CA2156370A1 - Mixed surfactant systems for low foam applications - Google Patents
Mixed surfactant systems for low foam applicationsInfo
- Publication number
- CA2156370A1 CA2156370A1 CA002156370A CA2156370A CA2156370A1 CA 2156370 A1 CA2156370 A1 CA 2156370A1 CA 002156370 A CA002156370 A CA 002156370A CA 2156370 A CA2156370 A CA 2156370A CA 2156370 A1 CA2156370 A1 CA 2156370A1
- Authority
- CA
- Canada
- Prior art keywords
- surfactant
- number ranging
- mixture
- group
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
Abstract
Machine dishwashing detergents are disclosed containing a compatible mixture of a low-foaming nonionic surfactant and a high-foaming nonionic surfactant. Dishes and other utensils are cleaned to a sparkling clean spot-free condition by the machine washing detergent composition of the present invention. The machine dishwashing detergent compositions of the present invention are effective especially in controlling foam encountered upon washing dishes and other utensils encrusted with soils generally encountered on dishes, specifically egg and milk-derived protein soils.
Description
21~637~
M~xEn SURFACTANT SYSTEMS FOR LOW FOA~I APPI-ICATIONS
BACKGROUND OF TT~ INVENTION
D~ 81,266-F
Field of the Inven¢ion This invention relates to a surfactant system useful in dl~ macbines, and more p~lh,~l~ly to a surfactant system comprising a compatible mixture of at least one uncapped ~tllw~y' ' nonionic medium-to-high foaming surfactant and at least one propylene oxide capped nonionic low foaming surfactant. This surfactant system is useful in d;~h aDh;llg detergents and as rinse aids which have a good wetting and drainage effect on hard surfaces.
1~- !~ ~ d ~nform~at~o~
Many cleaning ~ require surfactants'that are both low foaming and "'~''C Examples include automatic dishwasher detergents, textile processing, paper ore processing and metal cleaning. Here the tyypical ~ ~' ' nonionic surfactants must be subjected to a capping process to meet these 1~, Capping reactions with propylene oxide or other suitable chemicals are a costly extra step in the productjon of these c~rfs~t~ tc In the ar¢ of cleaning r-, - ~ for use in cleaning hard surfaces, ~ l~ly the art of cleaning tableware and oth food-soiled utensils in machine d;sh ~1l~, ~e problern of excessive foa~n buildup in the machine during operation is the result of high food soil ~ The use of alkyl phosphate ester defoamers such as IIIVII~ acid phosphate a_ disclosed in U.S. 3,314,891 has largely solved the problem of excessive foam buildup. Prior thereto, machine d;~l. ' ~ had atendency to foam .,.~
and/or leave ~ r ~;"~1~Ir spots and streaks on dishes a~d glassviare. The low foaming nonionic ~oU03 1240~ 2-2~3~a ,.
surfachnts contained in such detergent ~r~mroqiti~nq were ineffective in both removing food soil and providing suihble foam control where the aqueous cleaning solution became ' J with foam generating protein soils such as egg soil and soil from various milk products.
rhe generation of such foams is . Ii~ul~uly insidious in that the cleaning action of the machine dishwasher depends to a large extent upon the effective ~U~ ' of foam generation durirlg operation. Without effective foam ~U~ .Vll, the mechanical cleaning action of the machine dishwaqher is reduced as the result of foam buildup in the aqueous cleaning solution. The aqueouq washing fluid which is normally impelled against the hbleware in the machine dishwasher is less effective in cleaning becauqe it is forced against the tableware at reduced pressure.
An indication of the va~ious kinds of nonionic surfactants utilized in such machirle ~ ~ can be found in U.S. Pat. Nos. 3,314,891 and 3,359,207.
General disclosures of nonionic surfactants can be found in U.S. Pat. Nos. 2,677,600; 2,979,528 and 3,036,118. Low foaming washing and cleaning agents for use in machine d; ~ e are also disclosed in 3,382,176. Machirle ~..'~... ' _ detergent . , containing a non-phosphate salt builder have been disclosed in British Pat. No. 1,325,645; Canadian Pat. No.
941,707; U.S. Pat. No. 3,899,436; 4,127,496 and 4,092,258.
