Note: Descriptions are shown in the official language in which they were submitted.
~0~3~5
This invention relates to novel and useful builders
for detergent.
Builders, which are blended with detergents to improve
their surface active properties, are required to have character-
istics of excellent detergency, dispersing power, emulsifying
characteristics, stability in hard water, rust preventive power,
chelating effect, low environmental pollution characteristics
and the like.
Heretofore, inorganic compounds such as Glauber's
salt or sodium sulfate, sodium metasilicate, soda ash and sodium
tripolyphosphate have been effectively utilized as builders.
However, there has heretofore been no builder ~ -
possessing all of the above-mentioned desirable characteristics.
,
For instance, phosphate builders produce problems in waste water
~ treatment and in depletion of resources and silicate builders
- give problems of stability in hard water.
This invention provides a builder for detergent which
comprises trisodium imidobissulfate having the formula
': (NaS3) 2N'Na
It has been found that trisodium imidobissulfate is remarkably
superior in its stability, rust-preventative properties, and
detergency to other imidobissulfates such as neutral ;
imidobissulfates e.g. diammonium imidobissulfates [ (NH4S03)2NH ],
disodium imidobissulfates [(NaS03)2NH.2H20], dipotassium
imidobissulfates and dilithium imidobissulfates, and the basic
imidobissulfate triammonium imidobissulfates
[ (NH4S03)2NNH4.H20~.
. .
The builder of this invention may be used in
i combination with any kind of detergent.
.1.: . .
The typical detergents to be used in combination with
the builder of this invention are, for example, anionic
surfactants such as sodium alkyl-sulfates and sodium alkyl-
benzenesulfonates, amphoteric surfactants such as alkyl betaine,
~83~5
.,
nonionic surfactants such as polyoxyethylene alkylethers,
polyoxyethylene esters of higher fatty acids, polyoxyethylene
alkylphenylethers and polyoxyethylene sorbitan esters of fatty
acids, cationic surfactants such as alkylpyridinium halides
and alkyltrialkylammonium halides and polymeric surfac-tants
such as polyoxyethylene polyoxypropylene condensates and
alkylpolyvinylpyridinium halides.
There are no essential limits to the amount of the
builder of this invention to be added to the detergent, but
preferably within 20 - 500 parts by weight of the builder are
used per 100 parts by weight of the detergent.
The trisodium imidobissulfate may be easily prepared
by various methods.
For instance, it may be prepared as illustrated in
the following equations using sulfur and ammonia.
.~ .
S 2 1/2 2 (1)
2SO3 + 3NH3~ - ~(NH4SO3)2NH (2)
tNH4So3)2NH + 3NaOH
--------~~~~ (NaSO3)2NNa -~ 2NH3 + 3
Preparation of the imidobissulfate according to this
method is quite economical since the raw materials are low
priced sulfur and ammonia.
Since the builder of this invention may be easily
prepared from sulfur and ammonia, the manufacturing costs are
quite low and their sulfur contents are relatively high, for
instance, 25% in trisodium imidobissulfate [(NaSO3)2NNa.H2O]
as compared with 10% in sodium sulfate and, accordingly, this
invention is quite important in view of the available
exploitation of sulfur.
~. ~
2 -
~.J, ~ ~
.... .
83~S
Moreover, the molecules of the builder of this
invention contain es~entially no phosphorus, which may cause
various environmental pollutions, and the contents of
nitrogen are also very low. The content of N and P in the
builder of this invention is shown in the following Table 1.
Also, the pH values of its aqueous solutions is alkaline in
the preferable range for builders.
The pH values are also shown in the following
Table 1.
:
. ,
,
,; ~' ' . :'~
.' . ~.. .
. ~ .
