Note: Descriptions are shown in the official language in which they were submitted.
~ZV2854
001
Bleaching Detergent Composition
The present invention relates to a bleaching
detergent having an e~cellent storage stability.
More particularly, the present invention relates to
a bleaching detergent contalning sodium percarbonate
having the surface coated with a borate-containing
coating agent.
Sodium percarbonate has been known as a bleach-
ing agent or oxidizing agent. Like sodiurn perborate,
sodium percarbonate is a typical oxygen-containing
bleaching agent. Generally, sodium percarbonate is
produced by reacting sodium carbonate with hy~rogen
peroxide and is represented by the formula:
2Na2C3'3H22
Sodium percarbonate has a bleaching power
slightly lower than that of chlorine-cont~i n ing
bleaching agents at ambient temperature. However,
it has advantages that it does not yellow synthetic
fibers, animal fibers, resin-treated fibers or fibers
I~V;~8S4
002
treated with fluorescent brightening agents and it
does not damage the fibers. Further, it exhibits
sufficient bleaching effects at an elevated temper-
ature or in the presence o~ a decomposition accel-
erator. Therefore, sodium percarbonate has been
used as a domestic or commercial bleaching agent.
Reasons why sodium percarbonate has attracted
attention in the fieLd of general detergents and
domestic bleaching agents are that its decomposition
products ~o no-t cause environmental pollution and
that it can be used practically in any manner with-
out posing an~ problem.
However, sodium percarbonate has a ~ defect
that its storage stability is far inferior to that
of sodium perborate and available oxygen is lost
rapidly during the storage. The surface of sodium
percarbonate becomes wet and is decomposed in the
presence of even a very low moisture, since it has
a high affinity with water. Particularly when iron,
copper, manganese or cobalt lon is contained therein,
the decomposition is further accelerated and the
stability thereof is lower than that of sodium
perborate. When sodium percarbonate is stored alone
in a closed vessel, its storage stability is equal
to that of sodium perborate. However, when sodium
0285
00~
percarbonate is stored in the form of a mixture
with a detergent or in an open vessel, it exhibits
a high hygroscopicity and low storage stability,
though it has a high solubility.
Sodium tripolyphosphate (STPP) contained as a
builder in detergents invites eutrophication to
cause environmental pollution in a closed water
area. Under these circumstances, the demand of
low-phosphorus or phosphorus-free detergents has
been increased. In the production of the low-
phosphorus or phosphorus-free detergents, synthetic
zeolites ~aluminosilicates) have become into wide
use recently as a substitute for STPP.
~ owever, sodium percarbonate is quite unstable
in the zeolite-containing detergent. In the
zeolite-containing, phosphorus-free detergent,
available oxygen of sodium percarbonate is lost
rapidly by the catalytic decomposition due to the
zeolite.
Therefore, it has eagerly been demanded to
develop a technique capable of reducing the phos-
phorus content of the detergent or dispensing with
STPP and attaining a high storage stability of
sodium percarbonate contained therein.
There have been proposed processes for
X~{?Z8S4
004
stabilizing sodium percarbonate such as one wherein
sodium percarbona-te is coated with paraffin or one
wherein it is coated with polyethylene glycol having
a molecular weight of 3000 to ~000. However, in
the former process, the water solubility i5 reduced
seriously and impractically. In the latter process,
the long-term storage stability cannot be obtained,
since polyethylene glycol per se has a considerable
hygroscopicity, though the water solubility is not
deteriorated.
Another process has been proposed wherein at
least two stabilizers selected from the group con-
sisting oE phosphoric acid compounds, silicic acid
compounds, ethylenediaminetetraacetates and nitrilo-
triacetates are incorporated in an aqueous hydrogen
peroxide solution in the production of sodium per-
carbonate. However, these stabilizers do not exhibit
any practical stabilization effect when they are
mixed with water or detergents, though they exhibit
a stabilizing effect against te~lperature. In still
another process, sodium percarbonate is uniformly
coated with sodium pyrophosphate. However, this
process is not satisfactory with respect to the
stabilizing effect in the presence of water and
detergents, though the thermal decomposition rate
t3S4
is low.
An object of the present invention is to provide a
bleaching detergent containing sodium percarbonate which can be
stored s-tably until use even when sodium percarbonate is
incorporated into a low-phosphorus or phosphorus-free detergent.
According to the present invention there is provided a
bleaching detergent composition which comprises 1 to 99 percent
by weight of sodium percarbonate coated on the surface with a
borate-containing coating agent.
The invention provides a new composition suitable for
a bleaching detergent and a bleaching agent. The composition is
characterized by containing therein 1 to 99 percent by weight
of sodium percarbonate coated on the surface with a borate-
containing coating agent. The bleaching detergent composition
preferably comprises 1 to 40 percent by weight of said coated
sodium percarbonate. The bleaching composition preferably
comprises 40 to 99 percent b~ weight of said coated sodium
percarbonate.
The inver.-tion will be further described with reference
to the accompanying drawings in which:
~Z~IZ8S4
Figure 1 is a scanning electron microscope photograph
of uncoated sodium percarbonate particles, and Figure 2 is a
scanning electron microscope photograph of coated sodium
percarbonate particles, each at lOOX magnification. Figure 3
is an enlarged (440X magnification, photograph of a cross section
of the coated sodium percarbonate particles of Figure 2, and
shows a borate-coating layer on the surfaces of the particles.
The sodium carbonate of Figure 2 and 3 is coated with 3.7% of
sodium metaborate dihydrate.
The percarbonate contained in the bleaching detergent
according to the present invention is stabilized by coating the
same with a coating agent containing a borate, preferably sodium
borate, particularly sodium metaborate. The coating agent may
J~urther contain a sequestering agent such as ethylenediamine-
tetraacetate, nitrilotriacetate or phosphate.
The amount of the coating agent is preferably 0.1 to
30 wt.% based on sodium percarbonate. The amount of the borate
in the coating agent is preferably 10 to 100 wt.%.
--6--
., ~
oo~i~
8S4
It has be_n known that boric acid compounds
are used as a coating~granulating agent for pero-
xides to be incorporated in bleaching detergents.
For example, boric acid compounds (orthoboric,
metaboric or tetraboric acid) are disclosed as
coating agents for peroxides in the specification
of British Patent No. 1,57S,792. In the specifl-
cation of Japanese Patent Publication No. ~760/1974,
it is disclosed to add metaboric acid to a hydrogen
peroxide adduct to improve its storage stability.
However, these publications are silent on the coat-
ing of peroxides with the borates as in the process
of the present invention.
The inventors have found tha-t the borate coat-
ing has a hiyh spreadability and its sodium per-
carbonate-coating efficiency is quite high and that
powdery or granular sodium percarbonate having the
surface coated with the borate has a storage sta-
bility far higher than that of sodium percarbonate
coated with boric acid in a bleaching detergent.
The present invention has been attained on the
basis of this finding. Electron photomicrographs
show that the surfaces of sodium perborate particles
are uniformly coated with the borate. This fact
proves that the coating process of the present
oo~
9LZ()Z8S~
inventlon is highly efficient.
As the borates used for coating sodium per-
carbonate according to the present invention, sodium
borates are suitable. They include sodium tetra-
borate decahydrate (borax, Na20 2B203 10H2~), sodium
tetraborate pentahydrate (Na20 2s203 5H20), sodium
tetraborate tetrahydrate (Na20 2B203 4H20), (an-
hydrous) sodium tetraborate (Na20 2s2o3)~ sodium
octaborate tetrahydrate ~Na2o-4B203 4H203, sodium
pen-taborate pentahydrate (Na20-5B203-10H2~), sodium
metaborate tetrahydrate (NaB02 4-~20) and sodium
metaborate dihydrate (~aB02-2H20). Among them,
sodium metaborate dihydrate and sodium metaborate
tetrahydrate are particularly preferred.
The coating agent for sodium percarbonate used
in the present invention may contain various organic
or inorganic compounds in combination with the
sodium borates. The inorganic compounds are, for
example, sodium carbonate, Glauber's salt and
magnesium sulfate. The organic compounds are, for
example, organic high molecular compounds such as
polyethylene glycol, polyvinylpyrrolidone and
hydroxypropylcellulose. The sodium borates may be
used in combination with also a se~uestering agent
such as a nitrilotriacetate or ethylenediamine-
oo9
~Z~Z854
tet~aacetate. The amount of the secues.erina agentis prefera~lY O.01 to 3 wt.% based on sodium per-
carbonate.
Sodium percarbonate may be coated wlth the
coating agent containing the borate by an ordinary
coating method in the present invention. For
e~.cample, a solution of the coating agent or a
powder~ coating agent is mi~ed with wet or dr~
sodium percarbonate powder or granules to e,~rect
uniform adsorption and the mi~ture is dried. The
coated sodium percarbonate particles have an average
particle diameter of 100 to 2000 ~, preferably 250
to ~C00 u.
The inventors have made studies to find out a
process for the preparation of a borate-coated sodium
percarbonate which can be practiced industrially easily
and makes it possible to completely coat sodium per~
carbonate with a borate. As a result, we have found
that the desired sodium percarhonate can be obtained
by utilizing the characteristics of the borate in the
coating treatment.
The most advantageous method for obtaining a
surface-coated sodium percarbonate by treating its pow-
der with a coating agent containing a borate according
2854
010
to ~he pr~sent invention comprises wetting sodium
percarbonat~ with water, miclng the wetted sodium
percarbonate with a powdered coating agent containing
a borate to ~ake said agent to be adsorbed bv sodium
percarbonate, and then drying them at a temperature
not ]ower than that at which the borate begins to melt.
In the above advantageous method or the present
invention, it is believed that when a powdered borate
containing water or crystallization is sprinkled on
sodium percarbonate in a wetted state and t~en sodium
percarbonate is dried at a temperature not Lower
than the melting point of the borate (for example,
Na2B407-10H20: 75C, NaB0~ 4H2O: 57C, NaBO2 2H2~: ~0C
and NasO3 4H2O: 63C), the borate is dissolved itseli
in '~he water of cr-~stallization and becomes molten
and sodium percarbonate is completely wrapped up in
the molten borate.
D~ring this stage, water in sodium percarbonate
and water of crystallization in the borate are evaporated,
and the drying operation is completed. Thus, uniform
~ilm formation and drying are simultaneously conducted.
Usually, sodium percarbonate can be dried at a tem-
perature ranging from 40 to 160C. Drying can be
ef~ected even at a temperature below 40C, but it takes
too a long time to dry it. ~t a temperature above 1~0C,
sodium percarbonate undergoes inefrective decomposition
and su~'~ers a great loss OL- available o~ygen.
011
8S4
Thus it is preferred to conduct the drying at a tempe-
rature of not lower than the melting point of the borate,
but not higher than 160C in the present invention.
Anhydrous borates have higher melting points than
those of the corresponding hydrates (e.g., Na234O7
melts at 741~C), but the melting points of anhydrous
borates are lowered because of the inrluence of moisture
contained in the wetted sodium rpercarbonate which be~
haves just like water of crystallization. Hence the
anhydrous borates can be used in the present inve~tion,
although borates containing water of crystallization
are preferred. The amount of the borate in the
borate-coated sodium percarbonate is 0.04 to 10~ (W/W),
prererably 0.1 to 5% (r~/w) (in terms of boron) based on
dry sodium percarbonate. The smaller particle size of
the borate is preferred, but it is usually 50 to 300~,
preierably 100 to 150,u from the viewpoint or workability.
As the wetted sodium percarbonate used for the
production of the stable sodium percarbonate of the
present invention, one obtained by reacting sodium
carbonate with hydrogen peroxide in a conventional
manner followed by dehydration in a conventional manner
can be used as such. This percarbonate in a wetted
state has a moisture content or 7 to 18~ Since the
moisture serves as a necessary wetting water, the
012
~ZV~354
sodium percarbona~ can be used as such. But, sodium
percarbonate having a moisture content of lO to 16%
is preferred. r~hen sodium percarbonate having a
lower moisture content is used, it is preferred that
sodium percarbonate is wetted with an appropria-te
amount of water so that a powdered borate can be
uniformly sprin~led thereon.
