Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02300773 2000-03-17
POLYVALENT METAL SALTS OF SALICYLIC ACID RESIN
AND PRO(:ESS FOR THE PREPARATION THEREOF
Field of the Invention
s The present invention relates to a polyvalent metal salt of salicylic
acid resin, which is used as a color developer for recording material such
as pressure-sensitive copying paper, and to a process for the preparation
thereof. Furthermore, it relates to an aqueous dispersion and a color
development sheet prepared from the polyvalent metal salts of salicylic
io acid resin.
Background of the Invention
It is known that metal salts of salicylic acid derivative axe useful as
color developers for pressure-sensitive copying paper, and numbers of
is preparation processes and uses thereof were proposed. For example,
1 ) 3,5-disubstituted salicylic acid derivative is prepared from the
reaction of 2;,4-disubstituted-phenol derivative with carbon dioxide
by Kolbe-Schmitt reaction (Japanese Patent Publication No. 76-
25174 and LT.S. Patent No. 3,983,292). In this method, however,
ao two-step process is needed to prepare 3,5-disubstituted salicylic
acid derivative from phenol, and high-temperature high-pressure
facility is required in the reaction with carbon dioxide. In addition,
in case of using as color developer the metal salts of 3,5-
disubstituted salicylic acid derivative such as zinc salt of 3,5-di(a-
as methylbenzyl)salicylic acid, developed image might be lost on
water contaca.
2) 4-[a-methylbenzyl(a-methylbenzyl)]salicylic acid derivative is
prepared by reacting 1 mole of salicylic acid with 2 moles or more
CA 02300773 2000-03-17
of phenylethanol derivatives (Japanese Patent Publication No. 93-
61110 and IJ.S. Patent No. 4,754,063).
3) Polyvalent metal salts of 3,5-di(a-ethylbenzyl)salicylic acid
derivative a:nd polyvalent metal salts of 4-[a-methylbenzyl(a-
s methylbenzyl)]salicylic acid derivative are prepared by reacting 1
mole of salicylic acid with 2 moles or more of styrene derivatives
in the presence of aromatic sulfonic acid, and reacting the reaction
product thus prepared with polyvalent metal salts of inorganic acid
or lower aliphatic carboxylic acid (Japanese Patent Publication 93-
io 75736 and IJ.S. Patent No. 4,748,259). However, in case of using
the polyvalent metal salts (e.g., zinc salts) of 4-[a-methylbenzyl(a-
methylbenzyl)]salicylic acid thus prepared as color developer for
pressure-sensitive copying paper, developed image might be lost
on water contact.
is 4) 3,5-di(a-methylbenzyl)salicylic acid derivative is prepared by a
reaction of salicylic acid with styrene in the presence of aliphatic
carboxylic acrid using organic sulfonic acid or inorganic acid as a
catalyst (Jap<~nese Patent Application Laid-open Publication No. 90-
91043). However, in case of using the polyvalent metal salts of 3,5-
zo di(a-rnethylbenzyl)salicylic acid (e.g., zinc salt) as color developer,
developed image might be lost on water contact.
5) A process for preparing metal salts of polymeric salicylic acid resin
by reacting salicylic acid derivative with styrene derivative in the
presence of acid catalyst at 40-170°C, and reacting the reaction
Zs product with metal salt of fatty acid (Japanese Patent Application
Laid-open rro. 88-142537 and U.S. Patent No. 4,929,710).
However, the metal salts of salicylic acid resin thus prepared have
drawbacks i:n that it sometimes has coloring and its dispersion is
CA 02300773 2000-03-17
liable to coagulate because of the difficulty in making fine particles
at dispersion.
6) A process for preparing polyvalent metal salts of salicylic acid
resin is disclosed, which comprises reacting salicylic acid ester
s with styrene, hydrolyzing the reaction product thus obtained, and
then reacting with polyvalent metal compound (Japanese Patent
Application Laid-open Publication No. 89-133780 and U.S. Patent
No. 4,952,648). However, the thus prepaxed polyvalent metal salts
(e.g., zinc salts) of salicylic acid resin are disadvantageous in that
io its dispersion tends to coagulate due to the difficulty in making fine
particles at dispersion.
