DESCRIPTION
Title of Invention
GRANULAR DETERGENT COMPOSITION
5
Technical Field
[0001 ]
10
The present invention relates to a granular detergent composition useful for
washing of textile products such as clothing, especially for hand-washing.
Priority is claimed on Japanese Patent Application No. 2010-095383, filed April
16.2010. the content of which is incorporated herein by reference.
Background Art
[0002]
15 In a granular detergent composition used for washing of clothing and the like,
typically, a detergent builder is blended, along with an anionic surfactant being blended
as a cleansing component, with a purpose of improving detergency and granting other
\arious kinds of performance. As the detergent builder, an alkali builder such as
sodium carbonate or potassium carbonate, or a phosphorus-based builder such as sodium
20 tripolyphosphate (STPP) have become commonly used.
[0003]
As the anionic surfactant used in the granular detergent composition, a linear
alkylbenzenesulfonate (LAS) has been commonly used in the related art, however, in
recent years. an a-sulfo fatty acid alkyl ester salt has come to be used. An a-sulfo fatty
25 acid alkyl ester salt has advantages such as exhibiting excellent detergency. especially
x,..:; .
~, ~:':"_i
2
exhibiting excellent detergency even when hard water is used, and has good
biodegradability.
[0004]
A granular detergent composition is prepared by making an a-sulfo fatty acid
:) alkyl ester salt surfactant powder generally either alone or with other surfactants being
granulated, and then blending with other detergent ingredients.
For example, in Patent Document 1, a detergent composition containing an
a-sulfo fatty acid alkyl ester salt, a higher alcohol, and a detergent builder is disclosed.
Furthermore, in Patent Document 2, a granular detergent composition containing
lOan a-sulfo fatty acid alkyl ester salt, a higher alcohol having 6 or more carbon atoms, and
an alkali builder is disclosed.
In Patent Document 3, a granular detergent composition containing an a-sulfo
fatty acid alkyl ester salt, a higher alcohol, and a detergent builder is disclosed.
Citation List
I:) Patent Document
[0005]
[Patent Document 1] Published Japanese Translation No. HI0-500166 of the
PCT International Publication
[Patent Document 2] Japanese Unexamined Patent Application, First
20 Publication No. 2005-239865
[Patent Document 3] peT International Publication No. W004/094313
Summary of Invention
Technical Problem
3
[0006]
It is expected that the use of an a-sulfo fatty acid alkyl ester salt will increase in
the future in the regions in which hardness of water used in washing is high, from the
viewpoint of the above advantages, especially that it exhibits high detergency even when
5 hard water is used (high hard water-resistance).
However, in a detergent composition obtained by blending an a-sulfo fatty acid
alkyl ester salt, foam readily melts, and easily disappears (foam persistence is low)
compared to other anionic surfactants, for example, those in which LAS is blended.
There is a tendency that the higher the water hardness, the lower the foam persistence.
10 The low foam persistence works favorably when washing is carried out using a
fully automatic washing machine or a drum type washing machine, however, works
unfavorably when washing is carried out by hand. That is, in case of hand-washing,
especially when washing is carried out repeatedly using the same washing liquid,
detergency may be regarded as low if foam persistence is low since users tend to judge
15 the detergency with readiness of foam generation or foam persistence. Therefore, in
such applications, an improvement of foam persistence is required.
On the other hand, if foam persistence of a granular detergent composition is
simply improved, there is a problem in that it takes a lot of time and rinsing water since
lots of foam remains during rinsing.
20 The granular detergent compositions of Patent Documents 1 to 3 described
above cannot satisfy the foam persistence required at the time of hand-washing since the
use in washing machines is assumed. In addition, with the granular detergent
composition for hand-washing, there has been a need for improving the washing feeling
at the time of washing.
[0007]
4
Accordingly, the present invention has been made in view of the above problems,
and an object is to provide a granular detergent composition in which excellent
detergency and foam persistence are exhibited even when washing is carried out using
water of high hardness, rinsing property is favorable, and a favorable washing feeling
5 may be obtained.
Solution to Problem
[0008]
The inventors, as a result of intensive studies, have found that foam persistence
of an a-sulfo fatty acid alkyl ester salt is improved and favorable detergency and rinsing
I() property are balanced by combining a specific higher alcohol, a phosphorus-based
builder and an alkali builder. Further studies have been repeated based on this finding,
and the inventors have found that by controlling the particle diameter of the granular
detergent composition, a favorable washing feeling may be obtained, and have completed
the present invention.
15 [0009]
That is, there is provided a granular detergent composition containing following
(A) to (D) components, wherein particles with particle diameters of greater than 71 0 ~m
and less than or equal to 1,400 ~m are included in an amount of 10 to 50% by mass.
(A) component: an a-sulfo fatty acid alkyl ester salt represented by following Formula
20 (1).
RI-CH(S03M)-COOR2... (1)
(In Formula (1), R1 is an alkyl group or alkenyl group having 8 to 18 carbon atoms, R2 is
an alkyl group, and M represents a counter-ion.)
(B) component: a higher alcohol having 10 to 16 carbon atoms included in an
5
amount of greater than or equal to 0.1% by mass and less than 2% by mass with regard to
the total mass of the granular detergent composition.
(C) component: a phosphorus-based builder.
(D) component: an alkaline builder.
5 A mass ratio represented by [the content ofthe (A) component]/[the content of
the (B) component] is preferably 20 to 100, the granular detergent composition
containing the following (E) component is preferable, and the granular detergent
composition being used for hand-washing is more preferable.
(E) component: at least one anionic surfactant selected from a linear
10 alkylbenzene sulfonate, an alkyl sulfate, an alkenyl sulfate, an a-olefin sulfonate, an alkyl
ether sulfate, and an alkenyl ether sulfate.
Advantageous Effects of Invention
[0010]
According to the granular detergent composition of the present invention,
15 excellent detergency and foam persistence are exhibited even when washing is carried
out using water of high hardness, rinsing property is favorable, and a favorable washing
feeling may be obtained.
Description of Embodiments
20 [0011 ]
(Granular Detergent Composition)
A granular detergent composition of the present invention contains (A) to (D)
components.
The particle diameter of the granular detergent composition is not particularly
25 limited, however, the particle diameters of all particles are preferably in the range of
6
greater than 45 /lm and less than or equal to 1,400 /lm.
[0012]
The granular detergent composition includes 10 to 50% by mass of the particles
with particle diameters of greater than 710 ~LIn and less than or equal to 1,400 /lm, and
5 preferably includes 25 to 50% by mass of the particles with particle diameters of greater
than 710 /lm and less than or equal to 1,400 /lm. By including particles with particle
diameters of greater than 710 /lID and less than or equal to 1,400 /lm, a washing feeling
can be given to users due to a rough feeling of abrasives that such particles have, a
so-called a sense of scrub. If the particle diameter in the granular detergent composition
lOis less than or equal to 710 /lID, it is difficult to feel the sense of scrub, and if the particle
diameter is greater than 1,400 /lm, there is a concern that the granular detergent
composition remains in target laundry since the solubility of the granular detergent
composition in water is poor. Furthermore, if the particles with particle diameters of
greater than 710 /lm and less than or equal to 1,400 /lm in the granular detergent
15 composition are less than 10% by mass, it is difficult for users to feel the washing feeling
and if greater than 50% by mass, there is a concern that the granular detergent
composition remains in target laundry since the solubility of the granular detergent
composition in water is poor.
[0013]
20 In the present invention, the ratio of the particles with particle diameters of
greater than 710 /lm and less than or equal to 1,400 /lID ofthe granular detergent
composition may be measured, for example, in accordance with JIS K3362 using a sieve
A (mesh: 1,400 /lm), a sieve B (mesh: 710 /lID), a sieve C (mesh: 45 /lm), and a saucer D.
Specifically, on top of the saucer D, the sieve C, the sieve B and the sieve A are
IS
7
stacked in this order, a sample is obtained on the sieve A, the sieve is set by covering the
sieve A with a lid, in particular, and the granular detergent composition is sieved by
bumping the edges of this sieve set by hand. Particles on the sieve A and the saucer D
are removed, and the mass of the particles remaining on the sieve B (particles with
5 particle diameters of greater than 710 ~m and less than or equal to 1,400 ~m) and the
particles remaining on the sieve C (particle diameters of greater than 45 ~m and less than
or equal to 71 0 ~m) is measured, and may be calculated by following equation (1).
[0014]
Ratio of the particles with particle diameters of greater than 71 0 ~m and less
10 than or equal to 1,400 ~m (% by mass)={[the mass ofthe particles with particle
diameters of greater than 710 ~m and less than or equal to 1,400 ~m (g)]..;-[the mass of
the particles with particle diameters of greater than 71 0 ~m and less than or equal to
1.400 ~m (g)+the mass of the particles with particle diameters of greater than 45 ~m and
less than or equal to 71 0 ~m (g)]) x100 (1)
[0015]
Bulk density of the granular detergent composition is preferably 0.3 kg/dm3 or
more, more preferably 0.4 to 1.2 kg/dm3
, and even more preferably 0.5 to 1.1 kg/dm3
.
If the bulk density is 0.3 kg/dm3 or more, a space needed to store the granular detergent
composition (a storage place) may be more saved. On the other hand, if 1.2 kg/dm3 or
20 less. solubility in water is improved.
In addition, the bulk density represents a value measured in accordance with lIS
K3362-1998.
[0016]
The moisture content of the granular detergent composition is not particularly
8
limited, however, from the viewpoint of solubility and storage stability, 4 to 10% by mass
is preferable, 5 to 9% by mass is more preferable, and 6 to 8% by mass is even more
preferable. It should be noted that the moisture content may be determined by
measuring 5 g of the sample for 20 minutes at a surface temperature of 130°C using an
5 infrared moisture meter (manufactured by Kett Electric Laboratory).
[0017]
The pH (25°C) when the granular detergent composition is made to be an
aqueous solution of 1% by mass or an aqueous dispersion is preferably 5 to 12, and more
preferably 7 to 11.5. If the pH is in such a range, rough hands may be avoided even
10 \vhen the composition is used for hand-washing.
[0018]
«A) Component: a-Sulfo Fatty Acid Alkyl Ester Salt>
An (A) component is an a-sulfofatty acid alkyl ester salt represented by
following Formula (I).
15 [0019]
RI_CH(S03M)-COOR2 (I)
(In Formula (I), R1 is an alkyl group or alkenyl group having 8 to 18 carbon atoms, R2 is
an alkyl group, and M represents a counter-ion.)
[0020]
20 The alkyl group or alkenyl group RJ may have either a linear shape or a
branched shape and preferably have a linear shape. The number of carbon atoms of RI
is 8 to 18, and preferably 14 to 16. If the number of carbon atoms of RI is less than 8 or
greater than 18, favorable detergency may not be obtained sometimes.
The alkyl group of R2 may have either a linear shape or a branched shape and
9
preferably have a linear shape. The number of carbon atoms ofR2 is preferably 1 to 6,
more preferably 1 to 3, and even more preferably I. If the number of carbon atoms of
R2 is greater than 6, favorable detergency may not be obtained sometimes.
The R2 may include a methyl group, an ethyl group, a propyl group, an
5 isopropyl group or the like. preferably include a methyl group, an ethyl group, a propyl
group from the viewpoint of detergency being further improved, and particularly
preferably include a methyl group.
[0021 ]
As the counter-ion represented by M, a counter-ion capable of pairing with
10 anion R1CH(COOR2
) S03- by electrical neutralization and forming a water-soluble salt
with the above anion may be used and, for example, a cation formed from an alkali metal,
an alkaline earth metal, a protonated amine, an ammonium ion or the like, may be
included.