`~ `'"'" ',''' `~
. , ' ' '- ~
... ; ', ~' :
~83~
Table 1
I l
p% N% pH
Builders ~ NH4 ~ N 1~
diammonium imidobissulfate 0 13.3 0 6.6 7.0
disodium imidobissulfate (2) 0 0 0 5.5 7.0
triammonium imidobissulfate(~ ) 0 18.4 0 6.1 9.0 ,~
trisodium imidobissulfate (1) 0 0 0 5 4 10.9 j ~ ;
sodium tripolyphosphate (0) 25.- 0 0 0 9.7 .
. urea (0) 0 0 46.2 0 _ ~:
ammonium sulfate (0) 021.2 0 0 _
,. `~ ~
. * water of crystallization.
Water solubility is also one of the important charac- ::~
teristics for a builder. The builder of this invention has
excellent water solubility and accordingly it is not easily
salted out by other substances and does not easily salt out
; other substances. The solubility at various temperatures is
. 20 shown in the following Table 2. -~
~,
:~` - 4 - ~ ~:
~al83~
O ~ N
tl~N O d' . ~ ~ ~ ;
~. o o .'
Nl ¦ o ¦ l l r
E~ 0 ~ ~ 0 0 ,' "
o ~ ~I cn d' 0 ~ ` ',"~
'`.'
In ~ O, U~ ' ' " ~ ~'' ''
O ~ I~ ~ ~ .,' ~
~ r~ ~ ~ , ~ ,`
o ~ o co ~ ., .
. ~' ~
a~ :, .-
a~
:'.: '
lo ~ 8 ~ ~ ~4 :
s~ ~ a~ O ~ .~ -
~ ~ ~ 3 o ~ o o o o o o ~ o c
. 1 ~ ~ a~ ~ h J ~
~ " : :
- 5 -
-: :. : . , , - - . ,,;, . . ; :
:. : .. . . - . :: . .-
~ ~3~1(3S
One of the mos-t lmportant characteristics required
for builders is low toxicity. Although many of the conventional
builders give problems in toxicity (skin irritation, oral
toxicity, fish toxicity and the like), the builder of this
invention of~ers substantially no problem of toxicity, the acute
toxicity, skin irritation, eye mucous irritation, fish toxicity,
crustacean toxicity and mutating property are all being very
low.
EXAMPLE 1
This example shows test results of the builder effect :
of the imidobissulfate according to this invention to a polyoxy- ;
ethylene nonylphenyl ether (12 moles adduct).
: A : Sample
An aqueous (distilled water) solution containing 0.25
(W/V) of surfactant (polyoxyethylene nonylphenyl ether) and 0~75
of builder was prepared and used as samplè.
: Since neutral imidobissulfates are somewhat unstable,
the corresponding basic salts are used by adding a small amount
of base (about 1% as sodium hydroxide or ammonia to the anhydrous ~ .
20 salt.)
B : Testing method
(1) surface tension : measured by means of du No'uy surface
tensiometer at 22 - 24C.
(2) emulsifying characteristics : measured by putting 0.5 ml
of sample and 0.5 ml of oil (1.5 cm high) into a test
tube with a cap (8 x 50 mm), placing it in a beaker in a
water bath for 5 minutes, shaking it vertically through :
an amplitude of 25 cm for 20 times in 10 seconds, leaving
.. - , . . :: : . :
~83~l~5
it in a water bath at 90C for 30 minute~, and then
measuring the height of the emulsified phase.
Evaluation ~asis is as ~ollows.
~ ,
. Evaluation height of emulsified phase (cm)
.: _ .
: 5 1.5 ~
. 4 1.0 ~ 1.4
3 0.5 ~ 0.9
2 0.1 ~ 0.~
. .. __ O
As oils, cottonseed oil (HLB10) and liquid parrafin (HLB12) ~ ~
; were used. ~ ``
. ~:
:~ (3) dispersing power : measured by puttling 1 ml of sample
., -
and about 3 mg of carbon black into a test tube (the
: same a~ in (2)), shaking it vertically 25 cm/20 times/10
seconds, measuring the height ~h) of the dispersed phase -~ :
and observing the shade of color.
temperature : 22 ~ 24C ::
Evaluation basis is as follows. ,~ :
. I .
