Color developer composition, process for preparing aqueous dispersion thereof and pressure sensitive manifold sheet using thereof

The present invention provides a color developer composition characterized in that the composition contains a color developer comprising as its main component a nucleus-substituted salicylic acid salt represented by the formula (1) given below, and at least one amide compound selected from the group consisting of the compounds of represented by the formula (2) and formula (3) given below. ##STR1## wherein R.sub.1 to R.sub.10 are as defined in the specification.

The present invention relates to a color developer composition, a process 
for preparing an aqueous dispersion thereof, and pressure sensitive 
manifold sheet having an excellent initial color forming property and 
comprising a substrate having applied thereto a coating composition 
containing the composition or the dispersion. 
A pressure sensitive manifold sheet includes various sheets such as a top 
sheet, middle sheet and under sheet. The top sheet comprises a substrate 
coated over one surface thereof with a composition which comprises as its 
main component microcapsules having enclosed therein an oily substance in 
the form of an oily solution of electron-donating organic chromogenic 
material (hereinafter referred to simply as the "color former"). The 
middle sheet comprises a substrate coated over one surface thereof with a 
composition consisting essentially of an electron-accepting color 
developer ( hereinafter referred to simply as the "color developer") which 
forms a color upon contact with the color former, the other surface of the 
substrate being coated with the color former enclosing capsule 
composition. The bottom sheet comprises a substrate coated with the color 
developer composition over one surface thereof. Generally such sheets are 
used for copying in the combination of top sheet and under sheet, or of 
top sheet, middle sheet and under sheet as arranged in this order. Another 
type of pressure sensitive manifold sheet is also known as the 
self-contained type which comprises a substrate coated with the color 
former and the color developer over one surface thereof. 
Already known as color developers for these pressure sensitive manifold 
sheets are inorganic color developers such as acid clay, activated clay, 
attapulgite, zeolite, bentonite, silica, aluminum silicate and the like, 
and organic color developers such as phenol-aldehyde polymers, 
phenol-acetylene polymers and like phenol polymers, polyvalent metal salts 
of aromatic carboxylic acids or derivatives thereof, and the like. 
Among these, organic color developers have higher ability to produce a 
color than inorganic color developers and have another advantage in that 
the color images obtained do not decrease in density, for example, even if 
water adheres thereto or when preserved in the same manner as usual 
filing. However, they have the drawback of forming a color which is low in 
density immediately after printing and requires a period of time to reach 
the saturated density (the drawback of being low in initial color forming 
property). It is therefore desired to remedy the drawback. To overcome the 
drawback, accordingly, it has been conventional practice to lower the 
viscosity of the oily substance for dissolving the color former to 
expedite the contact between the color former and the color developer, 
whereas since the viscosity of the oily substance increases under 
low-temperature conditions, this method fails to achieve a satisfactory 
result. 
An object of the present invention is to provide a color developer 
composition suitable for pressure sensitive manifold sheet having an 
excellent initial color forming ability, a process for preparing an 
aqueous dispersion of the color developer composition, and pressure 
sensitive manifold sheet comprising a substrate coated with a coating 
composition containing the composition or the dispersion. 
The above and other objects of the invention will become apparent from the 
following description. 
The present invention provides a color developer composition characterized 
in that the composition contains a color developer comprising as its main 
component a nucleus-substituted salicylic acid salt represented by the 
formula (1) given below, and at least one amide compound selected from the 
group consisting of the compounds of the formula (2) and formula (3) given 
below. 
##STR2## 
wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each a hydrogen atom, 
halogen atom, alkyl having 1 to 15 carbon atoms, cycloalkyl, phenyl, 
nucleus substituted phenyl, aralkyl or nucleus-substituted aralkyl, two of 
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 adjacent to each other may be 
combined to form a ring, n is an integer of at least 1, and M is a 
polyvalent metal atom, 
##STR3## 
wherein R.sub.5 is a hydrogen atom, substituted or unsubstituted alkyl, 
cycloalkyl, substituted or unsubstituted phenyl, alkenyl, or substituted 
or unsubstituted aralkyl, R.sub.6 and R.sub.7 are same or different and 
are a hydrogen atom, substituted or unsubstituted alkyl, cycloalkyl, 
substituted or unsubstituted phenyl, alkenyl, or substituted or 
unsubstituted aralkyl, R.sub.6 and R.sub.7 may form a morpholine ring, 
##STR4## 
wherein R.sub.8, is lower alkyl, or substituted or unsubstituted aryl, 
R.sub.9 and R.sub.10 are each a hydrogen atom, substituted or 
unsubstituted alkyl having 1 to 12 carbon atoms, or cycloalkyl, and 
R.sub.9 and R.sub.10 may form a morpholine ring or piperidine ring. 
The present invention also provides a process for preparing an aqueous 
dispersion of color developer composition characterized by dissolving a 
color developer comprising as its main component a nucleus-substituted 
salicylic acid salt represented by the above formula (1), and at least one 
amide compound selected 1rom the group consisting o1 the compounds of the 
formula (2) and formula (3) in an organic solvent, emulsifying and 
dispersing the resulting solution in an aqueous medium with or without 
heating, and removing the organic solvent from the dispersion by 
distillation with heating. 
The present invention further provides a pressure sensitive manifold sheet 
characterized in that the sheet comprises a substrate having applied 
thereto a coating composition containing the above color developer 
composition or the aqueous dispersion of color developer composition. 
Although research has yet to be made to fully clarify the reason why 
pressure sensitive manifold sheet of excellent initial color forming 
property can be obtained according to the present invention, the excellent 
property appears attributable to the chelation of the lone pair electrons 
of the nitrogen atom in the compound of the formulas (2) and (3) with the 
metal atom of the nucleus-substituted salicylic acid salt, whereby the 
crystal structure of the acid salt is partly rendered amorphous. 
Presumably, this gives the substituted salicylic acid salt improved 
solubility in the oily substance containing the color former to afford 
pressure sensitive manifold sheet which is very excellent in initial color 
forming property. 