The alkali metal may include sodium, potassium, or the like.
15 The alkaline earth metals include calcium, magnesium, or the like.
In the protonated amine, the amine may be anyone of primary to tertiary, and
the total number of carbon atoms is preferably 1 to 6. The amine mayor may not have
a hydroxyl group, however, from the viewpoint of solubility at a low temperature during
washing and formulation, the amine preferably has a hydroxy group. Examples ofthe
20 amine may include an alkanolamine and the number of carbon atoms of the alkanol
group is preferably 1 to 3. Specific examples of the alkanolamine may include
monoethanolamine, diethanolamine, triethanolamine, or the like.
As M. a cation formed from an alkali metal is preferable, and among these, as
the alkali metal, sodium or potassium is more preferable and sodium even more
25 preferable.
10
As the (A) component, a-sulfo fatty acid methyl ester sodium salt (MES) in
which R1 of Formula (I) is a methyl group and M is a sodium cation, is preferable.
[0022]
As the (A) component, a component in which the number of carbon atoms of R'
5 is the same may be used alone or two or more components in which the number of
carbon atoms of R' is different may be suitably combined and used. Among these, in
the (A) component, [(A) component in which the number of carbon atoms ofR' is
14]:[(A) component in which the number of carbon atoms ofRI is 16] (mass ratio) is
preferably 45:55 to 95:5, and more preferably 60:40 to 90:10.
10 [0023]
The content of the (A) component in the granular detergent composition is
preferably 5 to 40% by mass and more preferably 10 to 20% by mass, if the (A)
component is not combined with a (E) component described later, that is, if the total
amount of anionic surfactant is the (A) component. If the content is less than 5% by
I 5 mass, there is a concern that favorable detergency may not be obtained, and if the content
is greater than 40% by mass, there is a concern that solubility may be insufficient.
In addition, ifthe (A) component is combined with a (E) component described
later, the content of the (A) component in the granular detergent composition is
preferably 3 to 30% by mass, and more preferably 5 to 20% by mass. If the content is
20 less than 3% by mass, there is a concern that favorable detergency may not be obtained,
and if the content is greater than 30% by mass, rinsing property sometimes becomes
\\orse.
[0024]
As the (A) component, commercially available products may be used or those
prepared by the method disclosed in peT International Publication No. W020041111166,
11
peT International Publication No. W02009/054406, and the like may be used. For
example, an a-sulfo fatty acid alkyl ester may obtained by sulfonation of a fatty acid
alkyl ester, and an a-sulfo fatty acid alkyl ester salt may be obtained by the sulfo group
of the a-sulfo fatty acid alkyl ester being neutralized with an alkali.
The alkali used in neutralization corresponds to the counter-ion of M.
In the preparation method, if necessary, after the sulfonation and before the
neutralization, esterification may be carried out using an alcohol such as methanol. By
performing the esterification step, if a bimolecular adduct of S03 remains in the reaction
product, detachment of the S03 is further promoted by the esterification of the alkoxy
10 moiety of the bimolecular adduct of S03 being proceeded. As a result, the formation of
hyproducts is suppressed, and the purity of the a-sulfo fatty acid alkyl ester in the
reaction product is improved.
Furthermore, in the preparation method, if necessary, before or after the
neutralization step described above, a bleaching treatment may be carried out using a
15 bleaching agent such as, for example, hydrogen peroxide, in order to make the color tone
of the a-sulfo fatty acid alkyl ester salt close to white.
Typically, a product after the neutralization step or the bleaching step is a paste
form with the solid content of approximately 50 to 80% by mass. Furthermore, if
necessary, processing such as concentration or becoming powder may be performed for
20 the product. Becoming powder may be carried out using known granulation methods
such as a kneading·extrusion granulation method (kneading·extrusion·grinding), a stirring
granulation method or a rolling granulation method.
[0025]
Typically, in the a-sulfo fatty acid alkyl ester salt obtained using the preparation
12
method described above, an a-sulfo fatty acid dialkali salt (R2 in Formula (I) is
substituted with the counter-ion ofM, hereinafter, sometimes referred to as a di-salt), and
the like, are sometimes included in addition to the a-sulfo fatty acid alkyl ester salt itself.
Although the di-salt has a poor function compared to that of the a-sulfo fatty acid alkyl
5 ester salt, however, has a function as a surfactant. Therefore, in the a-sulfo fatty acid
alkyl ester salt prepared as described above, the content of an active ingredient as a
surfactant (AI) may be determined as the content of the sum of the a-sulfo fatty acid
alkyl ester salt (pure components) and the di-salt.
In addition, in the a-sulfo fatty acid alkyl ester salt, organic substances such as
10 methyl sulfate, ethyl sulfate, propyl sulfate, lower·intermediate carboxylic acids or esters
thereof, ketones or aldehydes, or inorganic substances such as sodium sulfate is included
as a byproduct in addition to the a-sulfo fatty acid alkyl ester salt and the di-salt. The
amount of these byproducts is extremely small, and these byproducts do not particularly
affect the effects of the present invention.
15 [0026]
«B) Component: Higher Alcohol Having 10 to 16 Carbon Atoms>
A (B) component is a higher alcohol having 10 to 16 carbon atoms. As the (B)
component, a higher alcohol having 12 to 14 carbon atom is more preferable. The (B)
component is determined by taking into consideration of the types of the (A) component,
20 particularly, the number of carbon atoms of R1 in Formula (I).
As the types of the (B) component, for example, a decyl alcohol, a lauryl alcohol,
a myristyl alcohol, a cetyl alcohol or the like may be included, and these may be used
either alone or as an appropriate combination of two or more. Among these, [higher
alcohol having 12 carbon atoms]/[higher alcohol having 14 carbon atoms]= I to 9 (mass
13
ratio) is preferable.
[0027]
Furthermore, in the (B) component, the hydrocarbon chain may be either a linear
shape or a branched shape, and is preferably a linear shape. If the hydrocarbon chain is
5 a linear chain, foam persistence may be further improved.
[0028]
The content of the (B) component in the granular detergent composition is, for
example, preferably greater than or equal to 0.1% by mass and less than 2% by mass,
more preferably 0.1 to 1.5% by mass, and even more preferably 0.3 to 0.7% by mass. If
10 the content is less than 0.1% by mass, foam persistence is insufficient, and if the content
is greater than or equal to 2% by mass, rinsing property is inferior.
In addition, the mass ratio of the (A) component and the (B) component in the
granular detergent composition is preferably [the content of the (A) component]/[the
content of the (B) component]=13 to 200, and more preferably 20 to 100. If the ratio is
15 less than 13, rinsing property tends to be inferior, and if the ratio is greater than 200,
foam persistence tends to be reduced. If the ratio is 20 tol00, both effects of rinsing
property and foam persistence are excellent.
[0029]
«C) Component: Phosphorus-based Builder>
20 A (C) component is a phosphorus-based builder. As the (C) component,
phosphorus-based builders known in the art may be used and, for example, phosphate
salts such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate,
hexametaphosphate or phytate may be included, and among these, pyrophosphate or
tripolyphosphate is preferable. The form of the salt is not particularly limited, and may
include an alkali metal salt such as sodium or potassium, an alkaline earth metal salt such
5
14
as magnesium, an alkanolamine salt such as monoethanolamine or diethanolamine, or the
like, and among these, an alkali metal salt is preferable and a sodium salt is more
preferable. That is, as the (C) component, STPP or sodium pyrophosphate (TSPP) is
preferable.
As the (C) component, the above components may be used either alone or as an
appropriate combination of two or more.
[0030]
The content of the (C) component in the granular detergent composition is
preferably 3 to 30% by mass, and more preferably 10 to 20% by mass. If the content is
10 less than 3% by mass, it is difficult to obtain the cleaning effects of the (C) component,
and if the content is greater than 30% by mass, the particles are sometimes partially
dissolved and remain.
15
20
[0031 ]
« D) Component: Alkali Builder>
A (D) componenUs an alkali builder. As the (D) component, alkaline builders
known in the art may be used and, for example, an alkali metal carbonate or bicarbonate,
an alkali metal silicate, an amine, or the like, may be included.
The alkali metal carbonate may include sodium carbonate, potassium carbonate,
potassium sodium carbonate and sodium sesquicarbonate, or the like.
Specific examples of the alkali metal bicarbonate may include sodium
bicarbonate, potassium bicarbonate, or the like.
Specific examples of the alkali metal silicate may include sodium silicate,
layered sodium silicate, sodium metasilicate, sodium orthosilicate, or the like. As the
silicate, those with NazO/SiOz (molar ratio) being 1.0 to 4.5 is preferable, those with 1.6
25 to 4.0 is more preferable, and those with 2.0 to 3.5 is even more preferable.
15
Specific examples of the amine may include monoethanolamine, diethanolamine,
triethanolamine, or the like.
Among these, an alkali metal carbonate or an alkali metal silicate is preferable,
and sodium carbonate or sodium silicate is more preferable from the viewpoint of
5 detergency improvement.
As the (D) component, the above components may be used either alone or as an
appropriate combination of two or more.
[0032]
The content of the (D) component in the granular detergent composition is
10 preferably 5 to 40% by mass, and more preferably 10 to 20% by mass. If the content is
less than 5% by mass, it is difficult to obtain the cleaning effects of the (D) component,
and if the content is greater than 40% by mass, the particles are sometimes partially
dissolved and remain.
[0033]
15 «E) Component: At Least One Anionic Surfactant Selected from Linear Alkylbenzene
Sulfonate, Alkyl Sulfate, Alkenyl Sulfate, a-Olefin Sulfonate, Alkyl Ether Sulfate, and
Alkenyl Ether Sulfate>
An (E) component is, (E) component: at least one anionic surfactant selected
from a linear alkyl benzene sulfonate (LAS), an alkyl sulfate, an alkenyl sulfate
20 (hereinafter an alkyl sulfate and an alkenyl sulfate are sometimes referred to collectively
as AS), an a- olefin sulfonate (AOS), an alkyl ether sulfate and an alkenyl ether sulfate
(hereinafter, refer an alkyl ether sulfate and an alkenyl ether sulfate collectively as AES).
By containing the (E) component, in the granular detergent composition, foam
persistence may be further improved.
[0034]
16
The number of carbon atoms of the alkyl group of the LAS is preferably 8 to 18,
and that with 10 to 14 carbon atoms is more preferable from the viewpoint of detergency.
The alkyl group of the LAS may have either a linear shape or a branched shape. The
form of the salt is not particularly limited, and may include an alkali metal salt such as
5 sodium or potassium, an alkaline earth metal salt such as magnesium, an alkanolamine
salt such as monoethanolamine or diethanolamine, or the like, and among these, an alkali
metal salt is preferable and a sodium salt is more preferable.
[0035]
The number of carbon atoms of the alkyl group of the alkyl sulfate is preferably
10 10 to 20, and that with 10 to 14 carbon atoms is more preferable from the viewpoint of
detergency. The alkyl group of the alkyl sulfate may have either a linear shape or a
branched shape. The form of the salt is not particularly limited, and may include an
alkali metal salt such as sodium or potassium, an alkaline earth metal salt such as
magnesium, an alkanolamine salt such as monoethanolamine or diethanolamine, or the
15 like. and among these, an alkali metal salt is preferable and a sodium salt is more
preferable.