7) A process far producing polyvalent metal salts of salicylic acid
resin is disclosed, which comprises reacting salicylic acid or its
derivative with styrene or its derivative in the presence of sulfuric
is acid at -20 to 40°C, and further reacting with polyvalent metal
compound (:lapanese Patent Application Laid-open Publication No.
95-228042 and U.S. Patent No. 5525686). However, despite that
the color developer thus obtained is improved of its physical
properties, various problems still exist, such as complicated
Zo reaction process, environmental pollution, and productivity
decrease due; to low yield. Further, when preparing an aqueous
dispersion using the metal salts, the average particle size of the
metal salts is at most 1.5 pm.
Zs As described above, reaction products and their polyvalent metal
salts thereof obtained from the reaction of salicylic acid derivative with
styrene derivative show different physical properties depending on the
reaction conditions (e.g., catalyst, solvent, reaction temperature).
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Therefore, it is impossible to determine the physical properties of the
salicylic acid resin .and polyvalent metal salts thereof by a theoretical
method, or too difficult to infer them based on experiments. At present, it
is expected to establish their physical properties through experiment
s procedures.
Lately, there has been a desire for a color developer advantageous in
that it is easily brought into fine particles at dispersion, resulting
dispersion has high storage stability, and developed image shows superior
storage stability, high resistance to water and to abrasion when forming a
io color development sheet for pressure-sensitive copying paper using the
color developer.
As a result of intensive studies to solve the problems in the prior art
as described above, the present inventor discovered that polyvalent metal
salts of salicylic acid resin having superior physical properties could be
is produced in high yield under a specific catalyst, not an acid catalyst, and
specific temperature.
Summary of the Invention
An object of the present invention is to provide a process for
ao preparing polyvalent metal salts of salicylic acid resin.
It is another object of the present invention to provide polyvalent
metal salts of salicylic acid resin prepared by the process.
It is a further object of the present invention to provide an aqueous
dispersion of polyv;~lent metal slats of salicylic acid resin prepared by the
Zs process.
It is a further object of the present invention to provide a color
development sheet prepared by the process, where the developed image
has superior storage; stability, high resistance to water and to abrasion.
4
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Detailed Description of the Invention
The present invention provides a process for preparing polyvalent
metal salts of salicylic acid resin, comprising:
s reacting salicylic acid of the formula 1 or its derivative and styrene
of the formula 2 or :its derivative in the presence of zinc salt of organic
carboxylic acid or polyvalent metal compound or a mixture thereof at 50-
200°C,
reacting the resulting reaction product with polyvalent metal
to compound.
OH
C'.OOH
1
X1 'X2
Rl ,R:?
C C~R
3
2
X3 x4
is
s
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wherein, X, and X2 is hydrogen, alkyl, alkoxy or halogen,
respectively, and each of R,, R2 and R3 is hydrogen or alkyl, and X3 and X4
is hydrogen, alkyl, ;~.lkoxy, aralkyl, aryl or halogen, respectively.
For the compound of formula 1, each of X, and X2 is preferably
s hydrogen, C 1-C 12 alkyl, C 1-C 12 alkoxy, F, Cl or Br, and more preferably
hydrogen.
Examples of the compound of formula 1, though not limited, include
salicylic acid, 3-methylsalicylic acid, 4-methylsalicylic acid, 5-
methylsalicylic acid, 3-n-butylsalicylic acid, 6-methylsalicylic acid, 6-
io ethylsalicylic acid, :5-isopropylsalicylic acid, 4-n-pentylsalicylic acid,
5-
cyclohexylsalicylic acid, 5-n-octylsalicylic acid, 5-t-octylsalicylic acid, 4-
nonylsalicylic acid, 5-nonylsalicylic acid, 4-n-dodecylsalicylic acid, 4-
methoxysalicylic acid, 6-methoxysalicylic acid, 5-ethoxysalicylic acid, 4-
n-hexyloxysalicylic acid, 5-fluorosalicylic acid, 3-chlorosalicylic acid, 4-
is chlorosalicylic acid., 5-chlorosalicylic acid and 5-bromosalicylic acid.