It is advantageous that -the coating agent of
the present invention contains a conventional sta-
bilizer for sodlum percarbonate, such as an ethylene-
diaminetetraacetate, or a sequestering agent such as
a nitrilotriacetate which does not have an adverse
effect on the film formation of the molten borate.
In the preparation of the borate-coated sodium
percarbonate of the present invention, sodium per-
carbonate may be coated by spraying an aqueous solu-
tion of a borate on sodium percarbonate powder, mixing
said powder and then drying it. However, since dry
sodium percarbonate must be used in this method, it
is necessary to carry out the drying treatment twice.
Alternatively, sodium percarbonate may be coated
by using sodium percarbonate powder wetted with water,
particularly sodium percarbonate in a wetted state
obtained by reacting hydrogen peroxide with sodium
carbonate in an aqueous solution followed by dehydration,
lZ~Z854
i.e. by mixing said sodium percarbonate in the wetted state with
a powdered borate to make the borate to be adsorbed by sodium
percarbonate and then drying sodium percarbonate. I'his process
utilizes the characteristics of the borate and is an industrially
very advantageous process which can be easily conducted with less
energy consumption without a necessity of dissolving the borate.
It is observed from the attached photomicrographs that
in the borate-coated sodium percarbonate obtained by the process
of the present invention, the surfaces of sodium percarbonate
particles are uniformly coated with the borate.
The thus coated sodium percarbonate exhibits a quite
high storage stability when it is incorporated in an ordinary
powdery detergent (spray-dried detergent), particularly zeolite-
containing low-phosphorus or phosphorus-free detergent. l to 40
wt.~ of the obtained, coated sodium percarbonate ls incorporated
in a powdery detergent to obtain the intended bleaching detergent
of the present invention.
As disclosed before, the invention provides an improved
bleaching agent which contains 40 to 99 percent by weight of
said coated sodium percarbonate. It solves the below mentioned
problems in the state of arts.
- 13 -
,.
014
~2~Z8S4
However, sodium percarbonate has a drawback of
being liable to be decomposed by moisture, heavy
metal salts, or the like and hence is decomposed by
absorption of moisture, other ingredients incorporated
in the bleaching agent composition or impurities
originated in a container during an elongated storage.
As a result, -the amount of available oxygen is reduced.
However, it is necessary for sodium percarbonate for
use in domestic bleaching agents that it has a long-
term storage stability, does not absorb moisture after
opening of a container, is not affected by various for-
mulation ingredients such as bleaching activating agent,
enzyme, fluorescent dye, perfume, etc. incorporated in
order to improve bleaching performance and touch, nor
'nas an adverse effect on them. T~erefore, if sodium
percarbonate is stabilized so as not to be affected
by such other ingredients, it becomes possible to
provide a high-performance domestic bleaching agent
composition having good storage stability.
In a composition containing sodium percarbonate,
a transition metal salt such as cobalt, iron or copper
salt and a chelating agent, sodium percarbonate is
rapidly decomposed by the catalytic action of the
transition metal.
OL5
~ZVZ85
When the organic peracid precursor mentioned
above as a second e~ample is used, both the activating
agent and sodium percarbonate are decomposed by the
reaction therebetween. In addition thereto, its
commercial value as a domestic bleaching agent is
remar'cably reduced owing to the smell or a carboxylic
acid, particulary acetic acid formed by the decom-
position of the activating agent.
As stated above, when both the coated sodium
percarbonate and the bleaching activating agent are
blended in the present invention, there are advantages
in that a bleaching agent composi-tion having a high
bleaching activity as well as excellent storage
stability can be obtained, and it becomes possible
to widely choose formulation ingredients such as
per~ume.
The bleaching agent composition of the present
invention contains at least 40 wt.% of the coated
sodium percarbonate. The amount of the coated sodium
percarbonate to be blended is 40 to 99 wt.%, pre~erably
40 to 90 wt.%. The amount OL the bleaching activating
agent to be blended is 0.1 to 60 wt.%, preferably 1
to 40 wt.%.
Coated sodiu~ percarbonate used ln the pres2~t
inven~on has thus an e~tre~ely improv2d s.orage
staDi1it~ and, tnereLore, its in1uences on ot'ner
~Z~)2854
components contained in the detergent such as a
fluorescent d~e and an enzyme which exhibit thelr
efect in the washing step may be minimized. Thus,
even if sodium percarbonate is incorporated in a
detergent composition containing an enzyme and a
fluorescent dye which are easily influenced by the
decomposition of sodium percarbonate, the problem
o~ the stability of the composition can be solved
according to the present invention. Namely, accord
ing to the present invention, a phosphorus-free
detergent containing sodium percarbonate in com-
bination with the enzyme and fluorescent dye in
which the respective components have excellent
storage stabilities can be obtained.
The bleaching detergent composition of the
present invention may contaln, if desired, water-
soluble soaps, anionic, nonionic or amphoteric
surfactants, orsanic or inorsanic builders, seques-
tering agents, bulk fillers, enzymes effective for
the deterging, bleaching-activating agents, fluores-
cent brightening agents and perfumes as will be
described below. These additives are not particu-
larly limited but used according to the purposes.
[1] Surfactants:
1) Straight-chain or branched alkylbenzene~
() 1 '7
~Z~2854
sulfonates containing alkyl groups having 10 to 16
carbon atoms in average.
2) Alkyl or alkenyl ether sulfates containing
straight-chain or branched alkvl or alkenyl group
having 10 to 20 carbon atoms in average and contain-
ing 0.5 to 8 mol iIl average of ethylene oxide, pro-
pylene oxide or butylene oxide or two of these three
compounds in an ethylene oxide/propylene oxide ratio
of 0.1/9.9 to 9.9/0.1 or ethylene oxide/butylene
oxide ratio of 0.1/9.9 to 9.9/0.1.
3) Alkyl or alkenyl sulfates containing an
alkyl or alkenyl group having 10 to 20 carbon atoms
in average.
4) Olefinsulfonates having 10 to 20 carbon
atoms in average in the molecule.
5) Alkanesulfonates having 10 to 20 carbon
atoms in average in the molecule.
6) Saturated or unsaturated fatty acid salts
having 10 to 24 carbon atoms in average in the
molecule.
7) Alkyl or alkenyl ether carboxylic acid
salts containing an alkyl or alkenyl group having
10 to 20 carbon atoms in average and 0.5 to 8 mol
of ethylene oxide, propylene oxide or butylene oxide
or ethylene oxide/propylene oxide in a ratio of
~1~
lZ~J2854
0.1/9.9 to 9.9/0.1 or ethylene o~ide/butylene o~ide
in a ratio of 0.1/9.9 to 9.9/0.1.
8) ~-Sulfofatt~ acid salts or esters of the
formula:
R - C~C0
I
SO,j Z
wherein Y represents an alkyl group haviny
1 to 3 carbon atoms or a counter ion, Z re-
presents a counter ion and X represents an
alkyl or alkenyl group having 10 to 20 carbon
atoms.
As the counter ions in the anionic surfactants,
there may be men-tioned ions of alkali metals such
as sodium or potassium, those of alkaline earth
metals such as calcium or magnesium, ammonium ion,
and those of alkanolamines containing 1 to 3 alkanol
groups having 2 or 3 carbon atoms such as mono-
ethanolamine, diethanolamine, triethanolamine and
triisopropanolamine.
9) Amino acid-type surfactants of the general
formula:
No. 1 R1 - CO- ~- CE- COO~
1'2 1~ ~
01 ~
:~Z~28S4
wherein X1 represents an alkyl or alkenyl
group having 8 to 24 carbon atoms, R2 re-
presents a hydrogen or an alkyl group having
1 or 2 carbon atoms, R3 represents an amino
acid residue and X represents an alkali metal
or an alkaline earth metal ion.
No. 2 Rl - CO- h - ~ C 2 ) n CO
Rz
wherein R1, R2 and X have the same meaning as
above and n represents an integer of 1 to 5.
No. 3 R
~ N- (CE2)m- COO~
wherein Rl has the same meaning as a~ove and
m represents an integer of.l to 8.
_ .
No. 4 Rl - ~ - C~ - COO~
R~ R3
wherein Rl, R3 and X have the same meaning as
above and R4 represents a hydrogen or an alkyl
or hydroxyalkyl group having 1 or 2 carbon
atoms.
No. 5 R5 - N - C~- COOg
R2 R3
~i ) ()
lZ~28S9
wherein R2, R3 and X have the same meaniny
as above and R~ represents a ~-hydroxyalkyl
or ~-hydro~yalkenyl group having 6 to 28
carbon atoms.
No. 6 R5
> ~--C~--COO~
~5 I,
_
wherein R3, R5 and X have the same meaning
as above.
lO) Phosphate ester surfactants:
No. l Alkyl~or alkenyl) acid phosphates:
(R')n~ - P- (~)~'
wherein R- represents an alkyl or alXenyl
group having 8 to 24 carbon atoms, n'+m'=3
and n'=1~2.
No. 2 Alkyl(or alkenyl) phosphates:
O
(R')n~- P - (0~)~"
wherein R' has the same meaning as above,
n"+m"=3 and n"=1-3.
No. 3 Alkyl(or alkenyl) phosphate salts:
854
CR'o)_"- P ~ (O~r')~,
wherein R-, n" and m" have the same meaning
as above and M- represents Na, K or Ca.
11) Sulfonic acid-type amphoteric sulfactants
of the general formulae:
No. 1 R
~llCON~ - R12-~ - R
R13
wherein Rll represents an alkyl or alkenyl
group having 8 to 24 carbon atoms, R12 re-
presents an alkyl group having 1 to 4 carbon
atoms, R13 represents an alkyl group having
1 to 5 carbon atoms and Rl~ represents an
alkyl or hydroxyalkyl group haviny 1 to 4
carbon atoms.
No. 2 R15
Rll--N --Rl~--S O
R16
wherein Rll and R14 have the same meaning as
above and R15 and R16 represent an alkyl or
alkenyl group having 8 to 24 or 1 to 5 carbon
atoms.
02 '
~ZOZ854
No. 3 CC2H~O)n1~
R~ - Rl,~- SO3
(C2H~O) nl~
wherein Rll and R14 have the same meaning as
above and nl represents an integer of 1 to 20.
12) Betaine-type amphoteric surfactants of
the general formulae:
No. 1 R22
R - ~- R2j- COO~
R22
wherein R21 represents an alkyl, alkenyl,
~-hydroxyalkyl or 3-hydroxyalkenyl group
having 8 to 24 carbon atoms, R22 represents
an alkyl group having 1 to 4 carbon atoms
and R23 represents an alkyl or hydroxyalkyl
group having 1 to 6 carbon atoms.
No. 2 (C2H4)n2~
~21 - ~ - R23 - COO
( C2Fr4 O)n2E
wherein R21 and R23 have the same meaning as
above and n2 represents an integer of 1 to 20.
~Z~Z854
No. 3 R2~
R2 ~ R2 3 C O O
~2~
wherein R2l and R23 have t'ne same meaniny as
above and R24 represents a carboxyalkyl or
hydroxyalkyl group having 2 to 5 carbon atoms.
13) Polyoxyethylene alkyl or alkenyl ethers
containing an alkyl or alkenyl group having lO to
20 carbon atoms in average and l to 20 mol of
ethylene oxide.
14) Polyoxyethylene alkylphenyl ethers con-
taining an alkyl yroup haviny 6 to 12 carbon atoms
in average and l to 20 mol or ethylene oxide.
