CA1190357A - Surfactant-free stable hypochlorite paste - Google Patents
Surfactant-free stable hypochlorite pasteInfo
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- CA1190357A CA1190357A CA000407434A CA407434A CA1190357A CA 1190357 A CA1190357 A CA 1190357A CA 000407434 A CA000407434 A CA 000407434A CA 407434 A CA407434 A CA 407434A CA 1190357 A CA1190357 A CA 1190357A
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Abstract
ABSTRACT OF THE DISCLOSURE
This invention discloses a stable, surfactant-free, aqueous hypochlorite paste readily dispersible in hot or cold water, thickened with non-reactive inorganics without having alkali metal silicates, providing up to 10% available chlorine and with a viscosity ranging from about 25,000 CPS to about 2,000,000 CPS.
This invention discloses a stable, surfactant-free, aqueous hypochlorite paste readily dispersible in hot or cold water, thickened with non-reactive inorganics without having alkali metal silicates, providing up to 10% available chlorine and with a viscosity ranging from about 25,000 CPS to about 2,000,000 CPS.
Description
B 3 h 6 ( R ) SURFACTANT FREE STABLE HYPOCHLORITE PASTE
This invention re:la-tes to the field of bl.eaching agents, more particularly to aqueous chlorinated bleachi.ng pastes.
Hypochlor~te-coll-talniny compositions of various types are known as described in U.5. Patent Nos. 3,558,496;
3,666,679; 3,843,548; 4,07:L,463; 4,116,a49 and 4,155,871. Certai.n compositi.ons or processes use non-aqueous organic agents/ others employ low le~el~ of hypoch~orite, some are :Li.quids, still others use suractan-ts and various ingredients as a part of the process or composition. None of the above paten-ts discloses Applicants' particular composition of a sur~actant-free, aqueous hypochlorite paste thickened with non-reactive inorganics and which does not require alkali metal silicates and can provide up to 10~
available chlorine and which has a viscosity ranging from about 25,000 to about 2,000,000 CPS and is stable under ambient conditions.
The composition of the present invention is useEul in several ways including as a chlorine source in con~
junctiorl with paste- or gel-type automatic dishwasher detergents or, when used alone, as bleach pastes for the removal o localized sta.ins, etc. Furthermore, all paste compositions prepared according to our invention are readily dispersible in coLd or hot water. We may note that when used in conjunction with automatic dish-washer detergents, it is critical that the viscosity of the paste be not below about ].3,000 CPS so that any substantial leakage froln the dispenser cup is avoided.
It is, therefore, an object of the present invention to substantially overcome the limitations of the prior art and to provide a surfactant-free hypochlorite paste of improved chlorine stability.
,", ~.
.
.
~ ~ B 366 (R) It is a furthe.r object of the present, invention to provide inorgan.ic thlckening agen-ts which will promo-te good physical stabillty vf the thickened composltion without acceLerating the decompos.ition of the hypo-chlorite.
Other objects and advantage~ will appear as the des-crlpt.ion proceeds.
The attainment of the above ohjects is made possible by this inven-tion wh,ich includes a stable aqueous readily dispers.ible in hot or cold water ~ypochlorite paste composition having a viscosity from about 25,000 CPS to greater than about 2,000,000 CPS, consisting essentially of (a) from about 5~ to about 70% inorganic thickeners selec-ted from the group conslsting of natural colloidal clays, synthetic clays, metal oxides, , alkaL,ine earth metal carbonates, fumed silicas, pul verized amorphous silica gels and mi~ture~ thereof; (b) ; 20 about 5% to about 85~ of an aqueous sodium hypochlorite solution having from about 4.0% to about 1~ available chlorine; and (c) optionally a sufficient amount of an alXaline agent selected from the group consisting of alkali metal hydroxides whereby the pH of said pa~Qte i5 : 25 brought to a value of greater than about 12Ø
The viscosit.ies are measured by a Brookfield Synchro-Loctric Viscometer, Model LVT. All measur~ments were made with Spindle N 4, and the rpm employed varied 30 from 0.3 (for viscosities between 20,000 and 2,000,000 CPS) to 6.0 (for viscosities from 1000 to 100,000 CP5).
The thickeners employed according to the present invention are i.norganic materia:Ls which do not lnteract with 'hypochlorite. ~lese materiaLs, in finely yround ~orrn, are stirred into -the hypochlorite solution to Eorm stable, viscous suspensions. Materials sultable ....
3~ ~ B 366 (R) for this purpose incLude na-tural coLloidal clays, synthetic clay products, metal oxides, alkalin~ earth metal carbonates, silica-derlved produc-ts and mixtures thereof. The thickener level ranges from about 5% to about 70%. It i5 important to note that the inorganic thicXeners utilized be relatively ree ~rom heavy metal ion impUritles in order to prevent catalytic hypo-chlori-te decomposition and a resultant buildup of gaseou~ reac-tion productc~.