The above sali~;,ylic acid derivatives may be used individually or in
combination of two or more. Among them, salicylic acid or alkyl
substituted salicylic acid derivative such as 3-methylsalicylic acid is
preferable, and salicylic acid is especially preferred.
zo For the compound of formula 2, each of X3 and X4 is preferably
hydrogen, C 1-C 12 alkyl, C 1-C 12 alkoxy, C 1-C 10 aralkyl, C6-C 10 aryl, F,
Cl or Br, and most preferably X3 and X4 are both hydrogen. Also, each of
Rl, R2 and R3 is preferably hydrogen or C1-C4 alkyl, and most preferably
hydrogen.
as Examples of the compound of formula 2, though not limited to,
include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-
ethylstyrene, 4-ethylstyrene, 3-isoppropylstyrene, 4-isopropylstyrene, 4-n-
butylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-n-octylstyrene, 4-n-
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decylstyrene, 2,4-d:imethylstyrene, 2,5-dimethylstyrene, 3-methoxystyrene,
4-methoxystyrene, 4-ethoxystyrene, a-methylstyrene, a-ethylstyrene, a-n-
butylstyrene, a-isobutylstyrene, a,(3-dimethylstyrene, a,(3-diethylstyrene,
a-methyl-(3-isopropylstyrene, a-n-propyl-(3-methylstyrene, 4-(a,a-
s dimethylbenzyl)styrene, 4-phenylstyrene, 4-fluorostyrene, 2-chlorostyrene,
3-chlorostyrene, 4-chlorostyrene and 4-bromostyrene.
The above styrene derivatives may be used individually or in
combination of two or more. Among them, styrene or alkyl substituted
styrene derivatives such as 4-methylstyrene, or a-methylstyrene is
io preferable, and styrene is the most preferably used.
Hereinafter, each step of the process for the present invention will
be described in detail.
Reaction A: Step of reacting a compound of formula 1 with a
is compound of formula 2
The compound of formula 2 is reacted in an amount of 1 to 9
moles, preferably 1.,5 to 7 moles, and most preferably 1.6 to 6 moles to 1
mole of the compound of formula 1.
The reaction A is conducted in the presence of zinc salt of organic
Zo carboxylic acid and/or polyvalent metal compound. The kind and the
amount of used zinc; salt of organic carboxylic acid and polyvalent metal
compound is not particularly limited, but a large amount of use may cause
an adverse effect on the properties of the reaction products or decrease
working efficiency and production efficiency.
2s Therefore, adequate amount of zinc salt of organic carboxylic acid
and polyvalent metal compound may be at least 0.05% by weight,
preferably 0.5-50% by weight based on the weight of the compound of
formula 1. Further, higher purity in the zinc salt of organic carboxylic acid
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and polyvalent metal compound is preferred. As zinc salt of organic
carboxylic acid, zinc benzoate, zinc caprylate, zinc stearate and zinc
acetate may be used, and as polyvalent metal compound, water-soluble or
insoluble metal compound having valence of 2, 3 and 4 may be used.
s Examples of polyvalent metal compound include sulfates such as zinc
sulfate, magnesium sulfate, calcium sulfate and aluminum sulfate,
chlorides such as zinc chloride, magnesium chloride, calcium chloride,
barium chloride, nickel chloride, cobalt chloride and aluminum chloride,
acetates such as zinc acetate and manganese acetate, nitrate such as zinc
io nitrate, oxides such as zinc oxide, and hydroxides such as zinc hydroxide.