Another method of reducing the foaming tendency of dllV~ alcohols was to end cap them with an alkyl group. For exatnple, Henkel has a seri of patents using capped surfachnts to suppress foam. In the following, "EO" is an ethylene oxide residue, "PO" is a propylene oxide residue, "BO" is butylene oxide residue, and "AO" is an aLlcylene oxide HOU03: 12~038 ~ -3 -,~ 21~6~7~
residue. Henkel published patent application ZA 89/4027, 1990 discloses a low foaTn surfactant c.... ,.v~;l;.-.. that produces little foam and good wetting on plastics (especially pvl.r~,~ubv~ 3) and that are 1~.~ ' for rinse aid ,.1.~,1;. ,.t;"~; in automatic dlallw~h~l, The nonionic surfactttnts u3ed therein included C~"-O-(EO)X-C~,~ alone or in cv ~ .1 .-l ;.~. . with one or more of C,."-O-(EO),-(PO)h-H, C~ O-(EO)C-C~, and C,.,,-O-(EO)d-H, where a=2 to 6, b=3 to 7, c--7 to 12, d=20 to 50 and x 5 20 to 40. This patent application also discloses the processes for their production. DE 3,928,604 discloses .' ' ' ~ allcyl polyglycol ethers for detergents including C, ,~-O-(EO)2 ,-C,.,o which can be used in mixtures witn C~_,,(EO)7 ,0-H in ratios of 10: 90 to 90: 10- Suggested ~A are for machine d..21~
detergents. DE 3,935,374 discloses a compound with good anti-foaming activity and is shown by C,." O (EO)3., C4,. These are made with a narrow rttnge molecular weight .1; ~';1...1;.~..
~lhVA.~ catalyst. ~P 254206 discloses low-foam/foam-depressing surfactant mixtures containing CLI~_O_(EO)3 7_C~ and C~" O (EO) ~ 3-(PO)3 66-H optionally with C,~22-O-(PO), 3-H.
Henkel patent (DE 4,009,533, 1991) discusses rnixtures for laundry ~-~-l;~ - ;,.l..c in the form of: alkyl glucose ~ v ~ with R-O-(EO)0 ~5-(AO)~.20-OR' with R = C,..22 and R' = C~ ,0.
Encolab Inc., U.S. 4,973,423, 1990 claims foaTn inhibiting additives or low-foam cleaners. The additives are the allyl end-capped e:LIl~JA,~ alcohols C6 "-O-(EO)2 6-C~.~ used in, , with wetting agents such as nonionic surfact~dnts, including polyglycol ethers of the type obtain~d by adding ethylene oxide onto alcohols.
Due to the additional processing steps and cost involved in alkyl end-capping, the search continued and still continues for low foaming and defoaTning nonionic surfact~dnts which avoid such steps and cost.
HOU03:12~03~.1 -4-. .
Drackett Co., U.S. 4,226,736, 1980 discloses mixtures of surfactants and thickeners to make gel type automatic dishwasher detergents. The surfactant mixtures consist of poly~"v,uu~yl..~c.i pol~.,tl.v~-y' ' ethylene glycols and C,o l~-O-(EO/PO)55 80.,.-H.
Nippon Paint Co., U.S. 4,256,601, 1981 discloses a low foam surfactant with very good foam breaking abilities which is thc all para X-Ph-CR~R2-Ph-O(AO)320H. This material is mentioned in, ~ with nonionic substances that have a cloud point less than 40C such as alcohol clLu~y' , ~Lkyl~ .ol ethoxylates and block CUIJVI~ of the (EO)--(PO)--(EO) type. The weight ratio of the above compound to the noniorlics is given as a range of 1.0 to 0.05 up to 1.0 to 5Ø
Sandoz Ltd. patent (Abstracts of GB 2204321-B, 1991 and GB 2204321-A, 1988) discusses l.i.~ detergent . - for cleaning surfaces (metals, plastics, laundry) which in addition to an ;~ --P and l ~ agent include the mixture of a fatty alcohol pol~ glycol ether and a low foaming nonionic surfactant as I~IJlC.~ ,d by:C".22-O-(EO)525H(2-35%)andC~22-O-(EO),.,2(PO),.5H(0.5-5.0%),-~ Iy. According to GB æO4321-A, 1988, the preferred mixture in the surfactant ~ . was C,2_,6--O--(EO)5_,2H and C,~-O-(EO),-(PO),H. In Example 2 thereof, laboratory glassware ' with dried blood, brain substance and albumirl was immersed in a solution containing from 3 to 5% by weight of a ~.. ,...-:~;..,. contairling 12% by weight C,2"5--O--(EO),--H and 1% by weight C,2-O~EO),-(PO),-H for 2 to 3 hours at 80C. or 12 hours at room ~ There w~c no mention of lûw foam nor defoaming with this cv., ~ The remaining examples dealt with laundry detergents (continuous working HOU03: 124033.- -5-215~370 process through wash tunnel) and cleaning electronic ll~;u~u~,;lu~lib (immersion) and watch cases (ultrasorlic treatment).
