U.S. patent number 3,876,496 [Application Number 05/359,844] was granted by the patent office on 1975-04-08 for method and means for protecting documents.
Invention is credited to Ernesto B. Lozano.
United States Patent |
3,876,496 |
Lozano |
April 8, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Method and means for protecting documents
Abstract
A safety paper composition is provided for protective documents
in which a stabilized dye in the colloidal size range is dispersed.
The dye which is substantially masked from view is sensitive to
liquid ink eradicators such as bleach solutions and organic
solvents in which the dye is soluble. A dye formulation is also
provided, the dye being alcohol-soluble but which is stabilized
with an alkaline agent, e.g., caustic soda, to render it water
insensitive so that it can be easily dispersed together with either
potassium iodide or manganese sulfate in a paper pulp slurry
without dissolving away in the water and without coloring the paper
to any substantial degree.
Inventors: |
Lozano; Ernesto B. (Santiago,
CE) |
Family
ID: |
23415523 |
Appl.
No.: |
05/359,844 |
Filed: |
May 14, 1973 |
Current U.S.
Class: |
162/140; 8/620;
162/162; 162/181.4; 106/31.2; 106/31.17; 8/618; 8/919;
162/181.2 |
Current CPC
Class: |
B41M
1/36 (20130101); D21H 21/46 (20130101); Y10S
8/919 (20130101) |
Current International
Class: |
B41M
1/36 (20060101); B41M 1/26 (20060101); D21H
21/40 (20060101); D21H 21/46 (20060101); D21h
005/10 () |
Field of
Search: |
;162/140,162,181A ;8/7
;117/1 ;106/21,22 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Bashore; S. Leon
Assistant Examiner: D'Andrea, Jr.; Alfred
Attorney, Agent or Firm: Sandoe, Hopgood & Calimafde
Claims
1. As an article of manufacture a safety paper composition
characterized by a colloidal dispersion therethrough of a small but
effective amount of an alcohol-soluble dye consisting essentially
of Victoria Blue B stabilized with an alkaline agent selected from
the group consisting of carbonates and hydroxides of ammonia and
alkali metals, the paper also containing a small but effective
amount of one of the reinforcing compounds potassium iodode and
manganese sulfate such that the stabilized dye is uniformly masked
and rendered water insensitive and such that when a selected
portion of said paper is contacted by an ink eradicator selected
from the group consisting of a bleaching agent and an organic
solvent for said dye, the dye is caused permanently to strain said
paper at said selected
2. The safety paper of claim 1, wherein the average colloidal size
of said stabilized dye ranges from about 0.01 to 0.2 micron and
wherein the amount of dye in said paper ranges from about 0.02 to
0.5 percent by weight of
3. The safety paper of claim 2, wherein said dye is sodium
hydroxide-stabilized and wherein the amount of dye in said paper
ranges
4. The safety paper of claim 1, wherein said stabilized dye has an
average colloidal size ranging from about 0.01 to 0.2.mu., wherein
the amount of stabilized dye ranges by weight from about 0.02 to
0.5 percent, and wherein said reinforcing compound is potassium
iodide ranging by weight
5. In a method of producing safety paper, the improvement which
comprises, uniformly dispersing through said paper a small but
effective amount of a colloidal alcohol-soluble dye consisting
essentially of Victoria Blue B stabilized with an alkaline agent
selected from the group consisting of carbonates and hydroxides of
ammonia and alkali metals, said paper also having added thereto a
small but effective amount of one of the reinforcing compounds
potassium iodide and manganese sulfate such that the stabilized dye
is uniformly masked and rendered water insensitive and such that
when a selected portion of said paper is contacted by an ink
eradicator selected from the group consisting of a bleaching agent
and an organic solvent for said dye, the dye is caused permanently
to stain said
6. The method of claim 5, wherein the amount of dye dispersed in
said paper ranges by weight from about 0.02 to 0.5 percent and
wherein said reinforcing compound is potassium iodide ranging by
weight from about 0.02
7. A method of producing safety paper which comprises:
preparing a dye formulation comprising an aqueous colloidal
dispersion of about 0.5 to 5 percent by weight of an