The number of carbon atoms of the alkenyl group of the alkenyl sulfate is
preferably 10 to 20, and that with 10 to 14 carbon atoms is more preferable from the
\iewpoint of detergency. The alkenyl group of the alkenyl sulfate may have either a
20 linear shape or a branched shape. The form of the salt is not particularly limited, and
may include an alkali metal salt such as sodium or potassium, an alkaline earth metal salt
such as magnesium, an alkanolamine salt such as monoethanolamine or diethanolamine,
or the like, and among these, an alkali metal salt is preferable and a sodium salt is more
preferable.
25 [0036]
17
The number of carbon atoms of the AOS is preferably 10 to 20. The form of
the salt is not particularly limited, and may include an alkali metal salt such as sodium or
potassium, an alkaline earth metal salt such as magnesium, an alkanolamine salt such as
monoethanolamine or diethanolamine, or the like, and among these, an alkali metal salt is
5 preferable and a sodium salt is more preferable.
[0037]
The alkyl ether sulfate is not particularly limited, however, preferably includes
any of alkylene oxides having 2 to 4 carbon atoms, or that having an alkyl group in a
linear shape or a branched shape having 10 to 20 carbon atoms in which ethylene oxide
10 (EO) and propylene oxide (PO) (molar ratio EO/PO=0.1/9.9 to 9.9/0.1) is added at 0.5 to
10 moles on average.
Furthermore, the alkenyl ether sulfate is not particularly limited, however,
preferably includes any of alkylene oxides having 2 to 4 carbon atoms, or that having an
alkenyl group in a linear shape or a branched shape having 10 to 20 carbon atoms in
IS \vhich ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO/PO=0.1/9.9 to
9.9/0.1) is added at 0.5 to 10 moles on average.
[0038]
As the (E) component, among the above components, a linear sodium
alkylbenzene sulfonate having 10 to 14 carbon atoms or a sodium alkyl sulfate having 10
20 to 14 carbon atoms is preferable.
As the (E) component, the above components may be used either alone or as an
appropriate combination of two or more.
The content of the (E) component in the granular detergent composition may be
determined in consideration of the content of the (A) component, and the like, and for
example, is preferably 3 to 30% by mass and more preferably 5 to 20% by mass.
18
[0039]

In the granular detergent composition, surfactants other than the (A) component
and the (E) component (hereinafter, optional surfactants), detergent builders other than
.5 the (C) component and the (D) component (optional detergent builders), aromatics,
pigments, fluorescent brightening agents, enzymes, enzyme stabilizers, polymers,
anti-caking agents, reducing agents, metal ion scavengers, pH adjusting agents, bleaching
agents, bleach activators, bleach catalysts, ultraviolet absorbers, clay minerals, or the like,
may also be included as necessary within a range that does not impair the effects of the
I 0 present invention.
[0040]
«Optional Surfactant»
The optional surfactant is not particularly limited and may include anionic
surfactants other than the (A) component and the (E) component (optional anionic
I .5 surfactants), nonionic surfactants, cationic surfactants, and amphoteric surfactants, or the
like.
lOptional Anionic Surfactant]
(I) Any of alkylene oxides having 2 to 4 carbon atoms, or an alkyl (or alkenyl)
phenyl ether sulfate and a salt thereof having a linear or branched alkyl (or alkenyl)
20 group having 10 to 20 carbon atoms in which ethylene oxide and propylene oxide (molar
ratio EO/PO=0.1/9.9 to 9.9/0.1) is added at 3 to 30 moles on average.
(2) Any of alkylene oxides having 2 to 4 carbon atoms, or an alkyl (or alkenyl)
ether carboxylate and a salt thereof having a linear or branched alkyl (or alkenyl) group
having 10 to 20 carbon atoms in which ethylene oxide and propylene oxide (molar ratio
2.5 EO/PO=0.1/9.9 to 9.9/0.1) is added at 0.5 to 10 moles on average.
19
(3) An alkyl polyhydric alcohol ether sulfate and a salt thereof such as alkyl
glyceryl ether sulfonate having 10 to 20 carbon atoms.
(4) A long chain monoalkyl, dialkyl or sesquialkyl phosphate and a salt thereof.
(5) A polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate and a salt
5 thereof.
The form of the salt in such surfactants is not particularly limited, and may
include, for example, an alkali metal salt, an alkaline earth metal salt, a protonated amine
salt, an ammonium salt, or the like. The alkali metal, the alkaline earth metal, the
protonated amine may be the same as those exemplified as M in Formula (I), respectively.
10 Among these, an alkali metal salt is preferable.
These optional anionic surfactants may be used either alone or as an appropriate
combination of two or more.
[0041 ]
[Nonionic Surfactant]
15 As the nonionic surfactant, a variety of nonionic surfactants may be used
without being particularly limited as long as it is being conventionally used in detergents.
The nonionic surfactant may include, for examples, the following example.
(1) A polyoxyalkylene alkyl (or alkenyl) ether in which an alkylene oxide having
2 to 4 carbon atoms is added to an aliphatic alcohol having 10 to 18, more preferably 12
20 to 14 carbon atoms at 3 to 30 moles, preferably 4 to 20 moles, and more preferably 5 to
17 moles on average.
Among these, a polyoxyethylene alkyl (or alkenyl) ether or a polyoxyethylene
polyoxypropylene alkyl (or alkenyl) ether is preferable.
The aliphatic alcohols used here may include a primary alcohol or a secondary
alcohol. In addition, the alkyl group may have a branched chain. As the aliphatic
10
20
alcohoL a primary alcohol is preferable.
(2) A polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A long chain fatty acid polyoxyalkylene alkyl ester in which an alkylene
oxide is added between the ester bond of a long chain fatty acid alkyl ester.
(4) A polyoxyethylene sorbitan fatty acid ester.
(5) A polyoxyethylene sorbitol fatty acid ester.
(6) A polyoxyethylene fatty acid ester.
(7) A polyoxyethylene hydrogenated castor oil.
(8) A glycerin fatty acid ester.
(9) A fatty acid alkanolamide.
(10) A polyoxyethylene alkylamine.
(11) An alkyl glycoside.
(12) An alkylamine oxide.
These nonionic surfactants may be used either alone or as an appropriate
15 combination of two or more.
[0042]
20
[Cationic surfactant]
As the cationic surfactant, a variety of cationic surfactants may be used without
being particularly limited as long as it is being conventionally used in detergents.
As the cationic surfactant, for example, a mono-, di-, or trialkyl cation having 1
to 3 long chain (preferably 8 or more carbon atoms) hydrocarbon groups. In particular,
the cationic surfactant including 1 to 2 ester groups and 1 to 2 long chain hydrocarbon
groups in the molecule is preferable.
Specific examples of the cationic surfactant may include a mono long chain
25 alkyl trimethyl ammonium chloride including one long chain alkyl group or alkenyl
15
21
group having 8 to 22 carbon atoms, a di long chain alkyl trimethyl ammonium chloride
including two long chain alkyl groups or alkenyl groups having 8 to 22 carbon atoms, a
tri long chain alkyl trimethyl ammonium chloride including three long chain alkyl groups
or alkenyl groups having 8 to 22 carbon atoms, a
5 N-acyloxyethyl-N,N-dimethyl-N-hydroxyethyl ammonium chloride including one long
chain alkyl group or alkenyl group having 8 to 22 carbon atoms, a
N.N-diacyloxyethyl-N,N-dimethyl ammonium chloride including two long chain alkyl
groups or alkenyl groups having 8 to 22 carbon atoms, or the like.
These cationic surfactants may be used either alone or as an appropriate
10 combination of two or more.
[0043]
[Amphoteric Surfactant]
As the amphoteric surfactant a variety of amphoteric surfactants may be used
\vithout being particularly limited as long as it is being conventionally used in detergents.
As the amphoteric surfactant, for example, a sulfobetaine or a carboxybetaine
having one or two long chain (preferably having 8 or more carbon atoms) hydrocarbon
groups may be used.
The long chain hydrocarbon group may include an ester group, an amide group
or an ether group. The long chain hydrocarbon group may be either a one-chain type or
20 a two-chain type. In addition, in the long chain hydrocarbon group, the ratio of
saturated/unsaturated, distribution of the carbon chain length, and the ratio of cis/trans of
the unsaturated group are not particularly limited. Furthermore, the long chain
hydrocarbon group may be derived from a fatty acid or a fatty acid methyl ester which is
a raw material for preparation of the cationic surfactant described above. Specific
25 examples of the amphoteric surfactant may include betaines such as
22
N.N-diacyloxyethyl-N-methylammonioethyl sulfate or
N.N-diacyloxyethyl-N-methylammonioethyl carboxylate;
N-acyloxyethyl-N-hydroxyethyl-N-methylammonio betaines,
N-acylamidepropyl-N,N-dimethylammonio betaines,
5 N-acylamidepropyl-N,N' -dimethyl-N'-p-hydroxypropylammonio betaine, or the like.
In the amphoteric surfactant, an amino betaine such as a compound of which
nitrogen atom is not quatemized, an alkanolamine which is a raw material, a neutralized
substance thereof, or a quatemarized substance thereof may be included.
These amphoteric surfactants may be used either alone or as an appropriate
10 combination of two or more.
[0044]
The optional surfactant may be used either alone or as a combination of two or
more.
The content of the optional surfactant in the granular detergent composition may
15 be appropriately determined in consideration of the content of the (A) component and the
(E) component. The total amount of the (A) component, the (E) component, and the
optional surfactant is preferably an amount to be 5 to 40% by mass, more preferably an
amount to be 10 to 30% by mass, and even more preferably an amount to be 10 to 25%
by mass with regard to the total amount of the granular detergent composition. If the
20 content is less than 5% by mass, there is a possibility that detergency may be insufficient,
and if the content is greater than 40% by mass, there is a possibility that rinsing property
becomes worse.
[0045]
«Optional Detergent Builder»
25 The optional detergent builder may include inorganic builders or organic
23
huilders other than the (C) component and the (D) component.
Examples of such inorganic builders may include zeolites such as A-type zeolite,
P-type zeolite or X-type zeolite, an amorphous aluminosilicate, or the like.
Examples of the organic builder may include organic builders such as
5 aminocarboxylatessuch as nitrilotriacetate, ethylenediaminetetraacetate,
~-alaninediacetate, aspartic acid diacetate, methylglycinediacetate or iminodisuccinate;
hydroxyaminocarboxylates such as serine diacetate, hydroxyiminodisuccinate,
hydroxyethylethylenediaminetriacetate or a dihydroxyethylglycine salt;
hydroxycarboxylates such as hydroxyacetate, tartrate, citrate or gluconate;
10 cycloalkylcarboxylates such as pyromellitate, benzopolycarboxylate or
cyclopentanetetracarboxylte; ether carboxylates such as carboxymethyltartronate,
carboxymethyloxysuccinate, oxydisuccinate, or tartaric acid mono- or disuccinate; a
polymer having a carboxyl group with a weight average molecular weight of 10,000 or
less.
15 These optional detergency builders may be used either alone or as a combination
of two or more.
[0046]
<>
25
The aromatic is not particularly limited and, for example, aromatic ingredients
20 and aromatic compositions disclosed in Japanese Unexamined Patent Application, First
Publication No. 2002-146399 or Japanese Unexamined Patent Application, First
Publication No.2003-89800 may be used.
In addition, the aromatic composition is a mixture made of aromatic ingredients,
a solvent, an aromatic stabilizing agent, and the like.
The aromatic may be used either alone or as a combination of two or more.
24
The content of the aromatic in the granular detergent composition is preferably
0.001 to 10% by mass and more preferably 0.01 to 5% by mass.
