U.S. patent number 3,871,900 [Application Number 05/382,224] was granted by the patent office on 1975-03-18 for recording sheet.
This patent grant is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Takao Hayashi, Sadao Ishige, Hajime Kato.
United States Patent |
3,871,900 |
Hayashi , et al. |
March 18, 1975 |
Recording sheet
Abstract
A recording sheet comprising a support having thereon a color
developer layer capable of reacting with a color former to form
color images, said color developer layer containing (1) a metal
compound of an aromatic carboxylic acid and (2) at least one member
selected from the group consisting of ethers and alcohols.
Inventors: |
Hayashi; Takao (Fujinomiya-shi,
Shizuoka, JA), Kato; Hajime (Fujinomiya-shi,
Shizuoka, JA), Ishige; Sadao (Minami Ashigara-shi,
Kanagawa, JA) |
Assignee: |
Fuji Photo Film Co., Ltd.
(Minami Ashigara-shi, Kanagawa, JA)
|
Family
ID: |
13585441 |
Appl.
No.: |
05/382,224 |
Filed: |
July 24, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Jul 28, 1972 [JA] |
|
|
47-75758 |
|
Current U.S.
Class: |
503/210; 503/211;
503/212; 503/216; 503/225 |
Current CPC
Class: |
B41M
5/155 (20130101) |
Current International
Class: |
B41M
5/155 (20060101); B41m 005/00 () |
Field of
Search: |
;117/36.2,36.8 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Herbert, Jr.; Thomas J.
Attorney, Agent or Firm: Sughrue, Rothwell, Mion, Zinn &
Macpeak
Claims
What is claimed is:
1. A recording sheet comprising a support having thereon a color
developer layer capable of reacting with a color former to form
color images, said color developer layer containing (1) a metal
salt of an aromatic carboxylic acid and (2) at least one member
selected from the group consisting of ethers and alcohols, said
component (1) and said component (2) being present at a proportion
sufficient to increase the color-developing ability of said color
developer and said color former.
2. The recording sheet of claim 1, wherein said metal of said metal
salt of an aromatic carboxylic acid is a member of Group I B, Group
II A, Group II B, Group III B, Group IV A, Group VI A, Group VII B
or Group VIII of the Periodic Table.
3. The recording sheet of claim 1, wherein said aromatic carboxylic
acid is represented by the formula: ##SPC5##
wherein R may be the same or different and represents a hydrogen
atom, a hydroxy group, a halogen atom, a nitro group, an alkyl
group having 1 to 10 carbon atoms, the total carbon number in the
R's being less than 13, an aryl group, an arylamino group or an
alicyclic group, m is an integer of 0 to 7 and n is an integer of 0
to 5, or said aromatic carboxylic acid may be dimerized through the
substituent R as a methylene group.
4. The recording sheet of claim 3, wherein said metal of said metal
salt of an aromatic carboxylic acid is a member of Group I B, Group
II A, Group II B, Group III B, Group IV A, Group VI A, Group VII B
or Group VIII of the Periodic Table;
wherein said color developer layer contains from 10 to 250 parts by
weight of said ether and alcohol per 100 parts by weight of said
aromatic carboxylic acid and wherein said color developer layer is
present on said support at a level of at least 0.1 g/m.sup.2 as the
metal salt of the aromatic carboxylic acid;
said ether is represented by the formula:
ROX
wherein X is --(CH.sub.2).sub.p OR', --(CH.sub.2).sub.p OH,
--[(CH.sub.2).sub.n O].sub.q H, --[(CH.sub.2).sub.n O].sub.q R", an
alkyl group having up to 18 carbon atoms or an alkenyl group having
up to 18 carbon atoms, R is an alkyl group having up to 10 carbon
atoms, an aryl group having up to 10 carbon atoms or an alkenyl
group having up to 10 carbon atoms, R' and R" each is an alkyl
group having up to 18 carbon atoms, an aryl group having up to 18
carbon atoms or an alkenyl group having up to 18 carbon atoms, p is
an integer of 1 to 20 and q is an integer of 2 to 30; and
the alcohol is an aliphatic alcohol having from 1 to 18 carbon
atoms.
5. The recording sheet of claim 1, wherein said ether is a glycol
ether.
6. The recording sheet of claim 1, wherein said alcohol is an
alcohol having 4 or more carbon atoms.
7. The recording sheet of claim 1, wherein said color developer
layer contains a mixture of at least on ether and at least on
alcohol.
8. The recording sheet of claim 1, wherein said color developer
layer contains from 10 to 250 parts by weight of said ether and
alcohol per 100 parts by weight of said aromatic carboxylic acid
and wherein said color developer layer is present on said support a
level of at least 0.1 g/m.sup.2 as the metal salt of the aromatic
carboxylic acid.
9. The recording sheet of claim 1, wherein said ether is
represented by the formula:
ROX
wherein X is --(CH.sub.2).sub.p OR', --(CH.sub.2).sub.p OH,
--[(CH.sub.2).sub.n O].sub.q H, --[(CH.sub.2).sub.n O].sub.q R", an
alkyl group having up to 18 carbon atoms or an alkenyl group having
up to 18 carbon atoms, R is an alkyl group having up to 10 carbon
atoms, an aryl group having up to 10 carbon atoms or an alkenyl
group having up to 10 carbon atoms, R' and R" each is an alkyl
group having up to 18 carbon atoms, an aryl group having up to 18
carbon atoms or an alkenyl group having up to 18 carbon atoms, p is
an integer of 1 to 20 and q is an integer of 2 to 30.
10. The recording sheet of claim 1 wherein said alcohol is an
aliphatic alcohol having 1 to 18 carbon atoms.