15) Polyoxypropylene alkyl or alkenyl ethe~s
containing an alkyl or alkenyl group having lO to
20 carbon atoms in average and l to 20 mol of pro-
pylene oxide.
16) Polyoxybutylene alkyl or alkenyl ethers
containing an alkyl or alkenyl group having lO to
20 carbon atoms in average and l to 20 mol of
butylene oxide.
17) Nonionic surfactants containing an alkyl
or alkenyl group having lO to 20 carbon atoms in
average and l to 30 mol, in total, of ethylene
024
lZV'~854
oxide and propylene oxide or etnylene oxide and
butylene oxide (the ratio of ethylene oxide to
propylene oxide or butylene oxide is 0.1/9.9 to
9 . 9/0 . 1) .
18) Higher fatty acid alkanolamides or their
alkylene oxide adducts of the following formula:
R'
CCHCH 0) E
RllC0~ < 2 n~
(C C~zO~m3E
Rlz
wherein Rll represents an alkyl or alkenyl
group having 10 to 20 carbon atoms, R12
represents H or C~3, n3 represents an integer
of 1 to 3 and m3 represents an integer of
19) Sucrose/fatty acid esters comprising a
fatty acid having 10 to 20 carbon atoms in average
and sucrose.
20) Fatty acid/glycerol monoesters comprising
a fatty acid having 10 to 20 carbon atoms in average
and glycerol.
21) Alkylamine oxides of the general formula:
~)~5
Z854
R~
R~ ~ O
R15
wherein R13 represents an alkyl or alkenyl
group having 10 to 20 carbon atoms and Ri4
and Ri5 represent an alkyl group having 1 to
3 carbon atoms.
22) Cationic surfactants of the general
formulae:
No. 1 R2
Rl - N R~ ~'
R'
wherein at least one of Rl, R2, R3 and R4
represents an alkyl or alkenyl group having
8 to 24 carbon atoms and others represent an
alkyl group having 1 to 5 carbon atoms and
X~ represents a halogen.
No. 2
R2
Rl I C~I2 C 6 ~ 5
R'
~ZOZ8S~
wherein Rl, R2, R3 and X~ have the same
meaning as above.
No. 3
(R5O)~E
R ~ R 2 g '
I
~ (R5O)n E
wherein Rl, R2 and X' have the same me~ning
as above, R- represents an alkylene group
having 2 or 3 carbon atoms and n4 represents
an integer of 1 to 20.
It is desirable that the composition contains
at least 10 wt.~ of one or more of the above-men-
tioned surfactants.
[2] Sequestering agent:
The composition may contain 0 to 50 wt.% of
one or more builders selected from the group con-
sisting of alkali metal salts and alkanolamine
salts of the following compounds:
1) Salts of phosphoric acids such as ortho-
phosphoric, pyrophosphoric, tripolyphosphoric,
metaphosphoric, hexametaphosphoric or phytic acid.
2) Salts of phosphonic acids such as ethane-
l,l-diphosphonic, ethane-1,2-triphosphonic, or
ethane-l-hydroxy-l,l-diphosphonic acid and
l)2(
lZ~ 354
derivatives thereof, ethane-hydroxy-1,1,2-triphos-
phonic, ethane-1,2-dicarboxy-1,2-diphosphonic, or
methane-hydro~yphosphonic acid.
3) Salts of phosphonocarboxylic acids such
as 2-phosphonobutane-1,2-dicarbo~ylic, l-phos-
phonobutane-2,3,4-tricarbo~ylic or ~-methylphos-
phonosuccinic acid.
4) Salts of amino acids such as aspartic or
glutamic acid.
5) Salts of arninopolyacetic acids such as
nitrilotriacetic, ethylenediaminetetraacetic or
diethylenetriaminepentaacetic acid.
6) High-molecular electrolytes such as poly-
acrylic acid, polyaconitic acid, polyitacon:Lc acid,
polycitraconic acid, polyfumaric acid, polymaleic
acid, polymesaconic acid, poly-~-hydroxyacry]ic
acid, polyvinylphosphonic acid, sulfonated poly-
maleic acid, maleic anhydride/diisobutylene copoly-
mer, maleic anhydride/styrene copolymer, ma:Leic
anhydride/methyl vinyl ether copolymer, maleic
anhydride/ethylene copolymer, maleic anhydride/
ethylene cross-linked copolymer, maleic anhydride/
vinyl acetate copolymer, maleic anhydride/acrylo-
nitrile copolymer, maleic anhydride/acrylate
copolymer, maleic anhydride/bu-tadiene copolymer,
~8
~O~S4
maleic anhydride/isoprene copolymer, pol~ keto-
carboxylic acid deri..ved from maleic anhydride and
carbon monoxide, itaconic acid/ethylene copolymer,
itaconic acid/aconitic acid copolymer, itaconic
acid/maleic acid copolymer, itaconic acid/acrylic
acid copolymer, malonic acid/methylene copolymer,
mesaconic acid/fumaric acid copolymer, ethylene
glycol/ethylene terephthalate copolymer, vinyl-
pyrrolidone/vinyl acetate copolymer, l-butene-2,-
3,4-tricarboxylic acid/itaconic acid/acrylic acid
copolymer, polyester polyaldehyde carboxylic acid
containing a quaternary ammonium group, cis-isomer
of epoxysuccinic acid, poly[N,N-bis(carboxymethyl)-
acrylamide], poly(oxycarboxylic acids), starch
succinate, maleate or terephthalate, starch phos-
phate, dicarboxystarch, dicarboxymethylstarch or
cellulose succinate~
7J Non-dissociating high molecules such as
polyethylene glycol, polyvinyl alcohol, polyvinyl-
pyrrolidone or cold water-soluble, urethanized
polyvinyl alcohol~
8) Salts of organic acids such as diglycolic,
hydroxydiglycolic, carboxymethyloxysuccinic,
cyclopentane-1,2,3,4-tetracarboxylic, tetrahydro-
furane-1,2,3,4-tetracarboxylic, tetrahydrofurane-
U~9
)2854
2,2,5,5-tetracarbo.Yylic, citric, lactic or tartaric
acid, carboxymethylated products of sucrose, lactose
or raffinose, carboxymethylated pentaerythritol,
carboxymethylated gluconic acid, condensates of
polyhydrlc alcohols or sugars with maleic or succinic
anhydride, condensates of hydroxycarboxylic acids
with maleic or succinic anhydride, benzenepolycarbo-
xylic acids such as mellitic acid, ethane-1,1,2,2-
tetracarboxylic, ethene-1,1,2,2-tetracarboxylic,
butane-1,2,3,4-tetracarboxylic, propane-1,2,3-
tricarboxylic, butane-1,4-dicarboxylic, oxalic,
sulfosuccinic, decane-1,10-dicarboxylic, sulfotri-
carbollylic, sulfoitaconic, malic, hydroxydisuccinic
or gluconic acid, CMOS or builder M.
9) Aluminosilicates:
No. 1 Crystalline aluminosilicates of the
formula:
~'(MzO or ~"O)- ~ O~-y'(SiOz) w'(~O)
wherein M- represents an alkali metal atom,
M" represents an alkaline earth metal atom
exchangeable with calcium and x , y and w'
represent each a molar number of the respec-
tive components and generally, 0.7'x'_1.5,
0.8_y''6 and w~ being any positive number.
l)~o
~S4
No. 2 As the detergent ~uilders, -those of
the foLlowing general formula are
particularly preferred:
~a2o ~2o~ rlsio2 w 2
wherein n represents a nur~er of 1.8 to 3.0
and _ represents a number of 1 to 6.
No. 3 Amorphous aluminosilicates of the
formula:
~(~2o)-A~2o3-y(sio2~ 2o)
wherein M represents a sodium and/or potassium
atom and _, y and w represent each a molar_
number of the respective components within the
following ranges:
0.7<x~1.2
1.6_y'2.8
w being any positive number including 0.
No. 4 Amorphous aluminosilicates of the
formula:
~C~2~ ~203~Y(s1 2)-Z(P2os)-~(~2o)
wherein M represents Na or K and X, Y, Z and
represent each a molar number of the respec-
tive components within the following ranges:
~1
~2~ 5
0.20''~ 1.10
0.20=~- .00
0.001~Z~0.~0
~ being any positi~e numDer including 0.
[3~ Alkalis and inorganic electrolytes:
Further, one or more or alkali metal salts
shown below may be contained in t'ne composition in
an amount of 1 to 50 wt.~, preferabl~ 5 to 30 wt.~,
as alkalis or inorganic electrolytes: silicat-s,
carbonates and sul~ates. Organic alkalis include,
for example, triethanolamine, diethanolamine, mono-
ethanolamine ana triisopropanolamine.
The following explains in detail incorporation
of an alkali metal silicate into the coating agent.
As to the coating of sodium percarbonate which
is an indispensable step for improving its storage
stability, the mechanical strength of the coating is
remarkably improved when a borate is used in combination
with an alkali metal silicate. Thus, there is no fear
of damaging the coating during the course of handling,
particularly until the stage of blending with powdered
detergents.
~ZOZ854
Suitable alkali metal silicates are those of the
formula Na2O nSiO2, wherein n represents a molar rat;o
of SiO2/Na2O, and is 0.5 to 4. Examples of such alkali
metal silicates are an aqueous solution of a crystalline
sodium silicate such as sodium orthosilicate (2Na2O SiO2
xH2O, n = 0.5), sodium sesquisilicate (3Na2O 25iO2 xH2O,
n = 0.67), and sodium metasilicate (Na2O-SiO2 xH2O, n = 1),
an aqueous solution of an amorphous sodium silicate such
as Na2O nSiO2 (n = 1 - 4) and dehydrated sodium silicate
powder thereof.
The so-coated sodium percarbonate exhibits an
excellent storage sta~ility even when incorporated
in conventional powdered detergents (spray-dried
products), particularly low-phosphorus or phosphorus-free
detergents containing zeolite blended thereof. Further,
in addition to a synergistic coating effect obtained by
using the borate and the alkall metal silicate in com-
bination, the strength of particles and the coating
is improved by the use of the alkali metal silica-te
without deteriorating the solubility of sodium per-
carbonate. Thus, there is no ~ear of damaging the coat-
ing during stages until sodium percarbonate is blended
with powdered detergents.
12~Z85~
[~] Antiredeposition agents:
The composition mav contain 0.1 to 5% or one
or more Oc the followinq compounds as antiredeposi-
tion agents: polyethylene glycol, pol~yvinyl alcohol,
polyvinylpvrrolidone and carboxymethyl cellulose.
[5] Fluorescent dyes:
Fluorescent dyes represented by, for e.xample,
t'ne i-ollowing structural ror~ulae (w), (x) and (y)
may also be contained in the composition:
~34
~Z~Z854
~NE--~ ~ N~ C H
N~N
~N~ S O Na
C ~ (W)
SO~a ~ ~
C~I = CE~ C~= CE~ (~)
S03 ~a SO~ ~a
~¢ N~C~I=C13:~ N ~ O
H
S 0~; Na S O j Na
[6] Enzymes (those exhibiting their essential
enzymatic effects in the deterging step):
In respect of reactivity, enzymes may be
classified into groups of hydrolases, hydrases,
oxidoreductases, desmolases, transferases and
isomerases. Among them, hydrolases are particu-
larly preferred. They include protease, esterase,
carbohydrase and nuclease.
Particular examples of proteases are pepsin,
~i ~) s
12~Z~S4
trypsin, chymotrypsin, collagenase, keratinase,
elastase, su~tilisin, BPN, papain, bromelin,
carbo.~ypeptidases A and B, aminopeptidase, and
aspergillopeptidases A and B.
Particular ecamples of esterases are gastric
lipase, pancreatic lipase, vegetable lipases,
phospholipases, cholinesterases and phosphatases.