The substituted salicylic acid salts represented by the formula (1) are all 
excellent in color developing ability. Typical examples of such salts are 
polyvalent metal salts of the following salicylic acids. 
3-Methyl-5-isononylsalicylic acid, 3-methyl-5-isododecylsalicylic acid, 
3-methyl-5-isopentadecylsalicylic acid, 
3-methyl-5-(.alpha.-methylbenzyl)salicyclic acid, 3-methyl-5-(.alpha., 
.alpha.-dimethylbenzyl)salicylic acid, 3,5-di-sec-butylsalicylic acid, 
3,5-di-tert-butyl-6 methylsalicylic acid, 3-tert-butyl-5-phenylsalicylic 
acid, 3,5-di-tert-amylsalicylic acid, 3-cyclohexyl-5-isononylsalicylic 
acid. 3-phenyl-5-isononylsalicylic acid, 3-(c 
-methylbenzyl)-5-isononylsalicylic acid, 3-isopropyl-5-isononylsalicylic 
acid, 3-isononylsalicylic acid, 3-isononyl-5-methylsalicylic acid, 
3-isononyl-5-cyclohexylsalicylic acid, 3-isononyl-5-phenylsalicylic acid, 
3-isononyl-5-(.alpha.-methylbenzyl)salicylic acid. 
3-isononyl-5-(.alpha.,4-dimethylbenzyl)salicylic acid, 
3-isononyl-5-(.alpha., .alpha.-dimethylbenzyl)salicylic acid, 
3-(.alpha.,.alpha.-dimethylbenzyl)-5-isononylsalicylic acid, 
3-isononyl-6-methylsalicylic acid, 5-isononylsalicylic acid, 
3-tert-butyl-5-isononylsalicylic acid, 3,5-diisononylsalicylic acid, 
3-isododecylsalicylic acid, 3-isododecyl-5-methylsalicylic acid, 
3-isododecyl-6-methylsalicylic acid, 3-isopropyl-5-isododecylsalicylic 
acid, 3-isododecyl-5-ethylsalicylic acid, 5isododecylsalicylic acid, 
3-isopentadecylsalicylic acid, 3-isopentadecyl-5-methylsalicylic acid, 
3-isopentadecyl-6methylsalicylic acid, 5-isopentadecylsalicylic acid, 
3,5dicyclohexylsalicylic acid, 
3-cyclohexyl-5-(.alpha.-methylbenzyl)salicylic acid, 
3-phenyl-5-(.alpha.-methylbenzyl)salicylic acid, 3-phenyl-5-(.alpha. 
,.alpha.-dimethylbenzyl)salicylic acid, 3-(.alpha.-methylbenzyl)salicylic 
acid, 3-(.alpha.-methylbenzyl)-5-methylsalicylic acid, 
3-(.alpha.-methylbenzyl)-6-methylsalicylic acid, 
3-(.alpha.-methylbenzyl)-5-phenylsalicylic acid, 
3,5-di(.alpha.-methylbenzyl)salicylic acid, 
3-(.alpha.-methylbenzyl)-5-(.alpha.,.alpha.-dimethylbenzyl)salicylic acid, 
3-(.alpha.-methylbenzyl)-5-bromosalicylic acid, 
3-(.alpha.,4-dimethylbenzyl)-5-methylsalicylic acid, 
3,5-di(.alpha.,4-dimethylbenzyl)salicylic acid, 
3-(.alpha.,.alpha.-dimethylbenzyl)-5-methylsalicylic acid, 
3-(.alpha.,.alpha.-dimethylbenzyl)-6-methylsalicylic acid, 
3,5-di(.alpha.,.alpha.-dimethylbenzyl)salicylic acid, 
5-(4-mesitylmethylbenzyl)salicylic acid, benzylated styrenated salicylic 
acid, pinenated salicylic acid, 
2-hydroxy-3-(.alpha.,.alpha.-dimethylbenzyl)-1-naphthoic acid, 
3-hydroxy-7-(.alpha.,.alpha.-dimethylbenzyl)-2-naphthoic acid, etc. 
Examples of useful polyvalvent metals are magnesium, calcium, zinc, 
aluminum, iron, cobalt, nickel and the like, of which zinc is the most 
preferable. The substituted salicylic acid salts given above may be used 
singly or in admixture. According to the present invention, the terms 
isononyl, isododecyl and isopentadecyl groups refer collectively to the 
substituents resulting from the addition of propylene trimers, propylene 
tetramers or 1-butene trimers, and propylene pentamers, respectively. 
The substituted salicylic acid salts of the formula (1) wherein at least 
one of R.sub.1 and R.sub.3, is isononyl, isododecyl or isopentadecyl have 
the characteristics of being less likely to exhibit lower color developing 
ability even when the pressure sensitive manifold sheet is exposed to 
sunlight. These substituted salicylic acid salts include those which are 
crystalline singly and differ in softening point. Accordingly a color 
developer which is noncrystalline and having the desired softening point 
can be prepared by mixing some of these salts in a suitable combination to 
give the desired properties. 
Incidentally, if the color developer has too low a softening point, the 
color developer to be applied to the surface of paper and dried will 
penetrate and migrate into interstices between sheet fibers to result in a 
lower color density, or the aqueous dispersion of the color developer is 
Prone to solidify to exhibit poor stability when stored for a long period 
of time. It is therefore desired that the color developer be at least 
20.degree. C. in softening point. However, when having an exceedingly high 
softening point, the color developer almost fails to adhere to the surface 
of sheet by itself when applied thereto and dried, with the result that a 
large amount of binder needs to be used for fixing the color developer to 
the sheet surface. The binder then forms a film, which is likely to impede 
the migration of the color former dissolving oil which is present in the 
microcapsules. Thus, the color developer will exhibit slightly impaired 
color developing ability. Accordingly, it is more desirable to adjust the 
softening point of the color developer to about 30.degree. to about 
85.degree. C. 
