CA1083005A - Builder for detergent - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Builder for detergent comprising trisodium imidobissulfate of the formula, (NaSO3)2N.Na, is provided.
The builder is blended in detergent to prepare a detergent composition which is characterized by an excellent detergency, dispersing power, emulsifying power, stability in hard water, rust preventative power and low propensity for environmental pollution.

Description

~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 ~

~ " : :

-: :. : . , , - - . ,,;, . . ; :
:. : .. . . - . :: . .-~ ~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.

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 ;

.. ,' ~ .

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 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.

~

`,: ;' , ` ~

' ~

~' :

. .

:
~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~ . ~ ~

', '. ~.' :, .,. , : . . ,- .. ~. ~ . -1C~836~5 -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 . 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 ~''' , . ~ ' .,., ~ . ~ ,.
?- -,,,,--,-; , . 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.

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 :
., "

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

l. Detergent composition which comprises detergent and, as builder for the detergent, trisodium imidobissulfate having the formula, (NaSO3)2N.Na, said builder being present in an amount of from 20 to 500 parts by weight per 100 parts of the detergent.