Detergent builder process of manufacturing same and detergent composition containing same

A detergent builder is composed of a maleic acid copolymer having a weight-average molecular weight in a range of from 5,000 to 100,000, wherein a molar ratio of a maleic acid (salt) monomer to total monomers used in a process is in a range of from 0.1 to 0.9. The detergent builder is obtained by a copolymerization reaction of the monomers using a hydrogen peroxide and a persulfate as a polymerization initiator. As such detergent builder has high calcium ion stability constant and desirable property against iron particle deposition, it is suitably used as a detergent composition. The detergent builder may be prepared by granulation with agitation of powders containing the maleic acid copolymer as water-soluble polycarboxylic acid (salt) using a surface active agent. Such detergent builder has improved angle of repose, fluidity, and hygroscopicity, and the detergent builder having the described properties can be prepared by the dry-mixing process, thereby permitting the detergent composition having described excellent properties to be manufactured at low cost.

FIELD OF THE INVENTION 
The present invention relates to a detergent builder which prevents a 
deterioration of detergency of a detergent composition and such detergent 
builder of a powdered form which shows an improved mixability to the 
detergent composition. The present invention also relates to a process of 
manufacturing the above-mentioned two types of detergent builders and 
detergent compositions respectively containing such detergent builders. 
BACKGROUND OF THE INVENTION 
Conventionally, it is known that maleic acid copolymers as a polymer of 
water-soluble polycarboxylic acid (salts) having many carboxylic groups 
show excellent functions of chelation and dispersion. For these beneficial 
properties, such copolymers have been used in a variety of fields, such as 
a detergent builder of a detergent composition, a dispersant, a 
flocculating agent, a scale formation inhibitor, a chelating agent, and a 
fiber processing agent and the like. 
Among the described copolymers, those having many carboxylic groups in each 
molecule are suitably used for the above-mentioned respective uses. In the 
process of manufacturing such maleic acid copolymers, to overcome the 
deficiency that the polymerizability thereof is generally low, it has been 
proposed to increase the amount of the maleic acid component to be placed 
in a polymerization process to introduce many carboxylic groups. However, 
such method has the following drawbacks. 
(1) A still long time is required for the polymerization process because of 
the low polymerizability of the maleic acid component; 
(2) When the maleic acid component is placed at a higher proportion, a 
greater amount of hydrogen peroxide (polymerization initiator) is 
required; 
(3) The use of the hydrogen peroxide in a large amount results in a high 
content of residual hydrogen peroxide from the polymerization reaction; 
and 
(4) In spite of the fact that the hydrogen peroxide (polymerization 
initiator) is used in a large amount, a content of residual unreacted 
maleic acid component is still high. 
Furthermore, earnest researches have been made by the inventors of the 
present invention to find out important factors other than the content of 
the carboxylic acid of the maleic acid copolymer to improve the detergency 
of the detergent composition containing the maleic acid copolymer as a 
detergent builder. 
As a result, the inventors of the present invention have found that it is 
important to improve the property of the maleic acid copolymer in its 
calcium ion stability constant, and the property against iron particle 
deposition for preventing clothes from being yellowish. Additionally, in 
the case of the maleic acid copolymers of high gelation properties, when 
using water of high hardness as water for washing, the detergency is 
significantly lowered as being undissolved. Thus, the inventors of the 
present invention have also found that it is necessary to lower the 
gelation properties. 
As disclosed in the below-mentioned Gazettes, with the maleic acid 
copolymers produced under conventional reaction conditions, even if the 
hydrogen peroxide is used in a large amount as a polymerization initiator, 
it is difficult to effectively introduce the maleic acid component to a 
high molecular portion. Moreover, the problem of high content of residual 
unreacted maleic acid and hydrogen peroxide in the reaction solution upon 
the completion of the polymerization reaction has not been solved. 
Besides, the problem of high content of residual unreacted maleic acid and 
hydrogen peroxide remaining in the reaction solution upon completion of 
the polymerization reaction remains unsolved which results in low 
polymerizability. 
The maleic acid copolymers isolated from the copolymerization reaction 
solution upon completion of the reaction have high concentration of 
hydrogen peroxide and a high content of the residual maleic acid, and 
maleic acid copolymers do not show desirable functions of chelation and 
dispersion. Therefore, such copolymers are not suited for the 
aforementioned purposes, and do not have sufficient levels of essential 
properties to improve the detergency of a detergent composition such as 
calcium ion stability constant, a property against iron particle 
deposition and a anti-gelation properties. 
(1) Japanese Examined Publication No. 2167/1991 (Tokukohei 3-2167) 
discloses a process of manufacturing a maleic acid copolymer, wherein a 
maleic acid component is placed in a reaction vessel, and under the 
condition that the dropping of the maleic acid and the acrylic acid start 
and finish at the same time, a polymerization reaction of the maleic acid 
and acrylic acid is carried out at a pH in a range of from 3.5 to 5.0. The 
Gazette (1) discloses an example of using the maleic acid copolymer as a 
pigment dispersant. However, it fails to disclose the example of using an 
maleic acid copolymer as a detergent composition. 
In the method of manufacturing the maleic acid copolymer of Gazette (1), a 
large amount of maleic acid in the reaction solvent remains unreacted upon 
completion of the reaction, and the hydrogen peroxide also remains 
unreacted in spite of the fact that a large amount of hydrogen peroxide 
water solution is used in the polymerization reaction. Additionally, the 
resulting maleic acid copolymer is inefficient in its calcium ion 
stability constant, property against iron particle deposition, 
anti-gelation properties, and the like. 
(2) Japanese Laid-Open Patent Publication No. 218407/1987 (Tokukaisho 
62-218407) discloses respective examples of using a maleic acid copolymers 
as a dispersant and a detergent composition. However, the detergent 
composition does not show an improved detergency from the generally used 
detergent composition, nor have desirably balanced properties for the 
detergent. The Gazette (2) discloses the process of preparing the maleic 
acid copolymer wherein a maleic acid component is placed in a reaction 
vessel, and under the condition that the dropping of the acrylic acid and 
hydrogen peroxide start and finish at the same time, a polymerization 
reaction is carried out at a pH of around 4-6, thereby obtaining a maleic 
acid copolymer. 
In the method of manufacturing the maleic acid copolymer of Gazette (2), a 
large amount of maleic acid in the reaction solvent remains unreacted upon 
completion of the reaction in spite of the fact that a large amount of 
hydrogen peroxide is used in the polymerization process, and a large 
amount of hydrogen peroxide also remains unreacted. Besides, the resulting 
maleic acid copolymer is inefficient in its calcium ion stability 
constant, property against iron particle deposition property, 
anti-gelation properties, and the like. 
(3) Japanese Examined Patent Publication No. 14046/1991 (Tokukohei 3-14046) 
discloses a copolymer of ethylenically unsaturated monomer and 
dicarboxylic acid. The Gazette (3) discloses an example of using such 
copolymer as a skin formation inhibitor with respect to the detergent but 
fails to disclose a concrete example of using such copolymer. 
As in the case of the aforementioned Gazettes, the Gazette (3) discloses 
the process wherein the ethylenically unsaturated dicarboxylic acid 
component is placed in a reaction vessel, and a polymerization reaction is 
carried out under the condition that the dropping of the ethylenically 
unsaturated monocarboxylic acid and the hydrogen peroxide water solution 
start and finish at the same time. However, the resulting maleic acid 
copolymer is insufficient in its calcium ion stability constant, property 
against iron particle deposition, anti-gelation property, and the like. 
As described, the maleic acid copolymers resulting from the conventional 
reaction process are inferior in essential properties for various uses 
especially as the detergent composition. In addition, it is difficult to 
remove the maleic acid and hydrogen peroxide remaining in the resulting 
maleic acid copolymer from the conventional reaction. Besides, when using 
the maleic acid copolymer having a large amount of the residual maleic 
acid as a detergent composition, chelating and dispersing functions are 
adversely affected, and the detergency is lowered. Furthermore, when using 
the maleic acid copolymer having a high content of residual hydrogen 
peroxide as a detergent composition, the problem of unsafety arises as it 
may adhere to a skin of the user. 
In the case of using the above-mentioned conventional copolymer, for 
example, as a detergent builder for a detergent composition, it is 
preferable to use it in a powdered form rather than liquid form as it is 
less restricted in its density and mixing ratio. Besides, if the final 
product is in the powdered form, a cost required for the drying process of 
the product can be reduced. 
However, such copolymer of a powdered form has the problem of uneasy 
handling due to its extremely high hygroscopicity and very poor fluidity, 
etc. Therefore, most copolymers available in the market are in liquid form 
rather than the powdered form. 
The powdered detergent as the detergent composition is mainly available as 
a low density product resulting from the conventional spray-drying 
process. However, for convenience in view of transportation, carriage and 
storage place, etc., of the detergent, there is a tendency of using a 
compact powdered detergent of higher density. 
The density can be increased, for example, in such a manner that a raw 
material is first formed into powders by the spray-drying process, and 
then formed into a granule by an agitated granulator such as a mixer as 
disclosed by (4) Japanese Laid-Open Patent Publication No. 2000/1994 
(Tokukaihei 6-2000). For each step in the above-mentioned method, as at 
least one kind of liquid raw material is required, many processes of 
mixing, drying, granulating, drying, classification, etc., are required 
for each step. 
On the other hand, when all the materials are in the powdered form, the 
detergent composition can be prepared only by the dry-mixing process, and 
the multiple-steps of mixing, drying, granulating, drying, classifying, 
and the like required in the Gazette (4) can be omitted. Namely, as the 
density can be increased by carrying out only one step of mixing, a 
significant cost reduction can be achieved. 
However, the maleic acid copolymer used as one component of the detergent 
builder as one of the detergent composition has a problem of uneasy 
handling due to hygroscopicity when using it in the powdered form as 
previously described. Therefore, in practice, it is difficult to increase 
the density by applying the dry-mixing process to the detergent 
composition containing the copolymer. 
In addition, when applying the dry-mixing process to a powder of each 
detergent composition, it is required to structure such that respective 
compositions have the same bulk density in consideration of the problem of 
segregation after mixing the powder. When applying the dry-mixing process 
to each composition of the powdered form, the fluidity of each powder is 
extremely important. Besides, in the mixing process, it is necessary to 
have low hygroscopicity of each powder to prevent it from adhering to a 
line, a hopper, and the like, and the bulk density thereof has to be set 
as close as that of the detergent composition. 
However, as the copolymer has a desirable solubility to the washing water, 
it is difficult to satisfy the bulk density, fluidity and hygroscopicity 
sufficient for the dry-mixing process in the form of powder. 
DISCLOSURE OF THE INVENTION 
Object of the Invention! 
The object of the present invention is to provide a detergent builder 
containing a copolymer of maleic acid having a high calcium ion stability 
constant and a desirable property against iron particle deposition. The 
second object of the present invention is to provide a method of 
manufacturing the copolymer of maleic acid and a detergent composition 
containing the detergent builder. 