11. The recording sheet of claim 1 wherein said alcohol is selected
from the group consisting of n-butyl alcohol, n-amyl alcohol,
n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl
alcohol, n-decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl
alcohol, stearyl alcohol, isobutyl alcohol, sec-butyl alcohol,
isoamyl alcohol, tert-butyl alcohol, sec-butyl carbinol, diethyl
carbinol, 1-hexanol, 2-hexanol, 3-hexanol, cyclohexanol,
3-methyl-1-pentanol, 4-methyl-2-hexanol, allyl alcohol,
trans-crotyl alcohol, ciscrotyl alcohol, 2-methyl-3-buten-1-ol,
o-tolyl carbinol m-tolyl carbinol, p-tolyl carbinol and benzyl
alcohol.
12. The recording sheet of claim 1 wherein said aromatic carboxylic
acid is selected from the group consisting of benzoic acid,
nitrobenzoic acid, chlorobenzoic acid, toluic acid,
4-methyl-3-nitrobenzoic acid, 2-chloro-4-nitrobenzoic acid,
2,3-dichlorobenzoic acid, 4-methyl-3-nitrobenzoic acid,
4-acetylbenzoic acid, 2,4-dihydroxybenzoic acid,
2,5-dihydroxybenzoic acid, 1-napththoic acid, 2-naphthoic acid,
1-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid,
2-hydroxy-1-naphthoic acid, thiosalicyclic acid, salicylic acid,
3,5-dinitrosalicylic acid, 3-methylsalicyclic acid, 2,4-cresotinic
acid, 2,5-cresotinic acid, 3-methylsalicyclic acid, 2,4-cresotinic
acid, 2,5-cresotinic acid, 5-tert-butylsalicylic acid,
3-phenylsalicylic acid, 3-methyl-5-tert-butylsalicylic acid,
3,5-di-tert-butylsalicylic acid, 3,5-di-tert-amylsalicylic acid,
3-cyclohexylsalicylic acid, 5-cyclohexylsalicylic acid and
3-methyl-5-isoamylsalicylic acid.
13. The recording sheet of claim 1, wherein said metal salt of said
aromatic carboxylic acid is a copper, zinc, aluminum, tin or nickel
salt.
14. A pressure sensitive copying assembly comprising a color former
layer on a first support and a color developer layer on a second
support, said color developer layer and said color former layer
being brought together at the time of pressure sensitive copying to
permit color developer and color former to be brought into reactive
contact to form a color image, said color developer layer
containing (1) a metal salt of an aromatic carboxylic acid and (2)
at least one member selected from the group consisting of ethers
and alcohols, said component (1) and said component (2) being
present at a porportion sufficient to increase the color-developing
ability of said color developer and said color former.
15. The pressure sensitive copying assembly of claim 14 wherein
said color developer layer contains from 10 to 250 parts by weight
of said ether and alcohol per 100 parts by weight of said aromatic
carboxylic acid and wherein said color developer layer is present
on said support at a level of at least 0.1 g/m.sup.2 as the metal
salt of the aromatic carboxylic acid.
16. The pressure sensitive copying assembly of claim 15, wherein
said metal of said metal salt of an aromatic carboxylic acid is a
member of Group I B, Group II A, Group II B, Group III B, Group IV
A, Group VI A, Group VII B or Group VIII of the Periodic Table.
17. A pressure sensitive copying assembly comprising a color former
layer and a color developer layer carried on the same support, said
color developer layer and said color former layer being in
relationship such that at the time of pressure sensitive copying,
color developer and color former are brought into reactive contact
to form a color image. Said color developer layer containing (1) a
metal salt of an aromatic carboxylic acid and (2) at least one
member selected from the group consisting of ethers and alcohols,
said component (1) and said component (2) being present at a
proportion sufficient to increase the color-developing ability of
said color developer and said color former.
18. The pressure sensitive copying assembly of claim 17 wherein
said color developer layer contains from 10 to 250 parts by weight
of said ether and alcohol per 100 parts by weight of said aromatic
carboxylic acid and wherein said color developer layer is present
on said support at a level of at least 0.1 g/m.sup.2 as the metal
salt of the aromatic carboxylic acid.
19. The pressure sensitive copying assembly of claim 18, wherein
said metal of said metal salt of an aromatic carboxylic acid is a
member of Group I B, Group II A, Group II B, Group III B, Group IV
A, Group VI A, Group VII B or Group VIII of the Periodic Table.
Description
BACKGROUND OF THE INVENTION
1. FIELD OF THE INVENTION
The present invention relates to a recording sheet, and more
particularly to a recording sheet containing an improved color
developer.
2. DESCRIPTION OF THE PRIOR ART
Recording sheets utilizing a color reaction of an almost colorless
organic compound (hereinafter referred to as a "color former") such
as Malachite green lactone, benzoylleucomethylene blue, crystal
violet acetone, Rhodamine B lactam,
3-dialkylamino-7-dialkylaminofluoran and 3-methyl-2,2'-spirobi
(benzo[f]chromene), and an adsorbent or reactive material
(hereinafter referred to as a "color developer") capable of forming
a color when contacted with the color former are well known.
As the recording sheets practically using the phenomenon, there are
a pressure-sensitive recording sheet (see, for example, U.S. Pat.
Nos. 2,505,470; 2,505,489; 2,550,471; 2,548,366; 2,730,456;
2,730,457; 3,418,250, etc.) and a heat-sensitive recording sheet
(see, for example, Japanese Patent Publication Number 4160/68; U.S.
Pat. No. 2,939,009, etc.). Further, a printing method is known
wherein an ink containing the color former is applied to the color
developer sheet through a medium such as a stencil (see German
Patent OLS No. 1,939,62, etc.).
In many cases, the above mentioned phenomenon of the color reaction
between the color former and the color developer requires physical
conditions such as pressure with a pen or with a key of a
typewriter, heat, etc.
As the most representative embodiment of the recording sheets,
there is illustrated a pressure-sensitive copying paper. A
pressure-sensitive copying paper may be obtained by dissolving a
color former in a solvent such as chlorinated paraffin,
alkylnaphthalene, alkylated diphenylethane, alkylated
diphenylmethane, or the like, dispersing the resulting solution in
a binder or microencapsulating the solution, and then the coating
on a support such as paper, plastic film, etc.