The natural clays applicable to our invention fal1 prirnarily into two m~jor groups, namely attapulgites and ~mectit~s (rnontmorillonit:es). Attapulgites, for example, are represented by the Attagel-based clays of the Engelhard Minerals ~ Chemicals Corp. and smectites are represented by alkali and~alkaline earth metal bentonites such as Imvite FGB from Industrial M;LneraL
Ventures, Inc.
Synthe-tic clay products are exemplified by multi-layered silicates similar in structure to natural smectite clays. Such synthetic clays are available under the trade name of Barasym Synthetic Minerals from NL-Industries. ~ese materials vary in electrolyte sensitivity and must be individually selected to produce optimum physical stability of the thickened hypochlorite pastes.
It is critical in order to produce a stable hypo-chlorite paste that the level of thickeners be main-tained within certain limits. For Attagel, the critical level is ~rom about 10% to about 18~ by weight of the composition. The critical range for Bentonite 18 about 7~ to about 40% and or Barasym-PNS~the critical range is about 7% to about 20%.
Viscosities from about 25,000 CPS to greater than ~ dcn~ks ~ de m6~k ~ t~ B 366 (R)
This invention re:la-tes to the field of bl.eaching agents, more particularly to aqueous chlorinated bleachi.ng pastes.
Hypochlor~te-coll-talniny compositions of various types are known as described in U.5. Patent Nos. 3,558,496;
3,666,679; 3,843,548; 4,07:L,463; 4,116,a49 and 4,155,871. Certai.n compositi.ons or processes use non-aqueous organic agents/ others employ low le~el~ of hypoch~orite, some are :Li.quids, still others use suractan-ts and various ingredients as a part of the process or composition. None of the above paten-ts discloses Applicants' particular composition of a sur~actant-free, aqueous hypochlorite paste thickened with non-reactive inorganics and which does not require alkali metal silicates and can provide up to 10~
available chlorine and which has a viscosity ranging from about 25,000 to about 2,000,000 CPS and is stable under ambient conditions.
The composition of the present invention is useEul in several ways including as a chlorine source in con~
junctiorl with paste- or gel-type automatic dishwasher detergents or, when used alone, as bleach pastes for the removal o localized sta.ins, etc. Furthermore, all paste compositions prepared according to our invention are readily dispersible in coLd or hot water. We may note that when used in conjunction with automatic dish-washer detergents, it is critical that the viscosity of the paste be not below about ].3,000 CPS so that any substantial leakage froln the dispenser cup is avoided.
It is, therefore, an object of the present invention to substantially overcome the limitations of the prior art and to provide a surfactant-free hypochlorite paste of improved chlorine stability.
,", ~.
.
.
~ ~ B 366 (R) It is a furthe.r object of the present, invention to provide inorgan.ic thlckening agen-ts which will promo-te good physical stabillty vf the thickened composltion without acceLerating the decompos.ition of the hypo-chlorite.
Other objects and advantage~ will appear as the des-crlpt.ion proceeds.
The attainment of the above ohjects is made possible by this inven-tion wh,ich includes a stable aqueous readily dispers.ible in hot or cold water ~ypochlorite paste composition having a viscosity from about 25,000 CPS to greater than about 2,000,000 CPS, consisting essentially of (a) from about 5~ to about 70% inorganic thickeners selec-ted from the group conslsting of natural colloidal clays, synthetic clays, metal oxides, , alkaL,ine earth metal carbonates, fumed silicas, pul verized amorphous silica gels and mi~ture~ thereof; (b) ; 20 about 5% to about 85~ of an aqueous sodium hypochlorite solution having from about 4.0% to about 1~ available chlorine; and (c) optionally a sufficient amount of an alXaline agent selected from the group consisting of alkali metal hydroxides whereby the pH of said pa~Qte i5 : 25 brought to a value of greater than about 12Ø
The viscosit.ies are measured by a Brookfield Synchro-Loctric Viscometer, Model LVT. All measur~ments were made with Spindle N 4, and the rpm employed varied 30 from 0.3 (for viscosities between 20,000 and 2,000,000 CPS) to 6.0 (for viscosities from 1000 to 100,000 CP5).
The thickeners employed according to the present invention are i.norganic materia:Ls which do not lnteract with 'hypochlorite. ~lese materiaLs, in finely yround ~orrn, are stirred into -the hypochlorite solution to Eorm stable, viscous suspensions. Materials sultable ....