The third object of the present invention is to provide a detergent builder 
containing a copolymer of polycarboxylic acid (salts) such as a copolymer 
of maleic acid, etc., having improved hygroscopicity and fluidity and high 
bulk density, and to provide a method of manufacturing the detergent 
builder, and also to provide a detergent composition containing such 
detergent builder. 
Summary of the Invention! 
Earnest researches have been made by inventors of the present invention to 
achieve the first object of the present invention, and they have succeeded 
in achieving the present invention by focusing the researches on the 
calcium ion stability constant and property against iron particle 
deposition. 
Namely, the detergent builder of the present invention is characterized by 
being composed of a maleic acid copolymer having a weight-average 
molecular weight in the range of from 5,000 to 100,000, wherein a molar 
ratio of maleic acid monomer to a total monomers used in the process is in 
the range of from 0.1 to 0.9. 
For the maleic acid copolymer of the present invention, any copolymer 
obtained by the polymerization reaction with monomers including a maleic 
acid (salt) as a monomer component is used. Other than the maleic acid 
(salt), a water-soluble ethylenically unsaturated monomer is preferable 
for the other monomer. 
Examples of the water-soluble ethylenically unsaturated monomer include: an 
unsaturated monocarboxylic acid monomer such as acrylic acid, methacrylic 
acid, 60-hydroxy acrylic acid, crotonic acid, and the like, and salts 
thereof; unsaturated polycarboxylic acid monomer such as fumaric acid, 
itaconic acid, citraconic acid, aconitic acid, and salts thereof; vinyl 
acetate, and the like. 
The water-soluble ethylenically unsaturated monomer may be a compound of 
formula (1) 
##STR1## 
(in the formula, R.sup.1 and R.sup.2 independently represent a hydrogen 
atom or a methyl group but are not both methyl group, R.sup.3 represents a 
--CH.sub.2 --, --(CH.sub.2).sub.2 --, or --C(CH.sub.3).sub.2 -- group and 
the total number of the carbon atoms in R.sup.1, R.sup.2 and R.sup.3 
groups is 3, Y represents an alkylene group of carbon number 2 to 3, and n 
is 0 or an integer of 1 to 100). 
Examples of such water-soluble ethylenically unsaturated monomer include: a 
monomer containing unsaturated hydroxy group such as 3-methyl-3-butene-1ol 
(isoprenol), 3-methyl-2-butene-1-ol(prenol), 
2-methyl-3-butene-2-ol(isoplene alcohol), and monomers of 1 mole of 
3-methyl-3-butene-1-ol(isoprenol), 3-methyl-2-butene-1-ol(prenol), 
2-methyl-3-butene-2-ol(isoplene alcohol) to which respectively 1-100 mole 
of ethylene oxide and/or propylene oxide is added. 
The water-soluble ethylenically unsaturated monomer may be a compound of 
formula (2) 
##STR2## 
(in the formula, R.sup.1 represents a hydrogen atom or a methyl group, a, 
b, d, and f independently represent O or a positive integer of 1 to 100 
and the total number of a, b, d, and f is 0 to 100, the (OC.sub.2 
H.sub.4)-- and --(OC.sub.3 H.sub.6)-- units may be combined in any order, 
Z represents a hydroxyl, sulfonic acid, or phosphoric (or phosphorous) 
acid group when the sum of d and f is 0, and Z represents a hydroxyl group 
when the sum is a positive integer of 1 to 100). 
Examples of such water-soluble ethylenically unsaturated monomer include: 
3-ariroxy-2-hydroxypropane sulfonic acid and salts thereof; unsaturated 
(meth)allyl ether monomers such as glycerol monoallyl ether monomers, and 
1 mole of glycerol monoallyl ether monomers to which 1-100 mole of 
ethylene oxide and/or propyleneoxide is added; a monomer containing an 
unsaturated sulfonic acid group such as vinyl sulfonic acid, allyl 
sulfonic acid, methasulfonic acid, styrene sulfonic acid, 
2-acrylamide-2-methylpropane sulfonic acid, sulfoethyl(meth)acrylate, 
sulfopropy 1(meth)acrylate, 2-hydroxysulfopropyl (meth)acrylate, 
sulfoethyl maleimide, and salts thereof; an unsaturated ester monomer 
containing a terminal end alkyl group such as a monoester of alcohol 
having 0-100 mole of ethylene oxide and/or propylene oxide added to alkyl 
alcohol of 1-20 carbon atoms and (meth)acrylic acid, crotonic acid, etc., 
or maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic 
acid, etc., or salts thereof; or diester thereof; a monoester monomer 
having 1-100 mole of ethylene oxide and/or propylene oxide added to 1 mole 
of unsaturated carboxylic acid monomer such as (meth)acrylic acid, 
crotonic acid, etc., or a monoester having 1-100 mole of ethylene oxide 
and/or propylene oxide added to an unsaturated carboxylic acid monomer 
such as maleic acid, fumaric acid, itaconic acid, citraconic acid, 
aconitic acid, or salts thereof; or ester unsaturated monomer such as 
diester monomer, and the like. Only one kind of the above-listed monomer 
may be adopted, or two or more kinds thereof may be suitably mixed and 
adopted. Among all monomers listed above, (meth)acrylic acid (salts) is 
the most preferable water-soluble ethylenically unsaturated monomer. 
The method of preparing the maleic acid copolymer contained in the 
detergent composition of the present invention is not specifically 
limited. However, the maleic acid copolymer (to be described later) is 
preferably obtained by carrying out a copolymerization of a maleic acid 
(salts) and water-soluble ethylenically unsaturated monomer in an aqueous 
medium using hydrogen peroxide as a water-soluble polymerization 
initiator. 
The maleic acid copolymer of the present invention is preferably obtained 
by carrying out an aqueous solution copolymerization reaction of maleic 
acid (salt) (A) and a water-soluble ethylenically unsaturated monomer (B) 
using persulfate and hydrogen peroxide as a water-soluble polymerization 
initiator. 
It is especially preferable to employ a maleic acid copolymer obtained by 
carrying out a solution copolymerization reaction in such a manner that a 
concentration of hydrogen peroxide upon completion of the polymerization 
reaction is not more than 0.05 percent by weight with respect to the total 
amount of the reaction solution, and by isolating the copolymer from the 
copolymerization reaction solution having not more than 3 percent by 
weight of residual maleic acid with respect to the total amount of reacted 
product under conditions of a) through e) to be described later. 
The maleic acid (salts) used in preparing the maleic acid copolymer of the 
present invention may be introduced into the reaction vessel in any form 
of maleic acid, maleic acid monoalkali metal salts, and maleic acid 
dialkali metal salts. Only one kind of the above-listed material may be 
adopted, or two or more kinds thereof may be suitably mixed and adopted. 
The maleic acid may be obtained by hydrolyzing a maleic acid anhydride in 
a reaction vessel. The maleic acid monoalkali metal salts, maleic acid 
dialkali metal salt may be obtained by reacting a maleic acid and/or a 
maleic acid anhydride with a hydrolyzed product of alkali metal in a 
reaction vessel. 
To improve the calcium ion stability constant and property against iron 
particle deposition of the maleic acid copolymer, the process of preparing 
a maleic acid copolymer of the present invention is preferably performed 
under the condition a): 
a) Maleic acid (salt) and water-soluble ethylenically unsaturated monomer 
(other monomer) are used in an amount with respect to the water-soluble 
ethylenically unsaturated monomer as another monomer component with a 
molar ratio in the range of from 90/10 to 10/90 (mole ratio), more 
preferably in the range of from 60/40 to 15/85, and most preferably in the 
range of from 40/60 to 20/80. When the ratio of these materials deviates 
from the described range of from 90/10 to 10/90, it is detrimental to the 
performances of the resulting maleic acid in view of the calcium ion 
stability constant and property against iron particle deposition. 
Polymerization of the maleic acid copolymer of the present invention is 
preferably performed under the condition b): 
b) At least 70 percent by weight of maleic acid (salts) used in the 
reaction is placed beforehand in the reaction vessel, i.e., before the 
reaction is started. In view of reducing the amount of the residual maleic 
acid (salts) upon completion of the polymerization reaction and improving 
the calcium ion stability constant of the polymer, it is preferable that 
at least 90 percent by weight of maleic acid (salts) is placed beforehand 
in the reaction vessel. 
In view of improving the polymerizability, and the calcium ion stability 
constant of the maleic acid copolymer, it is preferable to perform a 
polymerization reaction under the condition c): 
c): The concentration of the maleic acid (salts) at the start of the 
polymerization reaction is not less than 35 percent by weight. To still 
improve the above-mentioned properties, the concentration of the maleic 
acid (salts) when the polymerization starts is preferably not less than 45 
percent by weight, more preferably not less than 60 percent by weight. 
The water-soluble ethylenically unsaturated monomer used in the 
polymerization reaction of the present invention is not especially 
limited, and any ethylenically unsaturated monomer having solubility to 
water may be used. However, those listed earlier are preferably used in 
the copolymerization reaction. It is still more preferable that the 
solubility of the water-soluble ethylenically unsaturated monomer is not 
less than 5 g in 100 g of water at 100.degree. C. 
The polymerization reaction of the present invention is preferably 
performed under the condition d): 
d) At least 70 percent by weight of water-soluble ethylenically unsaturated 
monomer is continuously introduced in the reaction vessel over a period in 
a range of from 30 to 500 minutes after the start of the copolymerization 
reaction. Less than 30 percent by weight of the unsaturated monomer may be 
placed in the reaction vessel beforehand. When placing not less than 30 
percent by weight of water-soluble ethylenically unsaturated monomer, the 
distribution of the molecular weight of the resulting maleic acid 
copolymer is spread, and a block polymerized non-uniform copolymer is 
produced. Thus, such condition is detrimental to the calcium ion stability 
constant and also to the property against iron particle deposition. 
It is preferable that the water-soluble ethylenically unsaturated monomer 
is introduced over a shorter period of time, because the distribution of 
the molecular weight of the resulting maleic acid copolymer becomes 
narrower, and the property against iron particle deposition can be 
improved. Besides, by introducing the monomer in a shorter period of time, 
an improved productivity can be achieved. 
The copolymerization reaction is preferably performed under the condition 
e): 
e) The water-soluble ethylenically unsaturated monomer is introduced over a 
time period in a range of from 30 to 180 minutes, and hydrogen peroxide, 
to be described later is introduced over a time shorter than the time 
required for introducing the water-soluble ethylenically unsaturated 
monomer, for example, a period in a range of from 20 to 170 minutes. The 
maleic acid copolymer obtained under the condition e) shows still improved 
property against iron particle deposition. 
However, when introducing successively the water-soluble ethylenically 
unsaturated monomer over a time period of less than 30 minutes, the 
problem may occur as the amount of residual maleic acid upon completion of 
the polymerization reaction increases, or it may be difficult to desirably 
remove heat as a large amount of reaction heat is released in a short 
period of time. 
