United States Patent [19] [11] 4,175,066

Shibazaki et al. [45] Nov. 20, 1979

[54] DISPERSANT FOR CALCIUM CARBONATE [56] References Cited

[75] Inventors: Hiroji Shibazaki, Takarazuka; Setsuji U.S. PATENT DOCUMENTS
Edagawa; Hisashi Hasegawa, both of 3,057,811 10/ 1 962 Trachtenburg .............. .. 260/29.6 M
Nishinomiya; Takashi Takeuchi; 3,196,122 7/1965 60/29.6 H
Noboru Moriyama, both of 3,635,915 1/1972 . 526/271
Wakayama; Yukihiro Fukuyama, 3,755,264 8/1973 526/271
Naga, all of Japan 3,940,550 2/ 1976 428/511
4,048,380 9/1977 428/511
[73] Assignee: Kao Soap Co., Ltd., Tokyo, Japan 4,05 8,648 11/ 1977 Louden .............................. .. 428/511
[21] Appl. No.: 893,696 Primary Examiner--Paul R. Michl
[22] Filed: Apr. 5, 1978 Attorney, Agent, or Firm-Blanchard, Flynn, Thiel,
[30] Foreign Application Priority Data Boutell & Tanis
Apr. 18, 1977 [JP] Japan ................................ .. 52/44259 [57] ABSTRACT
[51] Int. Cl.2 .............................................. .. C08K 3/26 Calcium carbonate is dispersed by a dispersant compris
[52] US. Cl. ..................... .. 260/29.6 M; 428/511 ing a salt of an acrylic acid/maleic acid copolymer.
[58] Field of Search ..... ., ........... .. 260/29.6 H, 29.6 M;
526/271, 317; 428/511 10 Claims, No Drawings
 4,175,066
1 2
flowability and a large quantity of the dispersant must
DISPERSANT FOR CALCIUM CARBONATE be added so as to attain a suf?cient flowability.

BACKGROUND OF THE INVENTION SUMMARY OF THE INVENTION

1. Field of the Invention _ We discovered that a salt of an acrylic acid/maleic
The present invention relates to a dispersant for cal acid copolymer is effective as a dispersant for calcium
cium carbonate. More particularly, the invention relates carbonate and it is unexpectedly more effective than the
to a dispersant for calcium carbonate comprising a salt prior art dispersants because the foregoing defects are
of an acrylic acid/maleic acid copolymer. not observed and it can exert a very excellent dispersing
10 effect. It was also found that when a salt of an acrylic
2. Description of the Prior Art
Precipitated calcium carbonate is mainly prepared by acid/maleic acid copolymer (hereinafter referred to as
a process comprising calcining limestone together with AM polymer) prepared by copolymerizing acrylic
anthracite coal or coke in a lime kiln to form unslaked acid with maleic acid so that the monomer molar ratio
lime, adding water to the resulting unslaked lime to (acrylic acid/maleic acid) is from 100/5 to 100/200,
form milk of lime and reacting the milk of lime with preferably from 100/10 to 100/ 100, and the average
carbon dioxide gas. Various precipitated calcium car molecular weight of the copolymer is 1000 to 20,000,
bonate products, differing in the particle size and shape, preferably 2000 to 10,000, is added to the above-men
can be obtained by adjusting the reaction conditions in tioned solid cake having a solid concentration of 40 to
the above process. More speci?cally, the particle size 60 wt. %, which is obtained by dehydration of the pre
can be changed in a relatively broad range of from cipitated calcium carbonate slurry by a ?lter press, a
0.02-0.10u to l-3u by adjusting the reaction conditions. suf?cient dispersing effect can be attained when the
Further, the particle shape can also be changed in the amount of AM polymer employed is much smaller than
range of from a substantially cubic shape to a needle the amount required when the conventional dispersant
like shape. Thus, various calcium carbonate products such as sodium polyacrylate or sodium hexametaphos
differing in the particle size and shape have been pre phate are used, and the effect of improving the flowabil
pared by adjusting the reaction conditions. ity obtained by the use of the AM polymer is very high.