Color developers as adjusted to the desired softening point can be 
prepared, first, by mixing together color developers of different 
softening points, and second, by adding to a color developer a substance 
for lowering the softening point, such as a metal salt of fatty acid, 
trialkylphenol, triaralkylphenol, styrene oligomer or the like, so as to 
lower the softening point of the developer. A third method is to add to a 
color developer having too low a softening point a substance for 
increasing the softening point, such as polystyrene, 
poly-.alpha.-methylstyrene, petroleum resin or the like. The mixing ratio 
is not limited specifically. The term "softening point" as used herein 
refers to a softening temperature at which the color developer has an 
equilibrated water content in water and which is usually about 50.degree. 
C. lower than the softening point of the color developer in a dry state. 
According to the present invention, at least one amide compound selected 
from the group consisting of the compounds of the formula (2) and formula 
(3) is used in combination with a color developer which comprises the 
aboveidentified substituted salicylic acid salt as its main component. 
Examples of amide compounds of the formula (2) are given below. However 
useful compounds are not limited to these examples. At least two of them 
are usable in combination. 
N,N-Di(2-ethylhexyl)formamide, N,N-dicyclohexylformamide, 
N,N-diphenylformamide, N,N-dibutylacetamide, N,N-dioctylacetamide, 
N,N-di(2-ethylhexyl)acetamide, N-[3-(2-ethylhexyloxy)propyl]acetamide, 
N,N-dicyclohexylacetamide, N,N-diphenylacetamide, N,N-dibenzylacetamide, 
N,N-di(2ethylhexyl)propionamide, N,N-dicyclohexylpropionamide, 
N,N-diethylcaprylamide, N,N-dibutylcaprylamide, 
N,N-di(2ethylhexyl)caprylamide, N,N-dicyclohexylcaprylamide, 
N,N-dimethyllauroylamide, N,N-diethyllauroylamide, 
N,N-dibutyllauroylamide, N-(2-ethylhexyl)lauroylamide, 
N,N-di(2-ethylhexyl)lauroylamide, N-lauryllauroylamide, 
N,N-diallyllauroylamide, N,N-dicyclohexyllauroylamide, 
N,N-dimethylmyristoylamide, N,N-diethylmyristoylamide, palmitoylamide, 
N,N-dimethylpalmitoylamide, N,N-diethylpalmitoylamide. stearoylamide, 
N,N-dimethylstearoylamide N,N-diethylstearoylamide, oleoylamide, 
N,N-dimethyloleoylamide, N,N-diethyloleoylamide, N,N-dibutyloleoylamide, 
N,N-dibutylphenoxyacetamide, N,N-di(2-ethylhexyl)phenoxyacetamide, 
N,N-dibutylphenylacetamide, N,N-di(2-ethylhexyl)phenylacetamide, 
N,N-di(2-ethylhexyl)cyclohexamide, N,N-diethylbenzamide, 
lauroylmorpholide, caprylmorpholide, oleoylmorpholide, etc. Among these 
amide compounds, preferable are di-substituted amide compounds of the 
formula (2) wherein R.sub.5 is alkyl having 1 to 17 carbon atoms or 
alkenyl having 2 to 17 carbon atoms, and R.sub.6 and R.sub.7 are each 
alkyl having 1 to 8 carbon atoms or cyclohexyl, and most preferable are 
N,N-di(2-ethylhexyl)acetamide, N,N-dicyclohexylacetamide, 
N,N-diethyllauroylamide, N,N-dibutyllauroylamide, N,N-dimethyloleoylamide, 
N,N-diethyloleoylamide and N,N-dibutyloleoylamide, which effectively 
afford the contemplated effect of the present invention. 
Examples of sulfonamide compounds of the formula (3) are given below. 
However useful compounds are not limited to these examples. At least two 
of them are usable in combination. 
N,N-Dioctylmethanesulfonamide, N,N-dicyclohexylmethanesulfonamide, 
N,N-dioctylethanesulfonamide, benzenesulfonamide, 
N-methylbenzenesulfonamide, N,N-dimethylbenzenesulfonamide, 
N-ethylbenzenesulfonamide, N,N-diethylbenzenesulfonamide, 
N-butylbenzenesulfonamide, N,N-dibutylbenzenesulfonamide, 
N-octylbenzenesulfonamide, N,N-dioctylbenzenesulfonamide, 
N-dodecylbenzenesulfonamide, N,N-dicyclohexylbenzenesulfonamide, 
toluenesulfonamide, N-methyltoluenesulfonamide, 
N,N-dimethyltoluenesulfonamide, N-ethyltoluenesulfonamide, 
N,N-diethyltoluenesulfonamide, N-butyltoluenesulfonamide, 
N,N-dibutyltoluenesulfonamide, N-octyltoluenesulfonamide, 
N,N-dioctyltoluenesulfonamide, N-dodecyltoluenesulfonamide, 
N-(2-hydroxyethyl)toluenesulfonamide. 
N-(3-methoxypropyl)toluenesulfonamide. 
N-(3-ethoxypropyl)toluenesulfonamide, 
N-(3-octoxypropyl)toluenesulfonamide, N-(toluenesulfonyl)morpholine, 
N-(benzenesulfonyl)piperidine, xylenesulfonamide, 
N,N-dimethylxylenesulfonamide. N,N-diethylxylenesulfonamide, 
N,N-dibutylxylenesulfonamide, N-octylxylenesulfonamide, 
chlorobenzenesulfonamide, N,N-diethylchlorobenzenesulfonamide, 
N,N-dibutylchlorobenzene-sulfonamide, N,N-dimethylbiphenylsulfonamide, 
N,N-diethyl-biphenylsulfonamide, etc. 
Among these sulfonamide compounds of the formula (3), most preferable to 
use in advantageously achieving the contemplated effect of the present 
invention are N,N-dibutyltoluenesulfonamide, 
N,N-dioctylbenzenesulfonamide, N,N-dioctylmethanesulfonamide, 
N-octylxylenesulfonamide and N-(toluenesulfonyl)morpholine. 