In the process of manufacturing the maleic acid copolymer of the present 
invention, it is preferable to use both persulfate and hydrogen peroxide 
as a water-soluble polymerization initiator. The content of the hydrogen 
peroxide is preferably in the range of from 0.1 to 3.0 percent by weight 
based on the total monomers used in the process, more preferably not less 
than 0.3 percent by weight. 
If the hydrogen peroxide is used in an amount of less than 0.1 percent by 
weight, the amount of residual maleic acid would increase, and the 
molecular weight of the resulting polymer would be too large, resulting in 
the maleic acid copolymer in undesirable color. On the other hand, if the 
hydrogen peroxide is used in an amount of more than 3.0 percent by weight, 
the property against iron particle deposition of the resulting maleic acid 
copolymer would be lowered, and the amount of residual hydrogen peroxide 
would increase, thereby presenting the problem of unsafe use. If the 
additional process of removing the residual hydrogen peroxide of the 
resulting maleic acid copolymer is performed, the greater number of steps 
are required to complete the manufacturing process, resulting in low 
productivity. 
The hydrogen peroxide and the persulfate are preferably used with a weight 
ratio in the range of from 1/50 to 1/2, more preferably with a weight 
ratio in the range of from 1/20 to 1/3 in view of improving the property 
against iron particle deposition and calcium ion stability constant. 
Examples of the other water-soluble polymerization initiator which can be 
used with hydrogen peroxide and persulfate include: persulfates such as 
ammonium persulfate, sodium persulfate, potassium persulfate, and the 
like; azo series compounds such as 2,2'-azobis (2 amidinopropane) 
hydrochloride; 4,4'-azobis-4-cyanovaleic acid, azobisisobutyronitrile, 
2,2'-azobis-4-methoxy-2,4-dimethylvalenonitrile, and the like; organic 
peroxide such as benzoyl peroxide, lauroyl peroxide, peracetic acid; 
succinic peroxide, ditertiary butylperoxide, tertiary butyl hydroperoxide, 
cumin hydroperoxide, and the like. Only one kind of the above-listed 
water-soluble polymerization initiator which can be used with hydrogen 
peroxide and persulfate may be adopted, or two or more kinds thereof may 
be suitably mixed and adopted. 
By carrying out the copolymerization reaction under the described 
conditions, the concentration of residual hydrogen peroxide upon 
completion of the polymerization reaction can be reduced to not more than 
0.1 percent by weight with respect to the total amount of the reaction 
solution, more preferably not more than 0.05 percent by weight, still more 
preferably to not more than 0.02 percent by weight. 
Additionally, under the above-mentioned copolymerization condition, the 
amount of the residual maleic acid upon completion of the polymerization 
can be reduced to not more than 3 percent by weight, more preferably not 
more than 0.3 percent by weight. If the content of the residual maleic 
acid exceeds 3 percent by weight, deposition of the maleic acid crystal 
may occur in cold areas in winter season. 
The pH in the polymerization reaction can be selected at random. 
Additionally, it is permitted to adjust a pH during the polymerization 
reaction. Examples of neutralization-use basic compound for use in 
adjusting a pH during the polymerization reaction include: hydroxide 
compounds of alkali metal or carbonate such as sodium, potassium, lithium, 
and the like; ammonia; alkyl amine compounds such as monomethylamine, 
diethylamine, trimethylamine, monoethylamine, dimethylamine, 
triethylamine, and the like; alkanol amine compounds such as 
monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, 
secondary butanolamine, and the like, pyridine and the like. Only one kind 
of the above-listed compound may be adopted, or two or more kinds thereof 
may be suitably mixed and adopted. 
Furthermore, to achieve improved properties of the maleic acid copolymer in 
view of calcium ion stability constant, property against iron particle 
deposition, the content of the residual maleic acid upon completion of the 
polymerization reaction, and further to improve the reaction efficiency, 
it is preferable to satisfy the following two copolymerization conditions: 
(Condition 1) 
The pH value when the polymerization reaction is started is selected to be 
in a range of from 13 to 4, and the pH value is reduced as the reaction 
progresses. 
(Condition 2) 
For the polymerization initiator, persulfate is used as well as hydrogen 
peroxide with a ratio of hydrogen peroxide to persulfate of from 1/50 to 
1/2. 
The condition 1 is effective especially in view of property against iron 
particle deposition, while the condition 2 is effective especially in view 
of calcium ion stability constant. 
Additionally, it is preferable to perform a polymerization reaction in a 
presence of polyvalent metal ion because the content of the residual 
maleic acid in the reaction solution upon completion of the polymerization 
reaction can be reduced, and also because the distribution of the 
molecular weight of the maleic acid copolymer can be reduced. Besides, the 
property against iron particle deposition can be improved. Examples of 
effective polyvalent metal compound include: an iron ion, a vanadium ion, 
a copper ion, and the like. For polyvalent metal ions, Fe.sup.3+, 
Fe.sup.2+, Cu.sup.+, Cu.sup.2+, V.sup.2+, V.sup.3+, VO.sup.2+, etc., are 
preferable. Among these ions, Fe.sup.3+, Cu.sup.2+, VO.sup.2+ and the 
like are more preferable. Only one kind of the above-listed compound may 
be adopted, or two or more kinds the reof may be suitably mixed and 
adopted. 
The concentration of polyvalent metal compound is preferably in the range 
of from 0.1 to 100 ppm with respect to the total amount of the reaction 
solution. If the concentration is less than 0.1 ppm, the effect can be 
hardly achieved. On the other hand, when the density is more than 100 ppm, 
as the resulting maleic acid copolymer is deeply colored, the maleic acid 
copolymer may not be able to be used as a detergent composition. 
For the polyvalent metal compound, any metal compounds and metals may be 
used in any form as long as they can be ionized in the polymerization 
reaction system. Examples of such metal compound include: water-soltble 
metal salts such as vanadium oxytrichloride, vanadium trichloride, vanadyl 
oxalate, vanadyl sulfate, anhydrous vanadic acid, ammonium methavanadic 
acid, ammonium hypovanadous sulfate (NH.sub.4).sub.2 
SO.sub.4.VSO.sub.4.6H.sub.2 O!, ammonium vanadous sulfate 
(NH.sub.4)V(SO.sub.4).sub.2.12H.sub.2 O!, water-soluble metal salts such 
as cupric acetate(II), cupric bromide (II), copper(II), acetyl acetate, 
ammonium cupric copper(II) chloride, copper carbonate, copper(II) 
chloride, copper(II) citric acid, copper(II) formic acid, copper(II) 
hydroxide, copper sulfate, copper naphthenic acid, copper(II) oleic acid, 
copper maleic acid, phosphoric acid, copper(II) sulfate, copper(I) 
chloride, copper(I) cyanide, copper iodide, copper(I) oxide, copper (I) 
thiocyanate, iron acetyl acetonate, iron ammonium citrate, iron (II) 
ammonium oxalic acid, iron (II) ammonium sulfate, iron citrate, iron 
fuaric acid, iron maleic acid, iron (I) lactic acid, iron (II) nitric 
acid, iron penthacarbonyl, iron (II) phosphoric acid, iron (II) 
diphosphate, and the like; metal oxides such as vanadium pentoxide, 
copper(II) oxide, iron(I) oxide, iron(II) oxide, and the like; metal 
sulfides such as copper (II) sulfide, iron sulfide, and the like; or other 
copper powder, iron powder, and the like. 
Among above-listed copolymers, those having narrow distribution in 
molecular weight of the copolymer and having a large amount of maleic acid 
introduced in a polymer portion are most preferable by more efficiently 
satisfying the conditions of the present invention. 
It is preferable that the weight-average molecular weight of the maleic 
acid copolymer of the present invention is in the range of from 5,000 to 
100,000. In view of calcium ion stability constant and property against 
iron particle deposition, it is more preferably in the range of from 
20,000 to 80,000, and most preferably in the range of from 30,000 to 
70,000. 
The function of preventing the property against iron particle deposition of 
the maleic acid copolymer of the present invention can be determined by 
values measured by the following methods: 
Condition of Measuring the Property against Iron Particle Deposition! 
Reaction Vessel: 500 ml beaker 
Test Solution: A mixed solution of 1-3: 
1 150 ml of 0.1 percent solution of iron(II) chloride hexahydrate; 
2 150 ml of 0.1 percent solution of sodium hydroxide; and 
3 150 ml of 0.1 percent solution of maleic acid copolymer (based on 
solids). In 3, 150 ml of pure water without a copolymer was used as a 
blank. 
Test method 
Using a magnetic stirrer, the test solution was stirred for 5 minutes. 
Then, the resulting mixed solution was left at rest for two hours. 
Thereafter, the test solution was filtered off with 5C filter paper. After 
drying the filter paper, using SZ optical sensor (color measuring system) 
available from Nihon Dennsyoku Co., Ltd., the property against iron 
particle deposition was determined from the following formula based on L 
values measured in such a manner that the filter paper is pressed with a 
weight whose back surface is in black, and is covered by the black box. 
Formula! 
EQU property against iron particle deposition=L value (with the maleic acid 
copolymer)-L value (blank without copolymer). 
The maleic acid copolymer of the present invention thus prepared shows the 
property against iron particle deposition of not less than 9.0. For the 
copolymer, the value of property against iron particle deposition is 
preferably not less than 11.0. In view of more effectively preventing the 
yellowish of the clothes, the property against iron particle deposition is 
most preferably selected to be not less than 13.0. If such property 
against iron particle deposition is selected to be not more than 9.0, the 
effect would be significantly reduced. 
In the copolymer, the calcium ion stability constant indicates how strong 
the calcium ion in water is chelated, and the higher is the constant, the 
stronger is the ability of removing the muddy dust from fiber by removing 
calcium ions in water. The calcium ion stability constant of the maleic 
acid copolymer contained in detergent composition of the present invention 
is determined by a value (Log K) obtained by substituting the value under 
the below-mentioned conditions for measurement in the formula 1.: 
1 Preparing calcium ion solution having densities of 0.002 mol/L, 0.003 
mol/L and 0.004 mol/L (using CaCl.sub.2), and 50 g of the calcium ion 
solution thus prepared were placed into 100 cc beaker. 
2 50 mg (based on solids) of maleic acid copolymer is added; 
3 A pH is adjusted to be 10. 
4 0.15 g of NaCl is added as a calcium ion electrode stabilizer. 
5 Using the calcium ion electrode, the density of the free calcium ion was 
measured. 
Next, the formula 1 will be explained by respectively defining the 
parameters as follows: 
Density of free calcium ion: Ca! 
fixed calcium ion density: CaS! 
free chelate site number: S! 
chelate cite number: S0! 
stability constant: Log K 
Then, the formula Ca!S!/CaS!=1/K is obtained, and from this formula, 
S!=S0!-CaS! can be obtained. 
Thus, the formula 1 is given as: 
EQU Ca!/CaS!=1/S0!.multidot.Ca!+1/S0!/.multidot.K. 
The respective values obtained from the formula 1 were plotted in the graph 
having Ca!/CaS! as a vertical axis and Ca! as a horizontal axis. From 
the given tilt of the plot and the intercept, S0!, K, Log k were 
calculated. 