alcohol-soluble dye consisting essentially of Victoria Blue B
stabilized with about 1 to 5 percent by weight of a dye-stabilizing
alkaline agent selected from the group consisting of carbonates and
hydroxides of ammonia and alkali metals, and the balance
essentially water, the pH of said solution being over 9,
preparing a paper pulp slurry,
adding to said slurry in amount of said dye formulation such that
the amount of Victoria Blue B dye in said slurry based upon the dry
weight of said paper pulp ranges from about 0.02 to 0.5
percent,
forming a paper product in the usual manner with a uniform
dispersion of said stabilized colloidal dye therein,
contacting said paper product with a solution containing 1 to 6
percent by weight of one of the reinforcing compounds potassium
iodide and manganese sulfate,
and then drying said paper,
whereby a safety paper is provided such that when a selected
portion of said paper is contacted with an ink eradicator selected
from the group consisting of a bleaching agent and an organic
solvent for said dye, a
8. The method of claim 7, wherein said alkaline agent is sodium
hydroxide and wherein said colloidal dye ranges in average size
from about 0.01 to
9. A method of producing safety paper which comprises:
preparing a dye formulation comprising an aqueous colloidal
dispersion of about 0.5 to 5 percent by weight of an
alcohol-soluble dye consisting essentially of Victoria Blue B,
about 1 to 5 percent by weight of a dye-stabilizing alkaline agent
selected from the group consisting of carbonates and hydroxides
selected from the group consisting of ammonia and alkali metals,
and about 1 to 6 percent by weight of one of the reinforcing
compounds potassium iodide and manganese sulfate dissolved
therein,
said aqueous dispersion having a pH of over 9,
preparing a paper pulp slurry,
forming a paper product from said slurry in the usual manner up to
the finishing stage thereof including passing said paper product
between heated rolls,
uniformly contacting said paper product with said foregoing aqueous
dispersion thereby absorbing said dispersion therein,
and then drying said paper,
whereby a safety paper is provided such that when a selected
portion of said paper is contacted with an ink eradicator selected
from the group consisting of a bleaching agent and an organic
solvent for said dye, a
10. The method of claim 9, wherein the alkaline agent is sodium
hydroxide, wherein the aqueous dispersion has a pH of at least
about 11 and contains by weight from about 1 to 3 percent Victoria
Blue B, about 1 to 3 percent sodium hydroxide and about 1 to 3
percent potassium iodide, and wherein said colloidal dye has an
average particle size ranging from about 0.01 to
11. A dye formulation for use in manufacturing safety paper which
comprises:
an aqueous dispersion of colloidal particles of an alcohol-soluble
dye of Victoria Blue B in an amount ranging from about 0.5 to 5
percent by weight stabilized with about 1 to 5 percent by weight of
a dye-stabilizing alkaline agent selected from the group consisting
of carbonates and hydroxides of ammonia and alkali metals, and also
containing dissolved therein about 1 to 6 percent by weight of one
of the reinforcing compounds potassium iodide and manganese
sulfate,
and the balance essentially water, the pH of said aqueous
dispersion being over 9,
said formulation being characterized such that when said stabilized
dye is uniformly dispersed in a paper product, the dye in the paper
is masked until contacted by a liquid ink eradicator, whereby said
dye causes a
12. A dye formulation for use in manufacturing safety paper which
comprises:
a dispersion of colloidal particles of an alcohol-soluble dye in an
average size range of about 0.0l to 0.2 micron consisting
essentially of Victoria Blue B in an amount ranging by weight from
about 1 to 3 percent, about 1 to about 3 percent of sodium
hydroxide, about 1 to 3 percent by weight of potassium iodide and
the balance essentially water, the pH of said dispersion being at
least about 11,
said formulation being characterized such that when said stabilized
dye is uniformly dispersed in a paper product, the dye in the paper
is masked until contacted by a liquid ink eradicator, whereby said
dye causes a permanent stain to appear.