A heat-sensitive recording sheet may be obtained by coating a color
former on a support together with a thermofusible material such as
acetanilide. As used herein, the term "thermofusible material"
means a material which is melted on heating to dissolve the color
former.
In general, the color former and color developer may be coated on
the same surface or opposite surfaces of a support, or on different
supports. Also, the color developer may be coated on or impregnated
into a support as an ink.
As the above-described color developer, clays such as acid clay,
activated clay, attapulgite, zeolite, bentonite, etc.; organic
acids such as succinic acid, tannic acid, gallic acid or phenol
compounds, and acidic polymers such as phenol resins are known.
Furthermore, a mixture of an aromatic carboxylic acid and a metal
compound; a metal compound of a polymer of an aromatic carboxylic
acid having at least one hydroxy group and an aldehyde; a metal
compound of an aromatic carboxylic acid; a metal compound of a
phenol compound having a pKa of not more than 8; and the like, are
effective as a color developer.
Of these, a metal compound of an aromatic carboxylic acid is
particularly effective as a color developer. That is, a color
developer sheet containing as a color developer a metal compound of
an aromatic carboxylic acid has the following excellent properties
in comparison with conventional color developer sheets.
1. Even when left in the air, reduction in color-developing ability
with the passage of time is small.
2. By using an aromatic carboxylic acid difficult to dissolve in
water, disappearance or reduction in density can be avoided even
when the color former on the color developer sheet is wet with
water.
3. The light fastness of the colored image on the color developer
sheet is excellent.
4. Since sufficient color-developing ability can be obtained using
a small coating amount, workability in coating is very good.
As is described above the properties of the recording sheet and the
various problems encountered in the production thereof have been
improved considerably by using a metal compound of an aromatic
carboxylic acid as a color developer instead of the conventional
color developers.
However, there remain the disadvantages that, in the production of
a metal compound of an aromatic carboxylic acid, the viscosity of
the prepared (coating) solution increases and the particle size of
the metal compound becomes coarse thereupon. Therefore, it is
difficult to prepare a stable coating solution and, unless the
particle size of the metal compound is made fine by means of a ball
mill or sand mill, there is room for improvement in the
color-developing ability and film surface strength of the coated
layer.
A primary object of the present invention is to improve the
color-developing ability of a color developer sheet containing a
metal compound of an aromatic carboxylic acid.
Another object of the present invention is to simplify the steps
for preparing a coating solution containing an aromatic carboxylic
acid.
Further object of the present invention is to improve the coating
characteristics of the coating solution containing an aromatic
carboxylic acid.
Still a further object of the present invention is to provide a
color developer having the above-described advantages.
Still a further object of the present invention is to provide a
recording sheet having the above-described advantages.
SUMMARY OF THE INVENTION
As a result of various investigations, it has been found that the
addition of at least one member selected from the ethers and
alcohols to a color-developing layer containing a metal compound of
an aromatic carboxylic acid achieves the above-described
objects.
DETAILED DESCRIPTION OF THE INVENTION
The ethers suitable for use in this invention can be represented by
the formula,
ROX
wherein X is --(CH.sub.2).sub.p OR', --(CH.sub.2).sub.p OH,
--[(CH.sub.2).sub.n O].sub.q H, --[(CH.sub.2).sub.n O].sub.q R", an
alkyl group (preferably, having up to 18 carbon atoms) or an
alkenyl group (preferably, having up to 18 carbon atoms), R is an
alkyl group (preferably, having up to 10 carbon atoms), an aryl
group (preferably, having up to 10 carbon atoms) or an alkenyl
group (preferably, having up to 10 carbon atoms), R' and R" each is
an alkyl group (preferably, having up to 18 carbon atoms), an aryl
group (preferably, having up to 18 carbon atoms) or an alkenyl
group (preferably, having up to 18 carbon atoms), p is an integer
of 1 to 20 (preferably, 2 or 3), and q is an integer of 2 to
30.
As specific examples of the ethers, ethers such as ethylene glycol
monomethyl ether, diethylene glycol monomethyl ether, diethylene
glycol mono-n-butyl ether, ethylene glycol monophenyl ether,
diethylene glycol dimethyl ether, 3-methoxybutyl acetate, ethylene
glycol monoethyl ether, ethylene glycol diethyl ether, diethylene
glycol acetate monoethyl ether, ethylene glycol diphenyl ether,
ethylene glycol dimethyl ether, ethylene glycol monobutyl ether,
ethylene glycol monopropyl ether, ethylene glycol monobenzyl ether,
ethylene glycol monooctyl ether, ethylene glycol monododecyl ether,
diethylene glycol monoethyl ether, dipropylene glycol monomethyl
ether, polyoxyethylene cetyl alcohol ether, polyoxyethylene oleyl
alcohol ether, polyoxyethylene stearyl alcohol ether,
polyoxyethylene lauryl alcohol ether, polyoxethylene octyl alcohol
ether, polyoxyethylene butyl alcohol ether, polyoxyethylene
nonyphenol ether, etc are suitable.
The alcohols are preferably aliphatic alcohols having 1 to 18
carbon atoms, although other alcohols can be employed. Specific
examples are alcohols such as n-butyl alcohol, n-amyl alcohol,
n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl
alcohol, n-decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl
alcohol, stearyl alcohol, isobutyl alcohol, sec-butyl alcohol,
isoamyl alcohol, tert-butyl alcohol, sec-butyl carbinol, diethyl
carbinol, 1-hexanol, 2-hexanol, 3-hexanol, cyclohexanol,
3-methyl-1-pentanol, 4-methyl-2-hexanol, allyl alcohol,
trans-crotyl alcohol, ciscrotyl alcohol, 2-methyl-3-buten-1-ol,
o-tolyl carbinol, m-tolyl carbinol, p-tolyl carbinol, benzyl
alcohol, etc., are suitable. Mixtures of ethers and alcohols can be
used where desired.