When the compound represented by the formula (2) or (3) is used in a large 
amount, the color developer sheet obtained for use in pressure sensitive 
manifold sheet is likely to exhibit an impaired color forming property, or 
the surface of the color developer layer is likely to become tacky to 
cause trouble, for example, during printing, so that it is desirable to 
incorporate into the coating composition 0.05 to 20 parts by weight, more 
desirably about 0.1 to about 10 parts by weight, of the compound of the 
formula (2) or (3) per 100 parts by weight of the substituted salicylic 
acid salt represented by the formula (1) based on dry weight. 
In the present invention, the color developer dispersion is prepared 
preferably by dissolving a color developer of the formula (1) in an 
organic solvent, and then emulsifying and dispersing the solution in an 
aqueous medium. The Preferred organic solvent to be used in one having 
relatively low solubility in water, permitting the color developer to 
exhibit good solubility therein, and being low in boiling point and less 
susceptible to chemical changes during preparation of the dispersion. When 
the compound represented by the formula (Z) or (3) is also dissolved in 
the organic solvent, the dispersion can be prepared easily, hence an 
advantage. 
Examples of useful organic solvents are benzene, toluene, xylene, 
chloroform, carbon tetrachloride, trichloroethane, chlorobenzene, methyl 
ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 
butanol, amyl alcohol, methyl tertiary butyl ether, etc. While the organic 
solvent is used in an amount suitably adjusted, for example, in accordance 
with the size of particles to be dispersed, the amount is preferably up to 
about 500 parts by weight per 100 parts by weight of the color developer. 
The organic solvent solution having the color developer and the compound of 
the formula (2) or (3) dissolved therein is emulsified and dispersed in an 
aqueous medium with or without heating. Examples of dispersants for use in 
this step are anionic surfactants such as alkali salts of alkylsulfates, 
alkali salts of alkylbenzenesulfonic acids, alkali salts of 
alkylnaphthalenesulfonic acids, alkali salts of oleic acid amide sulfonic 
acid and alkali salts of dialkylsulfosuccinic acids, nonionic surfactants 
such as polyoxyethylene alkyl ethers and polyoxyethylene fatty acid 
esters, natural high polymer substances such as gum arabic, sodium 
alginate, agar and gelatin, semi-synthesized high polymer substances such 
as carboxymethylcellulose. hydroxyethylcellulose, carboxymethylated 
starch, phosphorylated starch and sodium lignin sulfonate, alkali salts of 
polymers or copolymers such as methyl vinyl ethermaleic anhydride 
copolymer, ethylene-maleic anhydride copolymer, styrene-maleic anhydride 
copolymer, acrylic acid polymer, acrylic acid-methyl methacrylate 
copolymer, acryclic acid-acrylamide copolymer and vinylbenzenesulfonic 
acid polymer, synthetic high polymer substances such as polyvinyl alcohol, 
polyacrylamide and vinyl carboxylate-acrylamide copolymer, etc. 
Among these dispersants, vinylcarboxylate-acrylamide copolymer is 
especially preferable to use in the process of the invention. Most 
preferably, the acrylamide copolymer is one having a polymerization degree 
of at least 100 and a copolymerization ratio of 70 to 96 mole % of 
acrylamide and 4 to 30 mole % of the ester of alkyl or alkoxyalkyl having 
up to 4 carbon atoms with acrylic acid, methacrylic acid, itaconic acid or 
maleic acid since the copolymer has a remarkable property of protective 
colloid and is low in foaming property. 
The dispersant is used in an amount suitably adjusted, for example, in 
accordance with the size of Particles to be dispersed. Preferably, the 
amount is adjusted to the range of about 1 to about 30 parts by weight per 
100 parts by weight of the color developer. At least two dispersants are 
of course usable in combination. 
The color developer aqueous dispersion thus prepared is treated by heating 
to distill the organic solvent off, whereby an aqueous dispersion of color 
developer composition is obtained which comprises precisely spherical 
particles. 
The aqueous dispersion obtained may be further subjected to a dispersion 
treatment. Examples of useful machines for this treatment are various sand 
mill type pulverizers which employ a pulverizing medium, such as ball 
mill, pebble mill, sand grinder (vertical or horizontal type), Cobol mill, 
attritor and Daino mill, three-roll mill, highspeed impeller dispersing 
machine, high-speed stone mill, high-speed impact mill and like high-speed 
grinding devices, etc. In view of ease of setting the treating conditions, 
pulverizing efficiency, etc., it is desirable to use sand mill type 
pulverizers (vertical or horizontal type) and high-speed impeller 
dispersing device, among which the sand mill type pulverizers (vertical or 
horizontal type) are most desirable to use. 
The concentration of the color developer in the aqueous dispersion, which 
is adjusted usually to at least 10 wt.%, can be adjusted to as high as up 
to about 55 wt.% with the process of the invention. Such a 
high-concentration dispersion is less costly to transport, permits 
preparation of coating composition of high concentration, assures a higher 
drying efficiency in the coating procedure and is expected to give an 
improved quality to the color developer sheet obtained for use in pressure 
sensitive manifold sheet. 
The coating composition for forming the color developer layer is prepared 
usually by adding a binder to the aqueous dispersion of color developer 
composition thus prepared. Examples of useful hinders are starch, casein, 
gum arabic, carboxymethylcellulose, polyvinyl alcohol, styrene butadiene 
copolymer latex, vinyl acetate latex and the like. It is also possible to 
suitably add to the coating composition inorganic pigments such as zinc 
oxide, magnesium oxide, titanium oxide, aluminum hydroxide, calcium 
carbonate, magnesium sulfate and calcium sulfate, and various auxiliary 
agents already known for use in preparing pressure sensitive manifold 
sheet. 
The coating composition thus prepared for forming the color developer layer 
is applied to a suitable substrate such as wood-free paper, coated paper, 
synthetic paper or film using a usual coating device such as air knife 
coater, blade coater, roll coater, size press coater, curtain coater or 
short-dwell coater, followed by drying to obtain finished pressure 
sensitive manifold sheet. The amount of coating composition to be applied 
to the substrate, which is not limited specifically, is adjusted usually 
to the range of about 2 to about 8 g/m.sup.2, based on dry weight. 