The copolymer of the present invention has a calcium ion stability constant 
of not less than 4.5, and in view of improving the detergency, the calcium 
ion stability constant is more preferably in the range of from 4.7 to 7.0, 
and most preferably in the range of from 4.5 to 6.5. When the stability 
constant is too high, an metal ion in the enzyme may be removed when 
mixing an polymer with the enzyme, resulting in lower detergency. 
The calcium ion capturing ability of the maleic acid copolymer contained in 
the detergent composition of the present invention is determined by the 
calcium ion (mg) captured by 1 g of polymer, based on calcium carbonate. 
Conditions of Measuring the Calcium Ion Capturing Ability! 
Reaction Vessel: 100 ml beaker 
Solution: 50 mg of Ca.sup.2+ 1.0.times.10.sup.31 3 mol/1 solution 
polymer: 10 mg (based on solids) 
temperature: 25.degree. C. 
stirring time: 10 minutes (using a stirrer) 
To the solution of calcium carbonate prepared by the above-mentioned 
conditions, was added a polymer with agitation under the above-mentioned 
conditions. The respective densities of the calcium ion in the solution of 
calcium carbonate before and after agitation were measured by a calcium 
electrode (93-20) available from Orion Co., Ltd using an ion analyzer 
(EA920) available from Orion Co., Ltd. Based on the difference between the 
densities before and after agitation, the amount of the calcium ion 
captured by the polymer was converted to calcium carbonate mg, and the 
resulting value was determined to be calcium ion capturing ability. 
The calcium ion capturing ability of the copolymer is preferably not less 
than 300 mg CaCO.sub.3 /g (based on calcium carbonate captured by 1 g of 
maleic acid copolymer), more preferably not less than 380 mg CaCO.sub.3 
/g, and still more preferably not less than 400 mg CaCO.sub.3 /g. The 
higher is the calcium ion capturing ability, the more efficient is its 
performance as a detergent builder. 
The gelation property of the maleic acid copolymer of the present invention 
is determined by the absorptivity obtained by the following manner: 
Conditions of Measuring Gelation! 
Reaction Vessel: 500 ml tall beaker 
Polymer: 40 ppm (based on solids) with respect to test solution 
Test Solution: 400 g of CaCl.sub.2 400 ppm solution 
Temperature: 50.degree. C. 
pH: 8 
Measuring 
Method: After agitating test solution for 5 minutes using a stirrer, the 
sampling was performed. Then, using a cell of 50 mm, absorptivity (ABS) 
with UV of 380 nm was measured using 50 mm cell. 
In general, the polymer having high gelation properties is likely to be 
undissolvable in a washing solution. It has been found that especially 
when using water of high hardness, the washing ability is significantly 
lowered. In view of maintaining the excellent detergency of the maleic 
acid copolymer contained in the detergent composition in a stable 
condition, it is preferable to have low gelation properties, i.e., not 
more than 0.3. 
The gelation properties suggest the values showing how easy the polymer 
deposits in a presence of calcium ion, and white turbidity when heating 
the polymer in the presence of the calcium ion was measured based on 
absorptivity of UV. Here, the greater is the value, the higher is the 
turbidity, indicating that a large amount of polymer deposited in the 
presence of calcium ion. In addition, a large amount of calcium ions are 
contained in city water, and washing always comes with the problem of 
gelation. 
The character table for gelation properties are as shown below: Here, the 
smaller the value, the more effective as the detergent builder. 
______________________________________ 
character gelation property 
______________________________________ 
0.1 or below very low 
above 0.1-0.3 low 
above 0.3-0.4 high 
above 0.4 very high 
______________________________________ 
The detergent composition containing the detergent builder of the present 
invention may be used in combination with a surface active agent and, if 
an occasion demands, an enzyme. 
For such surface active agent of the present invention, an anionic surface 
active agent, a nonionic surface active agent, a amphoteric surface active 
agent, and a cationic surface active agent may be preferably used. 
Examples of the anionic surface active agent include: 
alkylbenzenephosphonic acid, alkyl or alkenyl ether sulfate, alkyl or 
alkenyl sulfate, .alpha.-olefin sulfate, .alpha.-sulfoaliphatic acid or 
ester salts, alkane sulfonic acid, saturated or unsaturated fatty acid 
salt, alkyl or alkenyl ether carboxylate, amino acid surface active agent, 
N-acylamino acid surface active agent, alkyl or alkenyl phosphoric acid 
ester or salts thereof. 
Examples of the nonionic surface active agent include: polyoxy 
alkylenealkyl or alkenyl ether, polyoxyethylene alkylphenyl ether, higher 
aliphatic alkanolamide or alkylene oxide additives thereof, sucrose 
aliphatic ester, alkylglycoside, aliphatic glycerin monoester, alkylamine 
oxide, and the like. 
Examples of the amphoteric surface active agent include: carboxylic or 
sulfobetaine amphoteric surface active agent, and the like. Examples of 
the cationic surface active agent includes: quaternary ammonium salts, and 
the like. 
The ratio of use of the above-mentioned surface active agent is usually in 
the range of from 5 to 70 percent by weight, preferably in the range of 
from 20 to 60 percent by weight with respect to the total weight of 
detergent composition. 
Examples of enzyme to be mixed in the detergent composition containing the 
detergent builder include: protease, lipase, cellulase, and the like. 
Especially, protease, alkalilipase, and alkalicellulase which show high 
activity in the alkali detergent are preferable. The content of the enzyme 
is preferably in the range of from 0.01 to 5 percent by weight with 
respect to the total weight of the detergent composition. If the content 
deviates from the range, the balance with the surface active agent would 
collapse, and the detergency of the detergent composition cannot be 
improved. 
The detergent composition containing the detergent builder of the present 
invention may include: known alkali builder, chelate builder, 
anti-readhesion agent, fluorescent agent, bleaching agent, perfume, and 
the like when an occasion demands. In addition, zeolite may be added. 
Examples of the alkali builder include: silicate, carbonate, sulfate, and 
the like. Examples of chelate builder include: diglycolic acid, 
oxycarboxylate, ethylenediamine tetraacetic acid (EDTA), ethylenetiamine 
hexaacetic acid (DTPA), citric acid, and the like, if an occasion demands. 
According to the structure and the method of the present invention, the 
maleic acid copolymer is prepared by carrying out an aqueous solution 
copolymerization reaction between the maleic acid (salts) and another 
monomer such as a water-soluble ethylenically unsaturated monomer in the 
presence of the polymerization initiator, wherein hydrogen peroxide and 
persulfate are used as the polymerization initiator with a weight ratio in 
the range of from 1/50 to 1/2. The described method enables the content of 
the hydrogen peroxide as the polymerization initiator to reduce to the 
level of from 0.1 to 3.0 percent by weight with respect to the total 
weight of the copolymerization reaction solution. 
The described copolymer enables the residual hydrogen peroxide in the 
reaction solution to be reduced to the permissible low level, and the 
copolymer having a large amount of carboxylic groups in a molecule can be 
obtained, thereby suppressing the residual maleic acid in the reaction 
solution. 
According to the described method, the concentration of the hydrogen 
peroxide and the content of the residual maleic acid of the maleic acid 
copolymer obtained after being isolated from the copolymerization reaction 
solution can be significantly reduced. As a result, the concentration of 
the hydrogen peroxide upon the completion of the reaction can be reduced 
to not more than 0.05 percent by weight with respect to the total weight 
of the reaction solution, and the content of the residual maleic acid can 
be reduced to not more than 0.3 percent by weight with respect to the 
total weight of the reaction solution. 
Moreover, in the described method, by reducing the time of introducing the 
water-soluble ethylenically unsaturated monomer to the level to an extent 
that an occurrence of a run-away reaction can be prevented, the 
copolymerization reaction can be performed with an improved efficiency. 
Furthermore, by mixing the polyvalent metal ion in the copolymerization 
reaction solution, the content of the residual maleic acid in the reaction 
solution can be still reduced, thereby improving the reaction efficiency. 
When carrying out the copolymerization reaction, it is preferable to 
increase the ratio of the maleic acid (salts) to be placed and increase 
the density of the maleic acid (salt) upon starting the reaction, because 
such conditions offer a higher reactivity of the maleic acid (salts) upon 
starting the polymerization. 
Additionally, when carrying out the copolymerization condition, by reducing 
the time of introducing the water-soluble ethylenically unsaturated 
monomer to the level to an extent that an occurrence of a run-away 
reaction would not occur, a narrower distribution of the molecular weight 
of the resulting maleic acid copolymer can be obtained. As a result, the 
property against iron particle deposition can be improved, while 
suppressing the gelation properties. 
The described maleic acid copolymer of the present invention having 
specially defined calcium ion stability constant and property against iron 
particle deposition is effective especially as the detergent composition. 
Such high performance maleic acid copolymer can be obtained by adopting 
the polymerization method wherein the hydrogen peroxide and persulfate as 
the polymerization initiator are used in a particular amount with a 
specific ratio. 
Although the exact reason why such high performance maleic acid copolymer 
is obtained is not known, it can be assumed that by uniformly introducing 
the maleic acid to the high-molecular portion of the polymer, the content 
of the residual low-molecular polymer can be reduced, and thus a polymer 
having narrow molecular weight distribution can be obtained. 
As a result, the maleic acid copolymer of the present invention shows 
excellent properties in its calcium ion stability constant and property 
against iron particle deposition which are essential factors in 
strengthening the detergency of the detergent composition, and also show 
well-balanced properties. For the described beneficial properties, when 
adopting the detergent builder containing the copolymer of the present 
invention in the detergent composition, the detergent composition shows 
excellent performance. 
To achieve the third object of the present invention, earnest researches 
have been made by the inventors of the present invention. As a result, 
they have succeeded in achieving a powdered detergent builder 
characterized by including a maleic acid copolymer which is a 
polycarboxylic acid or polycarboxylate copolymer having a molecular weight 
in the range of from 500 to 6,000,000 which shows high fluidity and high 
bulk density and very low hygroscopicity. 
Namely, the detergent builder of the present invention is characterized in 
that the water-soluble polycarboxylic acid (carboxylate) is in a powdered 
form containing the surface active agent. 
For the water-soluble polycarboxylic acid (carboxylate), it is preferable 
to have a molecular weight in the range of from 500 to 6,000,000, not less 
than 50 percent of a powdered portion having a particle diameter of 
100-900 .mu.m, not more than 10 percent of a powdered portion having a 
particle diameter of above 900 .mu.m, not more than 40 percent of a 
powdered portion having a particle diameter of less than 100 .mu.m, and a 
specific surface area of from 0.05 to 0.25 m.sup.2 /g in view of improving 
bulk density and hygroscopicity. 
Such detergent builder preferably satisfies the following conditions 1)-3). 
1) angle of repose: not more than 60.degree.; 
2) bulk density: not less than 0.5 g/ml; and 
3) hygroscopic degree: not more than 20 percent/day. 