3~ ~ B 366 (R) for this purpose incLude na-tural coLloidal clays, synthetic clay products, metal oxides, alkalin~ earth metal carbonates, silica-derlved produc-ts and mixtures thereof. The thickener level ranges from about 5% to about 70%. It i5 important to note that the inorganic thicXeners utilized be relatively ree ~rom heavy metal ion impUritles in order to prevent catalytic hypo-chlori-te decomposition and a resultant buildup of gaseou~ reac-tion productc~.
The natural clays applicable to our invention fal1 prirnarily into two m~jor groups, namely attapulgites and ~mectit~s (rnontmorillonit:es). Attapulgites, for example, are represented by the Attagel-based clays of the Engelhard Minerals ~ Chemicals Corp. and smectites are represented by alkali and~alkaline earth metal bentonites such as Imvite FGB from Industrial M;LneraL
Ventures, Inc.
Synthe-tic clay products are exemplified by multi-layered silicates similar in structure to natural smectite clays. Such synthetic clays are available under the trade name of Barasym Synthetic Minerals from NL-Industries. ~ese materials vary in electrolyte sensitivity and must be individually selected to produce optimum physical stability of the thickened hypochlorite pastes.
It is critical in order to produce a stable hypo-chlorite paste that the level of thickeners be main-tained within certain limits. For Attagel, the critical level is ~rom about 10% to about 18~ by weight of the composition. The critical range for Bentonite 18 about 7~ to about 40% and or Barasym-PNS~the critical range is about 7% to about 20%.
Viscosities from about 25,000 CPS to greater than ~ dcn~ks ~ de m6~k ~ t~ B 366 (R)
2,000,000 CPS of the paste may be obtained by using these critical Liml-ts.
Metal oxides are exemplified by zinc oxide, titanium dioxide, calcium oxide, magneslum oxide and the like.
It is critical that the level of zinc o~ide ~J.T. Baker Chem. Co., Zlnc Oxide Powder, Analyzed Reagent) when used alone as a thickener be maintained at about 55% by weight of the compositlon to ob-tain a stable product.
Below the 55% level of zinc oxide, the pas-te com~
position separates rapidly, whereas above 55% the com position loses its paste characteristics, solidifies rapidly and becomes difficul-t to stir and work with.
The critical level for titanium dioxide (J.T. Baker Chem. Co., Titanium Dioxide CP, Analyzed Reagent) i8 about S0~ to about 55% and for magnesium oxide (Fluka A.G., Magnesium Oxide puriss, p~a~) the critical level is about 50~ to about 58%, the viscosity obtained ther~from in both cases being about 2,000,000 CPS. It is to be understood that the critical l~vels of -these metal oxides would, of course, require adjustment with a change in particle size.
TyplcaL alkallne 0arth metal carbonates, of the type used in the compositions of the instant invention, are calcium carbonate and magnesium car`bonate. rrhe critical range for alkaline earkh metal carbonates, e.g. calcium carbonate, is about 60% to about 68~ by weight of the co~position, the viscosity ob-tained therefrom being about 40,000 to about 200,000 CPS.
Silica-derived products are representecl by fumed siLicas and puLveri~ed amorphous silica gels. An example of the latter are the Syloid brand silicas of ~5 W.R. Grace & Co.
The critical range for colloidal silica, e.g. Syloid-B 366 (R~
244, is about 11% to about 20~ by weight of the com-position, the VlSCoSity obtained therefrorn being about 30,00~ to ~out 700,000 CPS.
In addition to the inorganic th.ic]cening agent, the corn-positl~ns may aLso contai.n alkallne and sequestering agents. I-t is wel.L known i.n -the art that hypochlorite decomposition and the loss of available ch.Lorine can be slowed by mainta.inlng the hypochlorite-containing system at a relatively hi.gh pEI, e.g. abc~ut 1205 to 13~0. To maintain the required high pH, alkaline agents such as sodium, potassium, calcium or magner,ium hydxoxide and the li]ce may be added to -the com-positions. It should be understood that it i8 only the chlorine stability of the hypochlorite paste which is dependent on the pH of the composition, the viscosity and physical stability of the paste, per se, being independent of the high pH.
The presence of traces of heavy metals may catalyze hypochlorite decomposition and further induce chlorine losses. To minimize such losses, sequestering agents which do not react wlth hypochlorite may be incor-porated in the composltion o the i.nstant invention, e.g. polyphosphates, such as tetrapotassium pyro-phosphate or sodium tripolyphosphate.
The following examples, wi-thout l.imitation on the scope thereof, furt?ler illustrate our invent.ion. All pro-portions and percentages herein and in the appendedclaims are by weigh-t unless speclfied otherwise.