. ~ . _ . . ... _ I ... _.
Evaluation height h (~m) shade of color
, ... __ ... ...... _ . ,.
. 5 2.8 ~ 3.0 extremely deep :~
4 2.0 ~ 2.7 very deep
: 3 1.0 ~ 1.9 deep .
2 0.1 - 0.9 light
- 1 . . . transparent
:` ` ~'
~: ~ 7 ~
- A ~ ~
~8~ 5
(4) solubilizing power: measured by putting a 0.5 ml
sample into each of four test tubes (the same as in (2)),
putting 0.008 ml~ 0.011 ml, 0.014 ml and 0.017 ml of
isoamyl alcohol into each test tube, leaving them in hot
water at about 50C or 5 minutes, shaking ~hem vertically
25 cm~60 times/30 seconds, leaving them in hot water at
30C for 5 hours, and observing the solubilization state
(shaking after 3 hours in the same manner).
The evaluation basis depends on the maximum
amount of alcohol solubilized.
Evaluation solubilized amount (ml)
~: ... _. ... _. .....
0.018 ~
;~ 4 0.015 ~ 0.~17
3 0.012 ~ 0.014 ~`
2 0.008 ~ 0.011 `~
_ 0.007
(5) detergency: measured by putting 2 ml of sample
solution into a test tube with a cap (8 - 10 ml),
; dipping 3 pieces of arti~icially contaminated clothing
materials (8 x 8 mm) into the solution at 30C for 2
minutes, shaking it vertically under the condition of
25 cm~40 times/20 seconds, bringing out the washed
clothing materials, drying them, and measuring their
degree of whiteness by means of reflectance tester and
observing the turbidity of the waste water. contaminated
c~othing materials were prepared by contaminating cotton ;
.. ,' ~ .
- 8 -
33~
clothing materials wi-th a solution containing dissolved
liquid paraffin {65%) and cottonseed oil (35%) and dis-
pers2d carhon black in carbon tetrachloride, according
to ~. Am. oil Chemists' Soc. 28, 96 (1951).
Evaluation basis is as follows.
. _ _~
Evaluation Reflectance % Waste Water
30.1 - extremely black ~ :
428.5 - 30~0 somewhat black
~ 326.8 - 28.4 dark
; 225.1 ~ 26.7 pale dark
- 25.0 slightly muddy :~:
(6) wetting power: measured by putting 3 ml of sample
into a test tube (10 ml), putting a test piece (felt,
5 x 5 mm) gently on the liquid surface, and measuring
;. the time taken for the piece to sink from the liquid sur~
face into the liquid. ` ~
temperature: 22 - 24C ~ :
(7) rust preventive power: measured by putting 4 ml of
sample solution into a test tube with a cap (10 ml),
dipping 10 kinds of metal pieces twire of about 20 mm ~:
, :
length or metal plates of 3 x 20 x 1 mm) simultaneously
.~ into the solution, leaving it alone in hot water at 90C
: for 24 hours, and observing the piece.
Evaluation ba3is iS as follows. ;~
'.~.~' ;;:; .
~ 9 ~ ~: ~
Evaluation Surface State
.. , _ .___
no change
: 4 slight decrease in luster,
slightly rust-spotted,
~olution was slightly muddy
3 change of 4 somewhat more
: marked
: 2 rust generated on half of the
. surace
1 rust generated on all the
surface, solution was markedly
.: colored and precipitatlon
:. occurred
~ .
C: Test results ::
The test results are as ollows.
; ..
~ : :,
~:
. ~ .
. ~
... . .
.. ~ .