The angle of repose is a parameter of the fluidity, and if the angle of 
repose exceeds 60.degree., when supplying from a hopper, etc., the supply 
would not flow smoothly. For this reason, the angle of repose must be not 
more than 60.degree., preferably not more than 50.degree.. 
If the bulk density is less than 0.5 g/ml, the volume per weight of the 
powdered product becomes significantly large, and the transportation cost 
would be increased. Thus, such condition is unpreferable in consideration 
of transportation cost. Besides, when using such copolymer as the 
detergent composition, the bulk density would become greatly deviated from 
around 0.7 g/ml of the bulk density of the currently available powdered 
detergent, segregation or the like that may occur after mixing. Therefore, 
the bulk density is preferably not less than 0.5 g/ml, more preferably not 
less than 0.6 g/ml. 
The molecular weight of the water-soluble polycarboxylic acid or 
carboxylate used as the detergent builder is required to be in the range 
from 500 to 6,000,000, and preferably in the range from 500 to 100,000. 
When the absorbed amount of moisture after 24 hours has passed exceeds 20 
percent by weight, it is unpreferable because the detergent composition 
becomes greasy, or becomes completely solid, thereby presenting the 
problem that the fluidity is greatly reduced. Therefore, the 
hygroscopicity is required to be not more than 20 percent by weight/day. 
Furthermore, the content of the water-soluble polycarboxylic acid 
(polycarboxylate) in the detergent builder is preferably not less than 30 
percent by weight, more preferably not less than 50 percent by weight, and 
most preferably not less than 70 percent by weight to achieve sufficient 
level of calcium ion capturing ability and the clay diffusivity, etc. 
The detergent builder more preferably includes 0.1-20 percent of the 
surface active agent containing hydrocarbon having 5-20 carbon atoms. 
Namely, by adding the surface active agent having a hydrocarbon group of 
5-20 carbon atoms as a hydrophobic group, the hygroscopicity can be 
reduced. 
If the surface active agent includes a hydrocarbon group having less than 5 
carbon atoms, as hydrophobic property is insufficient, the effect of 
reducing the absorbed amount of moisture would be small. On the other 
hand, if the surface active agent includes a hydrocarbon group having more 
than 20 carbon atoms, it is unpreferable because the hydrophobic property 
becomes too high on the contrary, which results in the problem that in its 
practical applications, the solubility to water becomes poor. Therefore, 
the number of carbon atoms is preferably in the range of from 5 to 20, and 
most preferably in a range of from 8 to 14 in view of a balance between 
hydrophobic property and hydrophilic property. 
For such surface active agent of the present invention, generally used 
anionic surface active agents and nonionic surface active agents of from 5 
to 20 carbon atoms may be used. 
Examples of the anionic surface active agent include: alkylbenzene 
sulfonate, alkylsulfate, .alpha.-olefinsulfate, paraffin sulfate, 
alkylethoxy sulfate, and the like. 
Examples of the nonionic surface active agent include: polyoxyethylenealkyl 
ether, polyoxyethylenealkyl phenyl ether, and the like. The anionic 
surface active agent is preferable, and among the anionic surface active 
agents, those having 8-14 carbon atoms are especially preferable. 
If the content of the surface active agent is less than 0.1, sufficient 
effect cannot be achieved in view of reducing hygroscopicity. On the other 
hand, if the content of the surface active agent exceeds 20 percent, as 
the content of the polycarboxylic acid (salts) polymer is reduced, the 
properties the polycarboxylic acid (polycarboxylate) should have may not 
be ensured. 
For the described reasons, the content of the surface active agent is 
preferably in the range of from 0.1 to 20 percent, and more preferably in 
the range of from 0.5 to 10 percent. 
It is preferable that the detergent builder structures such that fine 
powders of the water-soluble polycarboxylic acid (salts) are bonded to 
each other by the surface active agent, more preferably structures such 
that the surface of the fine powders are covered by the surface active 
agent in view of improving bulk density and hygroscopicity. 
The polymer of the water-soluble polycarboxylic acid (polycarboxylate) 
preferably satisfies the following conditions: 
1) The calcium ion stability constant is not less than 4.0; and 
2) The calcium ion capturing ability is not less than 300 mgCaCo3/g. 
In considering the use of the detergent builder, the polymer contained in 
the detergent builder should have higher metal ion sealing function, and 
if the calcium ion stability constant is less than 4.0, and/or if the 
calcium ion capturing ability is less than 300 mg, the function cannot be 
fully exhibited. For the described reason, it is preferable that the 
calcium ion stability constant is not less than 4.5, and the calcium ion 
capturing ability is not less than 400 mgCaCo.sub.3 /g. 
Additionally, it is more preferable that the polymer satisfy the following 
conditions: 
3) The clay absorbability is in a range of from 30 to 70 percent; and 
4) The clay diffusivity is not less than 1.2. 
The clay absorbability and the clay difficivity are determined by values 
measured under the following conditions: 
Clay Absorbability! 
Conditions of Measurements 
Reaction Vessel: 100 ml measuring cylinder 
Polymer solvent: 1 ml of 0.5 percent (based on solids) polymer solution+100 
g of city water (Himeji City) 
Clay: 1.0 g of Amazon clay 
Stirring time: 10 minutes (magnetic stirrer) 
Placement time: 18 hours 
Measuring 
Method: 10 ml is sampled from the top of the measuring cylinder, and after 
the supernatant is filtered off, the measurement is performed by gel 
permeation chromatography (GPC). 
The same measurement was performed based on the values obtained from the 
described measurements without using clay, and the adsorption to the clay 
particles is computed from the following formula: Clay absorbability=Area 
of Polymer Peak with Clay/Area of Polymer Peak without Clay!.times.100 
(percent) 
Clay Diffusivity! 
Conditions Measurements 
Reaction Vessel: 100 ml measuring cylinder 
Polymer solvent: 1 ml of 0.5 percent (converted to solid) polymer 
solution+100 g of city water (Himeji City) 
Clay: 1.0 g Amazon clay 
Stirring time: 10 minutes (magnetic stirrer) 
Placement time: 18 hours 
Measuring 
Method: 10 ml is sampled from the top of the measuring cylinder, and the 
absorptivity coefficient (ABS) is measured at UV 380 nm using 1 cm cell, 
and the result is determined to indicate the clay diffusivity. 
Another required condition for the polymer is that the diffusivity is high. 
If the clay absorbability is less than 30 percent, the clay granule cannot 
be charged to the anion. On the other hand, if the clay absorbability is 
above 70 percent, other functions of the polymer, such as metal ion 
sealing function would be lowered. Therefore, such conditions are 
industrially unpreferable. Also, if the clay diffusivity is less than 1.2, 
desirable diffusivity cannot be obtained, and thus it is unpreferable. 
As long as the described performances are satisfied, any of the generally 
known water-soluble polycarboxylic acid (polycarboxylate) polymers may be 
used. However, acrylic acid (acrylate) copolymer and maleic acid (maleic 
acid salt) polymer are preferable, and a copolymer of acrylic acid 
(acrylate) and maleic acid (salt) is more preferable. 
For the method of manufacturing the detergent builder, it is preferable to 
granulate with agitation the water soluble polycarboxylic acid 
(polycarboxylate) using a solution of the surface active agent as a 
binder. Namely, the solution of polycarboxylic acid (polycarboxylate) 
polymer is once dried into powders so as to have fine powders having low 
bulk density, poor fluidity and high hygroscopicity, and if an occasion 
demands, such fine powders further granule by an appropriate granular. 
Thereafter, the resulting powdered product is subject to the granulation 
process with agitation using the above-mentioned surface active agent as 
the binder by the agitated granulator. 
The described method will be described in more detail. 
Any of the following method can be adopted: the spray-drying process using 
a spray dryer, etc., a dry-powder process wherein a polymer solution is 
dried by making it adhere to a thin film on a rotatable drum or disk that 
is heated to high temperature, for example, by introducing steam in the 
inside; and the like. Among the described methods, the dry-powder process 
is especially preferable in view of drying efficiency, dry processing 
ability, and the like. 
For the agitated granulator, generally used granulars of both horizontal 
type (for example, a high speed mixer available from Fukae Industrial Co. 
Ltd.) and vertical type (for example, Lodige mixer available from Lodige 
Co. Ltd.) may be used. However, it is preferable to adopt the vertical 
agitated granulator as it enables a shear to be exerted in a gravitation 
direction, and the bulk density to be increased without difficulties. 
Next, the vertical agitated granulator will be explained. As shown in FIG. 
1, the vertical agitated granulator includes a rotation shaft 2 which is 
horizontally placed in a cylindrical granulation vessel 1, and plural 
agitators 3 are provided in a direction of a diameter of the rotation axis 
so as to form the same angle at different positions in a direction of the 
rotation to each other. 
At a leading end of each agitator 3, a shovel blade 4 is provided for 
granulating powered product introduced in the granulation vessel 1 by 
pressing to the inner wall 1a of the cylinder portion of the granulation 
vessel 1. The shovel blade 4 includes a main portion 4a and a pair of 
sub-portions 4b. The main portion 4a is composed of a substantially 
triangular plate extending from a front side to a rear side in the 
rotation direction A of the rotation shaft 2. The pair of sub portions 4b 
is composed of a plate extending from each side portion of the main 
portion 4 a against the rotation direction A to the rotation shaft 2. In 
this arrangement, as the rotation shaft 2 is horizontally placed, the 
shovel blade 4 rotates in a longitudinal (vertical) direction. 
The main portion 4a faces the inner wall 1a of the cylinder portion that is 
curved in the granulation vessel 1, and it is set such that a distance 
from the inner wall 1a of the cylindrical portion becomes gradually 
smaller from the front portion to the rear portion of the main portion 4a. 
On the other hand, each sub portion 4b is projected from the surface of 
the main portion 4a to the inner wall 1a so that the height of the planes 
which face one another becomes gradually higher from the front portion to 
the rear portion of the main portion 4a. 
On an inner wall 1a of the granulation vessel 1, a chopper (not shown) are 
provided and a nozzle (not shown). The chopper rotates for pulverizing a 
coarse particle, i.e., a lump is provided such that the rotation axis of 
the chopper is directed to the rotation shaft 2 from the inner wall 1a. 
The nozzle is provided for spraying a binder towards the chopper. 
The described vertical agitated granulator may be equipped with a jacket 
cooler heater (not shown) for controlling a temperature of the granulation 
vessel 1 if an occasion demands. 
The operation of the vertical agitated granulator will be explained below. 
First, powdered product is introduced into the granulation vessel 1, and 
the rotation shaft 2 is rotated such that the powdered product is fully 
agitated, for example, by rotating the rotation shaft 2 at the peripheral 
speed of the leading end portion of the shovel blade 4 of not less than 
0.1 m/s, the powdered product is agitated by the shovel blade 4 and the 
agitator 3. 
While rotating the chopper at higher speed than the rotation shaft 2, by 
successively spraying the binder towards the chopper in the granulation 
vessel 1 from the nozzle, the binder is uniformly dispersed by the chopper 
in the powdered product. The powered product having the sprayed binder 
while agitating the described manner forms a granule by agglomerating by 
adhesion by introducing the binder. 