Henkel published patent application WO 91/03536, 1991 discloses foa~-inhibiting additives for low foaming cleansers. These additives are: C,2 20-O-(EO)2 ~H where the alkyl group is from a 2-braQched even alkanol and optionally mixed with CI.,,-O-(EO)26-(PO)3.rH where the alkyl group caQ be branched or liQear. The 2-branched aspect of the ~lh~ y~ ' alcohol is stressed iQ part by seizing on the uu~_-v~liu.. that slight structural changes produce sigr~ificaQt differences in the properties of nonionic surfactants. For exa[nple, DE 3,315,951 and 3,800,493 were compared. The primary differences ih~,.c': .. were the carbon residue of the alcohol used iQ each case. In the first, the carbon residue bad 8 to 18 carbon atoms aQd that of the other had 20 to 28 carbon atoms. Surfactants with highly branched chains generally show lower foam heights thaQ isomeric straight-chaiQ materials, except where the length of the II~L.~,hJbl., group becomes too long for straight-chain -U~ to have adequate water solubility for good defoan~iQg (e.g., greater than 16 carbon atoms at 4ûC). See "SurfactaQts aQd Interfacial PL~..v.n~,.~'' by Milton J. Rosen, p. 212, published by Wiley r..~ . (1978). As , ' '~ ' in this Henkel patent, the branched portioQ of the alkyl group rangGd from 4 to 8 carbon atoms with the straight portion of the alkyl group ranging from 8 to 12 carbon atoms. Accordingly, this Henkel patent teaches away from straight or ~ ' ' ' alkyl groups iQ the ~:LIIUA~Y' ' ' alcohol so as to effect a reduction in its foaming tendencies.
Henkel published patent application ZA 9ûll0,356, 1991 discloses industrial cleaners mainly used for cleaning aQd passivating in spray-cleaning units in the automotive HOW~: 12403a.t -6--2~S6370 . .
industry. The industriai cleaners use a .~, ..1; . '; ~ of surfactants for clearLing hard surfaces and which exhibit low foaming properties from 15C. to 80C. arld excellent wetting properties without leaving spots and stairls. The surfactant .v ~ " contains (a) C6 ,,-O-(EO)2 ,2-H and (b) C6 "-O-(EO)2 ,0 (Po)2J H
where the weight ratio of (a):(b) is within the range of 10:1 to 1:10. The carbon residue of a) and (b) are preferably linear. The surfactant ~ \ may further contain (c) C6 ,,-O-(EO)2 ,2-C-I..-HOW3:12~03~.- 7 21~370 SUMMARY OF THE INVENTION
This invention utilizes a compatible mixture of at least one linear, uncapped CLI~ y' ~ nonionic surfactant and at least one low foam nonionic surfactant capped with propylene oxide, which mixture retains tne properties of the low foam ~ s) while reducing the overall cost of the useful surfactt3nt system(s).
MOK pa~L~.ukul~ there is provided a low foaming d;_~" ' , having:
(a) at least one first nonionic surfactant having a general formula selected from the group consisting of general formula (I) Rl-O-(CH2CH~O)y-H (I) , wherein R' represents a linear alkyl or olefmic group having from about 6 to about 18 carbon atoms and y represents a number ranging from about 3 to about 15, and general formula (II) Np-O-(CH,CH2O)~-H (II) , wherein Np is the carbon residue of ~ l,' ' or u~,L~ and z rcpresents a number ranging from about 4 to about 200; and (b) at least one second nonionic surfactant having a general formula selected from the group consisting of general formula (III) R2-O-(CH2CH20)m-A'-H (111) ,wherein R2 represents a linear or branched alkyl or olefnic group having from about 6 to about 16 carbon atoms, m represents a number ranging from about 3 to about 15, and A' represents a group having the formula ~(CH2~CH(CH3)-O)q~~ -(CH(CH3)-CH~-O),- or a ....1~1...A~ thereof with q and r each .el,.c ~ a number ranging from 0 to about 30 and H~U03:12~031.1 -8-. .
the sum of q and v represents a numbcr ranging from about 4 to about 30, and general formula ([V) R3-o-A2-(CH2CH2o)c-A3-H (IV) , wherein R3 represents a linear or brarlched alkyl or olefinlc group having from about 6 to about 18 carbon atoms, n represents a number rangirlg from about 10 to about 25, A2 representC a group having the formula -(CH2-CH(CH3 )-O)t-, -(CH(CH3)-CH2-O)U- or a thereof with t and u each l~.c ~ a number ranging from 0 to about 15 and the sum of t and u represent_ a number ranging from about 2 to about 15, and A3 represents a group having the formula -(CH2-CH(CH3)-O)V-, -(CH(CH3)-CH3-O)W- or a .i.. l.. ~,.. ~
thereof with v and w each l~ l~g a number ranging from 0 to about 55 and the sum of v and w represents a number rangirlg from about 10 to about 55, wherein the ~---r ' a and b above are compatible with each other.
('~7mrn.ontc a arld b are preferably present in a mole ratio a:b ranging from about 95:5 to about 60:40.