The color developer composition and the process of the present invention 
can of course be used for pressure sensitive manifold sheet of the 
so-called self-contained type having a color developer layer and a color 
former layer which are formed on the same surface of a substrate or having 
a single recording layer formed by a coating liquid containing the color 
developer and an encapsulated color former.

To further clarify the advantages of the present invention, examples and 
comparative examples are given below, whereas the invention is not limited 
to the examples. In the examples to follow, the parts and percentages are 
all by weight unless otherwise specified. 
EXAMPLE 1 
Preparation of aqueous dispersion of color developer composition 
A solution was prepared from 2000 g of water and 400 g of zinc sulfate 
(heptahydrate) placed into a hollow cylindrical container made of 
stainless steel, having a capacity of 20000 ml and equipped with a stirrer 
and a thermometer. To the solution was added 8500 g of 10% aqueous 
solution of sodium 3,5-di(.alpha.-methylbenzyl)salicylate to effect double 
decomposition while vigorously stirring the solution. The mixture in the 
container immediately became a thixotropic viscous liquid. Separately, to 
methyl isobutyl ketone were added 150 g of .alpha.-methylstyrene-styrene 
copolymer (copolymerization ratio: 40:60 in mole %, average molecular 
weight: about 1500) and 20 g of N,N-dicyclohexylacetamide to obtain 900 g 
of a solution. Subsequently added within a short period of time to the 
mixture was 900 g of the methyl isobutyl ketone solution. Upon the 
thixotropic viscous mixture becoming smoothly flowable, the container was 
allowed to stand with heating at 75.degree. C. The above procedure 
produced a lower oily layer separated from an upper aqueous layer, and the 
lower layer entirely drawn off and placed into a hard glass beaker having 
a capacity of 5000 ml. To the oily layer were added 600 g of water, 2.5 g 
of sodium carbonate, 500 g of 5% aqueous solution of polyvinyl alcohol 
(saponification degree: 98%, polymerization degree: about 1700) and 60 g 
of 25% aqueous solution of ethyl acrylate-acrylamide copolymer 
(copolymerization ratio: 13:87 in mole %, polymerization degree: about 
400). The mixture was treated by a homomixer (Model M, product of Tokushu 
Kika Kogyo Co., Ltd.) at 35.degree. to 40.degree. C. at 8800 to 9000 
r.p.m. for 20 minutes to obtain an emulsion of the oil-in-water type. The 
emulsion was placed into a three-necked hard glass flask having a capacity 
of 10000 ml, equipped with a stirrer and thermometer, and having a 
distillation opening. With addition of 2000 g of water, the flask was 
heated while slowly stirring the mixture to boil the mixture. Methyl 
isobutyl ketone and a portion of water were drawn off through the 
distillation opening to give an emulsion free from methyl isobutyl ketone 
and having a total solids content of 38%. The dispersed particles of color 
developer obtained were 2.0.mu.m in mean particle size, and the dispersion 
phase was 78.degree. C. in softening point. 
Preparation of color developer coating composition 
A color developer coating composition was prepared by mixing together 18 
parts of the 38% dispersion of color developer composition obtained by the 
above procedure, 94 parts of calcium carbonate and 100 parts of water, and 
mixing 50 parts of 10% aqueous solution of polyvinyl alcohol and 10 parts 
of 50% carboxy-modified SBR latex (SN-307, product of Sumitomo Norgatac 
Co., Ltd.) with the resulting dispersion. 
Preparation of color developer sheet for pressure sensitive manifold paper 
The color developer coating composition was applied to one surface of paper 
weighing 40 g/m.sup.2 in an amount of 5 g/m.sup.2 by dry weight and dried 
to obtain a color developer sheet for use in pressure sensitive manifold 
paper. 
EXAMPLE 2 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 1.5 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
1 with the exception of using 20 g of N,N-diethyllauroylamide in place of 
20 g of N,N-dicyclohexylacetamide. A color developer sheet for pressure 
sensitive manifold paper was prepared in the same manner as in Example 1 
except that this aqueous dispersion was used. 
EXAMPLE 3 
A color developer sheet for pressure sensitive manifold paper was prepared 
in the same manner as in Example 1 except that the aqueous dispersion of 
color developer composition obtained in Example 1 was treated by a sand 
mill of the horizontal type (Grain mill GMH-S20M, product of Asada Tekko 
Co., Ltd. at an amount of 3 kg/min. to reduce the particle size of the 
color developer to a mean particle size of 1.8 .mu.m (total solids 
content: 38%). 
EXAMPLE 4 
A color developer sheet for pressure sensitive manifold paper was prepared 
in the same manner as in Example 2 except that the aqueous dispersion of 
color developer composition obtained in Example 2 was treated by a sand 
grinder (Model No. 0SG-8G, product of Igarashi Kikai Co., Ltd.) at an 
amount of 2 kg/min. to reduce the particle size of the color developer to 
a mean particle size of 1.4 .mu.m (total solids content: 38% ). Example 5 
A 1000 g quantity of zinc 3-isododecylsalicylate and 700 g of toluene were 
mixed together at 50.degree. C. to obtain a solution, in which 20 g of 
N,N-diethyllauroylamide was dissolved. The solution was placed into a 
stainless steel beaker having a capacity of 5000 ml. To the solution were 
added 600 g of water, 2.5 g of sodium carbonate and 100 g of 25% aqueous 
solution of ethyl acrylate-acrylamide copolymer (copolymerization ratio: 
13:87 in mole % , polymerization degree: about 400). The mixture was 
treated by a homomixer (Model M, product of Tokushu Kika Kogyo Co., Ltd.) 
at 35.degree. to 40.degree. C. at 8800 to 9000 r.p.m. for 20 minutes to 
obtain an emulsion of the oil-in-water type. 
The emulsion was placed into a three-necked hard glass flask having a 
capacity of 10000 ml, equipped with a stirrer and thermometer and formed 
with a distillation opening. With addition of 2000 g of water, the flask 
was heated while slowly stirring the mixture to boil the mixture. About 
700 g of toluene and about 650 g of water were drawn off through the 
distillation opening to give an emulsion free from toluene and having a 
total solids content of 38%. The dispersed particles of color developer 
obtained were 1.5 .mu.m in mean size, and the dispersion phase was 
63.degree. C. in softening point. 