Such particles are compacted between the shovel blade 4 and the cylinder 
inner wall 1a, and the agglomeration of particles are further progressed 
by the binder bleeding on the surface of the particles due to compaction, 
and the fine particles are reduced, and the particles grow, thereby 
progressing the agitating granulation process. 
In such agitating granulation process, a large particle remaining without 
being granulated, i.e., a clod if generated, is pulverized by a chopper, 
thereby progressing the granulation process by adjusting the particle size 
of particles in the granulation vessel 1. 
In the vertical agitated granulator, by applying a shear (stress) on each 
particle by the shovel blade 4, the compaction and an improvement in 
specific gravity are enabled. On the other hand, in the horizontal 
agitated granulator, the rotation shaft 2 of the vertical agitated 
granulator is provided in a horizontal direction and a vertical direction. 
In such vertical agitated granulator, when a shear (stress) is exerted onto 
each particle by a shovel blade 4, by the weight of each particle or 
powdered product, each granule and powder are more closely packed. 
Therefore, the vertical agitated granulator more effectively applies a 
shear (stress) to each particle than the horizontal agitated granulator, 
thereby improving a particle specific gravity of the powdered granular 
product. 
The content of the detergent builder as the detergent composition is 
preferably in the range of from 0.1 to 20 percent. The detergent builder 
shows excellent metal ion sealing function and clay diffusivity. For these 
beneficial properties, by adding from 0.1 to 20 percent, more preferably 
from 1 to 10 percent, of the detergent builder to the detergent 
composition, the detergency of the detergent composition can be improved. 
If the content of the detergent builder is less than 0.1 percent, a 
sufficient effect cannot be obtained. On the other hand, if the content of 
the detergent builder is above 20 percent, the contents of other mixing 
agents of the detergent composition become relatively small, and thus 
improved detergency cannot be obtained even if the content of the 
detergent composition is increased. 
The detergent composition of the present invention including detergent 
builder may be combined with the surface active agent, enzyme, if an 
occasion demands. 
For such surface active agent of the present invention, an anionic surface 
active agent, a nonionic surface active agent, an amphoteric surface 
active agent, and a cationic surface active agent may be preferably used. 
The content of the surface active agent is preferably in the range of from 
5 to 70 percent by weight, more preferably in the range of from 20 to 60 
percent by weight. 
Examples of enzyme to be mixed in the detergent composition containing the 
detergent builder include: protease, lipase, cellulase, and the like. 
Especially, protease, alkalilipase, alkalicellulase which show high 
activity in the alikai detergent are preferable. The content of the enzyme 
is preferably in a range of from 0.01 to 5 percent by weight. If the 
content deviates from the range, the balance with the surface active agent 
would collapse, and the detergency of the detergent composition cannot be 
improved. 
The detergent composition containing the detergent builder of the present 
invention may include: known alkali builder, chelate builder, 
anti-readhesion agent, a fluorescent agent, a bleaching agent, perfume, 
and the like when an occasion demands.

PREFERRED EMBODIMENT OF THE PRESENT INVENTION 
Hereinafter, the detergent builder and the method of manufacturing the 
detergent builder of the present invention are illustrated by the 
following examples of some preferred embodiments in comparison with 
comparative examples not according to the undermentioned examples. 
Furthermore, in the examples and comparative examples, the unit "percent" 
and "part(s)" respectively denote "percent by weight" and "part(s) by 
weight". In addition, "monomer" denotes "maleic acid (salt)". 
EXAMPLE 1 
In one-liter flask equipped with a thermometer, a stirrer, and a ref lux 
condenser were placed 196 parts of maleic acid anhydride (232 parts of 
maleic acid), 110.7 parts of deionized water, and 333.3 parts of 48 
percent of sodium hydroxide solution. The mixed solution has density of 50 
percent based on solid at a start of polymerization reaction and a pH 
value of 13. Then, the reaction mixture was heated to a boiling point with 
stirring under normal pressure. 
Thereafter, with stirring, 200 parts of 10 percent sodium persulfate 
solution (3.52 percent by weight based on a monomer weight), dropped over 
150 minutes, 6.65 parts of 35 percent hydrogen peroxide solution (0.41 
percent by weight based on a monomer weight), dropped over 120 minutes and 
560.78 parts of 60 percent acrylic acid solution (with molar ratio of 
maleic acid to acrylic acid of 3 to 7), dropped over 150 minutes are added 
in succession to complete a polymerization reaction. (At a start of 
polymerization reaction, the reaction solution has the monomer density of 
50 percent and a pH of 5.) The described polymerization process conditions 
employed are shown in Table 1. 
The determination of the weight-average molecular weight and the content of 
the residual maleic acid of the resulting maleic acid copolymer (1) was 
performed by gel permeation chromatography. The results are shown in Table 
2. In the analysis, Asahi chemical Asahi pack GFA-7MF is used for a 
column, and 0.5 percent phosphoric acid solution was used for the elute. 
As a sample for the molecular weight standard, the polyacrylic soda 
standard sample (available from Sowa Kagaku Co. Ltd.) was used. 
The performances of the detergent builder of the present invention, i.e., 
the property against iron particle deposition, the calcium ion stability 
constant, the calcium ion capturing ability, and the gelation properties 
were determined by the aforementioned methods. The color of the detergent 
builder was determined by the general method, and respective pH values 
from the start to the end of the polymerization reaction were determined 
by a commercially available pH meter. The results are shown in Table 2. 
EXAMPLE 2 
The same polymerization reaction as Example 1 was performed in the same 
manner except that 2.0 parts of 35 percent hydrogen peroxide (0.12 percent 
by weight basedon a monomer weight) and 300 parts of 10 percent sodium 
persulfate solution (5.28 percent by weight based on a monomer weight) 
were employed. The determination of properties of the resulting maleic 
acid copolymer was performed in the same manner as Example 1. The results 
are shown in Table 2 (At a start of polymerization reaction, the monomer 
density was 50 percent). The polymerization process conditions employed in 
this example are shown in Table 1. 
TABLE 1 
__________________________________________________________________________ 
initial hydrogen 
among of use of water- 
molar ratio 
48% NaOH 
35% hydrogen peroxide/per- 
maleic 
soluble ehtylenically 
of maleic 
(part) peroxide 
10% sodium 
sulfate 
polymeri- 
acid unsaturated monomer (B) 
acid (A)/ 
(neutraliz- 
(part) persulfate 
(weight 
zation 
Ex. 
copolymer 
(part) (B) ation %) 
(C) (part) (C) 
ratio) pH 
__________________________________________________________________________ 
1 (1) 60% (a) (560.78) 
3/7 333.3 (100%) 
6.65 (0.41) 
200 (3.52) 
1/8.6 13 .fwdarw. 5 
2 (2) 60% (a) (560.78) 
3/7 333.3 (100%) 
2.0 (0.12) 
300 (5.28) 
1/44 13 .fwdarw. 5 
3 (3) 60% (a) (560.78) 
3/7 333.3 (100%) 
32.5 (2.0) 
250 (4.4) 
1/2.2 13 .fwdarw. 5 
4 (4) 60% (a) (360.50) 
3/7 333.3 (100%) 
6.65 (0.519) 
200 (4.46) 
1/8.6 13 .fwdarw. 5 
5 (5) 60% (a) (1361.90) 
4/6 333.3 (100%) 
6.65 (0.22) 
200 (1.9) 
1/8.6 13 .fwdarw. 4 
6 (6) 60% (a) (42.41) 
15/85 333.3 (100%) 
6.65 (0.90) 
200 (7.77) 
1/8.6 13 .fwdarw. 7 
7 (7) 60% (a) (896.4) 
85/15 333.3 (100%) 
6.65 (0.367) 
200 (3.15) 
1/8.6 13 .fwdarw. 6 
8 (8) (b) 20% aq. (5087.0) 
3/7 333.3 (100%) 
6.65 (0.186) 
200 (1.6) 
1/8.6 13 .fwdarw. 7 
9 (9) (c) E05 additive (1428) 
3/7 333.3 (100%) 
6.65 (0.14) 
200 (1.2) 
1/8.6 13 .fwdarw. 10 
10 (10) (d) E05 additive (1297) 
3/7 333.3 (100%) 
6.65 (0.152) 
200 (1.3) 
1/8.6 13 .fwdarw. 10 
11 (11) glycerin monoallyl ether 
3/7 333.3 (100%) 
6.65 (0.274) 
200 (2.36) 
1/8.6 13 .fwdarw. 10 
(616) 
12 (12) 30% sodium acrylic acid 
3/7 333.3 (100%) 
6.65 (0.374) 
200 (2.98) 
1/8.6 13 .fwdarw. 11 
(1463.9) 
13 (13) 60% acrylic acid 
3/7 333.3 (100%) 
6.65 (0.41) 
200 (3.52) 
1/8.6 13 .fwdarw. 5 
solution (560.78) 
__________________________________________________________________________ 
In Table 1, E0 denotes ethylene oxide, and (C) denotes a monomer weight % 
(a) denotes acrylic acid solution, (b) denotes 3ariroxy-2-hydroxypropane 
sulfonic acid and Na salts, (c) denotes isoprenol, and (d) denotes 
aryllalcohol. 
TABLE 2 
__________________________________________________________________________ 
property Ca.sup.2+ 
maleic 
molecular 
against iron 
Ca.sup.2+ residual 
residual capturing 
acid weight 
particle 
stability 
gelation 
maleic acid 
H.sub.2 O.sub.2 (weight 
color 
ability 
Ex. 
copolymer 
(.times.10.sup.3) 
deposition 
constant 
properties 
(weight %) 
%) (Hz) 
(mg CaCO.sub.3 /g) 
__________________________________________________________________________ 
1 (1) 50 13.2 5.1 0.21 0.21 0.01 20 420 
2 (2) 50 12.5 4.5 0.22 0.23 0.00 35 410 
3 (3) 40 12.7 4.8 0.19 0.18 0.08 20 400 
4 (4) 30 12.4 4.7 0.20 0.09 0.01 25 400 
5 (5) 90 11.8 5.0 0.29 0.48 0.02 25 430 
6 (6) 13 12.1 4.7 0.25 0.07 0.01 30 400 
7 (7) 21 11.5 4.5 0.24 0.29 0.01 20 390 
8 (8) 22 11.8 4.5 0.13 1.25 0.01 60 385 
9 (9) 22 11.0 4.5 0.18 1.10 0.01 50 390 
10 (10) 21 10.8 4.5 0.20 1.50 0.01 40 380 
11 (11) 15 11.3 4.5 0.19 2.7 0.01 30 390 
12 (12) 70 11.2 4.8 0.23 0.41 0.01 30 410 
13 (13) 60 12.8 5.0 0.24 0.03 0.02 20 420 
__________________________________________________________________________ 
In Table 2, Ca.sup.2+ denotes a calcium ion, and H.sub.2 O.sub.2 denotes 
hydrogen peroxide. 