S~ hlxl.~ tbis invention maintains the low foam and defoaming ~ r needed for a number of low foam ~1." (e.g. automatic dishwasher detergenb, rinSe aids) while ~ '~ '.~ reducing the cost of the surfactants which form the major functional .(S) of the product~ used in these rr DES~RIPTION OF THI~ PREFFRR~n F.MRODIM~.~T
The Sl-t f~ror~t l'. . ~ of the invention contain from about 2% to about 5%, preferably from about 2% to about 3%, by weight of a compatible mixture of (1) uncapped ~LLu~y' HOU03:~2tO3~.~
2i~6370 .~ .
nonionic surfactants and (2) typical propylerle oxide capped low foarlung surfactants for use as automatic dishwasher detergents. It has oeen found that certain of these compatible mixtures perform in automatic dishwasher detergents without the loss of food soil removal and with a~ ly little loss of defoaming I r Mixtures of this type ai~lir~ ly reduce the overall cost of the surfactants useful for thes~ al~p~
We have ~ 51.Y found that compatible mixed nonionic surfactant systems (where at least one surfactant is the typical alcohol-~llw~.~' ylu~.u..~y' or alcohol-I"VI~U~Y' ~ lu~.y' -UlU~U~y' IOW foam type and at least one is the typical alcohol-ethoxylate of a moderate-to-high foam generation) afford dishwasher 1~ cc , in the area of film generation, equal to or superior to that of the low foam (defoaming) surfactant when used alone. It is further surprising that mixtures of surfactants that contain a major arnoumt of a typical ~ u~y' ' alcohol retain the low foam and defoaming properties of the more expensive capped low foaming surfactants and thus show equivalent or superior ~- 1.. - .-in r~ like automatic dishwasher detergents.
Nonionic surfactants can be broadly defined as ~ ---r- ~ prepared by well-known methods of adding an alkylene oxide compound to an alcohol a shown for example in U.S. 2,677,700; 3.956,401; 4,223,163; and 4,226,736, which are hereby u~,ul~ by reference. This process is also known as aLIwAy' A. Fthn~lated Alivhatic ~Irnhnlc Generally, the ~ . ' (I) may be prepared by reacting a primary, linear, IllOllOll.rll;c alcohol having an aLlcyl or olefinic group having from about 6 to about 18 carbon atoms, preferably from about 10 to about 16 carbon atoms, with ethylene oxide in amounts HOU03:124038.~ -IU-- = ~
~1~6370 such that the ethylene oxide residue i.e., -(CH2-CHz-O~-, content is on average about 3 to about 15 moles of ethylene oxide per mole of alcohol, as well as mixtures thereof. The reaction is carried out at an elevated L~ aLulc in the presence of alkaline catalysts such as the salts or hydroxides of the alkali metals or the alkaline earth metals, for example, KOH. A mixture of such alcohols may be used and this is generally true when using ,. ~,;al alcohols which are often available as a blend of several alcohols. ~ , the number of carbon atoms in the alcohol is referred to as an average nurnber. Al ~.ly, the number of carbon atoms in the alcohol mixture may be referred to, for example, C~0"z. The C~ z d~ign~tion, for example, means a mixture primarily having . , ~vith carbon residues having 10 and 12 carbon atoms with small amounts of r~ 1- having carbon residues of different carbon lengths. Useful surfactants of this type include those "~, available from Huntsman Chemical ~ n~ n, Austin, Texas, under the ~ ~iL - ;-- ~ L610-3; L10-3; L1270-2; L12-3;
L12-6; L24-1.3; L24-2; L24-3; arld L244.
B. F~h~lyvlated Alkvl Ph~-nnlc ~ ,.n r~ (Il) may be prepared by rcactlng in similar fashion alkyl phenols having an alkyl group containing from about 8 to about 12 carbon atoms in either a straight chain or branched chain c Ci_ with ethylene oxide in amounts such that the ethylene oxide residue content is on average from about 4 to about 200 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such .- . j.~. -.-l~ may be derived from JUI.y~ ,d propylene, d;i~ubu~yl~ , octene or nonene for example. Preferred alkyl phenols include nu..~l~ll..lol and OC~I,U~ OI. Useful surfactants of this type include those ~IOU0~:12103S.B -I 1-~ 21~637~
~,u~ ially available from Huntsman Chemical Corporation, Austin, Texas, under the ~ir~i~n~tir,n~ N--120, N--100 and N--40.
C. Ell~u~Y'a ~ PIU~JU~Y' ' Alinh~tir Alcohol Generally, the . . ' (lIl) may be prepared by reacting in similar fashion a primary, linear or branched, ~llullull~ , alcohol having an alkyl or olefinic group having from about 6 to about 18 carbon atoms with ethylene oxide in amounts such that the ethylene oxide residue, i.e., -CH2-CH2-O-, content is on aYerage about 3 to about 15 moles of ethylene oxide per mole of alcohol, as well as mixtures thaeof. Following this, proxylene oxide is added in the desired amounts using the same conditions to obtain an alcohol-pul~u"~ ,u~,-polyu,~ylu~ . reaction product. The propylene oxide residue, i.e., -CH2-CH(CH,)-O-and/or -CH(CH3)-CH2-O-, content ranges from 0 to about 30 for each type of such residue with the total averaging from about 4 to about 30.
Useful low foam, nonionic surfactants of this type include structures having the formula: R-(~O)~-(PO)y~H where x is on average from about 3 to about 15 with from about 5 to about 15 preferred, y is on average from about 4 to about 30 with from about 5 to about 15 preferred, and R is a linear or branched alkyl or olefinic group having from about 6 to about 18 carbon atoms with from about 6 to about 14 preferred. Useful surfactants of this type include those cùnl ~ y available from Huntsman Chemical ('r~lr~tirn, Austin, Texas, under the ' e LF--37, LF-17 and JL--80X; and from BASF Corporation, Parsippany, New Jersey, under the l- ~.~;.. ;.... DW-5.