.When calcium- carbonate is used in an aqueous me As the salts of the AM polymer, there are preferably
dium, for example, for coating papers or for preparing employed an alkali metal salt, such as sodium or potas
aqueous paints, it is required that the calcium carbonate sium, and an ammonium salt. Some of carboxylic
particles should have an excellent dispersibility. For groups may be left in the free acid state or they may be
example, when calcium carbonate is used for coating a in the form of a salt of an alkaline earth metal.
paper, if the dispersibility thereof is poor, the viscosity The differences of the capacities of the dispersant
and flowability of the coating suspension are degraded, according to the present invention in comparison with
a good coating cannot be otained and the printability of those of conventional dispersants are described in detail
the resulting coated paper is very poor, resulting in the in the Examples given hereinafter, but the excellent
occurrence of various troubles. When a coated paper is properties of the dispersant of the present invention will
prepared in this manner, water is removed after the be apparent from the following experimental data:
coating is applied. Accordingly, the use of a high con The viscosity of a calcium carbonate slurry having a .
centration pigment suspension having as low a water 40 solid concentration of 50 wt. % is very high (higher
content as possible is desired. Therefore, a dispersant than 10,000 cps) and this slurry has no substantial ?ow
capable of providing a high concentration suspension ability. When a conventional dispersant, sodium hexa
having a low viscosity, when only a small amount of the metaphosphate, is added to the slurry in an amount of 5
dispersant is used, is eagerly desired in the art. As dis~ wt. %, based on the weight of the calcium carbonate,
persants capable of meeting this requirement, there 45 the viscosity of the slurry is reduced to 7000 cps and
have been mainly used sodium pyrophosphate, sodium when sodium polyacrylate is added in an amount of 5
hexametaphosphate and sodium polyacrylate. wt. %, based on the weight of the calcium carbonate,
In Japan, ?nely divided precipitated calcium carbon the viscosity is reduced to 600 cps. In contrast, when
ate is mainly prepared by a process comprising intro the AM polymer salt of the present invention is added in
ducing carbon dioxide gas into an aqueous suspension of 50 an amount of 2.0 %, based on the weight of the calcium
calcium hydroxide to form calcium carbonate and pre carbonate, the viscosity of the slurry is reduced to 50
cipitating the thus-formed calcium carbonate. The cps.
?nely divided precipitated calcium carbonate prepared As will be apparent from the foregoing experimental
according to this process is recovered in the form of a data, the AM polymer salt of the present invention
slurry having a solid concentration of 15 to 25 wt. % 55 exerts a suf?cient dispersing effect when a much smaller
and water is removed therefrom by a ?lter press so that amount thereof is used, in comparison with the results
the solid concentration is elevated to 40 to 60 wt. %. obtained using the conventional dispersants, and the
The resulting water-containing cake is marketed as it is dispersing effect is much higher than that of the conven
or after it is dried and pulverized to form a powdery tional dispersants. Accordingly, when the AM polymer
product. The above-mentioned cake having a solid con 60 salt of the present invention is used as a dispersant, the
centration of 40 to 60 wt. %, which is obtained by dehy pigment concentration can be maintained at a much
dration using a ?lter press in the above-described pro higher level than the pigment concentration attainable
cess, is very hard and it is not ?owable at all. Accord by the use of the conventional dispersants, when the
ingly, the cake is rendered flowable by adding a disper comparison is made based on the same slurry viscosity.
sant, such as sodium pyrophosphate, sodium hexameta 65 That is, the water content in the slurry can be reduced
phosphate, sodium polyacrylate or the like. However, when the AM polymer salt of the present invention is
these dispersants are still insuf?cient and defective in used. Accordingly, when the slurry is used for coating
that it is dif?cult to obtain a slurry having a suf?cient paper, the surface condition, printability and other
 4,175,066
3 4
properties are remarkably improved in the resulting Table l-continued
coated paper.