EXAMPLE I
A thick, free-~lowing~ physically stable paste was obtained by mechanically mixing the following~ The term "stable" or "stability" as used herei.n lndicates that the composition essentially rernains physically un ~ de~70 ~es rade ~ 7 rk B 366 (R~
YV3~ii7 changed, the change in avallable chlorine level being substantially the same as in a corresponding un-thicXened hypoch.Lorite solution.
~ b~ Wei~ht Bentonite clay (Imvite FGB) 7.0 Sodium hypochlorite solu-tion l8.9 (10,6~ ava.ilable chlorine) D.istilled water 74 1 100.O
Adjus-ted with sodium hydroxide to p~ l.Z.4.
Theore-tical availa~le chlorine 2.00 Mea~ured available C12Initially l.99 Cl2 availability after s-torage at ambient conditlon~
for 2 weeks l.96 for 5 weeks l,92%
: for 8 weeks l,89 An unthickened aqueous sodium hypochlorite control with initial available Cl2 o 2.0~ contained l.95% avail~
able Cl2 after Eive weeks and l.93~ Cl2 after eight ~eeks at ambient conditions, indicating that the additlon of thickening agents according to the present invention did not affect the hypochlorite solution in any significant manner. I~ose skilled in the art know that a deterioration in the level of available chlorine readily occurs when certain conventional thickening snaterials are added to the hypochlorite solution. As the dat.a herein inc~sicate, our compositions remain stable ~ithout be.ing affected by the addition of the thickeners to the aqueous hypochlorite.
Availahle chlorine was determined by the ASTM method D2022-64.
. .
B 366 (R) '7 EXAMPLE II
paste composition of good physlcal stability was obtained by mechanically mixing the following:
Attapulgite clay (Attagel 40) 15.1 Sodium hypochlorite sol.ution 84.9 ~12.3% available Cl2~
100 . O
Adjustment with sodium hydroxide to pH 13Ø
10 Available chlorine level:
Theoretic : 10.50%
Measured: In,iti.ally 10.47 After s-torage at ambient conditions Eor 1 week 9.54%
for 10 weeks 5.53 An unthickened aqueous hypochlorite control with initia:L average C12 of 10.4%, dropped to g.79%
average C12 after one week and 6.99% average Cl2 ~fter ten weeks at ambient conditions.
The above composition remained physically stable beyond : . ten weeks.
.
_XAMP~E III
A physically stable, thick, li~ht coloured, semi--translucent paste was obtained by blending a synthetic, micron-sized, amorphous silica (Syloid 244) with sodi.um hypochlorite solu-tion:
% by Weight Syloid 244 11.10 Calcium hydroxide 0.20 Sodi~ hypoch:Lorite solution (11.78~ 42.44 DistiLLed water _46.26 3S 1~0.00 Adjustment w1th sodium hydrox:ide to pH 13.07.
,......... .
~ ~9~)3~ B 366 (R) Avai.Lable chlorlne level~
l~eoretical: 5,0 Measured. Initially 4.89 ~
After storage at ambi.ent conditions for 3 weeks 4.5 EXAMPLE IV
A vlscous, but free-flowirlg semi-translucent paste was obtained by thickening a sodium hypochlorite solution with a synthetic multi-layered silicate similar in structure to sm~ctite clay (Barasym PNS).
~ by Weight Barasym PNS 7.00 Sodium hypochlorite solution 18.48 (10.83% available C12) Water 74.52 100.00 The composition was adjusted to pH 130 Availabl~ chlorine level:
Th~oretical: -200~
Measured: Initially 2.0%
After storage at ambient condition~s for 36 weeks 1.27 This composition remained physicaily stable for 36 weeks.
F.XAMPLE V
A physically stable, highly viscous, semi translucent paste composition of high available hypochlorite con-c~ntration was obtained as ~oll.ows:
% by Weight Barasym PNS 21.26 Sodium hypochlori-te .solution78.74 (12~,7~ available C12) 100 . 00 ~ B 366 (R) ~he composi-tion was adju~ted to pH 13.
Thls paste had an lnitial avai:Lable CL~ o 10.0%.
I~i~ composi-tioll rema,ined physically stable Eor about 36 weeks.
EXAMP E VI
A physically stable, white opaque paste composition was obtained by blendin~ a finely ground calc,ite (CaCO3) material - Durcal 2NH, ex Ornya - with sodium hypo-chlorite solution. The ecllclte may serve the addi-tional function of a scouring aqerlt.
~ ~ ~ht Calcium carbonate (Durcal 2NH 59.2 Sodium hypochlorite solution 40.8 (12.24% availahle Cl2) 100 .0 The composition was adjusted to pH 12.70 '~he compositlon remained physically stable for over 20 weeks.