.`. ' "~
'` - 10 - ,~
``, ~-~
~83005
. . ~ _ _
~ -
* ~ ~ ~ ~ ~ ~ ~
1ead _ _ _ __ _ _ __ _ .. _ __ __ _
s~ solder ~ c~ ~ ~ ~ ~ .
o ~in-plate ~ ~ ~ L~ ~ ~) ~r) (~1
:~ zinc-plate c~ ~:
phosphor bronze ~ Lr ~ ~ ~ ~
brass ~ ~t ~ L~ :,
~ ~pper ~ ~ ~ ~ Lr~ t .
a~ ~ aluminium C`J ~ C~l ~ ~ N ~) ~U
:~ stee} ~ ~ ~ U~ N ~ . :
. .
so~t iron
.
. .
:., ~ ~ ~ co ~ ~ ~ u~ oo ,:
o wetting ~elt ( sec ) . . . . . . . .
~:: power . ,
al _
: ~ olubili2- . . .
ng power i.soam~l alcohol ~ ~ ~ ~ ~ ~ ~ ~
,' Q~ . :~ '
~ * ~ ~ ~ ,
: ~ ~ c~l cu r~ - ~ c~ ~ ~ ~ ~,
.: , ~ . a) _ _ _ __ _ _ __ _ _ _ _ _ _ __ _ _
:; ~ ~ cotton cloth ~ ~ ~ ~ N ~- ~ ~ :
~ ~ waste water N N ~ ~ ~ ~ ~ ~
''~' U ~S . `~
power carbon black ~ N ~ ~ N ~ ~ ~ ~ -~
o _ :5 ,
F. * ~ L~
.~ ~ . N ~ ~ ~ ~ ~ ~ ~ .
-rl ~ ~1 U _ _ _ _ _ _ _ _ _ _ _ ._ _ _ _ _ ___ ~ ~
: ~ u ~ li~uid paraffin N N N ~ ~ N N ~ ~ ~ ~
. . ~ ~ ~ cottonssed oil ~ ~ ~ ~ ~ ~ ~ ~ . :~:
", ~ ...
.: ~ surface tension (dyne/cm) o ~ ~ ~ o ~ ~ ~
.: Et ~ ~ ~ ~ ~ ~ .~. ,.
~) P~ ~)1~ tr) ~ ~ ty)
. ... '; ~ '`
:: . ~ ~ ~ I I I
. ~ n o ~1
u ,~ Ro ~ ~
~, ~ o~ ' , , ~ ~:
C)
(d ~ r~
~, o~ ~ - ~ ~ 3 ~
.. ~ ~ ~ ~ o .~ ", . ~
~ ~ e ~ o ~
h ,_~ al r~ -r~ O ~rl E~ ,-1 0 ~ U~ 1
~ ~1 ~: ~a 'd,~ rl r~ ~
.. u~ ~ O O O ~, O ~rl u~ ~1 tO h ,~
i ~1 S~ ~ ~ :.
. . _ _
-- 11 -- :-
:, . , ~-:
~L~8~ 5
EXAMPLE 2
The experiments were conducted in the same
manner set forth in Example 1 by using sodium dodecyl
sulfate as detergent.
The test results are shown in Table 4.
~
`,: ;'
, ` ~
' ~
~' :
. .
- 12 -
:
~4 ' ` ~.
. : . : . . : . . : ,
3[)~35
. __ . . . . . . .
* ~
CU ~ ~ ,~ . .
lead ~t tO ~)
solder
tin-plate ~ L~ ~t
zinc-plate c~
:: phosphor bronze cu ~ ~ ~
Q. brass ~ ~ ~t ~ :
copper - c~
aluminium ~ ~ C~l ~t
steel. ~ ~ ~ ~ ~ ~:
~1 90:Et ~ ron ~ ~ ~ ~
. ~ . , . ' ~
wetting felt (sec. ) ,~ o o
~power . 0 ,~ 0 0
~ ~__ . . - : ~:
~ing power isoamyl alcohol ,~ t ~ . ,:
o . ~
o ~ ~ _ , :~ .
u ~ cotton cloth c~ t .
~ ~ waste water ~ ~ ~ ~ : -~ .~ _ ~_. ~ ~ ~,
di ~Fe~ carbon blac}~ .