Amount of Viscosity (cps)
The AM polymer salt of the present invention has an dispersant
of 50% by weight
excellent dispersing effect for colloidal calcium carbon (% by weight aqueous slurry
ate having a particle size of 0.02 to 1.001;, light ?ne 5 Sample based on of calcium
calcium carbonate having a particle size of l to 5p, and No. Dispersant CaC03) carbonate
heavy calcium carbonate having a particle size of 3 to 1500) 1.5 7500
10p. Further, the AM polymer salt of the present inven sodium polyacrylate
(molecular weight =
tion has a high dispersing effect for clay, kaolin, tita 10 1500) 2.0 2200
nium oxide, red iron oxide, zinc ?ower, aluminum hy sodium polyacrylate
droxide, titanium white and other pigments. (molecular weight =
When a paper coating composition is prepared by 1500 3.0 1100
adding the dispersant of the present invention to a sodium polyacrylate
(molecular weight =
slurry of calcium carbonate and/or other pigment, and 1500 5.0 800
further adding casein, starch, a vinyl tape synthetic 15 sodium polyacrylate
latex or a mixture thereof to the slurry, because the (molecular weight =
dispersing effect of the dispersant of the present inven 1500) 7.0 1000
4 sodium polyacrylate
tion is higher than that of a conventional dispersant (molecular weight =
such as sodium polyacrylate or sodium hexametaphos 4000) 1.5 7000
phate, the intended dispersing effect can be attained 20 sodium polyacrylate
when there is used a very small amount of the AM (molecular weight =
400 2.0 2000
polymer, usually less than of the amount of the con sodium polyacrylate
ventional dispersant that is required for the same effect. (molecular weight =
The gloss, whiteness, opacity and other properties of 4000) 3.0 1000
the resulting coated papers are superior or at least simi 25 sodium polyacrylate
(molecular weight =
lar to those of coated papers prepared by using the 4000) 5.0 600
conventional dispersants. sodium polyacrylate
The present invention will now be further described (molecular weight =
in detail by reference to the following illustrative Exam 30 4000) 7.0 800
5 sodium polyacrylate
ples that by no means limit the scope of the invention. (molecular weight =
10000) 1.5 8000
EXAMPLE 1 sodium polyacrylate
A predetermined amount of a dispersant and water (molecular weight =
10000) 2.0 6000
were added to a cake of precipitated calcium carbonate 35 sodium polyacrylate
having a solid concentration of 52% by weight obtained (molecular weight 1.0
by dewatering a slurry using a ?lter press. The calcium 10000) 3.0 3000
carbonate was composed of ?ne particles having a cubic sodium polyacrylate
(molecular weight =
shape and an average particle size of 0.0811,. The amount 10000) 5.0 1100
of water added was selected so that the solid concentra 6 sodium polymaleate
tion of the system was 50 wt. %. The cake was im 4'0 (molecular weight =
1500 2.0 > 10000
mersed in a thermostat tank maintained at 25 C. until sodium polymaleate
the temperature was maintained constant for 1 hour, (molecular weight =
and then it was agitated for 5 minutes by a homogeniz 1500 3.0 5000
ing mixer (Type TK manufactured by Tokushu Kiki K. sodium polymaleate
K.). The apparent viscosity was measured by a B-type 45 (molecular weight =
1500 5.0 1500
viscometer (rotor No. 1). When no dispersant was w
added, the viscosity of the slurry was higher than 10,000 7 Na salt of acrylic 1.2 2500
cps. The kinds and amounts of the dispersants used and acid/maleic acid 1.5 230
the test results are shown in Table 1. copolymer, (molar
50 ratio = 100/2s, 2.0 60
Table 1 molecular weight = 3.0 60
Amount of Viscosity (cps) 4000)
dispersant of 50% by weight 8 Na salt of acrylic 1.0 1800
(% by weight aqueous slurry acid/maleic acid 1.2 1100
Sample based on of calcium copolymer, (molar
55 ratio = 100/50, 1.5 150
No. Dispersant CaCO3) carbonate
molecular weight = 2.0 50
WE. 4000) 3.0 6
sodium pyrophos 9 Na salt of acrylic 1.2 4000
phate 2.0 > 10000 acid/maleic acid 1.5 550
sodium pyrophos copolymer, (molar
phate 3.0 > 10000 6O ratio = 100/100, 2.0 100
1 sodium pyrophos molecular weight = 3.0 120
phate 5.0 > 10000 4000
2 sodium hexameta 10 Na salt of acrylic 1.2 6000
phosphate 2.0 > 10000 acid/maleic acid
sodium hexameta copolymer, (molar 1.5 1100
phosphate 3.0 > 10000 65 ratio = 100/50 2.0 90
sodium hexameta molecular weight =
phosphate 5.0 7000 8000 3.0 100
3 sodium polyacrylate 11 Na salt of acrylic 1.2 8000
(molecular weight = acid/maleic acid 1.5 1800
 4,175,066
Table l-continued Table 3 -continued
Amount of Viscusity (cps) Properties of Coated Papers
dispersam of 50% by weight White Paper Test Printing Testl
(% by weight aqueous slurry 5 White 0P3 Ink 55!