As the carbohydrases, there may be mentioned,
for e~ample, cellulase, maltase, saccharase,
amylase, pectinase, lysozyme, ~-glycosidase and
~-glycosidase.
The coated sodium percarbonate according to
the invention exists stably together with an enzyme
in the compostion. The stability of the composition
which comprises said coated sodium percarbonate and
an enzyme is further improved by incorporating therein
a synthetic zeolite in an amount of not less than
5 percent by weight. Such composition practically
comprises SO to 99 percent by weight of said coated
sodium percarbonate and 0.1 to 10 percent by weight,
as protease of 2.0 Anson uni-t per gram, and from
5 to 100 percent by weight, based on the weight of
said coated sodium percarbonate, of a zeolite. The
Anson unit is e~plained in Anson, M.L., Journal o~
General Physiolosy, vol. 22(1939), pages 79 to 89.
~);3t)
12~28S4
[7J Blueing agents:
Various blueing agents may be incorporated in
the composition, if necessary. Blueing agents oE,
for e~ample, the following structure are recon~ended:
~ N~
Il, I
~ C ~ ----(S03E)n
wherein D represents blue or purple monoazo,
disazo or anthraquinone dyestuff residue, X
and Y represent each a hydro~yl group, amino
group, aLiphatic amino group which may be
substituted with a hydro~yl, sulfonic acid,
lZ~8S4
carboxylic acid or alkoxyl group, or an
aromatic amino or alicyclic amino group which
may be substituted with a halogen atom or
hydroxyl, sulfonic acid, carboxylic acid,
lower alkyl or lower alkoxyl group and R
represents a hydrogen atom or a lower alkyl
group excluding a case in which R represents
a hydrogen atom and (1) both X and Y repre-
sent hydroxyl or alkanolamino groups at the
same time or (2) one of X and Y represents a
hydroxyl group and the other represents an
alkanolamino group, and n represents an
integer of at least 2,
and
D - N~ - C C -
,11 1
: ~ N
~ C ~
wherein D represents a blue or purple azo or
anthraquinone dyestuff residue and X and Y
represent the same or different alkanolamino
residue or hydroxyl group.
~8] Caking inhibitors:
The following caking inhibitors may also be
IZ~Z854
con~ained in the composition: p-toluenesulfonates,
xylenesulfonates, acetates, sulfosuccinates, talc,
finely pulverized silica, clay, calcium silicate
(such as Micro-cells of Johns-L~anvill Co.), calcium
carbonate or magnesium oxlde.
[9] Antioxidants:
The antioxidants include, for example, tert-
butylhydroxytoluene, 4,4'-butylidenebis(6-tert-
butyl-3-methylphenol), 2,2'-butylidenebis(6-tert-
butyl-4-methylphenol), monostyrenated cresol,
distyrenated cresol, monostyrenated phenol, di-
styrenated phenol and l,l'-bis-(4-hydroxyphenyl)-
cyclohexane.
~10] Bleaching activating agents:
The bleaching activating agents are compounds
which form organic peracids in the presence of
peroxy compounds in an aqueous alkali solution.
They may be classified into the following three
groups:
1) organic acid anhydrides,
2) ester compounds, and
3) N-acyl compounds.
As particular examples of the bleaching
activating compounds, there may be mentioned tri-
acetyl cyanurate (TACA), sodium p-acetoxybenzene-
u ~ ~l
~Z~2854
sulfonate (SABS), tetraacetylglycouryl (TAGU)acetylsalicylic acid, N-acetylimidazole (AID~,
N,N,N',N'-tetraacetylethylenediamine (T.~ED) and
pentaacetyl-~-D-glucose.
[11~ Stabilizers for peroxldes:
They include, for example, magnesium sllicate,
magnesium sulfate, magnesium oxide and magnesium
chloride.
Accordingly, sodium percarbonate to be incorporated
in the bleaching detergent of the present invention can
be stabilized by coating it wi-th a coating agent con-
taining a borate and a magnesium compound. As the
borates, sodium borate is preferred, and sodium metaborate
is particularly preferred. As the magnesium compounds,
preferably one or more members selected from the group
consisting of magnesium chloride, magnesium oxide, mag-
nesium sulfate and magnesium silicate are used.
Further, the coating agent may contain a sequestering
agent such as an ethylenediaminetetraacetate or a
nitrilotriacetate.
Sodium percarbonate is used in an amount of
preferably 0.1 to 30 wt.% based on the amount of the
coating agent. The borate is used in an amount of
preferably 10 to 95 wt.%, and the magnesium compound
is used in an amount of preferably 5 to 70 wt.% based on
u4ù
~2~2~S4
the amount of the coatlng agent. Generally, it is
preferred to use the magnesium compound in an amount
not more than that of the borate.
On the contrary, the inventors have made further
studies and found that when a borate and a magnesium
compound are used in combination, a coated sodlum
percarbonate having more excellent storage stability
can be obtained by -the synergistic effect of the
coating power of the borate and the stabili~ing
power of the magnesium compound, and that when this
coated sodium percarbonate is incorporated in powdered
detergents, bleaching detergents having remarkably
excellent storage stability can be obtained. The
present invention is based on these findings.
Examples of magnesium compounds include magnesium
sulfate, magnesium chloride, magnesium oxide, magnesium
hydroxide, magnesium silica-te, magnesium nitrate,
magnesium phosphate and magnesium carbonate in an
anhydrous form or in a hydrated form, and magnesium salts
of various organic acids. Among these, magnesium sul-
fate, magnesium chloride, magnesium oxide and magnesium
silicate in an anhydrous form or in a hydrated form are
particularly preferred.
~2~Z8S4
The followinq examples are provided to illustrate
the coated sodium percarbonate according to the invention.
Example 1
Wetted sodiurn percarbonate having a moisture
content of 10% and a dry average particle size of
480~ obtained by a reaction between hydrogen peroxide
and sodium carbonate in an aqueous solution, was
fed to a continuous mixer at a rate of 5.3 kg/min
by means of a continuous feeder. Sodium metaborate
dihydrate having an average particle si~e of 150~
was also fed to the this mixer at a rate of 0.178 kg/min
by means of a continuous feeder. The feed rate was
adjusted so as to give a residence time of 5 min in
the mixer. The mixture was continuously supplied to
a fluidized dryer to dry it at 130C.
The amount of boron in the coated sodium per-
carbonate was determined to be 0.42~ in terms of
boron. The coated sodium percarbonate was mixed with
~arious second components and the stability of the
mixtures was measured. The results are given in
Table 1. The stability was expressed by avaivable
oxygen residue obtained after a required amount of
a sample was charged in a resin vessel provided with
pinholes and left to stand at `50C and 80% RH for
24 hours.
IZ~854
TabLe 1
Uncoated PC Coated PC Second component Stability
(amount: %)(amount: %) ~amount: %) (~)
coated PC zeolite A-4 88.8
' (90) (10)
uncoated PC zeolite A-4 32.5
' (90) (10)
coated PC sodium metasilicate 45~6
(9~) (10)
uncoated PC sodium metasilicate 32.0
. ~90) (10)
coated PC acid sodium pyro- 98.2
(50) phosphate . (50)
uncoated PC acid sodium pyro- 90.2
(50) phosphate (50)
coated PC sodium tripolyphosphate 8
(50) (wet process) (50) 93'
uncoated PC sodium tripolyphosphate
(50) (wet process) (50) 82.8
Note: PC means sodium percarbonate.
Example 2
3.4g of wetted sodium percarbonate having a moisture
content of 12% and a dry average particle size of 400~
and O.lkg of sodium borate decahydrate were charged in
a batch mixer, and mixed together for one min.
~Z~Z8S4
The mixture was dried in a fluidized dryer at 160C.
The amount of boron in the coated sodium percarbonate
was determined to be 0.40~ in terms of boron.
For the purpose of comparison, the above pro-
cedure was repeated with the exception that 0.16Kg
of sodium carbonate, 0.78Kg of colloidal silica (SiO2
content of 20~) and 0.31Kg of No. 3 sodium silcate
were used as coating agents in place of sodium borate
decahydrate. The resulting coated sodium percarbonate
was mixed with a commercially available deterg~nt A
(a phosphorus-free detergent containing zeolite blended
therewith) in a mixing ratio of 9:1 in a resin vessel
provided with pinholes, and left to stand at 40C and
80% RH for two weeks. Thereafter, available oxygen
residue (stability) was measured. The results are
given in Table 2.
Table 2
Coating agent Stability (%)
Present sodium borate decahydrate 92.4
invention
Comparative sodium carbonate 55.7
example
colloidal silica 74.0
No. 3 sodium silicate 70.0
uncoated 44.6
044
~Z~;~54
Example 3
The coated PC's prepared in Examples 1 and 2 were
subjected to a storage stability test under the follow-
ing conditions:
(1) 10 wt.~ of the coated PC was mixed with a com-
mercially available detergent B (a phosphorus-free
detergent containing zeolite)
(2) 10 wt.~ of the coated PC was mixed with a com-
mercially available detergent C (a phosphorus-
containing detergent containing sodium tripoly-
phosphate).
lOg of each of the above mixtures was charged
in a 50 cc plastic vessel. The vessel was closed
and left to stand at 40C and 80% RH for 14 days.
Thereafter, available oxygen residue was determined
according to the following equation:
available oxygen residue (~)
= available oxygen after storage x 100
available oxygen be~ore storage
The available oxygen was measured accordinq to
a O.lN potassium permanganate titration method.
For the purpose of comparison, ~1) uncoated PC
obtained by drying wetted PC as such and (2) sodium
perborate (PB) in addition to the coated PC of the
present invention were also tested.
()45
~20~S~
PC coated with PC coated with Uncoated
NaBO2-2H2O NaB2O lOH2O PC PB
Commercially
available
(phosphorus-free, 90.1 88.0 30.7 91.0
and containing
zeolite~
Commercially
ava.ilable
detergent C 94.5 , 92.0 90.3 94.9
(containing
phosphorus
and sodium
tripolyphosphate)
O d~ 6
lZ~);~154
sulfonate (SABS), triacetylglycouryl (TAGU),
acetylsalicylic acid, N-acetylimidazole (AID),
N,N,N',N'-tetraacetylethylenediamine (TAED) and
pentaacetyl-~-D-glucose~
[11] Stabilizers for peroxides:
They include, for example, magnesium silicate,
magnesium sulfate, magnesium oxide and magnesium
chloride.
The following examples will further illustrate
the bleaching detergent composition~
Example 4
100 g of sodium percarbonate was charged in a
stirring type-mixer. A 25% aqueous solution of
5 g of sodium metaborate tetrahydrate (NaBO2 4H2O)
(prepared by dissolving under heating) was sprayed
thereon under stirring at 250 rpm. After stirring
for 10 min, the mixture was dried with hot air to
obtain coated sodium percarbonate.
For comparison, sodium percarbonate coated
with boric acid (2.4 g of boric acid per 100 g of
sodium percarbonate) was also prepared.
10 wt.% of the coated sodium percarbonate was
homogeneously mixed in a phosphorus-free powdery
detergent of the following composition to obtain a
~4'~
1~2854
bleaching detergent according to the present inven-
tion:
Phosphorus-free bleaching detergent composi~ion
(the present invention):
wt.%
sodium dodecylbenzenesulfonate 20.0
synthetic zeolite (type 4A~ 20.0
sodium silicate (JIS No. 2) 10.0
sodium carbonate 5.0
fluorescent dye 0.5
sodium salt of carboxymethylcellulose 1.0
enzyme (alcalase) 0.3
sodium percarbonate (coated with sodium
metaborate according to the invention) 10.0
water 5 0
sodium sulfate balance
Total 100
Three samples of the above composition con-
taining sodium percarbonate coated with sodium
metaborate according to the present invention,
sodium percarbonate coated with boric acid for
comparison and sodium percarbonate having no coat-
ing were subjected to storage stability tests in thesame way in Example 3. The results are shown in Table
1.