Description
This invention relates to safety paper and to a dye formulation
therefor, including a method of utilizing said formulation in
producing safety paper for protective documents.
Many methods have been devised for producing protective documents,
such as checks, negotiable instruments, drafts, bonds, stock
certificates or other instruments, to prevent such documents from
being tampered with. Some means which have been proposed involved
application to the paper of a special design which is affected by
any attempt at alteration. Other means include the printing of
various layers of ink on the paper, often with one of the layers
being printed in invisible ink, such that any attempt at alteration
causes a predetermined design to appear on the paper.
The use of other methods and formulations based on different
chemical compounds in the production of safety paper are also known
but generally such formulations are complicated and costly. For
example, a product formed of three layers of paper is known, in
which the middle layer is sensitized. Another method is to add a
sensitizing agent to a paper pulp slurry so that the papers
produced therefrom will react to certain types of ink eradicators.
In many instances, such agents are dyes which tend to color the
paper and also which tend to be water sensitive. Such papers,
therefore, should be kept in a relatively dry environment.
It is thus the object of my invention to provide a novel dye
formulation in which the dye is stabilized to the extent it will
not prematurely color the paper into which the dye is
dispersed.
Another object is to provide a safety paper composition
characterized by the presence of a colloidal dispersion of an
alcohol-soluble dye throughout the matrix of the paper, which dye
is hidden until such time that an attempt is made to alter the
paper by the addition thereto of a liquid ink eradicator, such as a
bleaching agent (e.g., a hypochlorite solution) or an organic
solvent which is capable of releasing said dye.
These and other objects of the invention will more clearly appear
when taken in conjunction with the following disclosure, the
appended claims and the accompanying drawing which is a schematic
representation of a paper making process of the present
invention.
Stating it broadly, one aspect of the invention resides in a safety
paper composition characterized by colloidal dispersion
therethrough (i.e., throughout the matrix thereof) consisting
essentially of a small but effective amount of an alcohol-soluble
dye of Azul Victoria B (generally known as Victoria Blue B
designated as Color Index 44045), stabilized with an alkaline
agent, for example, an alkaline agent selected from the group
consisting of carbonates and hydroxides of ammonia and alkali
metals, preferably caustic soda (NaOH).
As stated above, the stabilized dye should be colloidal in size.
Such dyes can be reduced to colloidal size in a colloid mill
consisting of a series of closely spaced discs, each rotating at a
very high speed in a direction opposite to that of its immediate
neighbors. The liquid dispersion medium, together with the
substance to be dispersed, and the stabilizing agent are passed
through the mill and, after a period of time, a colloidal
suspension results. The foregoing method is well known in the
art.
Thus, in preparing the dispersion, the dye Victoria Blue B (C.I.
44045), is subjected to the action of a colloid mill to produce
particles that may have an average size ranging from about 0.01 to
0.2.mu. (micron). The dye is reacted with a solution of an
inorganic alkaline reagent of pH over 9, and preferably at least
about 11, for example, alkaline agents selected from the group
consisting of carbonates and hydroxides of ammonia and alkali
metals (Na, K, Li), whereby the dye is stabilized. An aqueous
dispersion thereof together with potassium iodide or manganese
sulfate provides a solution that can be readily applied to or
absorbed by the paper near the finishing stages of paper making.
Sodium hydroxide is preferred as the stabilizing agent for said dye
and may be added to the colloid mill.
The amount of dye dispersion added to the paper composition is
small but effective to provide a telltale stain or color when the
paper is contacted by a bleaching agent (e.g., hypochlorite
solution) or an organic solvent, such as ethyl alcohol, methyl
alcohol, ether, acetone, and other organic solvents specific to the
dye. A range of composition in the paper with respect to the
stabilized dye is about 0.02 to 0.5 percent by weight of said dye,
a preferred range being about 0.05 to 0.2 percent, for example 0.1
percent. The potassium iodide or manganese sulfate in the paper may
range from about 0.02 to 0.5 percent by weight.