EXAMPLE 3 
The same polymerization reaction as Example 1 was performed in the same 
manner except that 32.5 parts of 35 percent hydrogen peroxide (2.0 percent 
by weight based on a monomer weight) and 250 parts of 10 percent sodium 
persulfate solution (4.4 percent by weight based on a monomer weight) were 
employed. The determination of properties of the resulting maleic acid 
copolymer was performed by the same manner as Example 1. The results are 
shown in Table 2. (At a start of polymerization reaction, the monomer 
density was 50 percent). The polymerization process conditions employed in 
this example are shown in Table 1. 
EXAMPLES 4-6 
The same polymerization reaction as Example 1 was performed in the same 
manner except that 60 percent acrylic acid solution was employed in an 
amount defined in Table 1 as the water-soluble ethylenically unsaturated 
monomer (B). The determination of properties of the resulting maleic acid 
copolymer was performed by the same manner as Example 1. The results are 
shown in Table 2. (At a start of polymerization reaction, the monomer 
density was 50 percent). The polymerization process conditions employed 
the examples are shown in Table 1. 
EXAMPLES 7-12 
The same polymerization reaction as Example 1 was performed in the same 
manner except that in replace of 60 percent acrylic acid solution, the 
water-soluble ethylenically unsaturated monomer (B) defined in Table 1 was 
employed. The determination of properties of the resulting maleic acid 
copolymer was performed by gel permeation chromatography. The results are 
shown in Table 2. (At a start of polymerization reaction, the monomer 
density was 50 percent). The polymerization process conditions employed in 
the examples are shown in Table 1. 
EXAMPLE 13 
The same polymerization reaction as Example 1 was performed in the same 
manner except that 0.04 parts of iron (II) ammonium sulfate hexahydrate 
was placed before the polymerization reaction started. The determination 
of properties of the resulting maleic acid copolymer was performed by the 
same manner as Example 1. The results are shown in Table 2. (At a start of 
polymerization reaction, the monomer density was 68.7 percent). The 
polymerization process conditions employed in the examples are shown in 
Table 1. 
Comparative Examples 1-3 (Effects of the Polymerization Initiator) 
The same polymerization reaction as Example 1 was performed in the same 
manner except that a solution of 35 percent hydrogen peroxide and 10 
percent sodium persulfate solution were employed in an amount defined in 
Table 3. The determination of properties of the resulting maleic acid 
copolymer was performed by in the same manner as Example 1. The employed 
polymerization process conditions in the comparative examples are shown in 
Table 3. The results are shown in Table 4. (At the start of polymerization 
reaction, the monomer density was 50 percent). 
Comparative Example 4 
The same polymerization reaction as Example 1 was performed in the same 
manner except that 7760 parts of 60 percent acrylic acid solution was 
employed, and in the meantime, 5000 parts of deionized water and 200 parts 
of 10% sodium persulfate solution (0.41 percent by weight based on a 
monomer weight were added in succession over 150 minutes. The 
determination of properties of the resulting maleic acid copolymer was 
performed in the same manner as Example 1. The polymerization process 
conditions employed in the comparative examples are shown in Table 3. The 
results are shown in Table 4. (At the start of polymerization reaction, 
the monomer density was 50 percent). 
TABLE 3 
__________________________________________________________________________ 
initial hydrogen 
maleic 
among of use of water- 
molar ratio 
48% NaOH 
35% hydrogen peroxide/per- 
acid 
soluble ehtylenically 
of maleic 
(part) peroxide 
10% sodium 
sulfate 
Comp 
copoly- 
unsaturated monomer (B) 
acid (A)/ 
(neutraliz- 
(part) persulfate 
(weight 
Ex. mer (part) (B) ation %) 
(C) (part) (C) 
ratio) 
__________________________________________________________________________ 
1 (1) 60% acrylic acid 
3/7 333.3 (100%) 
162 (10.0) 
568 (10.0) 
1/1 
solution (560.78) 
2 (2) 60% acrylic acid 
3/7 333.3 (100%) 
3.33 (0.2) 
1740 (30.0) 
1/150 
solution (560.78) 
3 (3) 60% acrylic acid 
3/7 333.3 (100%) 
0.81 (0.05) 
56.8 (1.0) 
1/20 
solution (560.78) 
4 (4) 60% acrylic acid 
7/93 333.3 (100%) 
6.65(0.048) 
200 (0.41) 
1/8.6 
solution (7760) 
5 (5) 60% acrylic acid 
85/15 333.3 (100%) 
6.65 (0.95) 
200 (8.19) 
1/8.6 
solution (42.41) 
6 (6) 60% acrylic acid 
3/7 333.3 (100%) 
6.65(0.41) 
200 (3.52) 
1/8.6 
solution (560.78) 
__________________________________________________________________________ 
In Table 3, (C) denotes a monomer weight %. 
TABLE 4 
__________________________________________________________________________ 
maleic property Ca.sup.2+ 
acid 
molecular 
against iron 
Ca.sup.2+ residual 
residual capturing 
Comp 
copoly- 
weight 
particle 
stability 
gelation 
maleic acid 
H.sub.2 O.sub.2 (weight 
color 
ability 
Ex. mer (.times.10.sup.3) 
deposition 
constant 
properties 
(weight %) 
%) (Hz) 
(mg CaCO.sub.3 /g) 
__________________________________________________________________________ 
1 (1) 8 7.8 4.4 0.35 0.10 2.5 50 340 
2 (2) 7 6.3 4.3 0.36 0.25 0.01 200 320 
3 (3) 150 7.5 4.3 0.50 2.8 0.00 250 380 
4 (4) 200 7.1 4.3 0.90 0.55 0.01 40 390 
5 (5) 1.8 4.1 3.9 0.25 13.5 0.02 110 220 
6 (6) 80 8.0 4.2 0.33 0.15 0.01 120 370 
__________________________________________________________________________ 
In Table 4, Ca.sup.2.sbsp.+ denotes a calcium ion, and H.sub.2 O.sub.2 
denotes hydrogen peroxide. 
Comparative Example 5 
The same polymerization reaction as Example 1 was performed in the same 
manner except that 60 percent acrylic acid solution was employed in an 
amount defined in Table 3. The determination of properties of the 
resulting maleic acid copolymer was performed by in the same manner as 
Example 1. The polymerization process conditions employed in comparative 
examples are shown in Table 3. The results are shown in Table 4. (The 
monomer density was 50 percent at the start of polymerization reaction). 
Comparative Example 6 
The same polymerization reaction as Example 1 was performed in the same 
manner except that 10 percent sodium persulfate solution, 35 percent 
hydrogen peroxide solution Find 60 percent acrylic acid solution were 
added respectively over 600 minutes. The determination of properties of 
the resulting maleic acid copolymer was performed in the same manner as 
Example 1. The polymerization process conditions of the comparative 
examples are shown in Table 3. The results are shown in Table 4. (At a 
start of polymerization reaction, the monomer density was 50 percent). 
As clearly shown in Table 2 and Table 4, respective maleic acid copolymers 
of Examples 1-13 exhibit superior performances as the detergent builders 
of the present invention in view of their properties against iron particle 
deposition, calcium ion stability constant, gelation properties, amount of 
residual maleic acid, amount of residual hydrogen peroxide, color, calcium 
ion capturing ability as compared to respective comparative maleic acid 
copolymers of comparative examples 1-6. For the described beneficial 
properties, the detergent builders of the present invention are suited for 
use as the detergent compositions. 
EXAMPLES 14-26 
The detergent compositions of the present invention were prepared by adding 
respective maleic acid copolymers of Examples 1-13 as detergent 
compositions of examples 14-26 in accordance with a detergent composition 
shown in Table 5. 
Next, the respective detergencies of the detergent compositions of Examples 
14-26 were evaluated by the following method. 
First, the artificial sludge defined in Table 6 was dispersed in carbon 
tetrachloride, and white cotton cloth was dipped into artificial sludge 
solution. Thereafter, the cloth was dried and cut into a piece of 10 
cm.times.10 cm. 
Using respective detergent compositions, the dirty cloth was washed under 
respective process conditions defined in Table 7. After being washed, the 
cloth was dried, and the reflectance thereof was measured. Based on the 
resulting reflectance, the detergency rate was computed by the below 
formula to determine the detergency of each detergent composition. The 
results are shown in Table 8. 
EQU Detergency Rate=(Reflectance after Washing-Reflectance before 
Washing)/(Reflectance of White Cloth after Washing-Reflectance of White 
Cloth before Washing).times.100 
TABLE 5 
______________________________________ 
Detergent Composition 
Component % by Weight 
______________________________________ 
straight chain alkylbenzene 
20 
sulfonic acid 
sodium (C = 11.5) 15 
polyoxyethylene alkyl ether 
(C = 12, EO = 8) 
zeolite 20 
enzyme (protease) 0.5 
maleic acid copolymer 
20 
sodium carbonate 15 
No. 1 sodium silicate 
9.5 
______________________________________ 
TABLE 6 
______________________________________ 
Artificial Sludge 
Component % by Weight 
______________________________________ 
carbon black (defined by 
0.5 
Oilchemical Association) 
clay 49.75 
myristic acid 8.3 
oleic acid 8.3 
stearic acid 8.3 
trioleic acid 8.3 
cholesterin 4.38 
cholesterinestearate 
1.09 
paraffin wax (m.p. 50-52.degree. C.) 
0.552 
squalene 0.552 
______________________________________ 
TABLE 7 
______________________________________ 
Washing Condition 
______________________________________ 
temperature 20.degree. C. 
bath ratio 1/60 
detergent concentration 
0.5 percent 
water city water 
Terg-O-Tometer 10 minutes 
______________________________________ 
TABLE 8 
______________________________________ 
Results of Detergency Rate 
detergency 
Examples maleic acid copolymer 
rate (percent) 
______________________________________ 
14 (1) 96 
15 (2) 95 
16 (3) 94 
17 (4) 94 
18 (5) 93 
19 (6) 93 
20 (7) 94 
21 (8) 92 
22 (9) 91 
23 (10) 92 
24 (11) 93 
25 (12) 94 
26 (13) 95 
______________________________________ 
Comparative Examples 7-12 
With regard to comparative maleic acid copolymers (1)-(6), the respective 
detergency ratios were determined in the aforementioned manner. The 
results are shown in Table 9. 
TABLE 9 
______________________________________ 
Results of detergency Rate 
Comparative detergency 
Examples maleic acid copolymer 
rate (%) 
______________________________________ 
7 (1) 75 
8 (2) 65 
9 (3) 70 
10 (4) 65 
11 (5) 60 
12 (6) 80 
______________________________________ 
As is clear from the results shown in Table 8 and Table 9, the detergent 
compositions containing the detergent builders of the present invention 
exhibit superior detergency ratios to the detergent builders of 
comparative examples 7-12 as respective above-mentioned properties are 
superior. 
Next, the powdered detergent builders, the manufacturing process thereof 
and the detergent compositions containing such detergent builders will be 
explained with the below-mentioned concrete examples A-B. It should be 
noted here that, these examples are presented by way of description and 
are not to be considered as limiting the scope of this invention which is 
defined in the appended claims. 