_AMPLE VII
A paste composition utilizing titanium dioxide ~TiO2) as a thlckener is illustrated below.
~ by Weight (active basis~
Sodium hypochlorite 4.7 Titanium dioxide55.0 Water ~.3 Stable for over 5 weeks.
Example VIII
A paste composition utilizing magnesium oxide (MgO) as a thickener is illustra-ted below.
Je~o~cs ~o~e ,7~
B 366 (R) % b~ Weight_ ac iv bac;1s) Sodiuln hypoclllorlte 4.76 Maynesium oxide55.60 Water _3906~
100.00 Stab.Le for a-t least 5 weeks.
_ AMPLE IX
We have di~covered that -the thickeners clescribed here~
toEore above, may be u~ed in combinat.ion with ~ach other to provide a stable, dispensihle (e.g. via a squeeze tube and the Llke) composition. In fact, we have made a surprisingly advantageous dlscovery tha-t past~ compositions prepared by combining different lS thi.ckeners require a Lower concentration o~ the thickeners -than do pastes which are thickened with only one thlckenerO Such compositions are illustrated in the formul.ation tabu:Lated ~elow and in Example X.
% by We Sodl~n hypochlorite 5.25 Zinc oxide 25.00 Attapulgite (Attagel 40) 8.00 Water 61.75 Total 100.00 ~e viscosity of this composition i~ greater than 2,000,000 CPS and it is stable over 5 weeks.
_XAMPLR X
The paste composition shown below was obtalned by mixing -the following:
% by Weight ~ttapu:Lyite clay (Att~el 40)9.9 Zinc oxi.de 5,0 Calciurn hydroxide 0.2 5odiuTn hypochlorite solution84.9 (11.78~ available C12) 100.0 r~ 366 (~) ()3Si~7 :L :1 Adjust.ment with sodi~n hyclroxlde -to p~l 13.07.
Aval:Lable chlorine :Level:
TheoretlcaL: 10.0 Measured: Initially 9.97 After storage at ambient condltions for 3 weeks 7.98~
Th.is co3nposition remained physlcally stable beyond 5 weeks.
It is understood that the examp:Les and embodiments des-cribed he~eln are for i:lLus-trative purposes only and that vari.ous modlfications or changes ln the l.ight thereof will be suggested -to persons skilled in the art and are to b~ lncluded within the spirit and purvie~ of this application and the scope o the appended claims.
;
:: .
Metal oxides are exemplified by zinc oxide, titanium dioxide, calcium oxide, magneslum oxide and the like.
It is critical that the level of zinc o~ide ~J.T. Baker Chem. Co., Zlnc Oxide Powder, Analyzed Reagent) when used alone as a thickener be maintained at about 55% by weight of the compositlon to ob-tain a stable product.
Below the 55% level of zinc oxide, the pas-te com~
position separates rapidly, whereas above 55% the com position loses its paste characteristics, solidifies rapidly and becomes difficul-t to stir and work with.
The critical level for titanium dioxide (J.T. Baker Chem. Co., Titanium Dioxide CP, Analyzed Reagent) i8 about S0~ to about 55% and for magnesium oxide (Fluka A.G., Magnesium Oxide puriss, p~a~) the critical level is about 50~ to about 58%, the viscosity obtained ther~from in both cases being about 2,000,000 CPS. It is to be understood that the critical l~vels of -these metal oxides would, of course, require adjustment with a change in particle size.
TyplcaL alkallne 0arth metal carbonates, of the type used in the compositions of the instant invention, are calcium carbonate and magnesium car`bonate. rrhe critical range for alkaline earkh metal carbonates, e.g. calcium carbonate, is about 60% to about 68~ by weight of the co~position, the viscosity ob-tained therefrom being about 40,000 to about 200,000 CPS.
Silica-derived products are representecl by fumed siLicas and puLveri~ed amorphous silica gels. An example of the latter are the Syloid brand silicas of ~5 W.R. Grace & Co.
The critical range for colloidal silica, e.g. Syloid-B 366 (R~
244, is about 11% to about 20~ by weight of the com-position, the VlSCoSity obtained therefrorn being about 30,00~ to ~out 700,000 CPS.
In addition to the inorganic th.ic]cening agent, the corn-positl~ns may aLso contai.n alkallne and sequestering agents. I-t is wel.L known i.n -the art that hypochlorite decomposition and the loss of available ch.Lorine can be slowed by mainta.inlng the hypochlorite-containing system at a relatively hi.gh pEI, e.g. abc~ut 1205 to 13~0. To maintain the required high pH, alkaline agents such as sodium, potassium, calcium or magner,ium hydxoxide and the li]ce may be added to -the com-positions. It should be understood that it i8 only the chlorine stability of the hypochlorite paste which is dependent on the pH of the composition, the viscosity and physical stability of the paste, per se, being independent of the high pH.