33mph based on of calcium ness city Gloss Gloss ting Time
No. Dispersant CaCOg) carbonate (%) (%) (60 60 ) (6O _60 ) (Sec)
using slurry
PO|Yme? (molar including 29.2 92.0 47.5 54.3 is
ratio = loo/50, 2.0 200 comparative
molecular weight = 3.0 200 10 Sample No. 4
15000 Coated paper
formed by
using slurry
The results obtained when aqueous dispersions of ?ne ggrrsrenilo 8 89's 92'6 480 ,54'7 14
calcium carbonate prepared in the above Example were 1 5 of present
used for coating paper are described. mvemlm
. . . . - _ Note:

_ The mlxlng ratio based on the sohds of starch/ca] 'The test was conducted by using an R1 tester manufactured by Akira Seisakusho.
cium carbonate were ?xed at to 16.7% by
Weight/333% by weight The dispersant and Water The embodiments of the invention in which an exclu
were added so that the viscosity shown in Table 2 was 20 sive property or privilege is claimed are defined as
obtained. The properties of the resulting slurry and the follows:
kinds and amounts of the dispersants used are shown in 1. An aqueous dispersion consisting essentially of
Table 2. water, calcium carbonate particles having a particle size
of from 0.02 to 10 microns and, as a dispersing agent,
Table 2 25 from about 1 to about 5 wt. %, based on the weight of
Dispersant said calcium carbonate particles, of a salt of an acrylic
Sample No. 4 Sample No. 8 acid/maleic acid copolymer or mixture thereof, the
on Table 1 on Table l molar ratio of acrylic acid/maleic acid monomer units
(comparative (dispersant of in said copolymer being in the range of from 100/5 to
30 100/ 200 and said copolymer having a molecular weight
sample), 2.0% present invention,
Properties of basedlon 1.0% based on of from 1,000 to 20,000.
Slurry CaCO3 CaCO3 2. An aqueous dispersion as claimed in claim 1 in
Solid Concentration2
which said molar ratio is from 100/10 to 100/100.
(%) of Slurry 48.4 48.6 3. An aqueous dispersion as claimed in claim 1 in
35 which the molecular weight of said copolymer is from
Viscosity (B-type
viscometer, cps, 2000 to 10,000.
60 rpm, 25'' C. 990 960 4. An aqueous dispersion as claimed in claim 1 in
Viscosity (Hercules which said salt is an alkali metal salt.
viscometer, cps, 5. An aqueous dispersion as claimed in claim 1 con
ll00 rmp, 25 C.) 28 27 taining from 40 to 60 wt. % of calcium carbonate.
pH (pH meter, 25 C.) 10.3 10.2 6. A method of preparing an aqueous dispersion of
Note calcium carbonate particles, said dispersion having a
1When the amount added of Sample No. 4 was 1.0%. the viscosity was too high and high concentration of calcium carbonate particles and a
no slurry could be formed. Accordingly, the sample No. 4 dispersant had to be low viscosity, which comprises blending into a mixture
added in an amount of 2.0%, so as to obtain the slurry shown in Table 2.
45 consisting essentially of water and calcium carbonate
2The total amount of CaCOJand starch are regarded as the solid content.
particles having a particle size of from 0.02 to 10 mi
The slurry shown in Table 2 was coated on an un crons, from 1 to 5 wt. %, based on the weight of said
calcium carbonate particles, of a salt of an vacrylic acid/
coated paper having a base weight of 105.3 g/m2 by maleic acid copolymer or mixture thereof, the molar
using a coating rod. The coated paper was dried at 50 ratio of acrylic acid/maleic acid monomer units in said
room temperature and was subjected to a super-calend copolymer being in the range of from 100/5 to 100/ 200
ering treatment (linear pressure=l00 Kg/cm, paper and said copolymer having a molecular weight of from
feed spced=20 m/min, chilled roll temperature=60 1,000 to 20,000.
(3., paper~passing frequency=5 times). The amount of 7. A method according to claim 6 in which said mix
the solids coated on the paper was ZOil g/m3. The ture contains from 40 to 60 wt. % of calcium carbonate
and the balance is essentially water, said mixture having
properties of the resulting coated papers are shown in been obtained by ?lter-pressing an aqueous slurry ob
Table 3. tained by blowing carbon dioxide into an aqueous sus
Table 3 pension of calcium hydroxide to form an aqueous slurry
containing 15 to 25 wt. % of calcium carbonate.
Properties of Coated Papers
8. An aqueous dispersion as claimed in claim l in
White Paper Test Printing Testl which said salt is an ammonium salt.
White- Opa- lnk Set 9. A method according to claim 6 in which said salt is
ness city Gloss Gloss ting Time an alkali metal salt.
('7') (%) (60-~60) (6060) (sec) 65 10. A method according to claim 6 in which said salt
Coated paper is an ammonium salt.
it * * ls *
formed by