Of the ethers to be used in the invention, glycol ethers are
particularly desirable and, of the alcohols, alcohols having 4 or
more carbon atoms are particularly preferable. That is, when a
glycol ether or an alcohol having 4 or more carbon atoms is used,
the color-developing ability is markedly improved and, when they
are used in combination, the color-developing ability is improved
to an even greater extent. In addition, when an alcohol having 4 or
more carbon atoms is used, water-immersion coloration of the color
developer layer is depressed. As used herein, the term
"water-immersion coloration" means the phenomenon of the coloring
of the color former upon immersing in water the color developer
layer in face-to-face contact with a color former layer followed by
drying.
A suitable amount of the ethers and alcohols which can be used is
from 10 to 250 parts by weight, preferably 50 to 150 parts by
weight, per 100 parts by weight of the aromatic carboxylic
acid.
The metal compound of the aromatic carboxylic acid to be used in
the color developer sheet of the invention is the compound prepared
by reacting an alkali metal salt, such as the sodium or potassium
salt, of an aromatic carboxylic acid with a water-soluble metal
salt in a solvent in which both are soluble. Generally, the alkali
metal salt of the aromatic carboxylic acid and the water-soluble
metal salt may be reacted with each other in optional porportions,
but preferably, they are reacted in gram equivalent amounts.
The metal compound of an aromatic carboxylic acid is a salt of such
an acid such as a zinc, tin, aluminum, nickel, magnesium or calcium
salt of an aromatic carboxylic acid, and these salts can be
obtained easily by stirring an aromatic carboxylic acid or an
alkali metal salt thereof with a metal hdyroxide, sulfate or
nitrate in the presence of an alkali. In this procedure, the pH
value, temperature and pressure are not critical.
The aromatic carboxylic acid is preferably represented by the
formula: ##SPC1##
wherein R may be the same or different and represents a hydrogen
atom, a hydroxy group, a halogen atom such as chlorine, a nitro
group, an alkyl group having 1 to 10 carbon atoms (preferably 3 to
6 carbon atoms), of which the total carbon atoms are less than 13,
an aryl group such as phenyl group, an arylamino group such as
anilino group, and an alicyclic group such as hexyl group, m is an
integer of 0 to 7 and n is an integer of 0 to 5, and the aromatic
carboxylic acid may be dimerized through the substituent R as a
methylene group.
More preferable compounds are those represented by the formula,
##SPC2##
wherein R, m and n are as defined above.
The most preferable compounds are those represented by the formula
##SPC3##
wherein R is as defined above, n is 1 or 2, and R is attached to
the meta-position relative to the hydroxy group.
Above all, aromatic carboxylic acids having at least one hydroxyl
group are especially effective and those having a hydroxyl group in
the o-position, i.e., the aromatic carboxylic acids represented by
the following formulae, are more effective. ##SPC4##
wherein R, m and n are as defined above.
The aromatic carboxylic acid used in the present invention
includes, for example, benzoic acid, nitrobenzoic acid (any of o-,
m- and p-derivatives may be used), chlorobenzoic acid (any of o-,
m- and p-derivatives may be used), toluic acid (any of o-, m- and
p-derivatives may be used), 4-methyl-3-nitrobenzoic acid,
2-chloro-4-nitrobenzoic acid, 2,3-dichlorobenzoic acid,
4-methyl-3-nitrobenzoic acid, 4-acetylbenzoic acid,
2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 1-naphthoic
acid, 2-naphthoic acid, 1-hydroxy-2-naphthoic acid,
2-hydroxy-3-naphthoic acid, 2-hydroxy-1-naphthoic acid,
thiosalicyclic acid, salicylic acid, 3,5-dinitrosalicyclic acid,
3-methylsalicyclic acid, 2,4-cresotinic acid, 2,5-cresotinic acid,
3-methylsalicylic acid, 2,4-cresotinic acid, 2,5-cresotinic acid,
5-tert-butylsalicylic acid, 3-phenylsalicylic acid,
3-methyl-5-tert-butylsalicylic acid, 3,5-di-tert-butylsalicylic
acid, 3,5-di-tert-amylsalicylic acid, 3-cyclohexylsalicylic acid,
5-cyclohexylsalicylic acid, 3-methyl-5-isoamylsalicyclic acid,
etc.
As the metals which form the metal compound of the aromatic
carboxylic acid used in this invention, there can be mentioned
metals of Group I B of the Periodic Table as, e.g., copper and
silver; metals of Group II A as, e.g., magnesium and calcium;
metals of Group II B, e.g. zinc, cadmium and mercury; metals of
Group III B, e.g., aluminum and gallium; metals of Group IV A,
e.g., tin and lead; metals of Group VI A, e.g., chromium and
molybdenum; metals of Group VII B, e.g., manganese; and metals of
Group VIII such as cobalt and nickel.
Of the metals salts to be used for producing the above-described
metal compound of the aromatic carboxylic acid, the chlorides,
sulfates, nitrates or acetates of copper, zinc, aluminum, tin,
nickel, etc. are particularly useful.
The color developer of the present invention may be provided on a
support in various manners. Since the effects of the present
invention are naturally produced when at least one or more of the
ethers or alcohols are present in the color developer layer, the
process for the production is not particularly limited. However,
for the purpose of simplifying the step of preparing a coating
solution containing an aromatic carboxylic acid, which is one
object of the present invention, it is desirable to add at least
one ether or alcohol before reacting the alkali metal salt of an
aromatic carboxylic acid with the water-soluble metal salt. In
addition, when a water-insoluble ether or alcohol is used, it is
necessary to add it before the reaction between the alkali metal
salt of the aromatic carboxylic acid and the water-soluble metal
salt occurs. Furthermore, where a water-soluble high molecular
weight material such as water-soluble polyvinyl alcohol, methyl
cellulose, hydroxymethyl cellulose, etc. as a viscosity reducing
agent, is added before the reaction between the alkali metal salt
of an aromatic carboxylic acid and the water-soluble metal salt
takes place, a metal compound of an aromatic carboxylic acid having
low viscosity and small particle size can be produced. Of such
water-soluble high molecular weight materials, partially saponified
polyvinyl alcohol having polymerization degree of not more than
1000 is particularly effective.