[0047]
5
10
«Pigment»
As the pigment, any of a dye or a coloring matter may be used. A pigment is
preferable from the viewpoint of storage stability, and particularly, a compound having
oxidation resistance such as an oxide or the like is preferable. Such compounds may
include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine,
ultramarine blue, Prussian blue, cyanine blue, cyanine green, or the like.
The pigment may be used either alone or as an appropriate combination of two
or more.
[0048]
«Fluorescent Brightening Agent»
Examples of the fluorescent brightening agent may include fluorescent
15 brightening agents such as 4,4'-bis-(2-sulfostyryl)-biphenyl salt,
4.4' -bis-(4-chloro-3-sulfostyryl)-biphenyl salt, a 2-(sulfostyryl)naphthothiazole
derivative, a 4,4' -bis (triazol-2-yl)stilbene derivative, a
bis-(triazinylaminostilbene)disulfonate derivative.
Examples of commercially available fluorescent brightening agents may include
20 Whitex SA. Whitex SKC (hereinbefore, trade name; manufactured by Sumitomo
Chemical Co., Ltd.), Tinopal AMS-GX, Tinopal DBS-X, or Tinopal CBS-X
(hereinbefore. trade name; manufactured by Khyati Chemicals Pvt., Ltd.), Lemonite
CBUS-3B (hereinbefore, trade name; manufactured by Khyati Chemicals Pvt., Ltd.), or
the like. Amo'ng these, Tinopal CBS-X or Tinopal AMS-GX is preferable.
25 The fluorescent brightening agent may be used either alone or as an appropriate
25
combination of two or more.
The content of the fluorescent brightening agent in granular detergent
composition is preferably greater than or equal to 0.001% by mass and less than or equal
to 1% by mass.
5 [0049]
«Enzyme»
The enzyme may include hydrolases, oxidoreductases, lyases, transferases,
isomerases. if classified by the reactivity of the enzyme, and all of these may be applied
in the present invention. Among these, protease, esterase, lipase, nuclease, cellulase,
10 amylase, pectinase, or the like, is preferable.
The protease may include pepsin, trypsin, chymotrypsin, collagenase, keratinase,
elastase, subtilisin, papain, bromelain, carboxypeptidase A or B, aminopeptidase,
aspargyropeptidase A or B, or the like. Commercially available proteases may include
Savinase, Alcalase, Kannase, Everlase, Deozyme (hereinbefore, trade name;
15 manufactured by Novozymes); API21 (trade name; manufactured by Showa Denko K.K);
MaxacaL Maxapem (hereinbefore, trade name; manufactured by Genencor, Inc.);
protease K-14 or K-16 (protease disclosed in Japanese Unexamined Patent Application,
First Publication No. H05-25492), or the like.
The esterase may include gastric lipase, pancreatic lipase, plant lipases,
20 phospholipases, cholinesterases, phosphotases, or the like.
The Lipase may include commercially available lipases such as Lipolase or
Lipex (hereinafter, trade name; manufactured by Novozymes), Liposam (trade name;
manufactured by Showa Denko Co., Ltd.), or the like.
The cellulase may include Celzyme (trade name; manufactured by Novozymes);
25 alkaline cellulase K, alkaline cellulase K-344, alkaline cellulase K-534, alkaline cellulase
26
K-539, alkaline cellulase K-577, alkaline cellulase K-425, alkaline cellulase K-521,
alkaline cellulase K-580, alkaline cellulase K-588, alkaline cellulase K-597, alkaline
cellulase K-522, CMC-ase I, CMC-ase II, alkaline cellulase E-II, and alkaline cellulase
E-lIl (hereinbefore, cellulases disclosed in Japanese Unexamined Patent Application,
S First Publication No. S63-264699), or the like.
The amylase may include commercially available Stainzyme, Termamyl,
Duramyl (hereinafter, trade name; manufactured by Novozymes), or the like.
The above enzymes may be used either alone or as an appropriate combination
of two or more.
10
IS
20
In addition, the enzyme is preferably used in a state where an enzyme is
separately granulated as stable particles and is dry blended into cleaning fabric
(particles ).
The content of the enzyme in the granular detergent composition is preferably
0.05 to 5% by mass.
[0050]
«Enzyme Stabilizer»
As the enzyme stabilizer, for example, calcium salt, magnesium salt, polyol,
formic acid. boron compound, or the like, may be blended. Among these, sodium
tetraborate, calcium chloride, or the like is preferable.
The above enzyme stabilizers may be used either alone or as an appropriate
combination of two or more.
The content of the enzyme stabilizer in the granular detergent composition is
preferably 0.05 to 2% by mass.
[0051 ]
25 «Polymers»
27
In the present invention, polyethylene glycol with an average molecular weight
of 200 to 200,000, a salt of acrylic acid and/or maleic acid polymer with an weight
average molecular weight of 1,000 to 100,000, a polyvinyl alcohol, a cellulose derivative
such as hydroxypropyl methylcellulose (HPMC) may be blended either as a binder or a
5 powder property modifier used to densify the particles of the granular detergent
composition, or in order to impart the effects of preventing recontamination for
hydrophobic particles (stain).
In addition, a copolymer of a repeating unit derived from terephthalic acid and a
repeating unit derived from ethylene glycol and/or propylene glycol, a terpolymer, or the
10 like may be blended as a stain releasing agent.
Furthermore, a polyvinyl pyrrolidone may be blended in order to impart the
effect of discoloration prevention.
Among the above polymers, HPMC is preferable from the viewpoint of the
effect of imparting flexibility to a target laundry or preventing recontamination, and
15 HPMC with a weight average molecular weight of20,000 or more is more preferable.
These polymers may be used either alone or as an appropriate combination of two or
more.
The content of the polymers in the granular detergent composition is preferably
0.05 to 5% by mass.
20 [0052]
«Anti-caking Agent»
Examples ofthe anti-caking agent may include a para-toluenesulfonate, a
xylenesulfonate, acetate, a sulfosuccinate, talc, finely powdered silica, clay, magnesium
oxide, or the like.
The anti-caking agent may be used either alone or as an appropriate combination
28
of two or more.
[0053]
«Reducing Agent»
Examples of the reducing agent may include sodium sulfite, potassium sulfite,
.5 or the like.
[0054]
«Metal Ion Scavenger»
The metal ion scavenger has an effect of suppressing the adsorption of metal
ions to a target laundry by trapping trace metal ions in tap water or the like.
10 The metal ion scavenger which may be blended into the granular detergent
composition may include, in addition to those included in the optional detergent builder,
aminopolyacetates such as ethylenediaminetetraacetic acid, nitrilotriacetic acid or glycol
ethylenediamine hexaacetic acid; an organic phosphonic acid derivative or a salt thereof
such as I-hydroxyethane-l, I-diphosphonic acid (HEDP-H), ethane-I, I-diphosphonic
15 acid, ethane-I,1,2-triphosphonic acid, hydroxyethane-l, 1,2-triphosphonic acid,
ethane-l ,2-dicarboxy-l ,2-diphosphonic acid, hydroxymethane phosphonic acid,
ethylenediamine tetra(methylene phosphonic acid), nitrilotris(methylene phosphonic
acid), 2-hydroxyethylimino di(methylene phosphonic acid), hexamethylenediamine
tetra(methylene phosphonic acid) or diethylenetriamine penta(methylene phosphonic
20 acid); an organic acid derivative or a salt thereof such as diglycolic acid, tartaric acid,
oxalic acid or gluconic acid, or the like.
The metal ion scavenger may be used either alone or as an appropriate
combination of two or more.
As the content of the metal ion scavenger in the granular detergent composition,
25 consideration is needed so that it is used in a range that does not impair the performance.
29
[0055]
«pH Adjusting Agent»
The pH adjusting agent may include, in addition to an alkali agent included as
the detergent builder, an alkaline compound such as sodium hydroxide, potassium
5 hydroxide. monoethanolamine, diethanolamine or triethanolamine, the metal ion
scavenger, alkali metal dihydrogen phosphate such as potassium dihydrogen phosphate,
an acidic compound such as lactic acid, succinic acid, malic acid, gluconic acid, sulfuric
acid. hydrochloric acid or citric acid, or the like. Furthermore, a buffer agent may also
be used in order to prevent a decrease in pH due to an acid component derived from stain
10 of the fiber when washing. These pH adjusting agents may be used either alone or as an
appropriate combination of two or more.
[0056]
(Preparation Method)
The granular detergent composition of the present invention may be prepared
15 using preparation methods known in the art. For example, the (A) to (0) components,
and the (E) component or the optional components as necessary, are dissolved·dispersed
in water and, and then a granular detergent composition may be obtained in a powder
form by spray drying. Also, for example, the (A) to (D) components, and the (E)
component or the optional components as necessary, are provided to apparatuses of
20 kneading· extrusion, stirring granulation, rolling granulation, and the like, and the
granular detergent compositions may be obtained in a desired form by carrying out
kneading or granulation, compression molding, and the like, and grinding or the like if
necessary.
[0057]
25 (Washing Method)
30
The washing method using the granular detergent composition of the present
invention is not particularly limited and may be the same as washing methods known in
the art. As specific examples, a method in which a granular detergent composition is
poured into water and a target laundry is washed in the water (washing water) may be
5 included. Washing of a target laundry may be either hand-washing or washing using a
washing machine (a two-tub washing machine, a fully automatic washing machine, a
drum type washing machine, or the like), however, in terms of the effectiveness of the
present invention, for example, hand-washing in which clothes are washed by pouring
water into a tub and dissolving a granular detergent composition is preferable. The
10 input amount of the granular detergent compositions in water varies depending on the
blending amount of the (A) component and other surfactants, however, the concentration
of the granular detergent composition in washing liquid is preferably greater than or
equal to 0.1% by mass and less than 10% by mass for hand-washing, and greater than or
equal to 0.01% by mass and less than 1% by mass for a washing machine.
15
20
The laundry object of the granular detergent composition of the present
invention may be the same as the laundry object (target laundry) of a general granular
detergent composition, and may include, for example, textile products such as clothing, a
dish cloth, a sheet or a curtain.
[0058]
According to the present invention, excellent detergency and foam persistence
are exhibited even when washing is carried out using water of high hardness (for
example, lOODH or more), and rinsing property is favorable since the (A) to (D)
components are included. In addition, in the granular detergent composition, a
favorable washing feeling may be obtained due to a sense of scrub of specific particles
since the specific particles are included 10 to 50% by mass.
31
[Examples]
[0059]
Hereinafter, the present invention will be described using examples, however,
the present invention is not limited to these examples.
5 In the present examples, "%" is "% by mass" and "parts" is "parts by mass"
unless otherwise specified.
The blending amount of each component in Tables 1 to 8 shows a blending
amount in terms of a pure component.
The blending amount of "Zeolite*" in the table shows the total amount of the
10 zeolite in particles for MES detergents and the zeolite separately added.
[0060]
(Raw Materials Used)
« A) component>
. a-sulfo fatty acid alkyl ester salt (MES): which is prepared according to the
15 following preparation example (in Formula (I), [(A) component having 14 carbon atoms
of R1
]: [(A) component having 16 carbon atoms ofR1]=90:10, the number of carbon
atoms ofR2 is 1, M is a sodium cation, AI ofMES=86.6%, zeolite 4.0%, moisture 3.4%,
sodium sulfate 2.2%, and methyl sulfate 3.8%).
