U.S. patent number 3,873,340 [Application Number 05/275,583] was granted by the patent office on 1975-03-25 for pressure-sensitive copying paper containing phenoxazine compounds.
This patent grant is currently assigned to Hodogaya Chemical Co., Ltd.. Invention is credited to Shiro Kimura, Yoshihide Miyazawa, Katsuichi Motohashi, Minoru Ozutsumi.
United States Patent |
3,873,340 |
Miyazawa , et al. |
March 25, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Pressure-sensitive copying paper containing phenoxazine
compounds
Abstract
A pressure-sensitive copying paper comprising an adsorbent solid
acid and a microencapsulated color former capable of forming a
distinct color when reacted with the adsorbent acid coated on the
same or a different surface of a support or supports, the
microencapsulated color former being at least one phenoxazine
compound represented by the formula ##SPC1## Wherein R.sub.1,
R.sub.2, R.sub.3, R.sub.4 and Y are as defined hereinafter, is
disclosed.
Inventors: |
Miyazawa; Yoshihide (Tokyo,
JA), Ozutsumi; Minoru (Tokyo, JA),
Motohashi; Katsuichi (Tokyo, JA), Kimura; Shiro
(Kanagawa, JA) |
Assignee: |
Hodogaya Chemical Co., Ltd.
(Tokyo, JA)
|
Family
ID: |
23052961 |
Appl.
No.: |
05/275,583 |
Filed: |
July 27, 1972 |
Current U.S.
Class: |
503/218; 544/103;
544/37 |
Current CPC
Class: |
C09B
19/00 (20130101); B41M 5/136 (20130101) |
Current International
Class: |
B41M
5/136 (20060101); B41M 5/132 (20060101); C09B
19/00 (20060101); B41m 005/16 () |
Field of
Search: |
;117/36.2,36.8
;260/243A,244R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Martin; William D.
Assistant Examiner: Pianalto; Bernard D.
Attorney, Agent or Firm: Sughrue, Rothwell, Mion, Zinn &
Macpeak
Claims
What is claimed is:
1. A pressure-sensitive copying paper comprising on a support a
layer of an encapsulated color former and on the same or a
different support a layer of an electron accepting solid, said
color former being a phenoxazine compound represented by the
formula ##SPC5##
wherein R.sub.1 and R.sub.3 each represents a lower alkyl group;
R.sub.2 is a member selected from the group consisting of a lower
alkyl group and a phenyl group; R.sub.4 is a member selected from
the group consisting of a hydrogen atom and a methyl group; and Y
is a member selected from the group consisting of an alkyl group,
an alkenyl group, a styryl group, a benzyl group, a
phenoxymethylene group, a phenyl group, a naphthyl group, a furyl
group, a thienyl group, a pyridyl group and a quinolyl group,
wherein the styryl, benzyl, phenoxymethylene, phenyl, and naphthyl
groups may be substituted in the nucleus thereof by a substituent
selected from the group consisting of a lower alkyl group, a lower
alkoxy group, a di-lower-alkylamino group, a hydroxy group, a
chlorine atom and a nitro group and wherein the quinolyl group may
be substituted in the 2-position thereof by a substituent selected
from the group consisting of a lower alkyl group and a phenyl
group.