Also, the effects of the present invention are not decreased at all
even when acidic resins such as phenol-formaldehyde resins, metal
oxides, metal hydroxides, clays or the chemically or physically
treated embodiments thereof are incorporated in the color developer
layer of the present invention.
To the coating solution, there may be added acid resins such as
phenol-formaldehyde resin such as p-phenylphenol-formaldehyde
resin, p-t-butylphenol-formaldehyde resin,
p-chlorophenol-formaldehyde resins, other color developers such as
Japanese acid clay and active clay, attapulgite, inorganic pigments
such as metal oxides and metal hydroxides or chemically or
physically treated-products thereof. Examples of the metal are Zn,
Mg and Al.
The Japanese acid clay, active clay or attapulgite is generally
used in an amount not less than 1 wt%, preferably 20 to 2000 wt%,
more preferably 500 to 1000 wt% based on the metal compound of
aromatic carboxylic acid, and the metal oxide or hydroxide is
generally used in an amount of from about 20 to 400 wt%, preferably
50 to 200 wt% based on the metal compound of aromatic carboxylic
acid.
In applying the coating solution of the invention to a support such
as paper, synthetic paper, synthetic resin film, etc., there can be
used, if necessary, binder material such as latexes, starches, gum
arabic, carboxymethyl cellulose or casein.
The coating solution, which is prepared as described above, may
contain a binder such as latex, polyvinyl alcohol, maleic
anhydride-styrene copolymer, starch and gum arabic. It is to be
uderstood that all binders well-known as film-forming materials can
be used in the invention. The binders can be classified into three
groups i.e., (1) a water soluble or hydrophilic binder, for
example, a natural compound such as proteins (e.g., gelatin, gum
arabic, colloid albumin, casein), celluloses (e.g., carboxymethyl
cellulose, hydroxyethyl cellulose), saccharoses (e.g., agar, sodium
alginate, starch, carboxymethyl starch), and a synthetic compound
such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylate,
polyacrylamide; (2) a water-dispersible binder, for example, latex
such as styrenebutadiene copolymer latex, styrene-maleic anhydride
copolymer latex; and (3) an organic solvent-soluble binder such
nitrocellulose, ethyl cellulose or polyester. These binders can be
used in the form of solution or dispersion in a solvent in the
invention, and the binder can be varied depending upon the type of
the solvent. Preferably, the water-soluble or dispersible binder
can be used in the aqueous solution or dispersion. Of course, the
metal compound of aromatic carboxylic acid can be coated without
using the binder. It is to be noted that the binder is optional
because it may not be necessary in case where the solvent is
organic in nature.
The amount of these binders to be used varies depending upon the
kind thereof and the kind of additives used, but an amount of from
5 to 30 parts by weight per 100 parts by weight of solid
ingredients contained in the coating solution generally is
desirable.
The coating solution is applied to the support in general a minimum
about of 0.1 g/m.sup.2 as the metal compound of the aromatic
carboxylic acid. Generally from about 0.1 to 10 g/m.sup.2
preferably from 0.2 to 5 g/m.sup.2, is suitable. The upper limit of
the coating amount is determined only by economic reasons, and the
effects of the present invention are not dissipated even when a
coating amount above the above-described range is used. In
addition, the recording sheet of the present invention may assume
any form known in the art. For example, the color developer and
color former may be provided on the same surface or opposite
surfaces of a support, or on different supports.
Since the recording sheet of the present invention is characterized
by the color developer, various conditions other than the aforesaid
conditions, i.e., various optional additives to the color developer
layer, the procedure of addition, the kind and form of color former
which couples with the developer and the kind of solvent used, may
be selected with ease based on common knowledge in the art.
According to the present invention, the color-developing ability is
markedly improved, the step for preparing a coating solution is
simplified, and a coating solution having low viscosity and
excellent coating characteristics are produced. As used herein the
nature of the low viscosity is a viscosity of the coating solution
such that the coating amount is not more than 5 g/m.sup.2 when the
coating solution is coated on a support using air knife coating of
which air knife pressure is 2000 mmH.sub.2 O and of which coating
speed is 400 m/min.
The recording sheet of the present invention will now be described
in the greater detail below by reference to the following examples.
These examples are given for the purposes of illustration and are
not to be interpreted as limiting the invention.
Additionally, the effects in examples were confirmed using the
combination of an upper sheet and a lower sheet, the upper sheet
being prepared by producing color former-containing microcapsules
in the following manner and applying them to a support, and the
lower sheet being prepared by applying a color developer of the
present invention to a support.
Microcapsules containing a color former can be produced by various
known processes. Typical of the capsule formation methods are those
utilizing the coacervation of a hydrophilic colloid sol as
described in U.S. Pat. Nos. 2,800,457, 2,800,458, and typical of
those utilizing interfacial polymerization are those described in
British Pat. Nos. 867,797, 950,443, 989,264 and 1,091,076. The
color former is dissolved in a solvent and then in
microencapsulated.
Representative of the many solvents which can be used are one or
more of the natural or synthetic oils, for example, chlorinated
biphenyls, chlorinated terphenyls, alkylated biphenyls, alkylated
terphenyls, chlorinated paraffins, chlorinated naphthalenes,
alkylated naphthalenes, kerosine, paraffin, naphthene oils and
cotton seed oil.