The presence of traces of heavy metals may catalyze hypochlorite decomposition and further induce chlorine losses. To minimize such losses, sequestering agents which do not react wlth hypochlorite may be incor-porated in the composltion o the i.nstant invention, e.g. polyphosphates, such as tetrapotassium pyro-phosphate or sodium tripolyphosphate.
The following examples, wi-thout l.imitation on the scope thereof, furt?ler illustrate our invent.ion. All pro-portions and percentages herein and in the appendedclaims are by weigh-t unless speclfied otherwise.
EXAMPLE I
A thick, free-~lowing~ physically stable paste was obtained by mechanically mixing the following~ The term "stable" or "stability" as used herei.n lndicates that the composition essentially rernains physically un ~ de~70 ~es rade ~ 7 rk B 366 (R~
YV3~ii7 changed, the change in avallable chlorine level being substantially the same as in a corresponding un-thicXened hypoch.Lorite solution.
~ b~ Wei~ht Bentonite clay (Imvite FGB) 7.0 Sodium hypochlorite solu-tion l8.9 (10,6~ ava.ilable chlorine) D.istilled water 74 1 100.O
Adjus-ted with sodium hydroxide to p~ l.Z.4.
Theore-tical availa~le chlorine 2.00 Mea~ured available C12Initially l.99 Cl2 availability after s-torage at ambient conditlon~
for 2 weeks l.96 for 5 weeks l,92%
: for 8 weeks l,89 An unthickened aqueous sodium hypochlorite control with initial available Cl2 o 2.0~ contained l.95% avail~
able Cl2 after Eive weeks and l.93~ Cl2 after eight ~eeks at ambient conditions, indicating that the additlon of thickening agents according to the present invention did not affect the hypochlorite solution in any significant manner. I~ose skilled in the art know that a deterioration in the level of available chlorine readily occurs when certain conventional thickening snaterials are added to the hypochlorite solution. As the dat.a herein inc~sicate, our compositions remain stable ~ithout be.ing affected by the addition of the thickeners to the aqueous hypochlorite.
Availahle chlorine was determined by the ASTM method D2022-64.
. .
B 366 (R) '7 EXAMPLE II
paste composition of good physlcal stability was obtained by mechanically mixing the following:
Attapulgite clay (Attagel 40) 15.1 Sodium hypochlorite sol.ution 84.9 ~12.3% available Cl2~
100 . O
Adjustment with sodium hydroxide to pH 13Ø
10 Available chlorine level:
Theoretic : 10.50%
Measured: In,iti.ally 10.47 After s-torage at ambient conditions Eor 1 week 9.54%
for 10 weeks 5.53 An unthickened aqueous hypochlorite control with initia:L average C12 of 10.4%, dropped to g.79%
average C12 after one week and 6.99% average Cl2 ~fter ten weeks at ambient conditions.
The above composition remained physically stable beyond : . ten weeks.
.
_XAMP~E III
A physically stable, thick, li~ht coloured, semi--translucent paste was obtained by blending a synthetic, micron-sized, amorphous silica (Syloid 244) with sodi.um hypochlorite solu-tion:
% by Weight Syloid 244 11.10 Calcium hydroxide 0.20 Sodi~ hypoch:Lorite solution (11.78~ 42.44 DistiLLed water _46.26 3S 1~0.00 Adjustment w1th sodium hydrox:ide to pH 13.07.
,......... .
~ ~9~)3~ B 366 (R) Avai.Lable chlorlne level~
l~eoretical: 5,0 Measured. Initially 4.89 ~
After storage at ambi.ent conditions for 3 weeks 4.5 EXAMPLE IV
A vlscous, but free-flowirlg semi-translucent paste was obtained by thickening a sodium hypochlorite solution with a synthetic multi-layered silicate similar in structure to sm~ctite clay (Barasym PNS).
~ by Weight Barasym PNS 7.00 Sodium hypochlorite solution 18.48 (10.83% available C12) Water 74.52 100.00 The composition was adjusted to pH 130 Availabl~ chlorine level:
Th~oretical: -200~
Measured: Initially 2.0%
After storage at ambient condition~s for 36 weeks 1.27 This composition remained physicaily stable for 36 weeks.
F.XAMPLE V
A physically stable, highly viscous, semi translucent paste composition of high available hypochlorite con-c~ntration was obtained as ~oll.ows:
% by Weight Barasym PNS 21.26 Sodium hypochlori-te .solution78.74 (12~,7~ available C12) 100 . 00 ~ B 366 (R) ~he composi-tion was adju~ted to pH 13.