[0061 ]
20 Preparation Example of MES
«1. Preparation ofMES in Paste Form»
330 kg of a fatty acid methyl ester mixture (a mixture in which methyl palmitate
(trade name "pastel M-16", manufactured by Lion Corporation) and methyl stearate
(trade name ··pastel M-180", manufactured by Lion Corporation) were mixed in advance
25 so as the mass ratio to be 9: 1) were poured into a reactor with 1 kL capacity equipped
32
with a stirrer, and while stirring, 5% of anhydrous sodium sulfate with regard to the
above fatty acid methyl ester mixture was supplied as a coloring inhibitor. Then, while
continuing the stirring, 110 kg (1.2 times moles with regard to the above fatty acid
methyl ester mixture) ofS03 gas (sulfonation gas) diluted to 4% by volume in nitrogen
5 gas was blowing at a constant speed over a period of 3 hours while bubbling at a reaction
temperature of 80°C, and subsequently was aged for 30 minutes while maintaining the
temperature at 80°C. After that, 14 kg of methanol as a lower alcohol (industrial grade
moisture 500 ppm or less, manufactured by Sumitomo Chemical Co., Ltd.) was supplied
and esterification was carried out. The esterification temperature was 80°C, and the
10 aging time was 30 minutes.
Subsequently, the esterified substance was withdrawn from the reactor, and was
continuously neutralized by adding an equivalent of aqueous solution of sodium
hydroxide (industrial grade, manufactured by Daiso Co., Ltd.) using a line mixer.
Subsequently, this neutralized substance was poured into a bleaching agent
15 mixture line, and 1% of 35% hydrogen peroxide (35% hydrogen peroxide for industrial
lise. manufactured by Mitsubishi Gas Chemical Company, Inc.) was supplied with regard
to AI concentration (total concentration of a-sulfo fatty acid methyl ester sodium salt
(MES-Na), and a-sulfo fatty acid disodium salt (di-Na salt)) in terms of a pure
component, mixed, and bleaching was performed while maintaining the temperature at
20 80°C, resulting in MES in a paste form.
[0062]
«2. Concentration ofMES Paste»
The MES paste obtained above was introduced at 35 kg/hr to a vacuum thin film
evaporator rotating at a rotational speed of 1,060 rpm and a blade tip speed of 11 mls
33
(heat transfer surface: 0.5 m2
, the inner diameter of a cylindrical-shaped processing unit:
205 mm. clearance between the heat transfer surface and the blade tip which is scraping
means: 3 mm. trade name "EXEVA", manufactured by Shinko Pantec Co., Ltd.) and was
concentrated under the conditions of a heating temperature of the inner wall (temperature
5 of the heat transfer surface) of 135°C and vacuum degree (pressure within the processing
unit) 01'0.007 to 0.014 MPa.
The temperature of the concentrate obtained was l15°C and the moisture content
\vas 2.5%.
The moisture content is a value at which approximately 0.05 g of the sample was
10 measured using a Karl Fischer moisture meter (manufactured by Kyoto Electronics
Manufacturing Co., Ltd., model: MKC-210, Method: 2, stirring rate 4).
[0063]
«3. Preparation ofMES Solid»
The MES paste obtained by concentration was continuously supplied at 222
15 kg/h to a double belt-type belt cooler (NR3-Lo. a cooler) manufactured by Nippon
Belting Co., Ltd. in which clearance between the input pulley was adjusted to 2 mm, and
was cooled. The belt moving speed at the time was made to be 6 mis, and the flow rate
of the cooling water on the belt side was made to be 1,500 Llh (cooled by a flow in a
countercurrent fashion on the rear surface of the belt) and under the belt side was made to
20 be 1.800 Llh (cooled by spraying on the rear surface of the belt), and the cooling water
supplying temperature was 20°C. The MES solid in a flake shape was obtained at 25°C
by shredding the sheet containing the surfactant obtained by being discharged from the
cooling belt at a rotational speed of 200 rpm using a shredder included which is installed
near the discharging pulley.
25 [0064]
34
«4. Preparation ofMES Particles for Detergents»
The MES solid in a flake shape obtained (temperature is 25°C) was continuously
supplied at a rate of 100 kg/h from the raw material inlet of a screw extrusion granulator
(manufactured by Hosokawa Micron Group, Extrud-O-mix EM-6 type, spindle speed 70
5 rpm). Then, MES solid in a noodle shape was obtained by being extruded from the
holes of a third orifice plate along with kneading the MES solid by rotating a first and a
second paddle at 100 rpm by rotating a screw shaft.
After cooling this noodle to room temperature to 30°C, 95 parts of
noodle-shaped MES was shredded by being introduced to a pulverizer (manufactured by
I () Okada Seiko Co., Ltd., speed mill ND-l 0 type, blade rotational speed 840 rpm, screen $4
mm together with 5 parts of powder A-type zeolite at a rate of 1 kg/min, and MES
particles for detergents were obtained with an average particle diameter of 500 ~m.
[0065]
« A) Component: Comparative Product of (A) Component>
15 . C12 Soap: sodium laurate, manufactured by Kanto Chemical Co., Inc.
[0066]
20
« B) component>
· Linear C8 higher alcohol: octyl alcohol, ConollOWS (trade name),
manufactured by New Japan Chemical Co., Ltd.
· Linear CI0 higher alcohol: decyl alcohol, Conol 1098 (trade name),
manufactured by New Japan Chemical Co., Ltd.
· Linear C12 higher alcohol: lauryl alcohol, Conol20P (trade name),
manufactured by New Japan Chemical Co., Ltd.
· C13 higher alcohol: containing those in which a carbon chain was branched (a
35
2-methyl compound), a linear compound was 49%, Diadol13 (trade name),
manufactured by Mitsubishi Chemical Corporation
· Linear C12114 higher alcohol: having 12 carbon atoms is 68 to 74% by mass
and having 14 carbon atoms is 24 to 30% by mass, CO-1270 (trade name), manufactured
5 hy P&G Chemicals
· Linear C14 higher alcohol: myristyl alcohol, Conol 1495 (trade name),
manufactured by New Japan Chemical Co., Ltd.
Linear C16 higher alcohol: cetanol, Conol1695 (trade name), manufactured
by New Japan Chemical Co., Ltd.
10 . Linear higher alcohol: stearyl alcohol, Conol 30SS (trade name), manufactured
by New Japan Chemical Co., Ltd.
[0067]
« C) component>
· Sodium tripolyphosphate (STPP): manufactured by Central Glass Co., Ltd.
15 . Sodium pyrophosphate (TSPP): manufactured by Nippon Chemical Industrial
Co.. Ltd.
[0068]
20
« D) component>
· Sodium carbonate: powder ash, manufactured by Asahi Glass Co., Ltd.
. Sodium silicate: sodium silicate No.2, powder soda silicate No.2 (trade name),
manufactured by Nippon Chemical Industrial Co., Ltd.
[0069]
«E) component>
· Sodium lauryl sulfate (AS-Na): SLS (trade name), manufactured by
20
36
PEPMACO MANUFACTURING CORPORATION
· Linear sodium alkylbenzene sulfonate (LAS-Na): a linear alkylbenzene
sulfonic acid with the number of carbon atoms of the linear alkyl group being 10 to 14
(Lipon LH-200 (manufactured by Lion Corporation) LAS-H (pure component 96%)) was
::; neutralized during slurry preparation for spray drying or during granulation. The
blending amount in the tables represents % by mass ofLAS-Na.
[0070]

· Polyoxyethylene alkyl ether (AE): a compound in which an ethylene oxide is
I 0 added at 9 moles on average to an alcohol (CO-1214 (trade name), manufactured by
P&G Chemicals) having an alkyl group of 12 to 16 carbon atoms (pure component 90%,
manufactured by Lion Corporation)
· Polyoxyethylenepolyoxypropylene alkyl ether (a compound in which EO and
PO were added to an alcohol): a compound in which an ethylene oxide is added at 15
15 moles on average and a propylene oxide is added at 3 moles on average to a higher
alcohol having 12 to C13 carbon atoms (Neodol23 (trade name), manufactured by Shell
Chemicals Japan Ltd.), manufactured by Lion Corporation
· Sodium sulfate: neutral anhydrous sodium sulfate, manufactured by Nippon
Chemical Industrial Co., Ltd.
· Zeolite: A-type zeolite, Zeolite Na-4A (trade name), pure component 80%,
manufactured by THAI SILICATE CHEMICALS
· Fluorescent brightening agent CBS: Tinopal CBS-X (trade name),
manufactured by BASF Japan Ltd.
· Fluorescent brightening agent AMS: Tinopal AMS-GX (trade name),
5
37
manufactured by BASF Japan Ltd.
· Enzyme: a mixture of protease (Savinase 12T)/amylase (Stainzyme 12T)llipase
(L1PEX 100T)/cellulase (Celluclean 4,500T)/glucosidase (Mannaway 4.0T)
(hereinbefore, all manufactured by Novozymes Japan Ltd.)=6/2/211/4 (mass ratio)
· Aromatic: an aromatic composition A shown in [Table 11] to [Table 18] of
Japanese Unexamined Patent Application, First Publication No. 2002-146399
· Pigment: Ultramarine Blue (manufactured by Dainichiseika Color &
Chemicals Mfg. Co., Ltd.)
[0071]
10 (Examples 1 to 27, Comparative Examples 1,3 to 11)
The granular detergent composition having the composition shown in Tables 1
to 4 and 7 to 8 was prepared using the following preparation method A. In the tables,
"balance" of sodium sulfate indicates an amount at which the total amount of the
granular detergent composition becomes 100%.
15 [0072]

For the preparation of the granular detergent composition, a FS-1200 high-speed
mixer/granulator (manufactured by Fukae Kogyo Co., Ltd.) was used. The (C)
component, the (D) component, sodium sulfate, part of the powder A-type zeolite (the
20 amount excluding the powder A-type zeolite for surface modification described later (the
amount equivalent to 1.6%)) were dry-blended for 60 seconds at a stirrer speed of 100
rpm and a shearer speed of 2,000 rpm using a mixer. Water (the amount equivalent to
0.375%) was added with the mixer being operated for 90 seconds at the same stirrer
speed and the shear speed. The temperature was maintained below 50°C using a
38
cooling jacket in which water passed through. Water as a binder (the amount equivalent
to 1.4%) and the nonionic surfactant (AE and the adduct of alcohol EO/PO) were added
to the mixer and granulation process was performed for 180 seconds at a stirrer speed of
100 rpm and a shearer speed of 2,000 rpm. The temperature was maintained below
5 500C using a cooling jacket in which water passed through. The product obtained in
this step was a granular solid. The shearer of the mixer was stopped, and while stirring
at a stirrer speed of 90 rpm for 120 seconds, the enzyme and the MES particles for
detergents were added, the powder A-type zeolite (the amount equivalent to 1.6% in
terms of a pure component) was further added, and the particles containing surfactants
10 \\ere obtained by modifying the surface and spraying the aromatic and the (B)
component. The particles containing surfactants, in order to color a part of them, were
sprayed with 20% aqueous dispersion liquid of the pigment while being transported to a
belt conveyor (speed: 0.5 rnIs) (height of the particle layer containing surfactants on the
belt conveyor 30 mm, layer width 300 mm), and a granular detergent composition with
15 4% moisture content was obtained.
[0073]
(Examples 28 to 30)
The granular detergent composition having the composition shown in Table 4
was prepared using the following preparation method B. In the tables, "balance" of
20 sodium sulfate indicates an amount at which the total amount of the granular detergent
composition becomes 100%.
[0074]

A slurry of 38% moisture was prepared in which LAS-Na or AS-Na, the (C)
25 component, the (D) component, sodium sulfate, the fluorescent brightening agent (CBS,
39
AMS), the (B) component, part of the powder A-type zeolite (the amount excluding the
sum of the amount introduced to Loedige mixer and the amount introduced to V-blender
described later (the amount equivalent to 2.4%» were dissolved or dispersed in water,
and this slurry was spray-dried under the conditions of hot air temperature of 300°C in a
5 countercurrent-type spray-drying tower, resulting in spray-dried particles.