In the practice of the invention the color former (which is an
electron donating colorless organic compound capable of forming a
distinct color when contacted with an electron accepting acid
compound) is not particularly limited but examples thereof are:
triarylmethane type compounds such as
3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, i.e.,
crystal violet lactone (which will hereinafter be referred to as
"CVL"), 3,3-bis-(p-dimethylaminophenyl)phthalide,
3-(p-dimethylaminophenyl)-3-(1,2-dimethylindole-3-yl)phthalide,
3-(p-dimethylaminophenyl)-3-(2-methylindole-3-yl)phthalide,
3-(p-dimethylaminophenyl)-3-(2-phenylindole-3-yl)phthalide,
3,3-bis(1,2-dimethylindole-3-yl)-5-dimethylaminophthalide,
3,3-bis(1,2-dimethylindole-3-yl)-6-dimethylaminophthalide,
3,3-bis(9-ethylcarbazole-3-yl)-5-dimethylaminophthalide,
3,3-bis(2-phenylindole-3-yl)-5-dimethyl-aminophthalide and
3-p-dimethylaminophenyl-3-(1-methylpyrrole-2-yl)-6-dimethylaminophthalide,
diphenylmethane type compounds such as
4,4'-bis-dimethylaminobenzhydrinbenzyl ether, N-halophenyl-leuco
auramine and N-2,4,5-trichlorophenyl leuco auramine, xanthen type
compounds such as rhodamine B-anilinolactam, rhodamine
B-p-nitroanilinolactam, rhodamine B-p-chloroanilinolactam,
7-dimethylamino-2-methoxyfluoran, 7-diethylamino-2-methoxyfluoran,
7-diethylamino-3-methoxyfluoran, 7-diethyl-amino-3-chlorofluoran,
7-diethylamino-3-chloro-2-methylfluoran,
7-diethylamino-2,3-dimethylfluoran,
7-diethylamino-3-acetylmethylaminofluoran,
7-diethylamino-3'-methylaminofluoran, 3,7-diethylaminofluoran,
7-diethylamino-3-dibenzylaminofluoran,
7-diethylamino-3-methylbenzylaminofluoran,
7-diethylamino-3-chloroethylmethylaminofluoran and
7-diethylamino-3-diethylaminofluoran, thiazine type compounds such
as benzoyl leuco methylene blue and p-nitrobenzyl leuco methylene
blue, spiro compounds such as 3-methyl-spiro-dinaphthopyran,
3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran,
3-benzylspirodinaphthopyran,
3-methylnaphtho-(3-methoxy-benzo)-spiro-pyran and
3-propyl-spiro-dibenzopyran.
Coating may be carried out by any coating system, such as, air
knife coating, blade coating, roll coating or by any known printing
system. In the Examples, the microcapsules were produced as follows
according to U.S. Pat. No. 2,800,457.
Hereinafter, all "percents" and "parts" are by weight.
10 Parts of acid-processed pigskin gelatin and 10 parts of gum
arabic were dissolved in 400 parts of water at 40.degree.C, and 0.2
part of Turkey red oil was added thereto as an emulsifier. Then, 50
parts of a color former oil was emulsified and dispersed therein.
The color former oil was prepared by dissolving 2% of crystal
violet lactone or 3-N,N-diethylamino-7-N,N-dibenzylaminofluoran in
an oil comprising 4 parts of chlorinated diphenyl and 1 part of
kerosene. The emulsification was discontinued when the average size
of the oil droplets became 5 microns. To this was added water at
40.degree.C to make a total of 900 parts while continuing the
stirring. At this time, care was taken so that the liquid
temperature did not become lower than 40.degree.C. Subsequently,
10% acetic acid was added thereto, and the pH of the solution was
adjusted to 4.0-4.2 to cause coacervation. The stirring was further
continued and, after 20 minutes elapsed, the coacervate film
deposited around the oil droplets was gelled by cooling with
ice-water. When the liquid temperature reached 20.degree.C, 7 parts
of 37% formalin was added thereto. When the temperature reached
10.degree.C, a 15% sodium hydroxide aqueous solution was added
thereto to adjust the pH to 9. Subsequently, the system was heated
for 20 minutes under stirring to raise the liquid temperature to
50.degree.C.
The thus obtained microcapsule dispersion was adjusted to
30.degree.C and applied to a 40 g/m.sup.2 paper in an amount of 6
g/m.sup.2 based on the amount of solid ingredients followed by
drying.
The following examples and comparative examples were conducted
using a sheet coated with microcapsules containing crystal violet
lactone or 3-N,N-diethylamino-7-N,N-dibenzylaminofluoran.
EXAMPLE 1
0.1 Mol of 5-tert-butylsalicylic acid was dissolved in a mixture of
0.1 mol of sodium hydroxide and 300 ml of water. To this solution
were added 30 g of a 10% polyvinyl alcohol (polymerization degree:
about 500; saponification degree: about 87%) aqueous solution and
an ether or alcohol as listed in the following table. Then, a
solution prepared by dissolving 0.1 mol of zinc chloride in 100 cc
of water was gradually added thereto under stirring. The resulting
coating solution was coated on a 50 g/m.sup.2 paper in an amount of
2 g/m.sup.2 based on the solid ingredients followed by drying. The
viscosity of the coating solution was low, and the coating
characteristics of the solution were good.
COMPARATIVE EXAMPLE 1
0.1 Mol of 5-tert-butylsalicylic acid was dissolved in a mixture of
0.1 mol of sodium hydroxide and 300 ml of water. To this solution
was added 30 g of a 10% polyvinyl alcohol (as described above)
aqueous solution. Then, a solution prepared by dissolving 0.1 mol
of zinc chloride in 100 cc of water was gradually added thereto.
Since the resulting coating solution contained coagulated material,
ultrasonic waves were applied thereto to make the coagulated
material fine. Thereafter, the coating solution was coated on a 50
g/m.sup.2 paper in an amount of 2 g/m.sup.2 on a solids basis,
followed by drying.