2. The pressure-sensitive copying paper according to claim 1,
wherein said color former is a compound selected from the group
consisting of 3,7-bis(diethylamino)-10-acetylphenoxazine,
3,7-bis(diethylamino)-10-crotonoylphenoxazine,
3,7-bis(diethylamino)-10-cinnamoylphenoxazine,
3,7-bis(diethylamino0-10-(p-nitrophenylacetyl)-phenoxazine,
3,7-bis(diethylamino)-10-(p-chlorophenoxyacetyl)-phenoxazine, 3,7
-bis(diethylamino)-10-benzoylphenoxazine,
3,7-bis(diethylamino)-10-(p-methylbenzoyl)-phenoxazine,
3,7-bis(diethylamino)-10-(p-methoxybenzoyl)-phenoxazine,
3,7-bis(diethylamino)-10-(p-dimethylaminobenzoyl)-phenoxazine,
3,7-bis(diethylamino)-10-(o-hydroxybenzoyl)-phenoxazine,
3,7-bis(diethylamino)-10-(p-nitrobenzoyl)-phenoxazine,
3,7-bis(diethylamino)-10-(2-furoyl)-phenoxazine,
3,7-bis(diethylamino)-10-(2-thienoyl)-phenoxazine,
3,7-bis(diethylamino-10-nicotinoylphenoxazine,
3,7-bis(diethylamino)-10-isonicotinoylphenoxazine,
3,7-bis(diethylamino)-10-(2-phenylcinchonoyl)-phenoxazine,
3-diethylamino-7-dimethylamino-8-methyl-10-(p-methylbenzoyl)-phenoxazine,
3-diethylamino-7-dimethylamino-8-methyl-10-(1-naphthoyl)-phenoxazine,
3-diethylamino-7-dimethylamino-8-methyl-10-(3-hydroxy-2-naphthoyl)-phenoxa
zine,
3-diethylamino-7-di-n-butylamino-10-(p-methoxybenzoyl)-phenoxazine,
3-(N-methyl-N-phenylamino)-7-diethylamino-10-(p-methoxybenzoyl)-phenoxazin
e and a mixture thereof.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a pressure-sensitive copying paper
and, more particularly, to a pressure-sensitive copying paper
having a microcapsule layer containing a novel phenoxazine compound
as a color former.
2. Description of the Prior Art
Pressure-sensitive copying papers generally comprise a transfer
sheet having thereon a layer of fine capsules containing therein a
solution of an electron donating colorless organic compound
(hereinafter referred to as "color former") in an organic solvent,
and a receiving sheet having thereon a layer of an electron
accepting solid. A suitable binder is generally used for coating
the solid.
When both sheets are put together in such a manner that an electron
donating layer is brought into contact with an electron accepting
layer and localized pressure is applied to the combination of
sheets by handwriting or typewriting, the capsules are ruptured and
the colorless color former contained in the capsules is adsorbed by
the electron accepting solid, which is usually a solid acid, to
form a color.
Pressure-sensitive copying paper systems comprising the aforesaid
transfer sheet (hereinafter referred to as "upper sheet") and a
receiving sheet (hereinafter referred to as "lower sheet") and an
intermediate sheet (hereinafter referred to as "middle sheet") are
also known. In these systems the middle sheet is usually coated, on
opposite surfaces, with a layer of microcapsules containing a color
former solution and with a layer of a solid acid and a binder,
respectively.
Another type of pressure-sensitive copying system is a recording
sheet which can be prepared by applying the above described
microcapsules and the adsorbent solid acid on the same surface of a
support.
The solid acid used in the conventional type of pressure-sensitive
copying papers includes active clay substances such as acid clay,
atapalgite, zeolite, bentonite and the like, solid organic acids
such as succinic acid, tannic acid, benzoic acid and the like, and
acidic organic polymers such as phenol-formaldehyde
polycondensates, phenol-acetylene copolymers, styrene-maleic
anhydride copolymers containing residual acidic radicals, salicylic
acid-formaldehyde polycondensates and the like. The organic solvent
for dissolving the color former which is conventionally used
includes, for example, ethylene glycol, chlorobenzenes and
chlorobiphenyls.
Benzoyl leuco methylene blue is well known as a color former
forming a blue color. Benzoyl leuco methylene blue slowly forms a
blue color on a lower sheet when an upper sheet having the benzoyl
leuco methylene blue thereon is superposed on a lower sheet coated
with an active clay substance such as acid clay and localized
pressure is applied to the assembly by, e.g., handwriting. However,
this compound does not form a clear blue color when a lower sheet
coated with an acidic organic polymer such as a phenol-formaldehyde
polycondensate is used. It has, therefore, strongly been desired to
develop pressure-sensitive copying papers which are capable fo
forming a blue color with an excellent fastness to light even on a
lower sheet coated with the above described acidic organic polymer,
because such pressure-sensitive copying papers are expected to be
useful in a wide variety of utilities.
An object of the present invention is, therefore, to provide
pressure-sensitive copying papers containing as a color former a
phenoxazine compound which rapidly forms a stable blue color having
excellent light fastness and water resistance when it is brought
into contact with a solid acid.