The dispersion was then treated by a sand grinder (Model No. 0SG-8G, 
product of Igarashi Kikai Co., Ltd.) at an amount of 2 kg/min. to reduce 
the particle size of the color developer to a mean particle size of 1.4 
.mu.m. 
A color developer sheet for Pressure sensitive manifold paper was prepared 
in the same manner as in Example 1 with the exception of using this 
aqueous dispersion of color developer composition. 
EXAMPLE 6 
A solution was prepared by mixing together 500 g of zinc 
3,5-di(.alpha.-methylbenzyl)salicylate, 150 g of 
.alpha.-methylstyrene-styrene copolymer (copolymerization ratio: 40:60 in 
mole %, average molecular weight: about 1500), 350 g of zinc 
3-isododecylsalicylate and 700 g of toluene at 50.degree. C., and 20 g of 
N,N-diethyllauroylamide was dissolved in the toluene solution. The 
solution was placed into a stainless steel beaker having a capacity of 
5000 ml. To the solution were added 600 g of water, 2.5 g of sodium 
carbonate and 100 g of 25% aqueous solution of ethyl acrylate-acrylamide 
copolymer (copolymerization ratio: 13:87 in mole %, polymerization degree: 
about 400). The mixture was treated by a homomixer (Model M, product of 
Tokushu Kika Kogyo Co., Ltd.) at 35.degree. to 40.degree. C. at 8800 to 
9000 r.p.m. for 20 minutes to obtain an emulsion of the oil-in-water type. 
The emulsion was placed into a three-necked hard glass flask having a 
capacity of 10000 ml. equipped with a stirrer and thermometer and formed 
with a distillation opening. With addition of 2000 g of water, the flask 
was heated while slowly stirring the mixture to boil the mixture. About 
700 g of toluene and about 650 g of water were drawn off through the 
distillation opening to obtain an emulsion free from toluene and having a 
total solids content of 38%. The dispersed particles o1 color developer 
obtained were 2.1 .mu.m in mean size, and the dispersion phase was 
73.degree. C. in softening point. 
A color developer sheet for pressure sensitive manifold paper was prepared 
in the same manner as in Example 1 with the exception of using this 
aqueous dispersion of color developer composition. 
EXAMPLE 7 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 1.2 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
1 with the exception of using 30 g of N,N-dibutyllauroylamide in place of 
20 g of N,N-dicyclohexylacetamide. A color developer sheet for pressure 
sensitive manifold paper was prepared in the same manner as in Example 1 
except that this aqueous dispersion was used. 
EXAMPLE 8 
A color developer sheet for pressure sensitive manifold paper was prepared 
in the same manner as in Example 7 except that the aqueous dispersion of 
color developer composition obtained in Example 7 was treated by a sand 
mill of the horizontal type (Grain mill GMH-S20M, product of Asada Tekko 
Co., Ltd.) at an amount of 4 kq/min. to reduce the particle size of the 
color developer to a mean particle size of 1.0 .mu.m (total solids 
content: 38%). 
EXAMPLE 9 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 1.4 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
1 with the exception of using 30 g of N,N-dimethyloleoylamide in place of 
20 g of N,N-dicyclohexylacetamide. A color developer sheet for pressure 
sensitive manifold paper was prepared in the same manner as in Example 1 
except that this aqueous dispersion was used. 
COMATIVE EXAMPLE 1 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 2.4 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
1 except that 20 g of N,N-dicyclohexylacetamide was not used. A color 
developer sheet for pressure sensitive manifold paper was prepared in the 
same manner as in Example 1 with the exception of using this aqueous 
dispersion. 
COMATIVE EXAMPLE 2 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 1.7 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
5 except that 20 g of N,N-diethyllauroylamide was not used. A color 
developer sheet 1or pressure sensitive manifold paper was prepared in the 
same manner as in Example 5 with the exception of using this aqueous 
dispersion. 
COMATIVE EXAMPLE 3 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 1.9 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
1 with the exception of using 20 g of 
2,2'-methylenebis(4-methyl-6-tert-butylphenol) in place of 20 g of 
N,N-dicyclohexylacetamide. 
A color developer sheet for pressure sensitive manifold paper was prepared 
in the same manner as in Example 1 except that this aqueous dispersion was 
used. 
COMATIVE EXAMPLE 4 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 2.9 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
1 with the exception of using 20 g of triethylene 
glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] in place 
of 20 g of N,N-dicyclohexylacetamide. 
A color developer sheet for pressure sensitive manifold paper was prepared 
in the same manner as in Example 1 except that this aqueous dispersion was 
used. 
The thirteen color developer sheets thus prepared were tested for quality 
by the following method. Table 1 shows the results. 
Preparation of top sheets 
Crystal violet lactone was dissolved in alkylated naphthalene, and the oily 
solution was encapsulated to obtain a capsule coating composition, which 
was then applied to one surface of wood-free paper in an amount of 4 
g/m.sup.2 by dry weight and thereafter dried to obtain top sheets. 
[Low-temperature color forming test] 
The color developer sheets and the top sheets were allowed to stand in an 
atmosphere of 1.degree. C. for 10 hours. The top sheet was then placed 
over each color developer sheet with the coating layers opposed to each 
other, and the sheet assembly was caused to form a color in an atmosphere 
of 1.degree. C. using a dropping type color forming tester (weight: 150 g, 
height: 10 cm). The density of color formed was measured 10 seconds and 
one day after the impression by a Macbeth reflective densitometer. 