In the step of the Reaction A, there is no particular limit on the
reaction operation. The zinc salt of organic carboxylic acid or polyvalent
metal compound or a mixture thereof, and a compound of formula 1 may
be mixed in a reaction vessel, and then a compound of formula 2 is added
is to the mixture. Otherwise, the organic carboxylic acid zinc salt and/or
polyvalent metal compound, a compound of formula 1, and a part of
compound of formula 2 are mixed in a reaction vessel, and then the rest of
the compound of formula 2 is added to the mixture. Further, the
substances mentioned above may be added at one time.
ao The rest of compound of formula 2 may be added continuously or
intermittently using known means (e.g., dropper and measuring pump). Of
course, other methods may be applied, as far as it is applicable in terms of
process technology.
The adding period of the compound of formula 2 is not particularly
Zs limited, but is generally about 0.5 to 13 hours, preferably about 1 to 9
hours.
It is preferat~le to conduct reaction A with stirring in order to
increase the reaction efficiency. The stirnng apparatus is not particularly
CA 02300773 2000-03-17
limited, but it is preferable to use one having sufficient stirring power to
guarantee the reaction efficiency. As an example of such apparatus, there
is a tank-typed reaction apparatus and tubular reaction apparatus with
stirrer such as propeller stirrer, turbine stirrer, paddle stirrer,
homogenizes,
s homomixer, line mixer or linehomo mixer. The reaction A may be
conducted in a batch process or continuously.
The reaction temperature of the reaction A may be 50-200°C, and
preferably 120-180"C.
In case of dropping compound of formula 2, reaction period is
io longer than adding period, and after adding the compound; the solution
may be left or subjected to stirnng at 50-200°C for the time. Usually,
the
reaction may be carried out for 0.5 to 20 hours, preferably for 1 to 12
hours.
Generally, reaction A may be carried out in atmosphere, and if
is necessary, reduced or elevated pressure may be adopted. For example, the
reaction may be conducted in the air, or in the presence of inert gas (e.g.,
nitrogen, helium or argon gas).
Resin prepared by reaction A (hereinafter, "Resin A") may be used
in subsequent reaction (Reaction B) with polyvalent metal compound.
so Resin A is a resin having complicated compounds consisting of
various compounds formed by various reactions of reactive oligomers.
Reaction B: Step of reacting the reaction product from Reaction A
with polyvalent metal compound
is Polyvalent metal salts of salicylic acid resin of the present
invention may be prepared by a reaction of Resin A and polyvalent metal
compound. There is no particular limit on the reaction process. For
example, melting Resin A and polyvalent metal compound (e.g., oxides,
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hydroxides, carbonates, silicates or organic carboxylate of polyvalent
metal) (Melting method), or reacting alkali metal salts, amine salts or
ammonium salts of Resin A with polyvalent metal compound in water
(Double decomposition method) may be used. Preferably, melting method
s is used to prepare polyvalent metal salts of salicylic acid resin of the
present invention.
In case of conducting Reaction B by melting method, Resin A is
heat-melted together with oxide, hydroxide, carbonate or silicate of
polyvalent metal with polyvalent metal salts of organic carboxylic acid
io such as zinc chloride, zinc carpronate, zinc stearate, zinc benzoate at 50-
200°C for 1-10 hours. In this case, a basic substance such as ammonium
acetate, ammonium carpronate, ammonium stearate and ammonium
benzoate may be added.
As polyvalent metal compound, water-soluble or insoluble metal
is compound having valence of 2, 3or 4 may be used. Examples of the
polyvalent metal compound include sulfates such as zinc sulfate,
magnesium sulfate, calcium sulfate and aluminum sulfate, chlorides such
as zinc chloride, magnesium chloride, calcium chloride, barium chloride,
nickel chloride, cobalt chloride and aluminum chloride, acetates such as
ao zinc acetate, manganese acetate and nitrates such as zinc nitrate, oxides
such as zinc oxide, :hydroxides such as zinc hydroxide, and these
compounds may be used individually or in combination of two or more.
Polyvalent metal compound may be used in solid forms or in
aqueous solution.
Zs The amount of the polyvalent metal compound used is 0.6 to 1.6
equivalents, and preferably 0.8 to 1.2 equivalents to 1 equivalent of Resin
A. Herein, when polyvalent metal compound is a metal compound of
io
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valence 2 (e.g., zinc; oxide), 1 equivalent of polyvalent metal compound
means 0.5 mole of metal compound of valence 2 to 1 mole- of resin A.