Thls paste had an lnitial avai:Lable CL~ o 10.0%.
I~i~ composi-tioll rema,ined physically stable Eor about 36 weeks.
EXAMP E VI
A physically stable, white opaque paste composition was obtained by blendin~ a finely ground calc,ite (CaCO3) material - Durcal 2NH, ex Ornya - with sodium hypo-chlorite solution. The ecllclte may serve the addi-tional function of a scouring aqerlt.
~ ~ ~ht Calcium carbonate (Durcal 2NH 59.2 Sodium hypochlorite solution 40.8 (12.24% availahle Cl2) 100 .0 The composition was adjusted to pH 12.70 '~he compositlon remained physically stable for over 20 weeks.
_AMPLE VII
A paste composition utilizing titanium dioxide ~TiO2) as a thlckener is illustrated below.
~ by Weight (active basis~
Sodium hypochlorite 4.7 Titanium dioxide55.0 Water ~.3 Stable for over 5 weeks.
Example VIII
A paste composition utilizing magnesium oxide (MgO) as a thickener is illustra-ted below.
Je~o~cs ~o~e ,7~
B 366 (R) % b~ Weight_ ac iv bac;1s) Sodiuln hypoclllorlte 4.76 Maynesium oxide55.60 Water _3906~
100.00 Stab.Le for a-t least 5 weeks.
_ AMPLE IX
We have di~covered that -the thickeners clescribed here~
toEore above, may be u~ed in combinat.ion with ~ach other to provide a stable, dispensihle (e.g. via a squeeze tube and the Llke) composition. In fact, we have made a surprisingly advantageous dlscovery tha-t past~ compositions prepared by combining different lS thi.ckeners require a Lower concentration o~ the thickeners -than do pastes which are thickened with only one thlckenerO Such compositions are illustrated in the formul.ation tabu:Lated ~elow and in Example X.
% by We Sodl~n hypochlorite 5.25 Zinc oxide 25.00 Attapulgite (Attagel 40) 8.00 Water 61.75 Total 100.00 ~e viscosity of this composition i~ greater than 2,000,000 CPS and it is stable over 5 weeks.
_XAMPLR X
The paste composition shown below was obtalned by mixing -the following:
% by Weight ~ttapu:Lyite clay (Att~el 40)9.9 Zinc oxi.de 5,0 Calciurn hydroxide 0.2 5odiuTn hypochlorite solution84.9 (11.78~ available C12) 100.0 r~ 366 (~) ()3Si~7 :L :1 Adjust.ment with sodi~n hyclroxlde -to p~l 13.07.
Aval:Lable chlorine :Level:
TheoretlcaL: 10.0 Measured: Initially 9.97 After storage at ambient condltions for 3 weeks 7.98~
Th.is co3nposition remained physlcally stable beyond 5 weeks.
It is understood that the examp:Les and embodiments des-cribed he~eln are for i:lLus-trative purposes only and that vari.ous modlfications or changes ln the l.ight thereof will be suggested -to persons skilled in the art and are to b~ lncluded within the spirit and purvie~ of this application and the scope o the appended claims.
;
:: .
Claims (20)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A stable aqueous, readily dispersible in hot or cold water hypochlorite paste composition having a viscosity of about 25,000 CPS to greater than about 2,000,000 CPS, consisting essentially of in percent weight of composition:
(a) from about 5% to about 70% inorganic thickeners selected from the group consisting of natural colloidal clays, synthetic clays, metal oxides, alkaline earth metal carbonates, fumed silicas, pul-verized amorphous silica gels and mixtures thereof;
(b) about 5% to about 85% of an aqueous sodium hypochlorite solution having from about 4.0 to about 14% available chlorine; and (c) optionally a sufficient amount of an alkaline agent selected from the group consisting of alkali or alkaline earth metal hydroxides whereby the pH of said paste is brought to a value of qreater than about 12Ø
(a) from about 5% to about 70% inorganic thickeners selected from the group consisting of natural colloidal clays, synthetic clays, metal oxides, alkaline earth metal carbonates, fumed silicas, pul-verized amorphous silica gels and mixtures thereof;
(b) about 5% to about 85% of an aqueous sodium hypochlorite solution having from about 4.0 to about 14% available chlorine; and (c) optionally a sufficient amount of an alkaline agent selected from the group consisting of alkali or alkaline earth metal hydroxides whereby the pH of said paste is brought to a value of qreater than about 12Ø
2. A hypochlorite paste composition according to claim 1 wherein said colloidal clays are selected from the group consisting of attapulgites, montmoril-lonites and mixtures thereof.