TABLE 1 
______________________________________ 
Low-temp. color forming property 
after 10 sec. 
after one day 
______________________________________ 
Ex. 1 0.38 0.67 
Ex. 2 0.39 0.67 
Ex. 3 0.40 0.72 
Ex. 4 0.41 0.70 
Ex. 5 0.33 0.69 
Ex. 6 0.38 0.70 
Ex. 7 0.40 0.69 
Ex. 8 0.43 0.72 
Ex. 9 0.39 0.69 
Com. Ex. 1 0.15 0.49 
Com. Ex. 2 0.18 0.57 
Com. Ex. 3 0.16 0.52 
Com. Ex. 4 0.10 0.46 
______________________________________ 
EXAMPLE 10 
Preparation of aqueous dispersion of color developer composition 
A solution was prepared from 2000 q of water and 400 g of zinc sulfate 
(heptahydrate) placed into a hollow cylindrical container made of 
stainless steel, having a capacity of 20000 ml and equipped with a stirrer 
and a thermometer. To the solution was added 8500 g of 10% aqueous 
solution of sodium 3,5-di(.alpha.-methylbenzyl)salicylate to effect double 
decomposition while vigorously stirring the solution. Separately, to 
methyl isobutyl ketone were added 150 g of .alpha.-methylstyrene-styrene 
copolymer (copolymerization ratio: 40:60 in mole %, average molecular 
weight: about 1500) and 30 g of N,N-dioctylbenzenesulfonamide to obtain 
900 g of a solution. Subsequently added within a short period of time to 
the mixture was 900 g of the methyl isobutyl ketone solution. Upon the 
mixture becoming smoothly flowable, the container was allowed to stand 
with heating at 75.degree. C. 
The above procedure produced a separated lower oily layer, which was 
entirely drawn off and placed into a hard glass beaker having a capacity 
of 5000 ml. To the oily layer were added 600 g of water, 2.5 g of sodium 
carbonate, 500 g of 5% aqueous solution of polyvinyl alcohol 
(saponification degree: 98%, polymerization degree: about 1700) and 60 g 
of 25% aqueous solution of ethyl acrylate-acrylamide copolymer 
(copolymerization ratio: 13:87 in mole %, polymerization degree: about 
400). The mixture was treated by a homomixer (Model M, product of Tokushu 
Kika Kogyo Co., Ltd.) at 35.degree. to 40.degree. C. at 8800 to 9000 
r.p.m. for 20 minutes to obtain an emulsion of the oil-in-water type. 
The emulsion was placed into a three-necked hard glass flask having a 
capacity of 10,000 ml, equipped with a stirrer and thermometer, and having 
a distillation opening. With addition of 2000 g of water, the flask was 
heated while slowly stirring the mixture to boil the mixture. Methyl 
isobutyl ketone and a portion of water were drawn off through the 
distillation opening to give an emulsion free from methyl isobutyl ketone 
and having a total solids content of 38%. The dispersed particles of color 
developer obtained were 1.0 .mu.m in mean particle size, and the 
dispersion phase was 75.degree. C. in softening point. 
Preparation of color developer coating composition 
A color developer coating composition was prepared by mixing together 27 
parts of the 38% aqueous dispersion of color developer composition 
obtained by the above procedure, 90 parts of calcium carbonate and 100 
parts of water, and mixing 50 parts of 10% aqueous solution of polyvinyl 
alcohol and 10 parts of 50% carboxy-modified SBR latex (SN-307, product of 
Sumitomo Norgatac Co., Ltd.) with the resulting dispersion. 
Preparation of color developer sheet for pressure sensitive manifold paper 
The color developer coating composition was applied to one surface of paper 
weighing 40 g/m.sup.2 in an amount of 4 g/m.sup.2 by dry weight and dried 
to obtain a color developer sheet for use in pressure sensitive manifold 
paper. 
EXAMPLE 11 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 1.1 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
10 with the exception of using 30 g of N,N-dibutyltoluenesulfonamide in 
place of 30 g of N,N-dioctylbenzenesulfonamide. A color developer sheet 
for pressure sensitive manifold paper was prepared in the same manner as 
in Example 10 except that this aqueous dispersion was used. 
EXAMPLE 12 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 1.2 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
10 except that 40 g of N,N-dioctylmethanesulfonamide was used in place of 
30 g of N,N-dioctylbenzenesulfonamide. A color developer sheet for 
pressure sensitive manifold paper was prepared in the same manner as in 
Example 10 with the exception of using this aqueous dispersion. 
EXAMPLE 13 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 1.6 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
10 except that 30 g of a N-octylxylenesulfonamide was used in place of 30 
g of N,N-dioctylbenzenesulfonamide. A color developer sheet for pressure 
sensitive manifold paper was prepared in the same manner as in Example 10 
with the exception of using this aqueous dispersion. 
EXAMPLE 14 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 1.1 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
10 except that 15 g of N-(p-toluenesulfonyl)morpholine was used in place 
of 30 g of N,N-dioctylbenzenesulfonamide. A color developer sheet for 
pressure sensitive manifold paper was prepared in the same manner as in 
Example 10 with the exception of using this aqueous dispersion. 
EXAMPLE 15 
A color developer sheet for pressure sensitive manifold paper was prepared 
in the same manner as in Example 10 except that the aqueous dispersion of 
color developer composition obtained in Example 10 was treated by a sand 
mill of the horizontal type (Grain mill GMH-S20M, product of Asada Tekko 
Co., Ltd.) to reduce the particle size of the color developer to a mean 
particle size of 0.9 .mu.m. 
EXAMPLE 16 
A color developer sheet for pressure sensitive manifold paper was prepared 
in the same manner as in Example 11 except that the aqueous dispersion of 
color developer composition obtained in Example 11 was treated by a sand 
grinder (Model No. 0SG-8G, product of Igarashi Kikai Co., Ltd.) to reduce 
the particle size of the color developer to a mean particle size of 1.0 
.mu.m. 
EXAMPLE 17 
A 1000 g quantity of zinc 3-isododecylsalicylate and 700 g of toluene were 
mixed together at 50.degree. C. to obtain a solution, in which 20 g of 
N,N-dioctylbenzenesulfonamide was dissolved. The solution was placed into 
a stainless steel beaker having a capacity of 5000 ml. To the solution 
were added 600 g of water, 2.5 g of sodium carbonate and 100 g of 25% 
aqueous solution of ethyl acrylate-acrylamide copolymer (copolymerization 
ratio: 13:87 in mole %, polymerization degree: about 400). The mixture was 
treated by a homomixer (Model M, product of Tokushu Kika Kogyo Co., Ltd.) 
at 35.degree. to 40.degree. C. at 8800 to 9000 r.p.m. for 20 minutes to 
obtain an emulsion of the oil-in-water type. 