HOU03 1Z~03~ ~ -12-21~637~
D. PropoxYlated-EthoxYlated P~v~u~.vL.~ irh~ lrnhrl Generally, the ~.,,.,I u , l~ (IV) may be prepared by reacting in similar fashion a primary, linear or branched, I.~u..vl..~L;., alcohol having an alkyl or olefinic group having from about 8 to about 18 carbon atoms with propylene oxide in amounts such that the propylene oxide residue, i.e., -CHrCH(CH3)-O- and/or-CH(CH3)-CH,-O-, content ranges from 0 to about 15 for each type with the total averaging from about 2 to about 15 moles of propylene oxide per mole of alcohol, as well as mixtures thereof. Following this, ethylene oxide is added in the desired amounts using the same conditions to obtain an alcohol-,vlupu~' cthoxylate reaction product. The ethylene oxide residue content is on average from about 10 to about 25 moles of ethylene oxide per mole of alcohol. Following this, propylene oxide is again added in the desired amoumts using the same conditions to obtain an ' ' -' ~u,vv~ v~y' -l~v~u~y` reaction product. This propylene oxide residue content ranges from 0 to about 55 for each type with total averaging from about 10 to about 55 moles of propylene oxide per mole of alcohol.
Useful low foam, nonionic surfactants of this type include structures having the formula: R-~PO)s-(EO),~-(PO),-H where z i5 on average from about 2 to 15 with from about 3 to 15 preferred, x is on average from about 10 to about 25 with from about 11 to about 20 preferred, y i5 on average from about 10 to about 55 with from about 13 to about 25 preferred, and R is a linear or branched alkyl or olefnic group having from about 6 to about 18 carbon atoms with from about 6 to about 14 preferred.
Useful surfactants of this tYpe include those cu .. ,.. "y available from Huntsman Chemical C~ . Austin, Texas, under the ~L~ n~ n LF-0312A and from HVU03:12403~,~ 13 21~6370 Olin Corporation, New Haven, C~nnP~tic~t ssnder the ~1~ci~natil~n Poly-Tergent SLF-18 which according to U.S, 4,464,281 and U.S. 4,973,419 has the structure C6 lo~(PO)3~(EO)lz--(P)16-H
A preferred ....1 ,ùJ;., ....1 of t~ise present invention includes a compatible surfactant mixture of (a) about 39 to about 42 wt.% Clo"2-O-(EO),-(PO)9.5-H and (b) about 58 to about 61 wt.% C,2"4-0-(E0)4-H.
Deters~ ncv 13uilder MAt~ri~l C~ of the invention cont_in from about 20% to about 95%, preferably from about 40% to about 90%, by weight of detergency builder ,- . t, or mixtures thereof, said ~ being determined on an arhydrous basis a'sthough the builders can be hydrated.
The detergency builder materia. can be any of t se detergent builder materia'Ss cnown in the art which include trisodium phosphate, t~ hwl" l~yll .' . ' , sodium sliuulyl ~ ' , sodium I , ' . ' . sodium silicates having SiOz:NazO weight ratios of from about 1:1 to about 3.6:1, sodium carbonate, sodium hydroxide, sodium citrate, borax, sodium ethylenediaminetetraacetatc, sodium nitrolotriacetate, sodium ,~Svu~ll._~l-..,.~ ' , sodium ~SVU~ IYIUA~ ' polyl' .' polymeric Ca~S~u~y' such as ~I~Iy' and mixtssres tLsereof. Preferably, ' organic detergency builder materia s comprise not more t,~3an about 10% of the ~ by weight.
Preferred detergency builder materiass have the ability to remove meta'S ions other than aka'si meta's ions from wasilsing solutions by ~ ., which as defsned herein includes chelation, or by ~!lc ." reactions. Sodium tripolyl' .' is a s.~~ d~ly ISOUo3 1Z403~.. 3 -14-~ 21563~û
preferred detergency builder material which is a ~-1 .t ;..~ agent. Sodium carbonate is a preferred IJIC . ' '- detergency builder, ~li._ul~ly when it is desirable to reduce the total pl.o~ .)lulls level of the c-~ c of the invcntion. ('1-~ ' trisodium Vl ll-U, ' . ' can act as both a chlorine bleach and a 1~ detergency builder material.
The inclusion of water-soluble silicates, especially sodium silicates having SiO2:Na20 weight ratios of from about 1:1 to about 3.6:1 is a ~ ul~ly preferred .... I.u.l:.. 1 of the invention. Such silicates are a source of alkalinity useful in the automatic di~ w!~lg process and also act to inhibit the corrosion of aluminum, glassware and ceramic glazes.
rcUli~ukul.~ preferred . , of the invention contain from about 15% to about 50% sodium h;~ulyl h . ' , from about 5% to about 40% of sodium silicate solids as described h~ r and from 0% to about 40% sodium carbonate by weight.
