets from a
limited group of reccording sheets.
For the counterpart color developer, a compound capable of forming
a stable record of high color concentration only upon contact with
the above-described ink of colorless or light-color appearance
containing the color coupler is used, contained in a coated layer.
In practical use, in general, it is necessary to dispose this
coated layer on a suitable supporting structure, that is, to
combine this layer with specific recording sheets.
Another feature of the recording materials of the invention is
that, when the ink is combined with the sheet, a durable record of
high color concentration and high stability is obtained. We have
found that a record thus obtained undergoes no discoloration
whatsoever due to sunlight, and the recorded inscription does not
run when immersed in water, and it may be said that the record made
according to the present invention can be permanently
preserved.
Still another feature of the recording materials of the invention
is the use of specific recording sheets of limited characteristics.
That is, the invention becomes particularly valuable in fields
wherein specific recording sheets are used. For example, the
invention can be applied in fields wherein specific papers such as
forms for stock certificates, standard drawing sheets, and paper
sheets bearing specific inscriptions in addition to the field of
recording materials for the above-mentioned various instruments and
equipment. In such other fields, the invention affords the
above-described advantages and is additionally advantageous in that
alterations and falsifications cannot be made on the paper
sheets.
An ink according to the invention is prepared, in general, by
dissolving a color coupler, constituting one component, in water
and further adding to the solution and dissolving therein necessary
additives such as glycerine or ethylene glycol as a hygroscopic
agent, dextrin or arabic gum as a permeation preventive agent, and
a surface-active agent for regulating the outward flow of the
ink.
The recording sheet to constitute the opposite component is
prepared, in general, by a process which comprises causing a color
developer which is capable of reacting with the color in the ink to
form a colored compound to dissolve or disperse in water or an
organic solvent, thoroughly mixing therewith reaction-assisting
agents such as a white fine powder, a stabilizer, and a binder to
render the process mixture into a uniform dispersion (or disperse
system), applying the resulting dispersion as a coating on a
suitable base sheet such as an original copy sheet or a film, and
then drying the coating.
The ccolor coupler and color developer thus using in accordance
with the invention are originally colorless or light-color
compounds which, upon reacting with each other, instantaneously
form a vividly colored and stable compound in an aqueous solution.
A representative example of such compound combination is the color
coupler sodium metavanadate and the color developer calcium
dihydroxynaphthalenesulfonate, which when used in combination in
accordance with the present invention yield a black color
instantly.
We have found that in the practice of the invention vanadium
compounds as color couplers and polyphenol derivatives as color
developers are particularly effective in producing good results.
When a polyphenol derivative is used as the color developer, it is
possible to obtain a durable black recording of especially high
color concentration.
Examples of polyphenol derivatives are polyphenolic carboxylic acid
esters and metallic salts. As for polyphenolic carboxylic acid
derivatives for use as color developers, esters of acids which
dissolve with difficulty or are insoluble in acid, such as gallic
acid, tannic acid dihydroxybenzene carboxylic acid, and
dihydroxynaphthalene carboxylic acid, are especially suitable. By
esterifying the polyphenolic carboxylic acids, polyphenolic
carboxylic acid derivatives which are colorless or light-colored,
and which dissolve with difficulty, i.e. are only slightly soluble,
or are insoluble in water are obtained. For example, polyphenolic
carboxylic acid esters of aliphatic alcohols such as lauryl alcohol
and stearyl alcohol and in general alkyl esters wherein the alkyl
group has more than six carbon atoms have the necessary low
solubility as well as the aromatic esters such as benzyl ester.
When an aliphatic or aromatic amine salt or a salt of a metal, such
as calcium or barium, of dihydroxynaphthalene sulfonic acid or
dihydroxybenzene sulfonic acid comes in contact with the ink
containing the color coupler, a jet black inscription is
instantaneously recorded.