Another object of the present invention is to provide
pressure-sensitive copying papers which can be colored various
colors by using a phenoxazine compound in combination with other
known color formers.
SUMMARY OF THE INVENTION
According to the present invention, there is provided a
pressure-sensitive copying paper containing as a color former a
phenoxazine compound represented by the formula ##SPC2##
wherein R.sub.1 and R.sub.3 each represents a lower alkyl group;
R.sub.2 represents a lower alkyl or a phenyl group; R.sub.4
represents a hydrogen atom or a methyl group; and Y is selected
from the group consisting of alkyl, alkenyl, styryl, benzyl,
phenoxymethylene, phenyl, naphthyl, furyl, thienyl, pyridyl and
quinolyl groups in which the styryl, benzyl, phenoxymethylene,
phenyl and naphthyl groups may be substituted in the nucleus
thereof by one of a lower alkyl, a lower alkoxy, a
di-lower-alkylamino, a hydroxy, a chloro or a nitro group and the
quinolyl group may be substituted in 2-position by either of a
lower alkyl or a phenyl group.
DETAILED DESCRIPTION OF THE INVENTION
As the result of detailed investigations on color formers capable
of forming a blue color on a lower sheet coated with an acidic
organic polymer as a solid acid, it was found that, a blue color
having an excellent light fastness is gradually formed on a lower
sheet when localized pressure is applied by, for example,
handwriting to an upper sheet coated with the phenoxazine compound
represented by the above formula (I) as a color former superposed
on a lower paper coated with an acidic organic polymer, active clay
substance or a mixture thereof as a solid acid. It was also found
that any desirable color having an excellent light fastness can be
formed on a lower sheet when localized pressure is applied by, for
example, handwriting to an upper sheet coated with the phenoxazine
compound of the above formula (I) in combination with a known color
former as a color former superposed on a lower sheet coated with an
acidic organic polymer, active clay substance or a mixture thereof
as a solid acid.
Representative examples of the phenoxazine compounds of the formula
(I) which are particularly useful in the pressure-sensitive copying
paper of the present invention and the processes for the synthesis
of the compounds are illustrated hereinafter. ##SPC3##
The compounds represented by the above formula (I) can be prepared
by reacting 1 mole of a leuco compound represented by the formula
(II) ##SPC4##
wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are as defined above
with respect to the formula (I), with 1.0 to 5.0 moles of an acid
halide represented by the formula (III).
Y -- CO -- X (III)
wherein X is a halogen atom and Y is as defined above with respect
to the formula (I), in the presence of 1.0 to 10.0 moles of an acid
acceptor such as sodium hydroxide, sodium carbonate, pyridine or
triethylamine in a volatile organic inert solvent such as
chloroform, benzene, toluene or chlorobenzenes or a mixture of such
a volatile organic inert solvent and water, optionally while
passing gaseous nitrogen through the reaction mixture, at a
reaction temperature of from 30.degree. to 130.degree.C for a
period of from 1 to 5 hours. After completion of the reaction, the
organic solvent layer is separated, and is treated with a 3 to 10%
by weight aqueous hydrogen peroxide solution, washed with water and
distilled under reduced pressure to remove any residual organic
solvent to obtain the desired color former having the formula (I).
If necessary, the color former thus obtained can further be
purified, for example, by recrystallization.
The preparation of the individual color formers as listed in the
previous table are illustrated by the following production examples
in which all parts given are by weight unless otherwise
indicated.
PRODUCTION EXAMPLE 1
Preparation of Color Former No. 1
A mixture of 2.8 parts of 3,7-bis(diethylamino)-phenoxazine, 2.4
parts of acetyl chloride and 3.4 parts of pyridine was heated at a
reaction temperature of from 50.degree. to 60.degree.C for 2 hours
in 100 parts of chloroform. Thereafter the mixture was treated with
a 3% aqueous hydrogen peroxide solution and thoroughly washed with
water. The chloroform layer was then separated and treated with an
activated carbon, distilled under reduced pressure to remove the
residual chloroform and recrystallized from ethyl alcohol to obtain
2.5 parts of a light brown-colored compound having a melting point
of 146.degree.-147.degree.C. A solution of the resulting compound
in benzene slowly turned blue when brought into contact with an
acid clay or a phenolformaldehyde polycondensate coated on a
paper.