Rl ' ~D~nts A wide variety of bleaching agents may be employed for use in the ~ .u~
of the present invention. Both halogen and peroxygen type bleaches are . . ' by this invention. Such bleaches are well-known. See for example U.S. 4,188,305; 4,464,281; and 4,601,844, which are hereby . ' by reference.
Among the suitable halogen donor bleaches are k~t.,.u~.~.' N-bromo and N-chloro imides such aS l.;.,Llc,~ ;hl~ .~ dibromo- and ~.' ' ' ~ . acids, and salts thereof with water-;ol-~bil Ig cations such as potassium and sodium. An example of the hydrated ~' '' ~.UI i~, acid is Clearon CDB56, a product, r ~:.i by Olin Corporation. Such bleaching agents may be employed in admixtures comprising two or more HOu03 l2qO3~.~ -15-~ 2156370 distinct chlorine donors. An exarnple of a commercial mixed system is one available from the Monsanto Chemical Comparly under the trademark ~ cign~tinn "ACL-66" (ACL signifying "available chlorine" and the numerical ~,~cien~inn "66" irldicatirlg the parts per pound of available chlorine) which comprises a mixture of potassium dh,hl~lu; ,o~ (4 parts) and U;~ VlU;lu~.1 ' aeid (I part).
Other N-bromo and N-chloro imides may also be used such aS N-brominated and N- ' ' ~ ~ ~ ' . phthalmide arld l~ h ~ Other cv~l~vullds include the 11.~' such as 1,3-dibromo arld 1,3-dichloro-5,5-dihl~~ ~.' N-~vllucllulu-5,5-~' ~L,.' Il.. ,ihyl~ N-bromo-5,5-dimethylhydantoirl); 1,3-dibromo and 1,3-dichloro 5,5-isvl,..~ LItù~, 1-3,dibromo and 1,3-dichloro 5-methyl-5-n-1L~d~ vhl~ and the like. Further useful hypohalite liberatirlg agents comprise L~;VI~ -' ' and tl;~,llul~ ' Dry, particulate, water-soluble anhydrous inorgarlic salts are likewise suitable for use herein such as lithium, sodium or calcium L.~ and L.~ulllul~ e.
The hypohalite liberatirlg agent may, if desired, be provided irl a form of a s~able solid complex or hydrate. Examples include sodium p- ' -salru-l,l-.. :~- h;l.J.' sodium benzene-sulfo~ dihydrate, calcium l..~t,uL,., t~,LI L,~.' calcium hypochlorite i ' ~.' , ete. r ' and chlorinated trisodiurn phosphate formed by the reaction of the cvll~ sodium hypohalite solution with trisodium phosphate (and water if necessary) likewise comprise efficaeious materials.
Other sources of available chlorine which can be used are: N,N'-di~,lllvlv~l~vyl~ urea; I ' .r .~ lvlv ,............................ 1;. r, N,N'-HOW3:12403~ ~ -16-2~5637Q
vi-' ' .._ ' I,ull~u,lide; N-~:LIVIUG~ YI urea; N,N'-dichlorobiuret; and chlorinated d;~,~/auv,iallliv~.
Preferred hlvl;~ldt;llg agents include potassium and sodium v~iulllùlv;~vu~r~al~
dihydrate,, ' ' ' trisodium phosphate and calcium ll.yl - ~.' raLLi.,ul .1~ preferred are the organic chlorine bleaches such as sodium and rotassium ViUIIIUIU~ ic~.huly sodium or potassium vi~,llulu;~ dihydrate.
Desirably, at least 0.1% availablo chlorine based on the weight of the detergent IC should be used. It has been found that automatic .1;~ . which have a source of available chlorine in an amount sufficient to provide available chlorine preferably equal to about 0.1% to about 5%, more preferably from about 0.5% to about 4%, by weight of the c.~...p~ . is used. A more preferred level is from about l.Z5% to about 3% by weight of the ~ Hypohalite liberating ~----r- ' may generally be employed in automatic d;~h.. -- ~ detergents at a level of from 0.5 to 5% by weight, preferably from 0.5 to 3%. A high level of available chlorine provides improved cleaning, especially on starch soils, and improved ~,uuLL~ Lllil~
For granular . , an inorganic chlorine bleach ingredient such as ' ' ' trisodium phûsphate and organic chlûrine bleaches such as the ~hIUIV~ can be utilized. Sodiurn h~ ' ' and other alkali metal 1~ ' ' can be used in aqueûus liquid or gel ~
Methods of 1 ~ .. :.. -g "available chlorine" for ~ - - illl,vl,uvlaLillg chlorine bleach materials such as 1.~ ' ' and ~hIUIUCY are well known in the art.
Available chlorine is the chlorine which can be liberated by ^ ~ of a solution of H0CJC3: 1 2~031.~ - I 1-2~637a ~ yu~ ' ' ions (or a material that can form l-~yO~,IIluliL~ ions in solution) and at least a molar equivalent amount of chloride ions. A ~u~ iu~l analytical method f ~ &
available chlorine is addition of an excess of an iodide salt and titration of the liberated free iodine with a reducing agent.