The emulsion was placed into a three-necked hard glass flask having a 
capacity of 10,000 ml, equipped with a stirrer and thermometer and formed 
with a distillation opening. With addition of 2000 g of water, the flask 
was heated while slowly stirring the mixture to boil the mixture. About 
700 g of toluene and about 650 g of water were drawn off through the 
distillation opening to give an emulsion free from toluene and having a 
total solids content of 38% . The dispersed particles of color developer 
obtained were 1.4 .mu.m in mean particle size, and the dispersion phase 
was 63.degree. C. in softening point. 
The dispersion was then treated by a sand grinder (Model No. 0SG-8G, 
product of Igarashi Kikai Co., Ltd.) to reduce the particle size of the 
color developer to a mean particle size of 1.3 .mu.m. A color developer 
sheet for pressure sensitive manifold paper was prepared in the same 
manner as in Example 10 with the exception of using this aqueous 
dispersion of color developer composition. 
EXAMPLE 18 
A solution was prepared by mixing together 425 g of zinc 
3,5-di(.alpha.-methylbenzyl)salicylate, 150 g of 
.alpha.-methylstyrene-styrene copolymer (copolymerization ratio: 40:60 in 
mole %, average molecular weight: about 1500), 425 g of zinc 
3-isododecylsalicylate and 700 g of toluene at 50.degree. C., and 20 g of 
N-octylxylenesulfonamide was dissolved in the toluene solution. The 
solution was placed into a stainless steel beaker having a capacity of 
5000 ml. To the solution were added 600 g of water, 2.5 g of sodium 
carbonate and 100 g of 25% aqueous solution of ethyl acrylate-acrylamide 
copolymer (copolymerization ratio: 13:87 in mole %, polymerization degree: 
about 400). The mixture was treated by a homomixer (Model M, product of 
Tokushu Kika Kogyo Co., Ltd.) at 35.degree. to 40.degree. C. at 8800 to 
9000 r.p.m. for 20 minutes to obtain an emulsion of the ofl-in-water type. 
The emulsion was placed into a three-necked hard glass flask having a 
capacity of 10000 ml, equipped with a stirrer and thermometer and formed 
with a distillation opening. With addition of 2000 g of water, the flask 
was heated while slowly stirring the mixture to boil the mixture. About 
700 g of toluene and about 650 g of water were drawn off through the 
distillation opening to obtain an emulsion free from toluene and having a 
total solids content of 38% . The dispersed particles of color developer 
obtained were 1.0 .mu.m in mean particle size, and the dispersion phase 
was 73% in softening point. A color developer sheet for pressure sensitive 
manifold paper was prepared in the same manner as in Example 10 with the 
exception of using this aqueous dispersion of color developer composition. 
COMATIVE EXAMPLE 5 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 1.2 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
10 except that 30 g of N,N-dioctylbenzenesulfonamide was not used. A color 
developer sheet for pressure sensitive manifold paper was prepared in the 
same manner as in Example 10 with the exception of using this aqueous 
dispersion. 
COMATIVE EXAMPLE 6 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 1.0 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
12 except that 40 g of N,N-dioctylmethanesulfonamide was not used. A color 
developer sheet for pressure sensitive manifold paper was prepared in the 
same manner as in Example 12 with the exception of using this aqueous 
dispersion. 
COMATIVE EXAMPLE 7 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 1.1 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
17 except that 20 g of N,N-dioctylbenzenesulfonamide was not used. A color 
developer sheet for pressure sensitive manifold paper was prepared in the 
sam manner as in Example 17 with the exception of using this aqueous 
dispersion. 
COMATIVE EXAMPLE 8 
An aqueous dispersion of color developer composition having dispersed 
therein color developer particles of 1.1 .mu.m in mean size and having a 
total solids content of 38% was prepared in the same manner as in Example 
18 except that 20 g of N-octylxylenesulfonamide was not used. A color 
developer sheet for pressure sensitive manifold paper was prepared in the 
same manner as in Example 18 with the exception of using this aqueous 
dispersion. 
The thirteen color developer sheets thus prepared were tested for quality 
by the following method. Table 2 shows the results. 
Preparation of top sheets 
Crystal violet lactone was dissolved in alkylated naphthalene, and the oily 
solution was encapsulated to obtain a capsule coating composition, which 
was then applied to one surface of wood-free paper in an amount of 4 
g/m.sup.2 by dry weight and thereafter dried to obtain top sheets. 
Low-temperature color forming test 
The color developer sheets and the top sheets were allowed to stand in an 
atmosphere of 0.degree. C. for 10 hours. The top sheet was then placed 
over each color developer sheet with the coating layers opposed to each 
other, and the sheet assembly was caused to form a color in an atmosphere 
of 0.degree. C. using a dropping type color forming tester (weight: 150 g, 
height: 15 cm). The density of color formed was measured 10 seconds and 
one day after the impression by a Macbeth reflective densitometer. 
TABLE 2 
______________________________________ 
Low-temp. color forming property 
after 10 sec. 
after one day 
______________________________________ 
Ex. 10 0.33 0.72 
Ex. 11 0.31 0.70 
Ex. 12 0.35 0.73 
Ex. 13 0.30 0.70 
Ex. 14 0.29 0.71 
Ex. 15 0.35 0.72 
Ex. 16 0.33 0.71 
Ex. 17 0.38 0.73 
Ex. 18 0.35 0.72 
Com. Ex. 5 0.16 0.63 
Com. Ex. 6 0.18 0.65 
Com. Ex. 7 0.19 0.67 
Com. Ex. 8 0.18 0.66 
______________________________________ 
The results given in Tables 1 and 2 reveal that the color developer sheets 
each having the color developer composition of the invention incorporated 
therein for use in pressure sensitive manifold paper were all excellent in 
low-temperature color forming property, particularly in initial color 
forming ability.