Where the dye is absorbed into the paper during the finishing
stages of paper making, it is preferred that the dye formulation
comprise said Victoria Blue B (C.I. 44045) dispersed in an aqueous
solution containing caustic soda and potassium iodide. This
provides a solution which is substantially colorless and which
assures a uniform paper with the color substantially masked from
view.
A typical solution formulation for applying to or for absorption
into the paper is one comprising about 0.5 to 5 percent or 1 to 3
percent by weight of said colloidal dye, about 1 to 5 percent or 1
to 3 percent by weight of the dye-stabilizing alkaline reagent,
about 1 to 6 percent or 1 to 3 percent potassium iodide or
manganese sulfate as a reinforcing agent, and the balance
essentially water.
It may be desirable to add 1 or 2 percent starch to the solution to
thicken the mixture where this is desired.
A specific aqueous composition found particularly useful is one
containing by weight about 2 percent of the dye, 2 percent caustic
soda, 2 percent potassiun iodide and the balance essentially
water.
When the foregoing solution is used, it is stirred rapidly to
assure a uniform suspension. The solution may be applied uniformly
to one side or both sides of the paper near the finishing stage
before the drying rolls and dried or it can be actually added to
the cellulose slurry during the paper making process with the
potassium iodide omitted, the potassium iodide being thereafter
applied to the paper near the finishing stage of the paper making
process.
The art of paper making is well known and need not be discussed
here. For example, a typical paper making process is the
Fourdrinier system using an endless wire screen or belt upon which
the paper pulp slurry is deposited. In this connection, reference
is made to the book Manual of Industrial Chemistry by Allen Rogers
(pages 1,050 to 1,065; published by D. Van Nostrand Co., 1926).
For example, during the making of the wet cellulose mix in the vat
in the well known manner, a solution containing 2 parts by weight
of Victoria Blue B, 2 parts by weight of the stabilizing agent NaOH
and the balance water is added to the vat in a proportion to
produce a cellulose slurry or paper pulp mix containing by weight 1
part of the dye, 1 part of NaOH and 998 parts of cellulose
determined on the screen-dried basis. The mixture is passed through
a shredder which provides a homogeneous pulp or slurry for delivery
to another mixer which then feeds the uniformly mixed material onto
an endless drying screen. The material is layed down to provide a
continuous uniform sheet which is dried on the screen and the sheet
then passed through and between an arrangement of contacting drying
rolls which are heated. The dried paper is then fed into a tank
containing a solution of potassium iodide, a typical solution being
one containing 3% KI and the balance essentially water. The treated
paper sheet is again passed through a series of drying rolls at the
finishing stage and then rooled up as paper stock.
The foregoing process is shown schematically in the drawing. A vat
10 is shown comprising stirrer 11, into which vat a wet cellulose
mix is added (wet paper pulp) and after preliminary mixing the wet
cellulose is passed through shredder 12. The details as to the
chemistry are given in the book mentioned hereinabove. Means are
provided to add water as shown when needed and the shredded
material then collected into mixer 13. The uniformly mixed pulp is
then discharged to endless dry screen 14 to provide a continuous
matrix of paper 15 which is then passed between drying rolls 16,
following which the paper is fed between rolls 17 into coating or
absorption tank 18 to be described later. Following this treatment,
the paper is passed between drying rolls 19 and the dried paper
coiled at coiler 20.
In the one embodiment described hereinbefore, an aqueous colloidal
dye dispersion containing by weight, for example, 2 percent
Victoria Blue B, 2 percent sodium hydroxide and the balance
essentially water is added to the cellulose either to vat 10 or
mixer 13, the amount being such as to provide a paper composition
taken on the dry basis comprising 1 part by weight of dye, 1 part
by weight of sodium hydroxide and 998 parts by weight of cellulose.
That is to say, the final paper product will contain approximately
0.1 percent of the stabilized dye. After the laying down of the
pulp on drying screen 14, the paper 15 with the dispersed dye is
passed between finishing drying rolls 16 and then led into coating
or absorption tank 18 via rolls 17, the tank containing an aqueous
solution containing about 3 percent by weight of potassium iodide,
the tank being located at the finishing stage of the paper making
process. The potassium iodide treated paper is then passed between
drying rolls 19 and then wound up on coiler 20.