Althûugh it is preferred to have a source of available chlorine present, acceptable products can be formulated without any such source. In the cæ of peroxygen bleaching agents, it is desirable to have enzymes present. Among the oxygen bleaches which may be included in the invention are alkali metal and salts of inorganic peroxygen c.. ,~ such as perborates, ~..,~ persulfates, ~ andthe like. Generally the inorganic oxygen compound will be used in with an activator such as TAED
(tetraacetyl ethylene diamine), sodium benzoyl u~b_~.._ sulfonate or choline ~ulruyh~
carbonate or a catalyst such as mangarlese or other transition metal, as is well known in the bleaching art. Insoluble orgarlic peroxides such as liy.,lu~ '~ ' acid (DPDA) or lauroyl peroxide may also be used. Generally, the peroxygen . ' are present at a level of from 0.5 to 20% by weight, 0.005 to 5% catalyst and I or 0.5 to 30% activator.
~l~yl r~- F~-r The automatic L~l.. ' _ . of the invention can optionally contain up to about 50%, preferably from about 2% to about 20%, based on the weight of cl~w~,y' ' nonionic surfactant of alkyl phosphate ester or mixtures thereof and wherein the alkyl preferably contains from about 16 to about 20 carbon atoms.
Suitable alkyl phosphate esters are disclosed in U.S. 3,314,891 issued to Schmoka et al., i . ' herein by reference.
HOU03:12403~ 18-The preferred aikyi phosphate esters contain from 16-20 carbon atoms. Highly preferred aikyl phosphate esters are ll~ul~uat~yl acid phosphate and monooleyl acid phosphate, or saits thereof, ~ aikaii metai saits, or mixtures thereof.
The alkyl phosphate esters of the invention have been used to reduce the sudsing of detergent C ~ suitable for use in automatic i;~l.w~'~.g machines. The esters are .ui~l~ effective for reducing the sudsing of . , comprising nonionic surfactants which are heteric ~:~Lu~y' ' E~lu!~u~yl...~,l or block polymers of ethylene oxide and propylene oxide.
Oth-~r Tnore~li,.nte In addition to the above Ul~y. ~' ', it may be desirable, if the product sudses too much, to ~ one of the many suds-~u~l. 3 ingredients disclosed in the above mentioned patents which have been r ' ~ by reference at a level of from about û.001%
to about 10%, preferably from about 0.05% to about 3%. The preferred suds ~ ;llg materiais are mono- and distearyl acid I ' ~ ' the seif-emuisified siloxane suds s..~
for example, as disclosed in U.S. 4,136,045 issued to Gauit et ai., and mixtures thereof. In generai, lower amounts of, or no, suds-~ q.~ are preferred. Less tban 0.2%, preferably less than 0.1% is desirablc, more preferably none for best spot/fiim, long term.
Enzymes are aiso desirable in c r "' which do not contain a source of available c_iorine. Suitable enzymes are those disclosed in U.S. 3,519,379 issued to Blomeyer et ai.; 3,655,568 issued to Zaici et ai.; 4,101,457 issued to Place et ai.; and 4,188,305 issued to Haias, ail of said patents being h~,v~ ' herein by reference.
HOU03 1 Z403~ ~ - ¦ 9--21~6370 Cbina protecting agents including sodium or potassium ~IIlrninnci 31 ' , etc. may be present in amounts of from about 0.1% to about 5%, preferably from about 0.5% to about 2%.
Filler materials can also be present including sucrose, sucrose esters, sodium chloride, sodium sulfate, etc. in amounts of from about 0.001% to about 60%, preferably from about 5% to about 30%.
Hydrotrope materials such as sodium benzene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, etc. can be present in minor amounts.
Dyes, perfurnes, crystal modifiers and tne like can also be added in minor amounts.
M~xEn SURFACTANT SYSTEMS FOR LOW FOA~I APPI-ICATIONS
BACKGROUND OF TT~ INVENTION
D~ 81,266-F
Field of the Inven¢ion This invention relates to a surfactant system useful in dl~ macbines, and more p~lh,~l~ly to a surfactant system comprising a compatible mixture of at least one uncapped ~tllw~y' ' nonionic medium-to-high foaming surfactant and at least one propylene oxide capped nonionic low foaming surfactant. This surfactant system is useful in d;~h aDh;llg detergents and as rinse aids which have a good wetting and drainage effect on hard surfaces.