Results of Comparison Test
__________________________________________________________________________
No. Kind Ether or Amount Color-developing* Color-develop- Alcohol
Added Ability Toward ing*Ability Crystal Violet Toward 3-N,N-
Lactone diethylamino-6, 8-diethylfluoran
__________________________________________________________________________
1 Com- parative -- -- 0.731 0.602 Ex. 1 2 Ex. 1 Butanol 15 g 0.873
0.710 3 Ex. 1 Diethylene Glycol 20 g 0.935 0.757 Monobutyl Ether 4.
Ex. 1 Ethylene Glycol 30 g 0.952 0.783 Monobutyl Ether 5 Ex. 1
3-Methoxy- butyl 20 g 0.894 0.720 Acetate 6 Ex. 1 Diethylene Glycol
20 g 0.855 0.698 Monomethyl Ether
__________________________________________________________________________
*In the examples the color developing ability was determined by an
optica densitometer (reflectance at 400 to 700 m.mu.). The
numerical value shows the color density at maximum.
EXAMPLE 2
0.1 Mol of 5-tert-butylsalicylic acid was dissolved in a mixture of
0.1 mol of sodium hydroxide and 300 ml of water. To this solution
were added 30 g of a 10% polyvinyl alcohol (as described in Example
1) aqueous solution, 10 g of diethylene glycol monobutyl ether and
10 g of talc. Then, a solution prepared by dissolving 0.7 mol of
zinc chloride in 100 cc of water and a solution prepared by
dissolving 0.3 mol of nickel sulfate in 300 cc of water were
gradually added thereto under stirring. To this solution was added
20 g of a styrene-methyl methacrylate (1:1 molar ratio) copolymer
latex to prepare a coating solution. The resulting solution was
applied to a 50 g/m.sup.2 paper in an amount of 3 g/m.sup.2 based
on the solid ingredients followed by drying. The viscosity of the
solution was low, and the coating characteristics of the solution
were good.
COMPARATIVE EXAMPLE 2
0.1 Mol of 5-tert-butylsalicylic acid was dissolved in 0.1 mol of
caustic soda and 300 ml of water. To this solution was added 30 g
of a 10% polyvinyl alcohol aqueous solution. Then, a solution
prepared by dissolving 0.7 mol of zinc chloride in 700 cc of water
and a solution prepared by dissolving in 300 cc of water 0.3 mol of
nickel sulfate were gradually added thereto under stirring. To this
solution was added 20 g of a styrene-methyl methacrylate copolymer
latex to prepare a coating solution.
Since the viscosity of the coating solution increased, many bubbles
were contained therein, and since the size of the particles became
large, ultrasonic waves were applied to the soluton. The solution
was then coated on a 50 g/m.sup.2 paper in an amount of 3 g/m.sup.2
on a solids basis, followed by drying.
Results of Comparison Test
__________________________________________________________________________
Run Kind Ether Amount Color-developing Color-developing No. Added
Ability Toward Ability Toward Crystal Violet 3-N,N-Diethyl- Lactone
amino-7-N,N- dibenzylamino- fluoran
__________________________________________________________________________
7 Com- parative -- -- 0.753 0.611 Ex. 2 8 Ex. 2 Diethylene 30 g
0.895 0.713 Glycol Mono Butyl Ether
__________________________________________________________________________
EXAMPLE 3
0.1 Mol of 3,5-di-tert-butylsalicylic acid was dissolved in a
mixture of 0.1 mol of sodium hydroxide and 300 ml of water. To this
solution were added 50 g of a 10% polyvinyl alcohol (as described
in Example 1) aqueous solution, 20 g of agalmatolite and an ether
or alcohol as shown in the following table. Then, a solution
prepared by dissolving 0.15 mol of zinc chloride in 1000 ml of
water was gradually added thereto under stirring. Furthermore, 50 g
of a styrene-butadiene copolymer latex was added thereto. The
resulting coating solution was applied to a 50 g/m.sup.2 paper in
an amount of 3 g/m.sup.2 on a solids basis. The viscosity of the
solution was low, and the coating characteristics of the solution
were good.
COMPARATIVE EXAMPLE 3
0.1 Mol of 3,5-di-tert-butysalicylic acid was dissolved in a
mixture of 0.1 mol of sodium hydroxide and 300 ml of water. To this
solution were added 50 g of a 10% polyvinyl alcohol (as described
in Example 1) aqueous solution and 20 g of agalmatolite. Then, a
solution prepared by dissolving 0.15 mol of zinc chloride in 1000
ml of water was gradually added thereto under stirring.
Furthermore, 50 g of a styrene-butadiene copolymer latex was added
thereto. The resulting coating solution was applied to a 50
g/m.sup.2 paper in an amount of 3 g/m.sup.2 on a solids basis. The
coating solution had a high viscosity and contained many bubbles,
and the particle size of the metal compound was large. Therefore,
the solution was coated on the support after applying ultrasonic
waves thereto.
Results of Comparison Test
__________________________________________________________________________
Run Kind Ether or Amount Color-developing Color-developing No.
Alcohol Added Ability Toward Ability Toward 3- Crystal Violet
N,N-Diethylamino- Lactone 7-N,N-dibenzyl- aminofluoran
__________________________________________________________________________
9 Com- parative -- -- 0.761 0.655 Ex. 1 10 Ex. 3 sec-Butyl 10 g
0.867 0.713 Alcohol 11 Ex. 3 n-Nonyl 10 g 0.798 0.677 Alcohol 12
Ex. 3 Ethylene 10 g 0.896 0.720 Glycol Di- methyl Ether 13 Ex. 3
Polyoxy- 10 g 0.790 0.684 ethylene Oleyl Alcohol Ether (22 ethenoxy
units)
__________________________________________________________________________
EXAMPLE 4
5 Grams of activated clay was dispersed in 50 cc of water. To this
was added 0.6 cc of a 20% sodium hydroxide. Then, a solution
prepared by dissolving 10 g of a 10% polyvinyl alcohol (as
described in Example 1) aqueous solution and 0.012 mol of zinc
sulfate in 10 cc of water was gradually added thereto under
stirring. Furthermore, after adding thereto an alcohol given in the
following table, a solution prepared by dissolving 0.01 mol of
3,5-di-tert-butylsalicylic acid and 0.01 mol of sodium hydroxide in
30 cc of water was gradually added thereto. After the completion of
the addition, 4 g of a styrene-butadiene latex was added thereto to
prepare a coating solution. The resulting coating solution was
coated onto a 50 g/m.sup.2 paper in an amount of 3 g/m.sup.2 on a
solids basis followed by drying.