In the alternative, instead of adding the dye to the pulp, all of
the constituents can be applied to the paper during the finishing
stage of the process by passing the paper without the dye from
drying rolls 16 into tank 18 which contains an aqueous dye
dispersion comprising by weight 2 percent colloidal Victoria Blue
B, 2 percent sodium hydroxide, 2 percent potassium iodide and the
balance essentially water.
As stated above, the advantage of stabilizing the dye with the
caustic soda or other inorganic alkaline agent is that the
colloidally dispersed dye can be carried through the aqueous media
of the paper making machine without being taken up by the water.
The advantage of working with colloidal dye particles is that the
dye can be dispersed uniformly in the paper product either by
adding it to the pulp during paper making or applying it to the
paper itself near the finishing operation.
Thus, the paper need contain only a small but effective amount of
the stabilized dye and the alkaline reagent and a small but
effective amount of potassium iodide. These materials can be
present in the paper in amounts by weight ranging from about 0.02
to 0.5 percent (preferably 0.05 to 0.2 percent) Victoria Blue B,
about 0.02 to 0.5 percent or 0.05 to 0.2 percent alkaline reagent
(e.g., NaOH) and 0.02 to 0.5 percent (preferably 0.05 to 0.2
percent) of KI and the balance essentially the paper matrix.
Summarizing the foregoing, dye formulation for use in manufacturing
the safety paper may comprise an aqueous dispersion of colloidal
particles of Victoria Blue B (C.I. 44045) in an amount ranging by
weight from about 0.5 to 5 percent stabilized with about 1 to 5
percent of the alkaline dye-stabilizing agent and containing 1 to 6
percent of potassium iodide or manganese sulfate, and the balance
water. The foregoing can be applied to the paper as stated
hereinbefore. A more preferred solution is one containing about 1
to 3 percent of the dye Victoria Blue B stabilized with about 1 to
3 percent sodium hyrdoxide, and also containing about 1 to 3
percent potassium iodide and the balance essentially water.
Broadly speaking, one method aspect of the invention comprises
preparing a dye formulation comprising a colloidal dispersion of
about 0.5 to 5 percent by weight of said alcohol-soluble dye
(Victoria Blue B, C.I. 44045) stabilized with about 1 to 5 percent
by weight of a dye-stabilizing alkaline agent. The pH of the
solution should be over 9 and preferably at least about 11. The
alkaline agent may be selected from the group consisting of
carbonates and hydroxides of ammonia and alkali metals, and the
balance essentially water. The additional steps include providing a
paper pulp slurry, adding to said slurry an amount of said dye
formulation such that the amount of said dye in the slurry based
upon the dry weight of said paper pulp ranges from about 0.02 to
0.5 percent, and then forming a paper product in the usual manner
with a dispersion of said stabilized colloidal dye therein. After
the paper product has passed through the drying rolls, it is then
contacted with a solution of potassium iodide which is absorbed
into the paper and the paper then dried by passage through the
drying rolls. The latter solution may contain 1 to 6 percent
potassium iodide or manganese sulfate. The dye in the formulation
preferably ranges in particle size from about 0.01 to 0.2.mu..
As stated hereinbefore, in the alternative, the solution containing
by weight about 0.5 to 5 percent of the dye, about 1 to 5 percent
of the alkaline reagent, about 1 to 6 percent potassium iodide or
manganese sulfate and the balance essentially water, may be applied
to the surface of the paper or absorbed into it at or near the
finishing stage of the paper making process and the paper
thereafter dried.
Although the present invention has been described in conjunction
with preferred embodiments, it is to be understood that
modifications and variations may be resorted to without departing
from the spirit and scope of the invention as those skilled in the
art will readily understand. Such modifications and variations are
considered to be within the purview and scope of the invention and
the appended claims.
* * * * *