The same color former was also obtained by repeating the above
procedure using acetyl bromide in place of acetyl chloride.
PRODUCTION EXAMPLE 2
Preparation of Color Former No. 6
To a mixture of 60 parts of toluene and 50 parts of water were
added 3.2 parts of 3,7-bis(diethylamino-phenoxazine and 4.8 parts
of benzoyl chloride, followed by the addition of 14.5 parts of a
17% aqueous sodium hydroxide solution. The mixture was then heated
at a reaction temperature of from 50.degree. to 55.degree.C for 3
hours and thereafter worked-up in the same manner as described in
Production Example 1 to obtain 3.7 parts of a light yellow-colored
color former having a melting point of 123.degree.-125.degree.C. A
solution of the resulting color former in benzene slowly turned
blue when brought into contact with an acid clay or a
phenol-formaldehyde condensate coated on a paper.
PRODUCTION EXAMPLE 3
Preparation of Color Former No. 21
To a mixture of 100 parts of toluene and 80 parts of water were
added 3.6 parts of
3-(N-phenyl-N-methylamino)-7-diethylamino-phenoxazine and 6.8 parts
of p-methoxybenzoyl chloride, followed by the addition of 14.5
parts of a 17% aqueous sodium hydroxide solution. The mixture was
then heated at a reaction temperature of from 55.degree. to
60.degree.C for 2 hours and thereafter worked-up in the same manner
as described in Production Example 1 to obtain 4.0 parts of a light
yellow-colored compound having a melting point of
141.degree.-143.degree.C. A solution of the resulting compound in
benzene slowly turned blue upon contact with an acid clay or a
phenolformaldehyde condensate coated on a paper.
PRODUCTION EXAMPLE 4
Preparation of Color Former Nos. 2 to 5, 7 to 13 and 17 to 20
Each of the Color Formers Nos. 2 to 5, 7 to 13 and 17 to 20 was
prepared in a similar manner as described in Production Example 2
but using appropriate starting compounds of the formulae (II) and
(III). The color formers thus obtained were slightly colored
crystals having melting points and an appearance as shown in the
following table.
______________________________________ Color Melting Point
Appearance of Crystals Former (.degree.C)
______________________________________ No.2 110 - 112 Light brown
powder No.3 134 - 135 Light yellow powder No.4 134 - 136 Light
brown powder No.5 125.5-127 Pale white powder No.7 122 - 124 Light
yellowish brown powder No.8 124.5-126 Light yellow powder No.9 162
- 163 Pale white powder No.10 85 - 90 Light green powder No.11 142
- 143 Light brown powder No.12 119 - 120 Light yellowish green
powder No.13 163 - 166 Light yellow powder No.17 121 - 123 Light
yellow powder No.18 103 - 105 Light yellowish green powder No.19
103 - 107 Light green powder No.20 92 - 93 Light yellow powder
______________________________________
PRODUCTION EXAMPLE 5
Preparation of Color Former Nos. 14 to 16
To a mixture of 150 parts of toluene and 10 parts of triethylamine
were added under a nitrogen stream 3.2 parts of
3,7-bis(diethylamino)-phenoxazine and the corresponding acid
halide, i.e., 5.3 parts of nicotinoyl chloride for Color Former No.
14, 5.3 parts of isonicotinoyl chloride for Color Former No. 15, or
9.8 parts of 2-phenylcinchonoyl chloride for Color Former No. 16.
The reaction mixtures in each instance was heated at a reaction
temperature of from 50.degree. to 55.degree.C for 2 hours under a
nitrogen stream and thereafter worked-up in the same manner as
described in Production Example 1 to obtain the desired color
formers, i.e., 3.8 parts of Color Former No. 14, 3.0 parts of Color
Former No. 15 or 4.2 parts of Color Former No. 16, as slightly
colored crystals in each instance. The melting points and
appearance of the color formers thus obtained are shown in table
below.