The spray-dried particles obtained were introduced (filling factor 50% by
volume) to a Loedige Mixer (manufactured by MATSDBO Corporation, M20 type) in
which a plow blade-shaped shovel is provided, and the clearance between the wall-shovel
is 5 mm, and were stirred at a spindle speed of 200 rpm and a chopper speed of 200 rpm.
10 The nonionic surfactant (AE and an adduct of alcohol EO/PO) was introduced thereto
over 2 minutes, the mixture was stirred for 5 minutes, part of the powder A-type zeolite
(the amount equivalent to 0.8% in terms of pure component) was introduced, the mixture
was stirred for 2 minutes, and particles containing surfactant were obtained.
The particles containing surfactant obtained, part of the powder A-type zeolite
15 (the amount equivalent to 1.6% in terms of pure component), the enzyme, the MES
particles for detergents were mixed in a V-blender, and sprayed with the aromatic. In
addition, in order to color a part of the particles containing surfactant, the particles
containing surfactant were sprayed with 20% aqueous dispersion liquid of the pigment in
the same manner as the preparation method A, and a granular detergent composition with
20 7% moisture content was obtained.
[0075]
(Examples 31 to 47, Comparative Example 2)
The granular detergent composition having the composition shown in Tables 4
to 7 was prepared using the following preparation method C. In the tables, "balance" of
25 sodium sulfate indicates an amount at which the total amount of the granular detergent
40
composition becomes 100%.
[0076]

Water was added in a jacketed mixing tank equipped with a stirring device, and
5 the temperature was adjusted to 50°C. Sodium sulfate, the fluorescent brightening
agent (CBS, AMS) was added thereto and the mixture was stirred for 10 minutes.
Subsequently, after the anionic surfactant (LAS-Na (which neutralized LAS-H with
NaOH), AS-Na or soap), the (C) component and the (D) component were added, the
mixture was stirred for 10 minutes, and part of the powder A-type zeolite (the amount
10 excluding the amount introduced to V-blender described later (the amount equivalent to
1.6%» was added. Slurry for spray-drying was prepared after stirring for additional 30
minutes. The temperature of the slurry for spray-drying obtained was 50°C. This
slurry was spray-dried using countercurrent-type spray drying apparatus equipped with a
pressure spray nozzle, and spray-dried particles were obtained.
15 The spray-dried particles obtained, part of the powder A-type zeolite (the
amount equivalent to 1.6% in terms of pure component), the enzyme (protease, amylase,
lipase, cellulase, glucosidase) were mixed using a V-blender. In addition, after the MES
particles for detergents were added, the aromatic, the nonionic surfactant (AE and an
adduct of alcohol EO/PO) and the (B) component were sprayed, and particles containing
20 surfactant were obtained. In order to color a part of the particles containing surfactant,
the particles containing surfactant were sprayed with 20% aqueous dispersion liquid of
the pigment in the same manner as the preparation method A, and a granular detergent
composition with 6% moisture content was obtained.
[0077]
(Adjustment of Particle Diameter)
41
For the granular detergent composition obtained, the particle diameter was
adjusted by the following procedures.
A sieve A (mesh: 1,400 /-lm), a sieve B (mesh: 710 /-lm), a sieve C (mesh: 45 /-lm),
and a saucer D of inner diameters of20 cm were prepared (all manufactured by Tokyo
5 Screen Co., Ltd.). The sieve was set such that the sieve C, the sieve B, the sieve A were
placed in this order on top of the saucer D. 100 g of the granular detergent composition
was placed on the sieve A by a single sieving operation. An operation of bumping the
sieve was carried out in accordance with JIS K3362 putting the top cover. The
operation of bumping the sieve was carried out such that, while tilting and holding the
10 sieve with one hand, bumping the edge of the sieve 150 times using the other hand so
that the granular detergent composition is spread evenly on the surface of the net. The
sieve was rotated approximately 1/6 for every 25th bumping.
Only the granular detergent composition remaining on the sieve B (particles
with particle diameters of greater than 710 /-lm and less than or equal to 1,400 /-lm) and
15 the granular detergent composition remaining on the sieve C (particle diameters of
greater than 45 /-lm and less than or equal to 710 /-lm) were mixed to be the ratio of the
particle of greater than 710 /-lm and less than or equal to 1,400 /-lm and the ratio of the
particle of greater than 45 /-lm and less than or equal to 710 /-lm in the table and was made
to be the granular detergent composition in each example.
20 [0078]
(Evaluation Method)

1 L of water in which adjustment of hardness was finished and the water
temperature was 25°C was placed in a washing tub (inner diameter 30 cm~, depth 10 cm).
42
The hardness of water was adjusted by 10000DH hard water being prepared by
dissolving 262.5 g of calcium chloride dihydrate in 10 L of ion-exchanged water, and
subsequently by dissolving in ion-exchanged water to make it 15°DH hard water
(1 °DH=10 mg (calcium oxide)/L (water)). One sheet (approximately 150 g) in which
5 dirty oil stain of the following composition was impregnated at 0.2% by mass with
regard to a cotton shirt was placed, and subsequently hand-washing was carried out for 1
minute sprinkling 1 g of the granular detergent composition of each example to the
cotton shirt, and then a sense of scrub was evaluated. The sense of scrub was evaluated
by 10 panelists using the following determination criteria and evaluation was carried out
10 by the average score obtained being classified by the following evaluation criteria.
[0079]
15
«Composition of Dirty Oil Stain»
Oleic acid: 45%
Triolein: 25%
Cholesterol oleate: 19.5%
Liquid paraffin: 4%
Squalene: 4%
Cholesterol: 2.5%
[0080]
20 «Determination Criteria»
3 points: there was a sense of scrub
2 points: there was a slight sense of scrub
1 point: there was no feeling of a sense of scrub
[0081 ]
25 «Evaluation Criteria»
43
© (pass): an average score is 2.5 points or more
o (pass): an average score is greater than or equal to 2.0 and less than 2.5 points
X (failure): an average score is less than 2.0 points
[0082]
5
A two-tub washing machine (CW-C30AI-I, manufactured by Mitsubishi
Electric Corporation) was filled with 30 L of water with a water temperature of 20°C and
a hardness of 15°DH, and 50 g of the granular detergent composition of each example
was added thereto, and the mixture was stirred for 30 seconds with standard water flow.
10 Next, 7 sheets (approximately I kg) in which the dirty oil stain was impregnated at 0.2%
by mass with regard to a black shirt were placed as test cloth and washed for 5 minutes
\vith soft water flow. After washing, dewatering was carried out, and the test cloth was
rinsed for 3 minutes using 30 L water with a water temperature of 20°C and a hardness of
15°DH. A rinsing operation was performed twice in total. The total number of the
15 particles adhered to the dewatered black shirt after the second rinsing, and evaluation was
carried out according to the following evaluation criteria.
[0083]
«Evaluation Criteria»
20
© (pass): No particles were adhered to the cotton shirt.
o (pass): Greater than or equal to I and less than 5 particles were adhered to the
cotton shirt.
~ (pass): Greater than or equal to 5 and less than 15 particles were adhered to
the cotton shirt.
X (failure): Greater than or equal to 15 particles were adhered to the cotton shirt.
5
44
[0084]

Detergency was evaluated by a washing ratio obtained using the following
method.
As the contaminated cloth, a commercially available contaminated cloth cut into
5X5 cm (WFK-IOD, manufactured by Washerei Forschungs Institute) was used. As a
washing tester, Terg-O-tometer (manufactured by UNITED STATES TESTING, Co.,
Inc.) was used.
900 mL of water with a water temperature of 25°C and a hardness of 15°DH,
10 and 2.7 g of the granular detergent composition of each example were placed in the
washing tester, and 10 sheets of the above contaminated cloth and a washed knitted cloth
were placed, and washed for 10 minutes at 120 rpm and 25°C with a bath ratio being set
at 30 times. After that, they were transferred to a two-tub washing machine (Model:
CW-C30AI-Hl, manufactured by Mitsubishi Electric Corporation), and after dewatered
15 for 1 minute, they were rinsed for 3 minutes in 30 L of water with a water temperature of
25°C and a hardness of 15°DH, and air-dried.
For the unwashed contaminated cloth and the contaminated cloth after washing,
each reflectivity was measured using a color difference meter manufactured by Nippon
Denshoku Industries Co, Ltd. (product name: SE200 type), and the washing ratio was
20 calculated using following Equation (2).
Washing ratio (%)=[(K1S of contaminated cloth before washing-K1S of contaminated
cloth after washing)/(K1S of contaminated cloth before washing- K1S of cloth which is
not dirty)]XI00 (2)
[In the equation, and K1S=(l-Ril 00i/(2R11 00), and R is reflectivity (%)]
Washing ratio (%) was determined for 10 sheets of the contaminated cloth, and
45
the average value of the washing ratio of the 10 sheets of the contaminated cloth was
calculated. The detergent composition with the average value of 65% or more was
considered as pass.
[0085]

3 g of the granular detergent composition of each example was dissolved in I L
of water with a water temperature of 25°C and a hardness of 15°DH and the solution was
prepared. 20 mL of the solution prepared and 5 ilL of dirty oil stain were introduced to
a cylindrical tube made of glass with an inner diameter of 3 cm and a height of 25 em.
10 Subsequently, while maintaining a temperature at 25°C, the resultant was shaken for I
minute with a shaker, and the height (mm) of the foam after 5 minutes from the shaking
being stopped was measured.
The detergent compositions with a height of the foam being 20 mm or more
after 5 minutes from the shaking being stopped was considered as pass.
15 [0086]

A two-tub washing machine (CW-C30AI-I, manufactured by Mitsubishi
Electric Corporation) was filled with 30 L of water with a water temperature of 25°C and
a hardness of 15°DH, and 50 g of the granular detergent composition of each example
20 was added thereto, and the mixture was stirred for 30 seconds with standard water flow.
Next 7 sheets (approximately 1 kg) in which the dirty oil stain was impregnated at 0.2%
by mass with regard to a cotton shirt were placed as test cloth and washed for 10 minutes
with standard water flow. After washing, dewatering was carried out, and the test cloth
was rinsed for 3 minutes using 30 L water with a water temperature of 25°C and a
46
hardness of 15°DH. A rinsing operation was performed twice in total. The state of the
rinsing liquid after the second rinsing was evaluated according to the following
e\aluation criteria.
[0087]
:; «Evaluation Criteria»
CD (pass): The size of the foam was 1 mm or less, and the foam was less than 10% of the
liquid surface.
o (pass): The size of the foam was 1 mm or less, and the foam occupied greater than or
equal to 10% and less than 50% of the liquid surface.
10 ~ (pass): The size of the foam was 1 mm or less, and the foam occupied 50% or more of
the liquid surface.
X (failure): The foam occupied 50% or more of the liquid surface, and there were foam
of approximately 2 to 3 mm.
[0088]
15 For the granular detergent composition of each example, evaluation of the sense
of scrub, evaluation of the residual amount of the dissolved particles, washing ratio
measurement, evaluation of the foam persistence, and evaluation of the rinsing property
were performed, and the results are shown in the tables.