__~ I ~ c~ ~ cu ~
o ~rl U ~ _ _ _ _ ___ _ ___ .
:~ e) rl liquid para:E~in ~ ~ ~ :~
~ ~ ~ ~; $ cottonseed oi~
`'`` E~ _ . :
s~c~ace tension (d~rne/cm) ~ ~ ~ ~D . ~:
.' 0 ~ ~ ~ ':
.... ~ ' ~
.~ . . ~
~ : ~
: .
... ~ 1 ~ 1 3 ~ : :
. ~ ~ _ . o o A u? ~ U~ . ~ ~
', '. ~.'
13-
:, .,. , : . . ,- .. ~. ~ . -
1C~836~5
EXAMPLE 3
-
This example shows th,e builder effect of
trisodium imidobissulfate on the detergency of LAS
(sodium linear alkylbenzene~ulfonate) under practical
conditions.
A: Samples
sodium linear alkylbenzenesulfonate 20
builder x
sodium silicate (type 2) 5
sodium carbonate 3
carboxymethyl cellulose
water 10
sodium sulfate _ balance
- 100
. B: Contaminated clothes
: i) artificially contaminated clothes (cotton)
~ . super hardened be~ef tallow l(part) _
:~ artiicially Wet
contaminated liquid paraffin 3 method
cloth (I) (CC14)~ ~:
carbon black 0.8
... ' ~%) ~
.; cottonseed oil 60
artificially cholesterol 10
: contaminated Wet
:. cloth ~II) oleinic acid 10 method .
;: (perclene)
. palmitic acid lO .
: paraffin 10
: carbon black trace ~ .
.
.', ' .
,'. '~ ' '
~8;~3~ii
. (%) - _
artificially myristic acid 16.7
contaminated l
cloth (III) oleinic acid 16.7 ¦
tristeurin 16.7 ¦
triolein 16.7 ¦ dry
cholesterin ~ 49.75 method
cholesteryl stearate 2~2 (sponge
paraffin wax 11.1 rubbine)
squalene 11.1
clay 49 75
carbon black 0.5
: ~,
ii) naturally contaminated collar cloth (IV)
~cotton-polyester mixspun)
C: Washing condition -
_ artificially con- naturally con- ~ ;~
taminated clothes taminated clothes
. ...... : ~
Concentration of 0.10 and 0.20 % 0.14%
detergent
Hardness of water 4 dH and 15 dH 4dH ` ~"
Temperature of water 20C same
; Wa~hing Time 10 min. same
Rinsing S min. with city same
water
Washing Machine Terg-0-Tometer same
_ ___ - (120 r.p.m.)
.
.',:
~ - 15 -
~; ~''.
: .. , . .:: , . , .: - - - , . ~
.005
bath ratio l/60 l/60 or 15 pieces
half cut clothes
capacity of lQ same
bath _ _
D: Calculation of detergency (%)
i) in the case of artificially contaminated clothes,
~ illustrated as index in comparison with detergency of
- standard detergent D(%) = lO0 (%) at concentration of
`'. 10 .`
detergent of 0.20~o and hardness of 4dH.
R - Ro
D = , x 100
; R O
(wherein R: reflectance o contaminated cloth after washing,
R': reflectance of original cloth and Ro reflectance of ~;
; contaminated cloth before washing).
ii) in the case of naturally contaminated clothes, by pair
comparison method, illustrated as index in comparison with ;
lO0 for standard detergent.
. : '
; 20 E: Test results ~
Detergency to the artificially contaminated clothes ;
(I) and (II) when the content of trisodium imidobissulfate
i is 2~o (sodium sulfate 41%) is as follows.
'''~' ~' ~"
~ ''~ ' '
1~ ' . `
Ç ~''' , . ~ '
- 16 -
.,., ~ . ~ ,.