3. A hypochlorite paste composition according to claim 2 wherein the level of attapulgites is about 10% to about 18%.
4. A hypochlorite paste composition according to claim 3 wherein the viscosity of said composition is from about 300,000 CPS to greater than about 2,000,000 CPS.
5. A hypochlorite paste composition according to claim 1 wherein said synthetic clay is selected from the group consisting of smectite clays and mixtures thereof.
6. A hypochlorite paste composition according to claim 5 wherein the level of said smectite is about 7% to about 20%.
7. A hypochlorite paste composition according to claim 6 wherein the viscosity of said composition is from about 28,000 CPS to greater than about 2,000,000 CPS.
8. A hypochlorite paste composition according to claim 1 wherein said metal oxide is selected from the group consisting of zinc oxide, titanium dioxide, calcium oxide, magnesium oxide and mixtures thereof.
9. A hypochlorite paste composition according to claim 8 wherein the level of said zinc oxide is about 55%.
10. A hypochlorite paste composition according to claim 9 wherein the viscosity of said composition is about 1,500,000 CPS.
11. A hypochlorite paste composition according to claim 8 wherein the level of titanium dioxide is about 50% to about 55%.
12. A hypochlorite paste composition according to claim 11 wherein the viscosity of said composition is about 2,000,000 CPS.
13. A hypochlorite paste composition according to claim 8 wherein the level of magnesium oxide is about 50% to about 58%.
14. A hypochlorite paste composition according to claim 13 wherein the viscosity of said composition is about 2,000,000 CPS.
15. A hypochlorite paste composition according to claim 1 wherein said alkaline earth metal carbonate is selected from the group consisting of calcium carbonate, magnesium carbonate and mixtures thereof.
16. A hypochlorite paste composition according to claim 15 wherein said alkaline earth metal carbonate is calcium carbonate.
17. A hypochlorite paste composition according to claim 16 wherein the level of said calcium carbonate is about 60% to about 68%.
18. A hypochlorite paste composition according to claim 17 wherein the viscosity of said composition is from about 40,000 CPS to about 200,000 CPS.
19. A hypochlorite paste composition according to claim 1 wherein the level of said silica gel is about 11% to about 20%.
20. A hypochlorite paste composition according to claim 19 wherein the viscosity of said composition is from about 30,000 CPS to about 700,000 CPS.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US28429281A | 1981-07-17 | 1981-07-17 | |
| US284,292 | 1981-07-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1190357A true CA1190357A (en) | 1985-07-16 |
Family
ID=23089629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000407434A Expired CA1190357A (en) | 1981-07-17 | 1982-07-16 | Surfactant-free stable hypochlorite paste |
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| Country | Link |
|---|---|
| CA (1) | CA1190357A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9040475B2 (en) | 2013-10-09 | 2015-05-26 | The Clorox Company | Intercalated bleach compositions, related methods of manufacture and use |
| US9074164B2 (en) | 2013-10-09 | 2015-07-07 | The Clorox Company | Intercalated bleach compositions, related methods of manufacture and use |
-
1982
- 1982-07-16 CA CA000407434A patent/CA1190357A/en not_active Expired
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9040475B2 (en) | 2013-10-09 | 2015-05-26 | The Clorox Company | Intercalated bleach compositions, related methods of manufacture and use |
| US9074164B2 (en) | 2013-10-09 | 2015-07-07 | The Clorox Company | Intercalated bleach compositions, related methods of manufacture and use |
| US9353336B2 (en) | 2013-10-09 | 2016-05-31 | The Clorox Company | Intercalated bleach compositions, related methods of manufacture and use |
| US9464262B2 (en) | 2013-10-09 | 2016-10-11 | The Clorox Company | Intercalated bleach compositions, related methods of manufacture and use |
| US9580671B2 (en) | 2013-10-09 | 2017-02-28 | The Clorox Company | Intercalated bleach compositions, related methods of manufacture and use |
| US9695386B2 (en) | 2013-10-09 | 2017-07-04 | The Clorox Company | Intercalated bleach compositions, related methods of manufacture and use |
| US9963659B2 (en) | 2013-10-09 | 2018-05-08 | The Clorox Company | Intercalated bleach compositions, related methods of manufacture and use |
| US10100271B2 (en) | 2013-10-09 | 2018-10-16 | The Clorox Company | Intercalated bleach compositions, related methods of manufacture and use |
| US10214710B2 (en) | 2013-10-09 | 2019-02-26 | The Clorox Company | Intercalated bleach compositions, related methods of manufacture and use |
| US10450536B2 (en) | 2013-10-09 | 2019-10-22 | The Clorox Company | Intercalated bleach compositions, related methods of manufacture and use |
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