Polyvalent metal salts of salicylic acid resin according to the
present invention m.ay also be prepared by reacting salicylic acid of
s formula 1 or its derivative with styrene of formula 2 or its derivative in
the
presence of polyvalent metal compound or a mixture of polyvalent metal
compound and zinc salt of organic carboxylic acid at 50-200°C. Herein,
the amount of all the substances is the same as described above.
The resulting polyvalent metal salts of salicylic acid resin of the
io present invention is a resin obtained from the reaction of Resin A and
polyvalent metal compound, and its composition is far more complicated
than Resin A.
Molecular weight of the polyvalent metal salts of salicylic acid
resin in the present invention depends on the amount of the compounds of
is formulae 1 and 2, and reaction conditions, but when used as a color
developer for pressure-sensitive copying paper, it is preferably 300-2000,
and more preferably, 400-1300.
The polyvalent metal salts of salicylic acid resin of the present
invention have softf;ning point of 50 -130°C.
Zo The present invention further provides an aqueous dispersion
where polyvalent metal slats of salicylic acid resin thus prepared are
dispersed in water.
Further, the present invention provides a color development sheet
prepared from the above polyvalent metal salts of salicylic acid resin..
as Hereinafter, the aqueous dispersion and the color development
sheet for pressure-sensitive copying paper prepared from the polyvalent
metal salts of salicylic acid resin as developer will be described.
Aqueous dispersion may be obtained by the following methods:
n
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8) Method of obtaining the desired aqueous dispersion by grinding
polyvalent metal salts of salicylic acid resin using dispersion
apparatus such as ball mill, sand grinder, dynomill, high speed
impeller dispersing apparatus or annular mill.
9) Method of obtaining the desired aqueous dispersion by dissolving
polyvalent metal salts of salicylic acid resin in an organic solvent,
emulsifying; in an aqueous medium using ultrasonic dispersing
machine, homogenizer, homomixer or line homomixer and by
eliminating the organic solvent.
l0 10) Method of obtaining the desired aqueous dispersion by directly
adding emulsifying dispersant to polyvalent metal salts of salicylic
acid resin and stirnng with high speed.
The emulsifying dispersant that can be used in an aqueous medium
includes ionic or nonionic surfactant. For example, synthetic or natural
is polymeric compounds such as polyvinyl alcohol, alkyl denaturated
polyvinyl alcohol, c;yanoethyl denaturated polyvinyl alcohol, ether
denaturated polyvinyl alcohol, polyacrylamide, polyacrylic acid,
acrylamide-alkylac:rylate copolymer, alkali metal salt of
polystyrenesulfonic; acid, malefic acid anhydride-isobutylene copolymer,
2o carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone,
starch and its deriv<~tive, casein, Arabic rubber, agar and gelatin; alkali
metal salts of alkylbenzensulfonic acid; alkali metal slats of
alkylnaphthalensulfonic acid; alkali metal salts of dialkylsulfosuccinic
acid; alkali metal slats of alkylsulfonic acid; polyoxyethylene alkyl ether;
2s polyoxyethylene alkyl phenyl ether and polyhydroxy alcohol fatty acid
ester. These emulsifying dispersants may be used individually or in
combination of two or more. No special limit exists on the amount used,
12
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but it is generally 0,.5-25 parts per weight to 100 parts of polyvalent metal
salts of salicylic acid resin.
Though no special limit exists on the amount of water when
preparing aqueous dispersion, concentration of the color developer in
s aqueous dispersion should be in the range of 10-60% by weight,
preferably, 20-50% by weight.