[0089]
[Table 1]
47
e
Example
1 2 3 4 5 6 7 8
MES Particles for Detergent 23.09 5.77 11.55 34.64 46.19 23.09 23.09 23.09
Breakdown
(A) Component: MES 20.00 5.00 10.00 30.00 40.00 20.00 20.00 20.00
Zeolite 0.92 0.23 0.46 1.39 1.85 0.92 0.92 0.92
(A') Component C12 Soap - - - - - - - -
C8 Higher Alcohol - - - - - - - -
C10 Higher Alcohol - - - - - 0.4 - -
C12 Higher Alcohol - - - - - - 0.4 -
(B) Component
C13 Higher Alcohol - - - - - - - 0.4
C12/14 Higher Alcohol 0.4 0.4 0.4 0.4 0.4 - - -
C14 Higher Alcohol - - - - - - - -
Composition C16 Higher Alcohol - - - - - - - - (% by Mass)
C18 Higher Alcohol - - - - - - - -
(C) Component
STPP 10 10 10 10 10 10 10 10
TSPP - - - - - - - -
(D) Component
Sodium Carbonate 10 10 10 10 10 10 10 10
Sodium Silicate - - - - - - - -
LAS-Na - - - - - - - -
(E) Component
AS-Na - - - - - - - -
Zeolite* 7 7 7 7 7 7 7 7
Others
AE 1 1 1 1 1 1 1 1
e
48
---
Alcohol EO/PO Adduct 1 1 1 I I 1 1 1
Fluorescent Brightening - - - - - - - -
Agent CBS
Fluorescent Brightening
Agent - - - - - - - -
AMS
Enzyme 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Aromatic 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Pigment 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Moisture 4 4 4 4 4 4 4 4
Sodium Sulfate Balance
Sum 100 100 100 100 100 100 100 100
Ratio of the particle of greater than 710 /lm and less than or
25 25 25 25 25 25 25 25
equal to 1,400 ~m (% by Mass)
Ratio of the particle of greater than 45 /lm and less than or
75 75 75 75 75 75 75 75
equal to 710 /lm (% by Mass)
(A) Component/(B) Component (Mass Ratio) 50 12.5 25 75 100 50 50 50
Preparation Method A A A A A A A A
Sense of Scrub © 0 © © © © © ©
Residual Amount of Dissolved Particles 0 © 0 ~ ~ 0 0 0
Evaluation Washing Ratio (%) 73 65 68 75 76 72 73 73
Results Foam Persistence
43 21 32 46 49 22 38 25
(Foam Height after 5 Minutes (mm))
Rinsing Property 0 © 0 ~ ~ 0 0 0
*Blended amount of Zeolite in Others section represents the total amount of Zeolite in MES particles for detergents and Zeolite separately
added (hereinafter the same).
~1'1l,'mIl!'!>'''''''!i'!!!!I!III!l •••••••••••••••••••••• _
[0090]
[Table 2]
49
e
Example
9 10 11 12 13 14 15 16
MES Particles for Detergent 23.09 23.09 23.09 23.09 23.09 23.09 23.09 23.09
Breakdown
(A) Component: MES 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00
Zeolite 0.92 0.92 0.92 0.92 0.92 0.92 0.92 0.92
(A') Component C12 Soap - - - - - - - -
C8 Higher Alcohol - - - - - - - -
C10 Higher Alcohol - - - - - - - -
C12 Higher Alcohol 0.2 0.3 - - 0.2 0.35 - -
(B) Component
C13 Higher Alcohol 0.2 0.1 - - - - - -
C12/14 Higher Alcohol - - - - - - 0.1 0.2
Composition C14 Higher Alcohol - - 0.4 - 0.2 0.05 - -
(% by Mass) C16 Higher Alcohol - - - 0.4 - - - -
C18 Higher Alcohol - - - - - - - -
(C) Component
STPP 10 10 10 10 10 10 10 10
TSPP - - - - - - - -
(D) Component
Sodium Carbonate 10 10 10 10 10 10 10 10
Sodium Silicate - - - - - - - -
LAS-Na - - - - - - - -
(E) Component
AS-Na - - - - - - - -
Others
Zeolite* 7 7 7 7 7 7 7 7
AE 1 1 1 1 1 1 1 1
50
~ -~_.
Alcohol EO/PO Adduct 1 1 1 1 1 1 1 1
Fluorescent Brightening - - - Agent CBS - - - - -
Fluorescent Brightening
Agent - - - - - - - -
AMS
Enzyme 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Aromatic 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Pigment 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Moisture 4 4 4 4 4 4 4 4
Sodium Sulfate Balance
Sum 100 100 100 100 100 100 100 100
Ratio of the particle of greater than 710 /.lm and less than or
25 25 25 25 25 25 25 25
equal to 1,400 /.lm (% by Mass)
Ratio of the particle of greater than 45 /.lm and less than or
75 75 75 75 75 75 75 75
equal to 710 /.lm (% by Mass)
(A) Component/(B) Component (Mass Ratio) 50 50 50 50 50 50 200 100
Preparation Method A A A A A A A A
Sense of Scrub © 0 © © © © © ©
Residual Amount of Dissolved Particles 0 0 0 0 0 0 0 0
Evaluation Washing Ratio (%) 73 72 73 72 73 72 73 73
Results Foam Persistence
28 32 31 21 40 41 23 39
(Foam Height after 5 Minutes (mm))
Rinsing Property 0 0 0 0 0 0 0 0
tit
[0091 ]
[Table 3]
51
e
Example
17 18 19 20 21 22 23 24
MES Particles for Detergent 23.09 23.09 23.09 23.09 23.09 23.09 23.09 23.09
Breakdown
(A) Component: MES 20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00
Zeolite 0.92 0.92 0.92 0.92 0.92 0.92 0.92 0.92
(A') Component C12 Soap - - - - - - - -
C8 Higher Alcohol - - - - - - - -
C10 Higher Alcohol - - - - - - - -
C12 Higher Alcohol - - - - - - - -
Composition C13 Higher Alcohol - - - - - - - -
(% by (B) Component
C12/14 Higher Alcohol 0.7 1.0 1.5 0.4 0.4 0.4 0.4 0.4
Mass)
C14 Higher Alcohol - - - - - - - -
C16 Higher Alcohol - - - - - - - -
C18 Higher Alcohol - - - - - - - -
(C) Component
STPP 10 10 10 - 5 3 10 10
TSPP - - - 10 5 - - -
(D) Component
Sodium Carbonate 10 10 10 10 10 10 - 5
Sodium Silicate - - - - - - 10 5
LAS-Na - - - - - - - -
(E) Component
AS-Na - - - - - - - -
Zeolite* 7 7 7 7 7 7 7 7
Others
AE 1 1 1 1 1 1 1 1
SI
I ~-
Alcohol EO/PO Adduct I I I I I I I I
Fluorescent Brightening - - - - - - - -
Agent CBS
Fluorescent Brightening
Agent - - - - - - - -
AMS
Enzyme 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Aromatic 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Pigment 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Moisture 4 4 4 4 4 4 4 4
Sodium Sulfate Balance
Sum 100 100 100 100 100 100 100 100
Ratio of the particle of greater than 710 !J.m and less than or
25 25 25 25 25 25 25 25
equal to 1,400 !J.m (% by Mass)
Ratio of the particle of greater than 45 !J.m and less than or
75 75 75 75 75 75 75 75
equal to 710 !J.m (% by Mass)
(A) Component/(B) Component (Mass Ratio) 28.6 20 13.3 50 50 50 50 50
Preparation Method A A A A A A A A
Sense of Scrub © © 0 © © © © ©
Residual Amount of Dissolved Particles 0 0 0 0 0 0 0 0
Evaluation Washing Ratio (%) 72 72 71 71 72 70 73 72
Results Foam Persistence
42 44 45 43 44 43 41 43
(Foam Height after 5 Minutes (mm))
Rinsing Property 0 0 ~ 0 0 0 0 0
•
[0092]
[Table 4]
53
•
Example
25 26 27 28 29 30 31 32
MES Particles for Detergent 23.09 23.09 23.09 34.64 23.09 23.09 17.32 11.55
Breakdown
(A) Component: MES 20.00 20.00 20.00 30.00 20.00 20.00 15.00 10.00
Zeolite 0.92 0.92 0.92 1.39 0.92 0.92 0.69 0.46
(A') Component C12 Soap - - - - - - - -
C8 Higher Alcohol - - - - - - - -
C10 Higher Alcohol - - - - - - - -
C12 Higher Alcohol - - - - - - - -
C13 Higher Alcohol - - - - - - - - (B) Components
C12/14 Higher Alcohol 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4
C14 Higher Alcohol - - - - - - - -
Composition C16 Higher Alcohol - - - - - - - -
(% by Mass)
C18 Higher Alcohol - - - - - - - -
(C) Component
STPP 10 10 10 10 10 10 10 10
TSPP - - - - - - - -
(D) Component
Sodium Carbonate 5 10 10 10 10 10 10 10
Sodium Silicate - - - - - - - -
LAS-Na - - - - 10 - - -
(E) Component
AS-Na - - - 10 - 10 5 10
Zeolite* 7 7 7 7 7 7 7 7
Others
AE 1 1 1 1 1 1 1 1
54
Alcohol EO/PO Adduct 1 I 1 1 1 I 1 1
Fluorescent
Brightening Agent - - - 0.1 0.1 0.1 0.1 0.1
CBS
Fluorescent
Brightening Agent - - - 0.1 0.1 0.1 0.1 0.1
AMS
Enzyme 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Aromatic 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Pigment 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Moisture 4 4 4 7 7 7 6 6
Sodium Sulfate Balance
Sum 100 100 100 100 100 100 100 100
Ratio of the particle of greater than 71 0 ~m and less than or
25 10 50 25 25 25 25 25
equal to 1,400 f.lm (% by Mass)
Ratio of the particle of greater than 45 ~lm and less than or
75 90 50 75 75 75 75 75
equal to 71 0 ~m (% by Mass)
(A) Component/(B) Component (Mass Ratio) 50 50 50 75 50 50 37.5 25
Preparation Method A A A B B B C C
Sense of Scrub © 0 © © © © © ©
Residual AmPaorutinctleosf Dissolved 0 © ~ ~ 0 0 © ©
Evaluation Results Washing Ratio (%) 70 73 72 79 76 75 73 71
Foam Persistence
47 40 40 61 55 58 51 53
(Foam Height after 5 Minutes (mm))
Rinsing Property 0 © ~ ~ 0 0 © ©
•
[0093]
[Table 5]
55 •
Example
33 34 35 36 37 38 39 40
MES Particles for Detergent 8.08 8.08 8.08 8.08 8.08 5.77 3.46 5.77
Breakdown
(A) Component: MES 7.00 7.00 7.00 7.00 7.00 5.00 3.00 5.00
Zeolite 0.32 0.32 0.32 0.32 0.32 0.23 0.14 0.23
(A') Component C12 Soap - - - - - - - -
C8 Higher Alcohol - - - - - - - -
CI0 Higher Alcohol - - - - - - - -
C12 Higher Alcohol - - - - - - - -
C13 Higher Alcohol - - - - - - - - (B) Component
C12/14 Higher Alcohol 0.3 0.3 0.3 0.3 0.3 0.4 0.1 0.4
C14 Higher Alcohol - - - - - - - -
Composition C16 Higher Alcohol - - - - - - - - (% by Mass)
C18 Higher Alcohol - - - - - - - -
(C) Component
STPP 30 - 10 10 10 10 10 10
TSPP - 20 - - - - - -
(D) Component
Sodium Carbonate 10 10 40 - 10 10 10 10
Sodium Silicate - - - 20 - - - -
LAS-Na 13 13 13 13 13 15 17 17
(E) Component
AS-Na - - - - - - - -
Zeolite* 7 7 7 7 7 7 7 7
Others
AE 1 1 1 1 1 1 1 1
56
Alcohol EO/PO Adduct 1 1 1 I 1 1 1 1
Fluorescent Brightening
0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Agent CBS
Fluorescent Brightening
Agent 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
AMS
Enzyme 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Aromatic 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Pigment 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Moisture 6 6 6 6 6 6 6 6
Sodium Sulfate Balance
Sum 100 100 100 100 100 100 100 100
Ratio of the particle of greater than 710 !-lm and less than or
25 25 25 25 25 25 25 25
equal to 1,400 /lm (% by Mass)