048
12~Z~S4
Table 3
Coating of Available
sodium oxygen
percarbonate residue ~)
5~ sodium
Bl.eaching detergent metaborate 75.3
of the invention (NaB02-4H20)
Comparative 2.4~ boric~51 2
Example 1 . id (H BO )
Comparative none 31.1
Example 2
*coating rate of NaB02: 2.4~.
It is apparent from Table 3 that the coating
effects of sodium metaborate in the bleaching
detergent of the present invention were far superior
o~9
~2~28S4
to those of boric acid coating.
The bleaching deteryent in this example was
an absolutely phosphorus-free detergent containing
zeolite. However, it had a high stability due to
the sodium metaborate coating.
Example 5
Sodium percarbonate was coated with a combina-
tion of sodium metaborate with another coating
agent in the same way as in Example 4. The coating agents used are
sh~n belcw. ~mounts of the coating agents are shown by wt. %
based on sodium percarbonate.
(1) 5% sodium metaborate (NaB02 ~H20) + 5%
polyethylene glycol (PEG, molecular weight:
6000),
(2) 5% sodium metaborate + 5% sodium carbonate,
(3) 5% sodium metaborate + 0.5% disodium ethylene
i diaminetetraacetate (EDTA),
(4) 5% sodium metaborate + 0.5% EDTA-di-triethanol-
amine salt, and
(5) 5% sodium metaborate + 0.5% trisodium nitrilo-
triacetate (NTA).
Six samples ti-e-, the above-mentioned five
samples of coated sodium percarbonate and non-coated
sodium percarbonate) were incorporated in the same
phosphorus-free bleaching detergent as in Example 4
~50
12~Z854
(amount of sodium percarbonate: 10 wt.%). The
resulting compositions were subje~ted to the same
storage stability test as in Example 4 to obtain
the results shown in Table 4.
Table 4
Coating of sodium percarbonate AVraesiadle o(%X)yg n
NaB02~4H20 + PEF 82.3
5% 5%
NaB02 4H20 + Na2C03 77.7
5% 5%
NaB02 4H20 + EDTA-2Na 83.0
5~ 0.5%
NaB02-4H20 ~ EDTA 2TEA* 86.6
5% 0.5%
NaB02 4H20 + NTA~3Na : 84.4
5% 0.5%
not coated 30.5
*EDTA di-triethanolamine salt.
It is apparent from Table 4 that when sodium
metaborate was used in combination with another
coating agent, a quite excellent storage stability
was obtained. Particularly when sodium metaborate
was used in combination with an organic high mole-
cular compound such as PEG or sequestering agent
051
~Z~Z~354
such as EDTA or NTA, a synergism was attained to
improve the storage stability.
Example 6
The solubilities, compression strengths and
disintegrating properties of the coated sodium
percarbonates prepared in Example 5 were examined
to obtain the results shown in Table 5.
[Test methods]
Solubility
1 Q of city water was charged in a 1 Q beaker.
1 g of granular sodium percarbonate was add~d
thereto and the mixture was stirred at 200 rpm.
A time required until electric conductivity of the
solution became constant after the initiation of
the stirring was measured and shown as dissolution
time.
Compression strength:
A load was applied to a given amount of a
sample under given conditions by means of an auto-
graphic recording device and the load required for
1 cm compression was determined.
Disintegrating properties:
100 g of a sample which passed through a 12-
mesh sieve but did not pass through an 80-mesh
sieve was charged in a 500 mQ wide-mouth bottle
05~
~Z[)Z854
made of a polymer. S0 g of stainless steel balls
(3~) were charged therein and a stopper was applied
to the bottle. The bottle was fixed on an agitating
device and agitated at 360 rpm for 10 min (ampli-
tude: 4.5 cm). The disintegrating properties were
expressed by the amount (wt.%) of the sample passed
through the 80-mesh sieve. The smaller the amount
(%), the better.
Table 5
Solubilit Compression Disintegrating
Coating of sodium percarbonate Y strength properties
(sec)(kg/cm2) (~)
NaBO ~4H O + PEG
2 2 96 20.3 13.0
5% 5%
NaBO2-4H2O + NaCO3 111 18.8 15.8
~% 5%
NaBO2-4H2O + EDTA-2Na 93 21.0 13.8
5% ~.5% ~ O
NaB024H20 + EDTA 2TEA 92 20.8 13.9
NaBO2-4H2O + NTA-3Na 95 20.8 14.2
5% 0.5%
not coated 90 20.6 13.4
(~54
2854
It is apparent from Table 5 that the solubility,
compression strength and disintegrating property
of the sodium percarbonate were substantially un-
changed by coating the same according to the process
of the present invention.
Example 7
20 kg of wet sodium percarbonate was charged
in a centrifugal diffusion type mixer (
mixer, FKM-130 D, T.M. Engineering Co., Ltd.).
A powdery coating agent was added thereto under
stirring and they were mixed for 10 min in total.
Then, the coated sodium percarbonate was taken out
and dried with hot air.
The coating agents used were as follows:
(1) 5% sodium metaborate (NaBO2 4H2O) + 0.5%
EDTA-2TEA,
(2) 4.54% borax (Na2B4O7-10H2o) + 0.5% EDTA-2TEA,
and
(3) 2.4% boric acid (H3BO3) + 0.5% EDTA 2TEA
(The percentages are given by weight based on sodium
percarbonate)
The three samples (i.e., two samples of coated
sodium percarbonate according to the present inven-
tion and one comparative sample) and uncoated sodium
percarbonate were incorporated in an amount o~
(~55
~Z()Z8S4
10 wt.~ in the following phosphorus-free bleaching
detergent composition in the same manner as in
Example 4 and 5 . The results of the storage
stability tests carried out in the same manner as
in Example 4 sre shown in Table 6. Residual activ-
ity of an enzyme (2.0 M alcalase) incorporated in
the same manner as above was also determined.
Enzymatic activity residue was determined according
to the following formula and also shown in Table 6:
enzymatic activity residue (~)
enzymatic activity after storage x 100
enzymatic activity before storage
The method of measuring the residual activity
of enzyme is described in J.B.C. 244 (4), pp. 789-
793 (1969) and Analyst 96, pp. 159-163 (1971).
Phosphorus-free bleaching detergent composition:
wt.%
sodium dodecylbenzenesulfonate 20.0
synthetic zeolite (type 4A) - 20.0
sodium silicate (JIS No. 2) 10.0
sodium carbonate 5.0
fluorescent dye 0.5
sodium salt of carboxymethylcellulose 1.0
enzyme (2.0 M alcalase) - 0.3
sodium percarbonate (coated) 10.0
056
~Zi~Z8S~
water 5.0
sodium sulfate balance
Total 100
Table 6
Available ~nzymatic
Coating of sodium percarbonate oxygen activity
residue (%) residue (~)
NaBO2~4H2O + EDTA-2TEA 90.1 95.4
5%* 0.5
2B47-1H2 + EDTA-2TEA 88.2 94.4
4.54%* 0.5%
H3BO3 + EDTA-2TEA 73.8 90.2
2.4% 0.5%
not coated 32.0 80.3
*Coating rate of anhydrous coating agent: 2.4% .
It is apparent from Table 6 that in the phos-
phorus~free bleaching deteryents ~1) and ~2)
according to the present invention, stability of
sodium percarbonate was extremely high and stability
of the en~yme was also excellent, though they con-
tained zeolite.
.xample 8
10 wt.% of the coated sodium percarbonate of
the present invention prepared in Exa~ple 7 ~sodium
057
~2()2~S4
percarbonate coated with NaBO2-4H2O or Na2B4H7-
lOH2O) or one of the two comparative samples
(sodium percarbonate coated with H3sO3 or uncoated
sodium percarbonate) was incorporated in a powdery
bleaching detergent of the following composition.
They were subjected to the storage stability test
to examine available oxygen residue in sodium per-
carbonate and enzymatic activity residue (2.0 M
alcalase). The results are shown in Table 5.
The test method was the same as in Example 4 and 7.
Bleaching deter~ent composition:
wt.%
sodium dodecylbenzenesulfonate 20.0
sodium tripolyphosphate 18.0
sodium silicate (JIS No. 2)10.0
sodium carbonate 5.0
Eluorescent dye 0.5
sodium salt of carboxymethylcellulose 0.5
enzyme (2.0 M alcalase) 0.3
sodium percarbonate 10.0
water
sodium sulfate balance
Total 100
058
~2V28S~
Total 7
A~ailable Enzymatic
Coating of sodium percarbonate oxygen ac-tivity
residue (~) residue (%)
NaB02 4~20 + EDTA~2TEA95.8 84.8
5% 0.5%
2B47~1H2 + EDTA~2TEA 96.0 85.0
5% 0.5%
83B03 + EDTA~2TEA 90.2 80.4
5~ 0.5%
not coated 88.8 60.5
The bleaching detergent composition in this
example con-tained STPP as in the conventional
detergent compositions. Samples (1) and (2) accord-
ing to the present invention exhibited quite excel-
lent storage stabilities. This fact indicates that
the bleaching detergents of the present invention
have a quite high storage stability irrespective of
the presence or absence of zeolite.
0 5 '~ ~ 13
lZ~)2854
Example 9
lO0 g of sodium percarbonate was charged in an
agitating mixer. A 25% aqueous solution of 5 g of
sodium m~taborate (Na2BO2 4H2O~ (prepared by dis-
solving the metaborate in water with heating) and
a 25% aqueous solution of l g (on a solid base) of
sodium silicate (JIS No. 3) (Na2O 3SiO2 aq) were
sprayed thereon with stirring at 250 r.p.m. After
stirring for lO min, sodium percarbonate was dried
with hot air to obtain coated sodium percarbonate.
For the purpose of comparison, sodium percarbo-
nate coated with only sodium metaborate (7.l g of
Na2BO2 4H2O per lO0 g of sodium percarbonate),
sodium percarbonate coated with boric acid (3.4 g
of boric acid per lO0 g of sodium percarbonate),
sodium percarbonate coated with boric acid and
sodium silicate (JIS No. 3) (2.4 g of boric acid
and l g (on a solid basis) of JIS No. 3 sodium
silicate per lO0 g of sodium carbonate), and sodium
percarbonate coated with only the silicate (3.4 g
(on a solid basis) of JIS No. 3 sodium silicate per
lO0 g of sodium percarbonate) were also prepared.
lO wt.~ of each of these coated sodium per-
carbonates was uniformly incorporated in a powdered
phosphorus-free detergent having the following com-
V60
285
position to obtain a bleaching detergent:
phosphorus-free bleaching
detergent composition wt.~
sodium dodecylbenzenesulfonate 20.0
synthetic zeolite (type 4A) 20.0
sodium silicate (JIS ~o. 2) 10.0
sodium carbonate 5.0
fluorescent dye O.S
sodium salt of carboxymethylcellulose 1.0
enzyme talcalase) 0.3
sodium percarbonate 10.0
water 5.0
sodium sulfate balance
Total 100
Six samples of the above compositions contain-
ing, as sodium percarbonate to be incorporated, one
coated with sodium metaborate and sodium silicate
according to the present invention, one coated with
only sodium metaborate, one coated with boric acid,
one coated with boric acid and sodium silicate, one
coated with only sodium silicate and uncoated sodium
percarbonate for the purpose of comparison were
subjected to a storage stability test. The results
are gi~en in Table 8.