When using the aqueous dispersion of the color developer thus
obtained as coating liquid to form a color developer layer on support,
binder and pigments may be added thereto.
to There is no special limit on the kinds of binder, and examples
include synthetic and natural polymeric compounds such as polyvinyl
alcohol, casein, starch and its derivative, Arabic rubber, methyl cellulose,
carboxymethylcellulose, polyacrylic acid, latex such as styrene-butadiene
copolymer latex, acrylic acid ester latex.
is The amount of binder, though not limited, is generally 5-40% by
weight, preferably 10-30% by weight based on the weight of total solid
part of the color developer coating liquid.
For the present invention, inorganic pigments may be used such as
zinc oxide, zinc carbonate, calcium carbonate, magnesium carbonate,
ao barium carbonate, rrlagnesium sulfate, barium sulfate, titanium oxide,
talc,
kaolin, active china clay, diatomite, zinc hydroxide, aluminum hydroxide,
magnesium hydroxide, alumina and silica; and organic paints such as
styrene microball, nylon particle, urea formaldehyde filler, polyethylene
particles, cellulose filler and starch particles.
as There is no special limit on the amount of pigments, but should be
30-90% by weight based on the weight of the total solid part of the color
developer coating liquid.
13
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In addition, various additives (e.g., IJV absorbing agent, defoaming
agent, pH adjusting agent, viscosity control agent, plasticizes and organic
polymeric compound) may be added to the coating liquid, if necessary.
Color development sheet may be prepared by applying on a support
s (e.g., plastic sheet, synthetic paper, or a combination thereof) the coating
liquid prepared as above using known means, for example, air knife coater,
blade coater, roll water, seize press coater, curtain coater or shortduwell
coater to form a color development layer.
No special Limit exists on the weight (coating amount) of the color
to developer layer on t;he support, but the dry weight may be at least
O.Sg/m2,
preferably, 0.5 to l Og/m2. Furthermore, the content of polyvalent metal
salts of salicylic acid resin of the present invention in the color developer
layer is generally 5~% by weight or more, preferably 5-70%.
In the preparation of color development sheet of the present
is invention, other color developers may be used with the polyvalent metal
salts of salicylic acid to the extent that the effect of the present invention
is
not impaired. Examples of such other additives include acidic clay
mineral such as acidic China clay, active China clay, attapulgite and
bentonite; phenol resin such as phenol-formaldehyde resin, phenol-
ao salicylic acid formaldehyde resin; zinc salt of aromatic carboxylic acid
such as phthalic acid, salicylic acid, 5-cyclohexylslicylic acid, 5-t-
octylsalicylci acid, :~-nonylsalicylic acid, 3,5-dinonylsalicylic acid, 3-(a-
methylbenzyl)salicylic acid, 5-(a-dimethylbenzyl)salicylic acid, 5-
phenylsalicylic acid, 3,5-di(a-methylbenzyl)salicylic acid, 3,5-di(a,a-
as dimethylbenzyl)salicylic acid and 3,5-di-t-butylsalicylic acid.
The color development sheet according to the present invention is
not limited in shape, but the following may be enumerated:
14
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11 ) CF sheet that may be used in combination with CB sheet whose
back side is coated with micro-capsule containing electron donating
color-developing compound and capsule oil
12) CF/CB sheet wherein micro-capsule layer is established in back
s side of sheet., and developer layer is established on the surface of the
sheet inserted between CB sheet and CF sheet in order for multiple
copy
13) Monocopy sheet wherein micro-capsule and developer are coated
in one side o f the sheet
io The present invention is further illustrated by the following Examples
below, which should not be construed as limiting the scope of the
invention.
Example 1
is 204g of salicylic acid, 20g of zinc acetate (dihydrate), 20g of zinc
stearate and 100g o:f styrene were charged into a glass reaction vessel. The
mixture was stirred at elevated temperature of 140°C. 287g of Styrene
was
dropped to the mixture over 3 hours and stirred at the same temperature for
two hours. Temperature of the reaction mixture was lowered to 115°C and
ao 60g of zinc oxide was added. After two hours of reaction at the same
temperature, 655g of zinc salt of salicylic acid resin was obtained (yield:
94.8%, softening point: 98°C, average molecular weight: 670).