Examples of some preferred color developers according to the
invention include lauryl gallate stearyl dihydroxybenzoate, calcium
dihydroxynaphthalenesulfonate and 2-ethylhexylammonium
dihydroxynaphthalenesulfonate.
A most important feature of the invention is the admixing of a fine
white powder with the color developer to form a coated layer in
order to increase the color-generating speed and color
concentration of the color developer. By merely causing only the
color developer to be coated on or impregnate the base sheet, it is
not possible to obtaine a sufficiently satisfactory
color-generating speed or color concentration. Unless an extremely
large quantity of the color developer is used, the desired color
concentration or strength cannot be obtained.
We have found that, when a fine white powder is added to form a
suspension in a solvent in which the color developer has been
dissolved or dispersed, and this suspension is applied on the base
sheet to form a coated layer, it is possible to produce recording
materials of a color concentration and color-generating speed which
are several times those obtainable without the addition of a fine
white powder. In a coated layer containing a fine white powder, of
course, a large quantity of the color developer is not required,
and a fully satisfactory inscription can be recorded with a minimum
required quantity of the developer.
One reason for this desirable phenomenon is that the addition of
the fine white powder causes the coated layer to become remarkably
porous, whereby its capacity to absorb the ink is greatly improved.
A further reason is that the color developer is distributed
uniformly over the outer surface of the ifne white powder and does
not permeate into the base sheet interior, and only a small
quantity of the color developer is used in a highly efficient
manner.
This result, in combination with the above-mentioned porosity of
the surface, produces a record without luster but with a color
concentration which is several times that attainable without the
fine white powder. The final result is not merely a record with an
increase in the contrast due to an increase in the whiteness of the
base sheet but a record of remarkable definition and high color
concentration due to the above-described phenomenon.
Examples of fine white powders we have found to be suitable are
calcium carbonate, silicon dioxide, talc, titanium dioxide,
aluminum oxide, and clays. Such inorganic fine powders are those
which can be used as white filters in papers. They must be
insoluble in water and fine enough. The effectiveness of this fine
white powder is indicated with respect to the recording materials
of Example 1 set forth hereinafter.
For causing the color developer and fine white powder to adhere to
the surface of the base sheet, a natural or synthetic high-polymer
substance is used as an adhesive. Examples of suitable adhesives
are water-soluble high-polymer substances such as dextrin, poly,
gelatines, high-polymer substances soluble in organic solvents,
such as vinyl resins, acryl resins, and styrene resins, and
high-polymer latex solvents.
Depending on the necessity, the durability of the recorded
inscriptions and the stability of the base sheet can be further
increased by adding stabilizers such as an agent for absorbing
ultra-violet rays, an oxidation-preventive agent and acids during
the formation of the caoted layer. While the color developer or the
colored record itself is substantially stable with respect to
sunlight and oxygen, the further addition of various stabilizers
affords full resistance to the effects of sunlight and oxidation,
whereby there is produced a recording material accompanied by
almost no discoloration or change in characteristics and
quality.
When a record is inscribed by means of an ink of the invention
containing a colorless or light-colored coupler on a recording
material produced in the manner disclosed above, a record of high
color concentration is instantaneously formed. The record thus
formed has high resistance to water and light and exhibits almost
no change over a long period. The recording material itself
undergoes almost no change in quality of characteristics when left
standing for a long time. Accordingly, it is possible to produce a
recording material in which there is no change in color and almost
no reduction of its color-generating performance.
While the recording materials of the invention are particularly
useful as recording materials of a large variety of industrial
instruments and equipment, the invention can be applied to various
other uses. For example, the ink of the invention can be used for
general writing and for various writing tools such as fiber-tip
pends and ball-point pens in combination with specific paper sheets
according to the invention.
Another example of application is the impregnation of stamp pads
with the ink of the invention, the ink thereby being used to stamp
inscriptions of specific paper sheets. Still another application is
the impregnation of the ink on a typewriter ribbon which is then
used in conjunction with a specific paper according to the
invention to form inscriptions thereon. A further application is
that of printing by means of printing presses.