Table 8
. * Available oxygen
Coating of sodlum percarbonate residue (%)
Bleaching detergent of 5% sodium metaborate (NaBO2-4H2O) 85.4
the present invention 1% sodium silicate (JIS No. 3)
Comparative Example 3 7.1% sodium metaborate (NaBO2-4H2O) 79.7
Comparative Example 4 3.4% boric acid (H3BO3) 60.8
r 2.4% boric acid (H3BO3) ~
Comparative Example 5 1% sodium silicate (JIS No. 3~ 63.3 O
Comparative Example 6 3.4% sodium silicate (JIS No. 3) 45.3
Comparative Example 7 none
* The amount (coating ratio) of the coating agent was 3.4% ~on a water-free
basis) based on sodium percarbonate in all cases.
062
~202854
It is apparent that the available oxygen
residue of the bleaching detergent containing sodium
percarbonate coated with sodium metaborate and
sodium silicate of the present invention, is higher
than those of the bleaching detergents of Compara-
tive Examples 3 to 7, and the bleaching detergent
of the present invention is superior in the coating
effect to those of Comparative Examples.
The bleaching detergent used in this example
does not contain phosphorus at all and is a phos-
phorus-free detergent containing zeolite blended
therewith. sut the bleaching detergent according
to the present invention exhibits a good stability
because of an excellent coating effect due to sodium
metaborate and sodium silicate.
Example 10
The solubility, compression strength and dis-
integrating property of the coated sodium percarbo-
nates prepared in Example 9 were examined. The
results are given in Table 9.
Table g
Coating of sodium Solubilit Compression Disintegrating
percarbonate* (sec) ~kg/cm2)property
Bleaching
detergent 5% NaBO ~H O 98 19.5 6.2
of the present 1% sodium silicate**
invention
Comparative 7 1% NaBO 4H O 96 20.7 13.9
Example 3 2 2
Comparative 3 4% boric acid (H BO ) 95 21.0 14.4
Example 4 3 3 0 c~
Comparative 2.4~ boric acid 96 l9.6 7.7 `~
1% sodium silicate
Comparative
Example 6 3.4% sodium silicate109 19.4 8.2
Comparative none 90 20.6 13.4
* The amount (on a water-free solid basis) of the coating was 3.4~.
** JIS No. 3, sodium silicate on a solid basis.
06~
lZC~Z8S4
It is apparant from Table 9 that the solubility
is substantially unchanged though sodium percarbo
nate is coated according to the process of the
present invention, and the disintegrating property
is remarkably improved when coated with sodium
metaborate and sodium silicate according to the
process of the present invention.
ExamPle 1 1
Sodium percarbonate was coated by the pro-
cedure of Example 9 using various sodium silicates
in combination with sodium metaborate. The follow-
ing coating agents were used:
5% NaB02 4H20 + 1% (on a solid basis) sodium
orthosilicate,
5% NaB02 4H20 + 1% (on a solid basis) sodium
metasilicate,
5% NaB02~4H20 + 1% (on a solid basis) sodium
silicate (JIS No. 1),
5% NaB02 4H20 + 1% (on a solid basis) sodium
silicate (JIS No. 2),
5% NaB02 4H20 + 1% (on a solid basis) sodium
silicate (JIS No. 3), and
7-1% NaB02 4H20
Each of seven samples (i.e., the above six
coated sodium percarbonates and uncoated sodium
~ 65
lZ02854
percarbonate~ in an amount of lO wt.% in terms of
sodium percarbonate was incorporated in a phos-
phorus-free bleaching detergent having the same
composition as that of Example 9. A storage
stability test was conducted in a similar manner
to that described in Example 9. Further, these
seven sodium percarbonates were subjected to a
disintegrating test in a similar manner to that
described inExample 10. The samples of sodium
percarbonates after the completion of the dis-
integrating test were further subjected to the
storage stability test. The results are given in
Table 10.
Table 10
Available Disin~egrating residue, % by
Coating of sodium percarbonate* residueproperty storage test after
(%) disintegration test
5% NaBO2 4H2O ~ 81.0 10.8 75.1
1% sodium orthosilicate
5% NaBO2-4H2O + 82.3 9.0 79.8
1% sodium metasilicate
2 2 . 82.3 7.8 82.1
1% sodium silicate (JIS No. 1) O p~
5% Na~O2-4H2O + 84.0 6.2 83.0 C~ ~n
1% sodium silicate (JIS No. 2)
5% NaBO2 4H2O + 85.4 6.2 84.4
1~ sodium silicate (JIS No. 3)
7-1% NaB2'4H2 79 7 13.9 72.9
~ none 31.1 13.4 30.5
* The coating ratio on a water-free basis was 3.4%.
067
lZO;~3S~
It is apparant from Table 10that products (l)
to (5) of the present invention exhibits an excel-
lent storage stability by the synergistic coating
effect of the borate and the silicate. By using
the borate and the silicate in combination, the
coated particles have a strength which could not
be obtained by the coating of only the borate.
As seen from the storage test result after the
disintegrating test, damage resistance can be
imparted to the coated particles. Therefore, the
coating of the coated particles of the present
invention is hardly damaged on the way of trans-
portation in the blending stage with bleaching
detergents and, even when the particles are dam-
aged, the storage stability is not substantially
deteriorated.
Example 12
Sodium percarbonate was coated by the pro-
cedure of Example 9 with the exception that sodium
metaborate and sodium silicate were used in com-
bination with other coating agents shown below.
The amount of the coating agent was wt.% based on
sodium percarbonate.
5% NaBO2 4H2O + 1% (on a solid base) sodium
silicate (JIS No. 3) + 5% polyethylene glycol
068
~2~8S~
(PEG, molecular weight = 6000),
5% NaBO2 4H2O + 1% (on a solid basisJ sodium
silicate (JIS No. 3) + 5% sodium carbonate,
5% NaBO2 4H2O + 1% (on a solid basis) sodium
silicate (JIS No. 3) + 0.5% disodium ethylene-
diaminetetraacetate (EDTA),
5% NaBO2 4H2O + 1% (on a solid basis) sodlum
silieate (JIS No. 3) + 0.5~ EDTA diitriethanol-
amine) salt, and
5% NaBO2~4H2O + 1% (on a solid basis) sodium
silicate (JIS No. 3) + 0.5~ trisodium nitrilo-
triaeetate (NTA)
lO wt.% of eaeh of si~ samples (i.e., the above
five-eoated sodium percarbonates and uneoated sodium
perearbonate) was ineorporated in the phosphorus-
free bleaehing detergent having the same eomposition
as that of Example 9. A storage stability test was
eonducted in a similar manner to that described in
Example 9. The results are given in Table 11.
Table 11
' Coating of sodium percarbonate residue (%)
NaB02-4H20 + No. 3 sodium silicate + PEG 87. 2
5~ 1~ 5%
NaB02-4H20 + No. 3 sodium silicate + Na2C03 86.6
5% 1~ 5
NaB024H20 + No. 3 sodium silicate + EDTA-2Na 87.7
5% 1% 0.5%
NaB024H20 + No. 3 sodium silicate + EDTA- 2TEA go g ~ C~
5% 1% 0.5%
NaB02-4H20 + No. 3 sodium silicate + NTA-3Na 88.8
5% 1~ 0.5%
none 30.5
070
120;285
It is apparent fromTable 11 that sodium per-
carbonate exhibits an excellent storage stability
aLso when coated with sodium perborate, sodium
silicate and other coating agents in combination.
Particularly, when sodium perborate and sodium
silicate are used in combination with an organic
high-molecular compound such as PEG or a sequester-
ing agent such as EDTA or NTA, a synergistic effect
can be obtained and the storage stability is furhter
improved.
Example 13
20 kg of wet sodium percarbonate was charged
in a centrifugal diffusion type mixer (Lodige Mixer,
FKM-130D, T.M. Engineering Co., Ltd.). A powdered
coating agent was added thereto with stirring.
Mixing was conducted for lO minutes in total. Then
the coated sodium percarbonate was taken out and
dried with hot air. The following coating agents
were used.
5% sodium metaborate (NaBO2 4H2O) + 1% (on a
solid basis) sodium silicate (JIS No. 3) +
0.5% EDTA-2TEA,
4.54% borax (Na2B4O7 lOH2O) + 1% (on a solid
basis) sodium silicate (JIS No. 3) + 0.5%
EDTA-2TEA and
0'71
lZOZ8S~c
2.4~ boric acid (H3BO3) + l~ (on a solid
basis) sodium silicate (JIS No. 3) + 0.5
EDTA-2TEA.
Note: The percentage is wt.~ based on sodium
percarbonate.
lO g of each of four samples [i.e., the above
three coated sodium percarbonàtes (two samples of
the present invention and one sample of comparative
example) and uncoated sodium percarbonate] was
incorporated in a phosphorus-free bleaching
detergent composition having a composition given
below as in Examples 9 and 10. A storage stability
test was conducted in a similar manner to that
described in Example 9. The results are given in
Table 12. Further, the residual activity bf an
enzyme (alcalase 2.OM~ simultaneously incorporated
in the composition was also measured.
/
072
~2028S4
(1971~.
Phosphorus-free bleaching
detergent composition wt.%
sodium dodecylbenzenesulfonate 20.0
synthetic zeolite (type 4A) 20.0
sodium silicate (JIS No. 2) 10.0
sodium carbonate 5 0
fluorescent dye 0,5
sodium salt of carboxymethylcellulose 1.0
enzyme (alcalase 2.0M) 0.3
sodium percarbonate (coated) 10.0
water 5.0
sodium sulfate balance
Total 100
Table 12
Available Enzymatic
Coating of sodium percarbonate*oxygen activity
residue (%) residue (%)
22 + sodium silicate + EDTA-2TEA 93 9 96.8
5% 1 1% 0.5%
Na2B2O7-10H2O + sodium silicate + EDTA-2TEA 89.0 94.6
4.54% 1% 0.5%
C
H3BO3+ sodium silicate + EDTA-2TEA 75 0 9O 4
2.4% 1% 0.5% ~D C;
~P
~ none 32.0 80.3
* The coating rate on a water-free basis was 3.9% in all cases.
** sodium silicate (JIS No. 3)
0'74
~;Z028S4
It is apparent from Table 12that sodium per-
carbonate exhibits very good stability and the
enzyme also has an excellent stability, though the
bleaching detergents ~ and ~ of the present in-
vention contain zeolite blended therewith.
Example 1~
lO wt.~ of each of the coated sodium percarbo-
nates (coated with NaB02 4H20 and Na2B407 lOH20 in
combination with sodium silicate) of the present
invention prepared in Example 13and two comparative
samples (one coated with H3B03 in combination with
sodium silicate and prepared in Example 5 and
uncoated sodium percarbonate) was incorporated in
a powdered bleaching detergent having a composition
given below. A storage stability test was conducted
in a similar manner to that described in Examples
9 and 13. The test results on the available oxygen
residue of sodium percarbonate and enzymatic
activity residue of alcalase 2.OM are given in
Table 13,
Bleaching detergent composition wt.~
sodium dodecylbenzenesulfonate 20.0
sodium tripolyphosphate 18.0
sodium silicate (JIS No. 2) lO.O
oi75
Z~3S~
sodium carbonate 5.0
fluorescent dye 0.5
sodium salt of carboxymethylcellulose 0~5
enzyme (alcalase 2.OM) 0.3
sodium percarbonate 10.0
water 50
sodium sulfate balance
Total 100
Table 13
Available Enzyrnatic
Coating of sodium percarbonate*oxygen activity
residue (%) residue (~)
22 + sodium silicate + EDTA-2TEA 97 0 84.8
5% 1% 0.5%
Na2B2O7 10H2O + sodium silicate + EDTA-2TEA 96.0 86.0
4.54% 1% 0.5%
8B3 + sodium silicate + EDTA-2TEA 90.8 81.0 ;~
2.4% 1% 0-5%
~ none 88.8 60.5
* The coating rate on a water-free basis was 3.9%.
iZ~5
0'7'~
This example shows the use of a conventional
bleaching detergent composition contalning STPP.
Here also, the composition of the present inven-
tion exhibits a very excellent storage stability.