First, the process of preparing a copolymer solution of sodium 
acrylate/sodium maleate (molecular weight of 12000) as a polycarboxylic 
acid polymer which serves as a base material of the detergent builder will 
be explained. 
In one-litter flask equipped with a thermometer, a stirrer, and a reflux 
condenser were placed 196 parts of maleic acid anhydride (232 parts of 
maleic acid), 110.7 parts of deionized water, and 333.3 g of 48 percent of 
sodium hydroxide solution (polymerization initial solid density: 50 
percent). Then, the reaction mixture was heated to a boiling point with 
stirring under normal pressure. 
Thereafter, with stirring, 75.5 parts of 35 percent hydrogen peroxide 
solution (8.26 percent by weight maleic acid (salts) (A)), dropped in 
succession over 60 minutes after the polymerization started, 309 parts of 
60 percent acrylic acid solution, dropped in succession over 150 minutes 
after the polymerization started, and further 38.1 parts of 15 percent 
solution of sodium persulfate (3.52 percent by weight based on a monomer 
weight), dropped in succession from 60 minutes elapsed to 150 minutes 
elapsed after the polymerization started, were added to complete a 
polymerization reaction. The properties of the copolymers were determined 
in the aforementioned manner, and the below-mentioned results were 
obtained. 
Calcium Ion Stability Constant (pKCa): 4.8 
Calcium Ion Capturing Ability: 400 mgCaCO.sub.3 /g 
Clay adsorbability: 50 percent 
Clay diffusivity: 1.6 
Preparation of the Powdered Detergent Builder! 
Next, the powdered detergent builders of the present invention will be 
explained based on respective detergent builders of the following Examples 
A and B prepared using the aforementioned polymer solution. 
Example A 
The polymer solution was dried using a CD dryer available from Nishimura 
Iron Co. Ltd., and ground to fine mesh by a feather mill available from 
Hosokawa Micron Co. Ltd. (screen 3 .PHI.). Then, the granulation with the 
below-mentioned surface active agent (25 percent solution of sodium alkyl 
benzene sulfonate) as a binder was carried out by a M-20-type Lodige mixer 
(vertical agitated granulator) under the below-listed conditions. The 
resulting powdered product was dried by leaving it at rest with no wind 
over 1 hour at 105.degree.C. Then, the dried powdered product was passed 
through a sieve with a mesh of 1000 micron, thereby obtaining a sample A. 
Granulation Condition! 
Placed Amount: 4.2 kg 
Binder: solution of 25 percent sodium alkylbenzene sulfonate 
Amount of Binder Added: 0.5 kg 
Granulation Time: 20 minutes 
Number of Rotations of Shovel: 240 rpm 
Number of Rotations of Chopper: 6000 rpm 
Example B 
The polymer solution was dried using a CD dryer available from Nishimura 
Iron Co. Ltd., and ground to fine mesh by a hammermill available from 
Fujipowdal Micron Co. Ltd. (screen 1 .PHI.). Then, the granulation with 
the below-mentioned surface active agent (25 percent solution of alkyl 
benzene sulfonic acid soda) as a binder was carried out by a NSK-850S-type 
new speed mixer available from Okada Seiko Co., Ltd. (horizontal agitated 
granulator) under the below-listed conditions. In the same manner as 
Example A, the resulting powdered product was formed into a sample B. 
Granulation Condition! 
Placed Amount: 500 g 
Binder: solution of 25 percent sodium alkylbenzene sulfonate 
Amount of Binder Added: 60 g 
Granulation Time: 3 minutes 
Number of Rotations of Agitator: 800 rpm 
Number of Rotations of Chopper: 1100 rpm 
Comparative Example C 
The polymer solution was dried using a CD dryer available from Nishimura 
Iron Co. Ltd., and ground to fine mesh by a feathermill available from 
Hosokawa Micron Co. Ltd. (screen 3.PHI.). Then, the resulting powdered 
product, i.e., non-granulated product was used as a comparative sample C. 
Comparative Example D 
The polymer solution was dried using a CD dryer available from Nishimura 
Iron Co. Ltd., and ground to fine mesh by a feathermill available from 
Hosokawa Micron Co. Ltd. (screen 3.PHI.). Then, the granulation was 
carried out by a M-20-type Lodige mixer (vertical agitated granulator) 
under the below-listed conditions without using the surface active agent 
as a binder. In the same manner as Example A, the resulting powdered 
product was formed into a comparative sample D. 
Granulation Condition! 
Placed Amount: 2.8 kg 
Binder: 10 percent polymer solution 
Amount of Binder Added: 0.2 kg 
Granulation Time: 20 minutes 
Number of Rotations of Shovel: 240 rpm 
Number of Rotations of Chopper: 6000 rpm 
Comparative Example E 
The polymer solution was subject to the spray-drying process by a spray 
dryer equipped with No. 67 steam injector with an inner fluidized bed 
available from Annhydro Co., Ltd. The respective conditions for the drying 
process and the granulation condition are as listed below. The resulting 
powdered product was used as a comparative sample E. Without applying a 
post process, the comparative sample E had a water content and a grain 
size sufficient for comparing with respective samples of Examples A and B. 
Drying Condition! 
Hot Air Temperature: 150.degree. C. 
Exhausted Air temperature: 85.degree. C. 
Raw Material Field Amount: 65 L/hr 
Granulation Condition! 
Binder: 25 percent solution of sodium alkylbenzene sulfonate 
Amount of Binder Added: 20 L/hr 
Granulation Time: 20 minutes 
In the present specification, the distribution of particle diameter, the 
specific surface area, the angle of repose, and the absorbed amount of 
moisture (hygroscopicity) were measured in the following manner. 
Distribution of Particle Diameter! 
First, the classification of Powders resulting from the granulation process 
was performed using JIS seive of 18 mesh (900 .mu.m) and 150 mesh (100 
.mu.m), and a weight of a powder of each powder was measured. 
Specific Surface Area! 
The specific surface area was measured by Kr gas adsorption process. 
Measuring Instrument: Yuasa Ionics full automatic surface area measuring 
instrument 4-sorb 
(Yuasa Ionics: type 2SU2 C) 
Measuring Conditions! 
Drying Temperature: 200.degree. C. 
Drying time: 60 minutes 
(Average of the results of 3 measurements) 
Bulk Density! 
The bulk density (g/ml) was determined by powder weight (g)/powder volume 
(ml). 
Angle of Repose! 
The angle of repose was measured by the injection method. This measurement 
was performed by the eye-estimation using a protractor. 
Absorbed Amount of Moisture! 
To avoid the effect from the difference in grain size, about 1 g of powder 
resulting from the classification of the sieve with 850 micron and 180 
micron was placed in a alminium open cup and was left for 24 hours in a 
room under normal temperature and normal humidity (temperature 23.degree. 
C. and humidity 65 percent). Then, the amount of increase in weight of the 
powder was measured. Absorbed Amount of Moisture (percent)=(Weight after 
24 hours-Initial Weight)/Initial Weight.times.100 
Results of Measurement! 
The results of the measurement with regard to Examples A and B, and 
Comparative Examples C-E are shown in Table 10. 
TABLE 10 
______________________________________ 
Example Comparative Example 
Sample A B C D E 
______________________________________ 
Particle Diameter 
(percent content) 
100-900 .mu.m 
75 65 35 45 28 
below 100 .mu.m 
17 26 55 41 45 
above 900 .mu.m 
8 9 10 14 27 
specific surface 
0.18 0.17 0.28 0.26 0.35 
area 
bulk density 
0.66 0.57 0.26 0.60 0.30 
(g/cc) 
angle of repose 
50 45 70 50 50 
(degree) 
absorbed amount 
17 19 26 24 21 
of moisture 
(percent) 
______________________________________ 
As is clear from the results shown in Table 10, the sample of the 
comparative example C as the non-granulated product was inferior in all 
properties. For example, as the sample had low bulk density as compared to 
the average bulk density 0.7 (g/ml) of the detergent composition such as 
powdered detergent, and the like, the hygroscopicity thereof was high. 
Even in the mixed by drying form with the detergent composition such as 
the powdered detergent, etc., the segregation may occur during the 
transportation, thereby presenting the problem that such product becomes 
greasy by being absorbed while being stored, or becomes of uneasy use as 
being solidified. 
As to the sample of comparative example E, although the angle of repose was 
improved by the fluid bed granulation, but the bulk density was not 
improved, thereby presenting the same problem such as segregation, etc., 
would occur. On the other hand, the bulk density was improved for the 
sample of comparative example D. However, as the surface active agent was 
not used in the granulation process as a binder, the hygroscopicity was 
not improved, and the sample was inferior in its handling as in the case 
of the above-mentioned comparative examples. 
In contrast, the respective powdered detergent builders of Examples A and B 
have excellent properties of suppressing the deterioration of their 
detergency. Besides, these builders are superior to those of comparative 
samples in their specific surface area, bulk density, angle of repose and 
hygroscopicity, and have respective properties of sufficient levels for 
practical applications. 
The described excellent properties of each detergent builder is obtained by 
such a structure that particles of the polycarboxylic acid polymer are 
bonded to each other by the surface active agent, and that the surface 
active agent is distributed to the surface of each particle so as to be 
covered by the surface active agent. 
For the described structure, when mixing each builder to the detergent 
composition such as powdered detergent composition, etc., with a ratio of 
from 01 to 20 percent, more preferably in a range of from 1 to 10 percent, 
the drying mixing process can be adopted. Therefore, the detergent 
composition including the detergent builder can be manufactured at low 
cost. 
According to the process of manufacturing the detergent builder of the 
present invention, by the granulation process with agitation with the 
surface active agent as a binder, the detergent builder having described 
excellent properties and characteristics can be manufactured at low cost. 
With the process of manufacturing the detergent builder of the present 
invention, each powder of the polycarboxylic acid polymer can be 
granulated with compressive agitation, thereby manufacturing the detergent 
builder having excellent properties and characteristic under stable 
condition. 
Possible Industrial Application 
The detergent builder containing a maleic acid copolymer of the present 
invention has high calcium ion stability constant and property against 
iron particle deposition. For these beneficial properties, by applying it 
in a detergent composition, a detergent composition of significantly 
improved detergency by preventing the deterioration in detergency by 
calcium ion, the yellowish of fiber due to iron ion. Moreover, as such 
detergent builder also permits a ratio of residual maleic acid or hydrogen 
peroxide to be reduced, the maleic acid would not adversely affect the 
chelating function and diffusing function. As a result, the detergent 
composition containing the detergent builder can be effectively used 
especially as detergents for clothes. The powdered detergent builder of 
the present invention has desirable fluidity, high bulk density and very 
low hygroscopicity. For these beneficial properties, when mixing it into 
the detergent composition such as powdered detergent, etc., the dry-mixing 
process of the detergent composition can be performed easily under stable 
conditions. As a result, the detergent composition show improved fluidity 
of detergent composition, anti-caking property, and reduced segregation of 
each composition, thereby enabling high-quality detergent composition to 
be manufactured at low cost.