______________________________________ Color Melting Point
Appearance of Crystals Former (.degree.C)
______________________________________ No. 14 139 - 141 Light
yellowish green powder No. 15 117 - 118 Light green powder No. 16
183 - 185 Light yellow powder
______________________________________
In preparing pressure-sensitive copying papers using the
phenoxazine compounds represented by the formula (I) as color
formers, the well-known process disclosed in U.S. Pat. Nos.
2,800,457 and 2,800,458, i.e. a process which utilizes the
phenomenon of complex coacervation can advantageously be employed.
In this process, the color former is generally used in the amount
of from 0.5 to 5.0% by weight relative to the amount of an organic
solvent such as ethylene glycol, chlorobenzene or chlorobiphenyl as
previously described.
The preparation of pressure-sensitive copying papers using some of
the color formers represented by the formula (I) is illustrated in
the following examples, in which all parts given are by weight
unless otherwise indicated.
EXAMPLE 1
Preparation of Pressure-sensitive Copying Paper
Two parts of Color Former No. 21 was dissolved in 100 parts of
trichlorobiphenyl and to the solution were added 20 parts of gum
arabic and 160 parts of water while stirring at 50.degree.C to form
an emulsion. To the emulsion were added, with stirring 20 parts of
an acid treated gelatin and 160 parts of water followed by the
addition of acetic acid to adjust the pH to 5. 500 parts of water
was then added to the emulsion to effect the coacervation thereby
forming a dense liquid film of gelatin-gum arabic around the
surface of each droplet of trichlorobiphenyl having the color
former dissolved therein and, after adjustment of the pH of the
mixture to 4.4, 3.8 parts of 37% formalin was added thereto to
harden the liquid film. The emulsion was then cooled to 10.degree.C
and, after adjustment of the pH to 9 by addition of an aqueous
sodium hydroxide solution, allowed to stand to complete the
encapsulation process. The liquid containing the microcapsules was
applied using, for example, a roll coating or air-knife coating
procedure to a paper and dried to obtain a colorless coated paper,
i.e., an upper sheet. When the upper sheet thus obtained was
superposed on a lower sheet coated with, as a solid acid, an acidic
organic polymer, active clay substance or a mixture thereof in such
a manner that the layer of microcapsules was brought into contact
with a layer of the above solid acid and localized pressure was
applied to the assembly of sheets by e.g., handwriting, a blue
color was gradually formed in the pressed areas of the lower sheet.
This blue color changed to a deep shade within several hours. No
substantial discoloration of the completely developed blue color
was observed when the lower sheet was exposed directly to sun light
for a long period of time.
EXAMPLE 2
Preparation of Pressure-sensitive Copying Papers
2.0 parts of each of Color Former Nos. 1 to 20 were separately
processed in the same manner as described in Example 1 to form
separate liquids containing microcapsules. The liquid was then
applied to a paper and dried to obtain a colorless upper sheet.
When the upper sheet was superposed on a lower sheet coated with,
as a solid acid, an acidic organic polymer, active clay substance
or a mixture thereof and localized pressure was applied to the
assembly of sheets by, e.g., handwriting, a blue color was formed
immediately in the pressed areas of the lower sheet. No substantial
discoloration of the blue color was observed when the lower sheet
was exposed directly to sun light for a long period of time.
EXAMPLE 3
Preparation of Pressure-sensitive Copying Papers
A blend of 1 part of Color Former No. 6 and 1.5 parts of crystal
violet lactone was processed in the same manner as described in
Example 1 to form a liquid containing microcapsules which was then
applied to a paper and dried in the same manner as described in
Example 1 to obtain a colorless upper sheet. When the upper sheet
was superposed on a lower sheet coated with an acidic organic
polymer, active clay substance or mixture thereof as a solid acid
and localized pressure was applied to the assembly of sheets by,
e.g., handwriting, a blue color was formed immediately in the
pressed areas of the lower sheet. No substantial discoloration of
the blue color was observed when the lower sheet was exposed
directly to sun light for a long period of time. While the
invention has been described in detail and in terms of specific
embodiments thereo, it will be apparent to those skilled in the art
that various modifications and variations can be made therein
without departing from the spirit and the scope of the
invention.
* * * * *