This fact shows that the bleaching detergent of
the present invention has a very excellent storage
stability, irrespective of whether zeolite is
present or not.
lZ~ 8S~
078
Example 15
100 g of sodium percarbonate was charged in
an agitating mixer. A 25% aqueous solution of 5 g
of sodium metaborate tetrahydrate (NaBO2 4H2O)
(prepared by dissolving the metaborate in water
with heating) and a 25~ aqueous solution of 1 g
of anhydrous magnesium sulfate (MgSO4) were sprayed
thereon with stirring at 250 r.p.m. After stirring
for 10 min, sodium percarbonate was dried with hot
air to obtain coated sodium percarbonate.
For the purpose of comparison, sodium per-
carbonate coated with only sodium metaborate (7.1 g
of NaBO~-4H2O per 100 g of sodium percarbonate),
one coated with boric acid (3.4 g of boric acid
per lQ0 g of sodium percarbonate), one coated with
boric acld and anhydrous magnesium sulfate (2.4 g
of boric acid and 1 g of MgSO4 per 100 g of sodium
percarbonate), and one coated with only anhydrous
magnesium sulfate (3.4 g of MgSO4 per 100 g of
sodium percarbonate) were also prepared.
10 wt.~ of each of these coated sodium per-
carbonates was uniformly incorporated in a powdered
phosphorus~free detergent having the following
composition to obtain a bleaching detergent:
~;~V;~854
0'~9
phosphorus -f ree bleaching
detergent composition wt.%
sodium dodecylbenzenesulfonate 20.0
synthetic zeolite (4A type) 20.0
sodium silicate (JIS No. 2) lO.0
sodium carbonate 5.0
f luorescent dye O.S
sodium salt of carboxymethylcellulose l.0
enzyme (alcalase) 0.3
sodium percarbonate lO.0
water 5.0
sodium sulf ate balance
Total lO0
Six samples of compositions conta;ning, as
sodium percarbonate to be incorporated in the above
composition, one coated with sodium metaborate and
MgSO4 according to the present invention, one coated
with only sodium metaborate, one coated with boric
acid, one coated with boric acid and MgSO4, one
coated with only MgSO4 and uncoated sodium percarbo-
nate, were subjected to a storage stability test.
The results are given in Table 14,
Table 1 ~
~~~~~-- Available oxygen
~ Coating of sodium percarbonate* residue (%)
Bleaching detergent of 5% sodillm metaborate (NaBO2-4H2O) 86.2
the present invention ~% MgSO4
Comparative Example 8 7.1% sodium metaborate (NaBO2-4H2O) 79.7
Comparative Example 9 3.4% boric acid (H3BO3) 60.8
2.4~ boric acid ~H3BO3) 65.0 O
Comparative Example 10 1~ MgSO4 C 3~
Comparative Example 11 3-4% MgSO4 50.8 ~n
Comparative Example 12 none 3l.l
* The ratio (coating ratio) of coating agent to sodium percarbonate was 3.4%
on a water-free solid basis in all cases.
:~OZ85
081
It is apparent that the availa~le oxygen
residue of the bleaching detergent containing
sodium percarbonate coated with sodium metaborate
and MgS04 according to the present invention is
higher than those of Comparative Examples 8 and 12,
and the bleaching agent of the present invention
is superior in the coating effect to those of
Comparative Examples 8 to 12.
The bleaching detergent used in this example
does not contain phosphorus at all and is a phos-
phorus-free detergent containing zeolite blended
therewith. But the bleaching detergent according
to the present invention exhibits a good stability
because of an excellent coating-stabilizing effect
due to sodium metaborate and MgS04.
Example 16
Sodium percarbonate was coated by the pro-
cedure of Example 1susing various magnesium com-
pounds in combination with sodium metaborate.
The following coating agents were used:
5% NaB02 4H~O + l~ (on a water-free solid
basis) MgS04,
5~ NaB02 4H20 + 1% (on a water-free solid
basis) MgCQ~,
5~ NaB02 4H20 + l~ (on a water-free solid
lZ~)Z8S4
082
basis) 2MgO-3SiO2,
@ 5% NaBO2 4H20 + 1% ~on a water-free solid
basis) MgO and
7-1% NaBO2-4H20
l0 wt.% of each o~ six samples (i.e., the
above five coated sodium percarbonate and uncoated
sodium percarbonate) was incorporated in the phos-
phorus-free bleaching detergent having the same
composition as that of ~xample 15. A storage
stability test was conducted in a similar manner
to that described in Example 15. The results are
given in Table 15.
Table 15
Available
Coating of sodium percarbonate* oxygen
residue, %
5% NaBO2 4H20 + 1% MgS04 85.8
5% NaBO2 4H20 + 1% MgCQ2 83.9
5% NaBO2 4H20 + 1% 2MgO 3SiO2 84.0
5% NaBO2 4H20 + 1% MgO82.1
7-1% NaB2 4H2 79 7
none 3l.l
*The coating ratio was 3.4% (on a wa-ter-free
basis) based on sodium percarbonate in all
cases.
~Z~)Z85
(~3
It is apparent that cornpositions ~ to ~ of
the present in~ention exhibit a very excellent
storage stability by the synergistic effect of
the coating power of the borate and the stabilizing
power of the magnesium compound.
Example 17
Sodium carbonate was coated by the procedure
of Example 15with the exception that sodium metabo-
rate and magnesium sulfate were used in combination
with other coating agents shown below. The amounts
of the coating agents were wt.% based on sodium
percarbonate.
5% NaBO2 4H2O + 1% (on a water-free solid
basis) MgSO4 + 5% polyethylene glycol (PEG,
molecular weight -- 6000),
5% NaBO2 4H2O + 1% (on a water-free solid
basis) MgSO~ + 5% sodium carbonate,
5% N~aBO2 4H2O + 1% (on a water-free solid
basis) MgSO~l + 0.5% disodium ethylene-
diaminetetraacetate (EDTA 2Na),
5% NaBO2 4H2O + 1% (on a water-free solid
basis) MgSO4 + 0.5% EDTA di(triethanolamine)
salt (2TEA) and
5% NaBO2 4H2O + 1% (on a water-free solid
basis) MgSO4 + 0.5% trisodium nitrilotri-
3~Z(;~2854
08d~
acetate (NTA-3Na).
lO wt.% of each of six samples (i.e., the above
five coated sodium percarbonate and uncoated sodium
percarbonate~ was incorporated in the phosphorus-
free bleaching detergent having the same composition
as that of Example 15. A storage stability test was
conducted in a similar manner to that described in
Example 15. The results are given in Table 3.
Table 16
Available
Coating of sodium percarbonate oxygen
residue, %
NaBO2 4H2O + MgSO4 +- PEG 88.0
NaB2'4H2 + MgSO4 Na2 3
5% 1% 5% 86.0
5% 1% 0.5% 86.0
NaBO2 4H2O + MgSO4 + EDTA 2TEA 9l.8
NaBO2 4H2O + MgSO4 + NTA 3Na 90.6
none 30.5
It is apparent that sodium percarbonate exhibit
a very excellent storage stability alsc when coated
~;~0~8S4
085
with sodium metaborate, magnesium sulfate and other
coating agents in combination. Particularly, when
sodium metaborate and MgS04 are used in combination
with an organic high-molecular compound such as
PEG or a sequestering ayent such as EDTA or NTA,
the storage stability is further improved by the
synergistic effect.
Example 18
The solubility, compression strength and dis-
integrating property of the coated sodium percarbo-
nates prepared in Example 17were examined. The
results are given in Table 17,
Table 17
. .t Compression Disintegrating
Coating of sodium percarbonate S(usebl) Y (kg/cm2) property
NaBO2 4H2O + MgSO4 + PEG 94 18.9 15.0
5% 1% 5%
NaBO2 4H2O + MgSO4 + Na2CO3 93 19.6 14.7
5% 1~ 5
O2-4~2O + MgSO4 + EDTA-2Na 91 19.2 14.6
5% 1% 0~5%
24H20 + MgSo4 + EDTA.2TEA 9O 21.3 13,3 0~ ~0
5% 1% 0;5%
O2 4H2O + MgSO4 + NTA-3Na 95 22.1 13.3
5% 1~ 0.5%
none 90 20.6 13.4
lZO'~8S~
0~7
It is apparent fromTable 17 tha-t the solubil-
ity, compression strength and disintegrating pro-
perty of sodium percarbonate coated according to
the process of the present invention are nearly
equal to those of uncoated sodium percarbonate
Example 19
20 kg of wet sodium percarbonate was charged
in a centrifugal diffusion type mixer (Lodige Mixer,
FKM-130D, T.M. Engineering Co., Ltd.~. A powdered
coating agent was added thereto with stirring.
Mixing was conducted for 10 minutes in total.
Then the coated sodium percarbonate was taken out
and dried with hot air. The following coating
agents were used:
5% sodium metaborate (NaBO2 4H2O) ~ 1% (on a
water-free solid basis) MgSO4 + 0.5% EDTA-2TEA,
4.54% borax (Na2B4O7~l0H2O) + 1% (on a water-
free solid basis) MgSO4 + 0.5% EDTA-2TEA and
2.4% boric acid (H3BO3) + 1% (on a water-free
solid basis) MgSO4 + O.S~ EDTA-2TEA
Note: The percentage is wt.~ based on sodium
percarbonate.
lO wt.% of each of four samples [i.e., the above
three coated sodium percarbonates (two samples of
the present invention and one sample of comparative
854
088
example) and uncoated sodium percarbonate] was
incorporated in a phosphorus-free bleaching
detergent composition having a composition given
below as in Examples 15 and 16.A storage stability
test was conducted in a similar manner to that
described in Example 15, The resu~-ts are given in
Table 18. Further, the residual activity of an
enzyme (alcalase 2.OM) simultaneously incorporated
in the composition was also measured.
phosphorus-free.bleaching
detergent composition wt.~
sodium dodecylbenzene sulfonate 20.0
synthetic zeolite (type 4A) 20.0
sodium silicate (JIS No. 2~ lO.O
sodium carbonate 5.0
fluorescent dye
sodium salt of carboxymethylcellulose l.O
enzyme talcalase 2.OM) . 0.3
sodium percarbonate (coated) lO.O
water 5.0
sodium sulfate balance
Total lOO
Table 18
. . Available oxygen Enzymatic activity
Coat1ng of sodlum percarbonate* residue (~)residue (~3
O2 4H2O ~ MgSO4 + EDTA-2TEA 92.8 96.0
5~ 1% 0.5%
2 4O710H2O + MgSO4 + EDTA-2TEA 89.8 96.0
4.54% 1~ 0.5
H3BO3 + MgS04 + EDTA-2TEA 74.0 90 p~
2.4~ 1~ 0.5% o
- O P~;
~ none 32.0 81.0 ~ cn
* The coating ratio on a water-free solid basis was 3.9~ based on sodium
percarbonate in all cases.
~z~
o9o
It is apparent fromTable 18 tha-t ln the phos-
phorus-free bleachiny detergents ~ and ~ of the
present invention, sodium percarbonate exhibits
a very good stability and the enzyme also has an
excellent stability, though zeolite is incorporated
therein.