To the resin thus obtained, 30g of polyvinyl alcohol, 3g of sodium
dodecylbenzene sulfonate and 840g of purified water were added, and then
2s obtained 1528g of aqueous dispersion of which the solid content is 45%
and the average particle size is 0.38~,m.
is
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Example 2
68g of salicylic acid, 0.8g of zinc oxide and 128g of styrene were
charged into a glass reaction vessel. The resulting mixture was stirred at
elevated temperature of 155°C, and reacted for 2-3 hours. At
150°C, 19.3g
s of zinc oxide was added. The reaction was conducted for 2 hours at 140-
155° C to obtain 240g of zinc salt of salicylic acid resin (yield:
94.4%,
softening point: 98°C, average molecular weight: 690)
The resin thus obtained was emulsified with lOg of polyvinyl
alcohol and 262g of purified water to obtain 476g of aqueous dispersion of
to which the solid content is 45% and the average particle size is 0.41 ~.m.
Example 3
Except for using styrene in an amount of 400g instead of 387g, and
using 30g of zinc stearate with no use of zinc acetate, the reaction was
conducted in the same manner as in Example l, and 640g of zinc salt of
is salicylic acid resin 'was obtained (yield: 92.2%, softening point:
99°C,
average molecular weight: 715).
Example 4
Except that styrene was used in an amount of 120g instead of 100g,
that dropping amount was reduced from 287g to 267g, and that 30g of zinc
ao acetate was used with no use of zinc stearate, reaction was conducted in
the same manner as in Example 1 to obtain 656g of zinc salt of salicylic
acid resin (yield: 96.3%, softening point: 110°C, average molecular
weight: 730).
Example 5
2s According to the method as in Example 1 except that 15g of zinc
caprylate was used instead of zinc acetate and zinc stearate, 632g of zinc
salt of salicylic acid resin was obtained (yield: 94.9%, softening point:
96°C, average molecular weight: 680).
16
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Example 6
In the same manner as in Example 1 except that 184g of salicylic
acid and 22.Sg of 4-methylsalicylic acid were used instead of 204g of
salicylic acid, the reaction is conducted to prepare 657g of zinc salt of
s salicylic acid (yield. 94.7%, softening point: 112°C, average
molecular
weight: 705).
Example 7
In the same :manner as in Example 1 except for using 256g of
styrene and 35g of 4-methylstyrene instead of 287g of styrene, 658g of
io zinc salt of salicylic acid resin was obtained (yield: 94.7%, softening
point:
113°C, average molecular weight: 710)
Example 8
204g of salicylic acid, 30g of zinc acetate and 387g of styrene were
charged into a glass reaction vessel. After stirring for 3 hours at
150°C,
is 60g of zinc oxide was added at 135°C, and reacted for 2 hours to
obtain
635g of zinc salt of salicylic acid resin (yield: 93.2%, softening point:
99°C, average molecular weight: 685).
Example 9
In glass reaction vessel, 129g of styrene, 36g of zinc oxide and 80g
ao of salicylic acid were charged, and the mixture was stirred for 5 hours at
elevated temperature of 157°C, and 245g of zinc salt of salicylic acid
resin
was obtained (yield:: 85%, softening point: 114°C, average molecular
weight: 803).
Example 10: Preparation of a color development sheet for pressure-
as sensitive copy
According to the following process using the aqueous dispersion
obtained from example 1 as a color developer, a color development sheet
for pressure-sensitive copy was prepared.
i7
CA 02300773 2000-03-17
Dispersion (A) was obtained by dispersing a mixture with the
following composition. Herein, the pH was adjusted to 7.5.
Water 105.8g
s Calcium carbonate 24 g
Clay 49g
Oxidized starch (20%) 22.2g
Latex (48%) 11.6g
Dispersant (40%) 6.8g
io Lubricant (50%) 4.Sg
Ammonia water adequate amount
2.61 g of the color developer obtained by Example 1 was mixed
with 22.4g of dispersion (A), and the resulting liquid was coated in a dried
is amount of S.Og/m2 onto a paper (SOg/m2) to obtain a color development
sheet.
is