COMPARATIVE EXAMPLE 4
5 Grams of activated clay was dispersed in 50 cc of water. To this
was added 0.6 cc of 20% sodium hydroxide. Then, a solution prepared
by dissolving 10 g of a 10% polyvinyl alcohol (as described in
Example 1) aqueous solution and 0.012 mol of zinc sulfate in 10 cc
of water was gradually added thereto under stirring. Furthermore, a
solution prepared by dissolving 0.01 mol of
3,5-di-tert-butyl-salicylic acid and 0.01 mol of sodium hydroxide
in 30 cc of water was gradually added thereto under stirring. After
the completion of the addition, 4 g of a styrene-butadiene latex
was added thereto to prepare a coating solution. The resulting
coating solution was coated on a 50 g/m.sup.2 paper in an amount of
3 g/m.sup.2 on a solids basis followed by drying.
Results of Comparison Test
__________________________________________________________________________
Run Kind Alcohol Amount Color-developing Color-develop- No. Added
Ability Toward ing Ability Crystal Violet Toward 3-N,N- Lactone
Diethylamino- 7-N,N-dibenzyl- amino fluoran
__________________________________________________________________________
14 Com- parative Ex. 4 -- -- 0.745 0.615 15 Ex. 4 n-Butyl Alcohol
0.5 g 0.852 0.701 16 Ex. 4 do. 2.0 g 0.898 0.718 17 Ex. 4 n-Hexyl
Alcohol 0.5 g 0.753 0.656 18 Ex. 4 Diacetone Alcohol 1.0 g 0.887
0.711 19 Ex. 4 n-Octyl Alcohol 0.5 g 0.766 0.662 20 Ex. 4 do. 3.0 g
0.895 0.720
__________________________________________________________________________
Additionally, the coating solution of the present invention was low
in viscosity and the particle size of the metal salt of the
aromatic carboxylic acid formed by the reaction was small. In
addition, water-immersion coloration was particularly small when
n-octyl alcohol or n-hexyl alcohol was used. However, n-butyl
alcohol and diacetone alcohol also provided sufficient effects.
EXAMPLE 5
5 Grams of kaolin was dispersed in 50 cc of water. To this was
added under stirring a solution prepared by dissolving 10 g of a 5%
hydroxymethyl cellulose and 0.01 mol of tin sulfate in 10 cc of
water. Furthermore, after adding thereto 3 g of diethylene glycol
monobutyl ether, a solution prepared by dissolving 0.01 mol of
3,5-di-tert-amylsalicylic acid and 0.01 mol of potassium hydroxide
in 30 cc of water was gradually added thereto under stirring. After
the completion of the addition, 3 g of a vinyl acetate-acrylate
copolymer was added thereto to prepare a coating solution. The
resulting coating solution was applied to a 50 g/m.sup.2 paper in
an amount of 4 g/m.sup.2 as solids, followed by drying.
COMPARATIVE EXAMPLE 5
5 Grams of kaolin was dispersed in 50 cc of water. To this was
added under stirring a solution prepared by dissolving 10 g of 5%
hydroxymethyl cellulose and 0.01 mol of tin sulfate in 10 cc of
water. Furthermore, 0.01 mol of 3,5-di-tert-amylsalicylic acid and
0.01 mol of potassium hydroxide were dissolved in 30 cc of water
and gradually added thereto. After the completion of the addition,
4.3 g of vinyl acetate-acrylate (1:1 molar ratio) copolymer was
added thereto to prepare a coating solution. The resulting coating
solution was applied to a 50 g/m.sup.2 paper in an amount of 4
g/m.sup.2 on a solids basis, followed by drying.
Results of Comparison Test 5 ______________________________________
Run Kind Color-developing Color-developing No. Ability Toward
Ability Toward Crystal Violet 3-N,N-Diethylamino- Lactone
N,N-dibenzylamino- fluoran ______________________________________
21 Comparative 0.750 0.618 Example 5 22 Example 5 0.902 0.727
______________________________________
EXAMPLE 6
The procedures described in Example 1 were repeated except for
adding 2 g of diethylene glycol monobutyl ether and 0.5 g of
n-octyl alcohol in place of 3 g of diethylene glycol monobutyl
ether. Thus, there were obtained the following results.
______________________________________ Color-developing Ability
Color-developing Ability Toward Crystal Violet Toward
3-N,N-Diethylamino- Lactone 7-N,N-dibenzylaminofluoran
______________________________________ 0.900 0.723
______________________________________
Also, the water-immersion coloration was sufficiently low. Thus,
the resulting sheet was found to be a practical recording
sheet.
From the results of the above-described test, it has been found
that the color-developing ability toward crystal violet lactone and
3-N,N-diethylamino-7-N,N-dibenzylaminofluoran is markedly improved
by adding at least one of an ether or alcohol to a color developer
layer containing a metal compound of an aromatic carboxylic acid.
Similar effects also were observed with respect to other color
formers.
The step for preparing a coating solution was simplified and, in
addition, the viscosity of the coating solution was so low that the
coating solution had excellent coating characteristics.
The water-immersion coloration was also remarkably depressed and
the commercial value of the resulting sheet was markedly improved.
Additionally, the light fastness, and water resistance of the color
image, the activity of the color developer sheet with the passage
of time, and the like were not affected at all.
While the invention has been described in detail and with reference
to specific embodiments thereof, it will be apparent to one skilled
in the art that various changes and modifications can be made
therein without departing from the spirit and scope thereof.
* * * * *