Example 2~
10 wt.% o~ each of the coated sodium percarbo-
nate (coated with NaB02-4H20 and Na2B407 lOH20 in
combination with MgS04) of the present invention
prepared in Example 5 and two comparative samples
(one coated with H3B03/~gS04 prepared in Example 5
and uncoated sodium percarbonate) was incorporated
in a powdered bleaching detergent having a composi-
tion given below. A storage stability test was
conducted in a similar manner to that described in
Examples 15 and 19.The test results on the avail~
able oxygen residue of sodium percarbonate and the
enzymatic activity residue of alcalase 2.OM are
given in Table 19,
Bleaching detergent composition wt.%
sodium dodecylbenzenesulfonate 20.0
sodium tripolyphosphate 18.0
sodium silicate (JIS No. 2) lO.O
~2~Z8S4
091
sodium carbonate 5.0
fluorescent dye 0.5
sodium salt of carboxymethylcellulose 0.5
enzyme (alcalase 2.0M) 0.3
sodium percarbonate 10.0
water 5.0
sodium sulfate balance
Total 100
Table 19
Coating of sodium percarbonate* Available oxygen Enzymatic activity
residue ~%~ residue (%)
O2 4H2O + MgSO4 + EDTA~2TEA 96.8 86.1
5% 1% 0-.5%
Na2B4O7 10H2O + MgSO4 + EDTA 2TEA 97.8 87.2
4.54% 1% 0.5%
H3BO3 + MgS04 + EDTA~2TEA 80.5
2.4~ 1% 0.5% O
~ none 88.8 60.5
* The coating, ratio on a water-free solid basis was 3.9~.
~2(~ 54
0~3
This example shows the use of a conventlonal
bleaching detergent composition containing STPP.
Here also, the composition of the present invention
exhibits a very excellent storage ability. This
fact shows that the bleaching detergent of the
present invention has a very excellent storage
stability, irrespective of whether zeolite is pre-
sent or not.
lZO;~8S4
, . ..
094
Example 21
100 g of sodium percarbonate was charged in
an agitating mixer. A 25% aqueous solution of 5 g
of sodium metaborate tetrahydrate (NaBO2 4H2O)
(prepared by dissolving the metaborate in water
with heating) was sprayed thereon with stirring at
250 r.p.m. After stirring for 10 min, sodium
percarbonate was dried with hot air to obtain
coated sodium percarbonate.
For the purpose of comparison, sodium per-
carbonate coated with boric acid (2.4 g of boric
acid per 100 g of sodium percarbonate) was prepared.
Each of these coated percarbonates (one coated
with sodium metaborate according to the present
invention and the other coated with boric acid for
the purpose of comparison) and uncoated sodium
percarbonate was uniformly incorporated in a
bleaching agent composition (1) having the follow-
ing composition. These three samples of the
bleaching agent compositions were subjected to a
storage stability test. At the same time, their
smells were examined.
Bleaching agent composition (1) wt.%
sodium percarbonate 30
)Z~3S4
0~
sodium pyrophosphate lO
sodlum lauryl sulfate 5
Glauber's salt 15
granular activating agent A* 40
Total 100
* This agent was prepared by ~ranulating 50 wt.~ of
glucose pentaacetate, 10 wt.% of polyethylene
glycol having an average molecular weight of
6000 and 40 wt.~ of sodium sulfate in a granulator
(X-Pelleter 60-D, manufactured by Fuji Powdaru K.K.)
under pressure while passing through a screen of
0.77 ~m~.
)Z~35
O
Table 20
-
\ Coating of Available
\ sodium o~ygen Smell
\ percarbonate residue (~)
Bleaching agent *5% sodium
of the present metaborate 79 good
invention (NaB02-4H20)
Comparative 2 4% boric 61 slightly
Example 1 acid (~3B03) bad smell
Comparative smell of
Example 2 none 40 acetic acid
* The amount (on a water-free solid basis) of the coating
was 2.4% based on sodium percarbonate.
It is apparent from Table 20that the bleaching
agent composition of the present invention is much
superior in storage stability to those of Compara-
tive Examples (boric acid-coated sodium percarbonate
and uncoated sodium percarbonate). The product of
the present invention has no problem on smell.
Example 22
Each of three samples (sodium percarbonate
coated with sodium metaborate according the present
invention, sodium percarbonate coated with boric
acid for the purpose of comparison, and uncoated
sodium percarbonate) used inExample 21 was uni-
formly incorporated in a bleaching agent composi-
tion (2) having a different composition from that
~2V285
o ~>7
of Example 21. These samples were subjected to the
same storage stability test as that of Example21.
The results are given in Table 21.
Bleaching agent composition (2)wt.
sodium percarbonate 40
sodium tripolyphosphate lO
fluorescent dye 0.3
perfume 0.3
Glauber's salt balance
granular activating agent B* 40
Total lO0
* This agent was prepared by granuIating S wt.% of
CuSO4 5H2O, 5 wt.~ of picolinic acid, 20 wt~% of
polyethylene glycol having an average molecular
weight of 6000 and 70 wt.% of sodium sulfate in
a granulator (X-pelleter 60-D, manufactured by
Fuji Powdaru K.K.) under pressure while passing
through a screen of 0.7 mm~.
S4
09~
Table 21
~ Coating ofAvailable
\ sodium oxyyen
\ percarbonate residue (%)
Bleaching agent *5% sodium
of the present metaborate 66
invention (NaBO2 4H2O)
Comparative 2.4% boric acid 25
Example l (H3BO
Comparative
Example 2 none 3
* The amount (on a water-free solid basis) of the
coating was 2.4% based on sodium percarbonate.
It is apparent from Table 21that the bleaching
agent composition of the present invention has also
an excellent storage stability in the example where
a transition-metal activating agent was blended.
Example 2~
~ odium percarbonate was coated with sodium
metaborate in combination with other coating agent
in a similar manner to that described in Example 21.
The following combinations of sodium percarbonate
with other coating agents were used. The amounts
of other coating agents are wt.% based on the amount
of sodium percarbonate.
5% sodium metaborate (NaBO4 4H2O) + 5% poly-
ethylene glycol (PEG, molecular weight = 6000),
28S9L
0~'~
5% sodium metaborate + 5~ sodium carbonate,
5% sodium metaborate + 0.5% disodium ethylene-
diaminetetraacetate (EDTA),
5% sodium metaborate + 0.5~ EDTA di~triethanol-
amine) salt, and
5~ sodium metaborate + 0.5% trisodium nitrilo-
triacetate (NTA).
Each of six samples (i.e., the above mentioned
five samples of the coated sodium percarbonate and
uncoated sodium percarbonate) was uniformly in-
corporated in ~ach of bleaching agent compositions
having the following compositions (3-l) and (3-2).
These compositions were subjected to the same
storage stability test as that described in
Example 21. The results are given in Table 22.
Bleaching agent Bleaching agent
composition composition
(3-1)(3-2)
sodium percarbonate 40 ~ 30
sodium tripolyphosphate lO
sodium pyrophosphate - lO
sodium silicate - 2
fluorescent dye 0.3 0.3
perfume 0-30-3
Glauber's salt balance balance
120Z85
100
granular activating agent C* 40
granular activating agent D* - 40
Total 100 100 wt.%
* These agents were prepared in the foLlowing manner.
Mixtures composed of the following composition C
and D were heated at about 140C and stirred until
a uniform paste was formed. The paste was cooled
to room temperature to solidity it. The solid
was crushed and granules having a particle size
of 250 to 1000 ~ were employed.
C D
sucrose octaacetate 70
FeSO~ 5H2O - 5
CoSO ~7H O - 1
sodium iminodiacetate - 5
polyethylene glycol 10 60
(average molecular weight=6000)
corn starch 10 10
Glauber's salt 10 19
Table 22
Available oxygen Available oxygen
Coating of sodium residue in residue in
percarbonatecomposition 3-1composition 3-2
(%) ~%)
NaBO2 4H2O + PEG 84 70
5~ 5%
NaBO2 4H2O + NaCO380 69
5% 5%
NaB02 4H20 + EDTA-2Na 79 69 c~
5% 0.5% G P;
NaB024H20 + EDTA-2TEA 89 72 ~- ~R
5% 0.5%
NaBO2 4H2O + NTA-3Na 86 71
5% 0.5%
not coated 42 5
~1;20;~8S4
102
It is apparent from Table 22that the composi-
tions of the present invention have also an excel-
lent storage stability even when sodium percarbonate
is used in combination with other coating agents.
Particularly, when sodium metaborate is used in
combination with an organic high-molecular compound
such as PEG or a sequestering agent such as EDTA
or NTA, a synergistic effect can be obtained and
the storage stability is further improved.
Example 24
20 kg of wet sodium percarbonate was charged
in a centrifugal diffusion type mixer (Lodige
Mixer, FKM-130D, manufactured by T.M. Engineering
Co., Ltd.). A powdered coating agent was added
thereto with stirring. ~ixing was conducted for
10 min in total. Then the coated sodium percarbo-
nate was taken out and dried with hot air. The
following coating agents were used.
- ~ 5~ sodium metaborate (NaBO2 4H2O) + 0.5%
EDT~-2TEA,
4.54~ borax (Na2B4O7-10H2O) + O.S~ EDTA.2TEA
and
2.4% boric acid (H3BO3) + 0.5~ EDTA-2TEA
(the percentages are given by weight based on
sodium percarbonate).
~;~o;~
Each of four samples (i.e., three samples of
two coated sodium percarbonate according to the
present invention and one coated sodium percarbo-
nate of comparative example, and uncoated sodium
percarbonate) was uniformly incorporated in each
of bleaching agent compositions having the following
compositions (4-1) and (4-2). These compositions
were subjected to the same storage stability test
as that described in Example 21. The results are
given in Table 23.
Bleaching agent 31eaching agent
compositioncomposition
(4-1~ (4-2)
sodium percarbonate 30 40
sodium carbonate (anhydrous) - 10
sodium silicate 2 2
fluorescent dye 0.3 0.3
perfume 0-3 0-3
carboxymethylcellulose 2 2
Galuber's salt balance bala
granular activating agent E* 40
granular activating agent F* - 40
Total 100 100 wt.
* These agents were prepared in the following manner.
Acetone was added to mixtures having the following
~0;~8~4
104
compositions E and F. They were thoroughly
kneaded ln a mortar and acen-tone was removed
therefrom under reduced pressure. After drying,
the residue was crushed to coarse grain. Granules
having a particle size of 250 to 1000 ~ were
employed.
E F
tetraacetylethylenediamine 70
tetraacetylglycollyl - 70
polyethylene gLycol 10 10
(average molecular weight=6000)
hydroxypropyl starch 10 10
magnesium silicate 5 S
Galuber's salt 5 5
Table 23
Available oxygen Available oxygen
Coating of sodium residue in residue in
percarbonatecomposition 4-1 co~position 4-2
NaBO2 4H2O + EDTA-2TEA 92 90
5%* 0.5~
7 1H2O + EDTA~2TEA 88 91
4.54%* 0.5~
H3BO3 + EDTA-2TEA . 54 60
2.4% 0.5~ ~ O
~ not coated 40 41 ~
* The amount (on a water-free solid basis) of the coating was 2.4%.
~ILZ(~;~8~i4
10~)
In this experiment, -~he coating of sodium
percarbonate was carried out in a larger-scale
than in Examples 21 to 23. It is apparant from
Table 23 that thecoated products (l) and (2) of
the present invention are superior in the storage
stability of scdium percarbona-te to the compara-
tive products (3) and (4).
iZ~)2~54
ln7
Example 25
The coated sodium percarbonate obtained in
Example 24 was added to each!of two enzyrne-containing
bleaching compositions given below. The resulting
compositions were each examined in respect to the
storage stability after they had been stored at
50 c for 20 days. Results are shown in Table
24.
composition (1) composition (2)
coated sodium80 wt. ~ 80 wt.%
percarbonate
sodium carbonate10 10
alcalase 2.0M 2 2
as enzyme
zeolite of 4A type - 5
sodium sulfate 8 3
total amount 100 100
This example does not contain a surfactant and
Nos. l and 2 among them fall within the scope of
the invention, but Nos. 3 and 4 do not. It is understood
from the results thàt Nos.`l and 2 were superior
to the controls 3 and 4 with respect to the storage
stability of the sodium percarbonate and the enzyme.
Moreover the stability of the enzyme was improved
in the composition (2), containing the zeolite, than
in the composition (1).
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-- 108 --