In order to indicate still more fully the nature and utility of the
invention, the following examples of practice cconstituting
preferred embodiments of the invention and results are set forth,
it being understood that these examples are presented as
illustrative only and that they are not intended to limit the scope
of the invention.
EXAMPLE 1
A. Preparation of aqueous ink. Recipe, quantities in g. vanadium
pentoxide 9 sodium hydroxide 6 sodium alkylnaphthalenesulfonate 1
polyvinyl pyrrolidone 20 water 964
The vanadium pentoxide and sodium hydroxide are added to and
agitated with the water to dissolve the vanadium compound, and then
the polyvinyl pyrrolidone and sodium alkylnaphthalenesulfonate are
added to and dissolved in the resulting solution to prepare a
colorless ink.
______________________________________ B. Preparation and
application of base-sheet coating Recipe, quantities in g. lauryl
gallate (ester) 1 vinyl resin 2 mineral acid 1 organic acid 2
silicic acid, fine powder 3 ethyl acetate 10
______________________________________
The first four ingredients set forth are successively added to and
dissolved in the ethyl acetate, and then the silicic acid powder is
dispersed uniformly in the resulting solution to prepare a coating
dispersion. This dispersion is applied as a coating on a sheet of
white instrument recording paper of a weight of 50 g./square meter
by means of a suitable coating device as, for example, a roll
coater or a bar coater, in a quantity such that the coating
thickness after drying will be from 8 to 10 microns. The ethyl
acetate is dried off, whereupon a white recording sheet is
obtained.
This recording sheet is useful as a recording material in medical
and industrial measuring instruments. When the above-described ink
is used in conjunction with this recording sheet, a jet-black
recording without interrupted ink inscription or ink blotches can
be obtained.
REFERENCE EXAMPLE 1
For the purpose of comparison, the ink and recording sheet of
Example 1 were prepared, and a record was inscribed on the sheet
with the ink and compared with that on a recording sheet ccoated
with a dispersion prepared in the manner specified in Example 1
except for the omission of the fine powder of silicic acid. The
results of this comparison are set forth in Table 1 and indicate
the importance of the use of a white powder in accordance with the
invention.
Table 1 ______________________________________ TESTED RECORDING
SHEET RECORDING SHEET OF PROPERTY OF EXAMPLE 1 EXAMPLE 1 WITHOUT
SILICIC ACID POWDER ______________________________________ Color
jet black greyish black Intensity high low Definition remarkably
high record in small type definition illegible Color-generat-
instantaneous 5 to 10 seconds re- ing speed quired to develop full
color ______________________________________
EXAMPLE 2
A. Preparation of aqueous ink Recipe, quantities in g. ammonium
metavanadate 10 glycerine 200 dextrin 50 water 740
The ammonium metavanadate and dextrin are added to and dissolved in
the water, and the glycerine is added to and mixed with the
resulting solution to form a colorless ink.
______________________________________ B. Preparation and
application of base-sheet coating. Recipe, quantities in g. calcium
dihydroxynaphthalenesulfonate 1.0 polyethylene glycol-600 0.4
4-tertiary-butylphenyl salicylate 1.0 mineral acid 0.3
styrene-maleic anhydride copolymer resin 7.5 silicic acid, fine
powder 3 methyl alcohol 2 methylethyl ketone 4
______________________________________
The above ingredients are dissolved or dispersed in the solvent to
prepare a coating dispersion, which is applied as a coating on a
sheet of white paper of a weight of 35 g./square meter by means of
a suitable coating device in a quantity such that the coating
thickness after drying will be from 7 to 9 microns. The solvent is
then dried off, whereupon a white recording sheet is obtained. This
recording sheet is useful as a recording medium for medical
measuring instruments and for use in conjunction with a stamp pad
and fiber-tip pens.
* * * * *