?- -
,,,,--,-; , . 1
1C~83~
Table 5
hardness (dH~ 15
concentration;(%) 0.10.2 0.1 0.2
contaminated (I) 28.542.5 16.334.4
cloth
(II) 21.2 38.114.1 26.8
Detergency is stronger at higher concentration ~ ~
and at lower hardness and in the contaminatecl cloth (I) ~. -
than in (II).
The detergency to naturally contaminated collar
cloth as compared with using sodium sulate alone (61%)
is as follows.
Table 6
_ ' ~
trisodium sodium ~ . .
imidobissulfate sulfate .
.~
mixing ratio 20/41 0/61 ~ ~
naturally 101.7 100.0 : :
contami~ated
cloth (III) ~
Detergency to artificially contaminated cloth ~ ;
(III) using 20 - 40O/o of trisodium imidobissulfate (sodium
sulfate 41 - 21%) in comparison with using 20~/o of sodium
tripolyphosphate (sodium sulfate 41%) is shown in
Figures 1 and 2. ~ ~
As is clear from Figures 1 and 2, detergency ~ ~-
: when trisodium imidobissulfate is used is stronger than : - :
., .
- 17 - ~ :
: :. . - :- . . . . , .: , .
83~(~5
when sodium sulfate alone is used, and the moxe the
amount of trisodium imidobissulEate added the stronger
the detergency.
EXAMPLE 4
Six kinds of toxicity tests were conducted
using trisodium imidobissulfate (monohydrate).
Three other imidobissulfates were al~o used in
connection with the fish toxicity test.
A: Testing method
(1) acute toxicity test: acute oral toxicity test on mice
was conducted (1 group - 10 mice)
(2) skin irritation test: skin irritation test on rabbits
(~apanese white species) was conducted in accordance
with the closed patch testing method. ~-
(3) eye mucous irritation test: irritation test to eye
mucous of rabbit (Japanese white sp~cies) was con-
ducted in accordance with the Draize method.
(4) fish toxicity test: TLm value for 48 hours to killi-
fish was measured in accordance with a fish toxicity
testing method (B No. 2735, Nov. 25, 196S).
(5) crustacean toxicity test: in~luence on artemia (brine -;
shrimp), or fatal ratio o~ artemous hatched in
artificial sea water was examined.
(6) mutating test: Rec-assay to Bacillus subtilis was
examined. -
B: Test re~ults ;~ The acute toxicity test result shows LD50 value
of 11.85 g~kg which is a very low toxicity corresponding
:'
- 18 - ~
~ ` '~ . .
o~ ~
to general medicine levels. In the skin irritation test no
change is recognized at all, even at a high concentration of
50% (super saturated solution).
In the eye mucous irri~ation test there is no change
in dropsical swelling, and no keratitis or the like is recognized
even with an aqueous 30% solution.
The fish toxicity test results show TLm values of
2,000 ppm and 1,480 ppm for trisodium imidobissulfate, of more
than 100,000 ppm for disodium imidobissulfate, of 1,400 ppm
for triammonium imidobissulfate, and of 8,600 ppm for diammonium
imidobissulfate, each of which is a very low toxicity.
The crustacean toxicity test result shows that even
with contents of 10,000 ppm the same result is obtained as with
pure sea water containing no imidobissulfate and accordingly ;~
there appear~ to be no toxicity to artemia.
In the mutating test, no growth obstructing action `
is recognized with B subtilis r~-45, H-17 and no Rec action is
recognized. ;~
It is apparent from the test results of Examples 1 - 4
that the imidobissulfate of this invention shows builder effects ;~
comparing favorably with the conventional builders such as
sodium sulfate, sodium metasilicate and also show lower toxicit~
and lower environmental pollution characteristics in comparison ;
with the conventional builders such as sodium tripolyphosphate ;
and accordingly the imidobissulfate of this invention can be
more favorably utilized as builder in combination with convention- ~ `
al detergent. ~
: ,:
'.: ` ', : '
;' ' ` `
, ~
;: - 19 ~
.. ` ;~ ~ , `
'.'-'1 1 .
... ~.~,~ I :
., "