Ratio of the particle of greater than 45 !-lm and less than or
75 75 75 75 75 75 75 75
equal to 710 !-lm (% by Mass)
(A) Component/(B) Component (Mass Ratio) 23.3 23.3 23.3 23.3 23.3 12.5 30 12.5
Preparation Method C C C C C C C C
Sense of Scrub 0 0 0 0 0 0 0 0
Residual Amount of Dissolved Particles © © © © © © © ©
Evaluation Washing Ratio (%) 77 75 76 75 72 70 70 71
Results Foam Persistence
54 56 54 55 53 51 49 52
(Foam Height after 5 Minutes (mm))
Rinsing Property © © © © © © © ©
•
[0094]
[Table 6]
57
•
Example
41 42 43 44 45 46 47
MES Particles for Detergent 5.77 5.77 5.77 5.77 5.77 5.77 5.77
Breakdown
(A) Component :MES 5.00 5.00 5.00 5.00 5.00 5.00 5.00
Zeolite 0.23 0.23 0.23 0.23 0.23 0.23 0.23
(A')
C12 Soap - - - - - - Component
-
C8 Higher Alcohol - - - - - - -
CI0 Higher Alcohol - - - - - - -
C12 Higher Alcohol - - - - - - -
(B) C13 Higher Alcohol - - - - - - -
Component C12114 Higher Alcohol 0.4 0.4 0.3 0.2 0.1 0.35 0.4
C14 Higher Alcohol - - - - - - -
Composition C16 Higher Alcohol - - - - - 0.05 - (% by Mass)
C18 Higher Alcohol - - - - - - -
(C) STPP 10 10 10 10 10 10 9
Component TSPP - - - - - - -
(D) Sodium Carbonate 10 10 10 10 10 10 10
Component Sodium Silicate - - - - - - -
(E) LAS-Na 20 10 15 15 15 15 15
Component AS-Na - - - - - - -
Zeolite* 7 7 7 7 7 7 9
Others AE 1 1 1 1 1 1 1
Alcohol EO/PO Adduct 1 1 1 1 1 1 1
58 •
Fluorescent Brightening Agent CBS 0.1 ().1 0.1 () .1 0.1 0.1 0.1
Fluorescent Brightening Agent
0.1 0.1 0.1 0.1 0.1 0.1 0.1
AMS
Enzyme 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Aromatic 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Pigment 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Moisture 6 6 6 6 6 6 6
Sodium Sulfate Balance
Sum 100 100 100 100 100 100 100
Ratio of the particle of greater than 710 ~m and less than or equal to 1,400
25 25 25 25 25 25 25
~m (% by Mass)
Ratio of the particle of greater than 45 ~m and less than or equal to 71a~m
75 75 75 75 75 75 75
(% by Mass)
(A) Component/(B) Component (Mass Ratio) 12.5 12.5 16.7 25 50 12.5 12.5
Preparation Method C C C C C C C
Sense of Scrub 0 0 0 0 0 0 0
Residual Amount of Dissolved Particles © © © © © © ©
Washing Ratio (%) 74 69 70 70 70 70 70
Evaluation Results
Foam Persistence
(Foam Height after 5 Minutes (mm))
55 45 49 47 45 50 51
Rinsing Property © © © © © © ©
[0095]
[Table 7]
59 -
Comparative Example
1 2 3 4 5 6 7
MES Particles for Detergent - - 23.09 23.09 23.09 23.09 23.09
(A) Component :MES - - 20.00 20.00 20.00 20.00 20.00
Breakdown
Zeolite - - 0.92 0.92 0.92 0.92 0.92
(A')
C12 Soap - 20 - - - - -
Component
C8 Higher Alcohol - - - - - 0.5 -
C10 Higher Alcohol - - - - - - -
C12 Higher Alcohol - - - - - - - --
(B) C13 Higher Alcohol - - - - - - -
Component C12/14 Higher Alcohol 0.4 0.4 - 0.04 2.5 - -
C14 Higher Alcohol - - - - - - -
Composition C16 Higher Alcohol - - - - - - -
(% by Mass) C18 Higher Alcohol - - - - - - 0.5
(C) STPP 10 10 10 10 10 10 10
Component TSPP - - - - - - -
(D) Sodium Carbonate 10 10 10 10 10 10 10
Component Sodium Silicate - - - - - - -
(E) LAS-Na - - - - - - -
Component AS-Na - - - - - - -
Zeolite* 7 7 7 7 7 7 7
Others AE 1 1 1 1 1 1 1
Alcohol EO/PO Adduct 1 1 1 1 1 1 1
60 -
Fluorescent Brightening Agent CBS - 0.1 - - - - -
Fluorescent Brightening Agent
- 0.1 - - - - - AMS
Enzyme 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Aromatic 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Pigment 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Moisture 2 6 4 4 4 4 4
Sodium Sulfate Balance
Sum 100 100 100 100 100 100 100
Ratio of the particle of greater than 71 0 ~m and less than or equal to 1,400
25 25 25 25 25 25 25
~m (% by Mass)
Ratio of the particle of greater than 45 ~m and less than or equal to 71 0 ~m
75 75 75 75 75 75 75
(% by Mass)
(A) Component/(B) Component (Mass Ratio) - - - 500 8 40 40
Preparation Method A C A A A A A
Sense of Scrub X © © © 0 © ©
Residual Amount of Dissolved Particles © ~ 0 0 © 0 0
Washing Ratio (%) 50 60 73 73 67 73 73
Evaluation Results
Foam Persistence
(Foam Height after 5 Minutes (mm))
0 10 13 14 36 15 13
Rinsing Property © © 0 0 X 0 0
[0096J
[Table 8]
61
e
Comparative Example
8 9 10 11
MES Particles for Detergent 23.09 23.09 23.09 23.09
Breakdown
(A) Component: MES 20.00 20.00 20.00 20.00
Zeolite 0.92 0.92 0.92 0.92
(A') Component C12 Soap - - - -
C8 Higher Alcohol - - - -
C10 Higher Alcohol - - - -
C12 Higher Alcohol - - - -
C13 Higher Alcohol - - - - (B) Component
C12/14 Higher Alcohol 0.4 0.4 0.4 0.4
C14 Higher Alcohol - - - -
C16 Higher Alcohol - - - -
Composition C18 Higher Alcohol - - - -
(% by Mass)
STPP - 20 10 10
(C) Component
TSPP - - - -
Sodium Carbonate 20 - 10 10
(D) Component
Sodium Silicate - - - -
LAS-Na - - - -
(E) Component
AS-Na - - - -
Zeolite* 7 7 7 7
Others
AE 1 1 1 1
Alcohol EO/PO Adduct 1 1 1 1
Fluorescent Brightening Agent CBS - - - -
62
e
Fluorescent Brightening Agent - - - -
AMS
Enzyme 1.5 1.5 1.5 1.5
Aromatic 0.1 0.1 0.1 0.1
Pigment 0.01 0.01 0.01 0.01
Moisture 4 4 4 4
Sodium Sulfate Balance
Sum 100 100 100 100
Ratio of the particle of greater than 710 11m and less than or equal to 1,400 11m (% by Mass) 25 25 4 60
Ratio of the particle of greater than 45 11m and less than or equal to 710 J.lm (% by Mass) 75 75 96 40
(A) Component/(B) Component (Mass Ratio) 50 50 50 50
Preparation Method A A A A
Sense of Scrub © © X ©
Residual Amount of Dissolved Particles 0 0 0 X
Evaluation Results
Washing Ratio (%) 62 64 74 72
Foam Persistence
(Foam Height after 5 Minutes (mm))
28 51 31 25
Rinsing Property 0 0 © X
63
[0097]
As shown in Tables 1 to 6, in the granular detergent composition of Examples 1
to 47 in which the present invention is applied, all the results of the evaluation of the
sense of scrub. the evaluation of the residual amount of the dissolved particles, the
5 washing ratio measurement, the evaluation of the foam persistence, and the evaluation of
the rinsing property were favorable. In particular, in Examples 28 to 47 in which the
(E) component was included, the foam persistent was 45 or more, and the foam persistent
\vas excellent.
On the other hand, in Comparative Examples 1 and 2 in which the (A)
10 component was not included, the washing ratio was 60% or less, and detergency was
inferior when compared to those of Examples 1 to 47. In Comparative Example 3 in
which the (B) component was not included, Comparative Example 4 in which the content
of the (B) component was 0.04% by mass, Comparative Examples 6 to 7 in which the
number of carbon atoms of the higher alcohol was outside the scope of the present
15 invention, the foam persistent was low. In Comparative Example 5 in which the content
of the (B) component was 2.5% by mass, the rinsing property was "X" and the odor of
the alcohol was significant.
In Comparative Examples 8 to 9 in which the (C) component and the (0)
component were not included, the washing ratio was less than 65%. In Comparative
20 Example 10 in which the ratio of the specific particles was less than 10% by mass, the
evaluation of the sense of scrub was "X", and in Comparative Example 11 in which the
ratio of the specific particles was greater than 50% by mass, the evaluation of the residual
amount of the dissolved particles and the evaluation of the rinsing property were both
25 From the above results, in the granular detergent composition in which the
64
present invention was applied is particularly suitable for hand-washing since excellent
detergency and foam persistence are exhibited even when washing is carried out using
water of high hardness, rinsing property is favorable, and a favorable washing feeling
may be obtained.
5 Industrial Applicability
[0098]
According to the granular detergent composition of the present invention,
excellent detergency and foam persistence are exhibited even when washing is carried
out using water of high hardness, rinsing property is favorable, and a favorable washing
10 feeling may be obtained.

CLAIMS
1. A granular detergent composition comprising following (A) to (D)
components:
wherein particles with particle diameters of greater than 710 /lm and less than or
equal to 1,400 /lm are included in an amount of 10 to 50% by mass. (A) component: an
a-sulfo fatty acid alkyl ester salt represented by following Formula (I),
RI-CH(S03M)-COOR2 (I)
(In Formula (I), R1 is an alkyl group or alkenyl group having 8 to 18 carbon atoms, R2 is
lOan alkyl group, and M represents a counter-ion),
(B) component: a higher alcohol having 10 to 16 carbon atoms included in an
15
20
amount of greater than or equal to 0.1% by mass and less than 2% by mass with regard to
the total mass of the granular detergent composition,
(C) component: a phosphorus-based builder, and
(D) component: an alkaline builder.
2. The granular detergent composition according to Claim 1,
wherein a mass ratio represented by [the content of the (A) component]/[the
content of the (B) component] is preferably 20 to IOO.
3. The granular detergent composition according to Claim 1 or 2, further
comprising a following (E) component:
(E) component: at least one anionic surfactant selected from a linear
alkylbenzene sulfonate, an alkyl sulfate, an alkenyl sulfate, an a-olefin sulfonate, an alkyl
25 ether sulfate, and an alkenyl ether sulfate.
66
4. The granular detergent composition according to anyone of Claims 1 to 3,
wherein the granular detergent composition is for hand-washing.