1~- !~ ~ d ~nform~at~o~
Many cleaning ~ require surfactants'that are both low foaming and "'~''C Examples include automatic dishwasher detergents, textile processing, paper ore processing and metal cleaning. Here the tyypical ~ ~' ' nonionic surfactants must be subjected to a capping process to meet these 1~, Capping reactions with propylene oxide or other suitable chemicals are a costly extra step in the productjon of these c~rfs~t~ tc In the ar¢ of cleaning r-, - ~ for use in cleaning hard surfaces, ~ l~ly the art of cleaning tableware and oth food-soiled utensils in machine d;sh ~1l~, ~e problern of excessive foa~n buildup in the machine during operation is the result of high food soil ~ The use of alkyl phosphate ester defoamers such as IIIVII~ acid phosphate a_ disclosed in U.S. 3,314,891 has largely solved the problem of excessive foam buildup. Prior thereto, machine d;~l. ' ~ had atendency to foam .,.~
and/or leave ~ r ~;"~1~Ir spots and streaks on dishes a~d glassviare. The low foaming nonionic ~oU03 1240~ 2-2~3~a ,.
surfachnts contained in such detergent ~r~mroqiti~nq were ineffective in both removing food soil and providing suihble foam control where the aqueous cleaning solution became ' J with foam generating protein soils such as egg soil and soil from various milk products.
rhe generation of such foams is . Ii~ul~uly insidious in that the cleaning action of the machine dishwasher depends to a large extent upon the effective ~U~ ' of foam generation durirlg operation. Without effective foam ~U~ .Vll, the mechanical cleaning action of the machine dishwaqher is reduced as the result of foam buildup in the aqueous cleaning solution. The aqueouq washing fluid which is normally impelled against the hbleware in the machine dishwasher is less effective in cleaning becauqe it is forced against the tableware at reduced pressure.
An indication of the va~ious kinds of nonionic surfactants utilized in such machirle ~ ~ can be found in U.S. Pat. Nos. 3,314,891 and 3,359,207.
General disclosures of nonionic surfactants can be found in U.S. Pat. Nos. 2,677,600; 2,979,528 and 3,036,118. Low foaming washing and cleaning agents for use in machine d; ~ e are also disclosed in 3,382,176. Machirle ~..'~... ' _ detergent . , containing a non-phosphate salt builder have been disclosed in British Pat. No. 1,325,645; Canadian Pat. No.
941,707; U.S. Pat. No. 3,899,436; 4,127,496 and 4,092,258.
Another method of reducing the foaming tendency of dllV~ alcohols was to end cap them with an alkyl group. For exatnple, Henkel has a seri of patents using capped surfachnts to suppress foam. In the following, "EO" is an ethylene oxide residue, "PO" is a propylene oxide residue, "BO" is butylene oxide residue, and "AO" is an aLlcylene oxide HOU03: 12~038 ~ -3 -,~ 21~6~7~
residue. Henkel published patent application ZA 89/4027, 1990 discloses a low foaTn surfactant c.... ,.v~;l;.-.. that produces little foam and good wetting on plastics (especially pvl.r~,~ubv~ 3) and that are 1~.~ ' for rinse aid ,.1.~,1;. ,.t;"~; in automatic dlallw~h~l, The nonionic surfactttnts u3ed therein included C~"-O-(EO)X-C~,~ alone or in cv ~ .1 .-l ;.~. . with one or more of C,."-O-(EO),-(PO)h-H, C~ O-(EO)C-C~, and C,.,,-O-(EO)d-H, where a=2 to 6, b=3 to 7, c--7 to 12, d=20 to 50 and x 5 20 to 40. This patent application also discloses the processes for their production. DE 3,928,604 discloses .' ' ' ~ allcyl polyglycol ethers for detergents including C, ,~-O-(EO)2 ,-C,.,o which can be used in mixtures witn C~_,,(EO)7 ,0-H in ratios of 10: 90 to 90: 10- Suggested ~A are for machine d..21~
detergents. DE 3,935,374 discloses a compound with good anti-foaming activity and is shown by C,." O (EO)3., C4,. These are made with a narrow rttnge molecular weight .1; ~';1...1;.~..
~lhVA.~ catalyst. ~P 254206 discloses low-foam/foam-depressing surfactant mixtures containing CLI~_O_(EO)3 7_C~ and C~" O (EO) ~ 3-(PO)3 66-H optionally with C,~22-O-(PO), 3-H.
Henkel patent (DE 4,009,533, 1991) discusses rnixtures for laundry ~-~-l;~ - ;,.l..c in the form of: alkyl glucose ~ v ~ with R-O-(EO)0 ~5-(AO)~.20-OR' with R = C,..22 and R' = C~ ,0.
Encolab Inc., U.S. 4,973,423, 1990 claims foaTn inhibiting additives or low-foam cleaners. The additives are the allyl end-capped e:LIl~JA,~ alcohols C6 "-O-(EO)2 6-C~.~ used in, , with wetting agents such as nonionic surfact~dnts, including polyglycol ethers of the type obtain~d by adding ethylene oxide onto alcohols.
Due to the additional processing steps and cost involved in alkyl end-capping, the search continued and still continues for low foaming and defoaTning nonionic surfact~dnts which avoid such steps and cost.
HOU03:12~03~.1 -4-. .
Drackett Co., U.S. 4,226,736, 1980 discloses mixtures of surfactants and thickeners to make gel type automatic dishwasher detergents. The surfactant mixtures consist of poly~"v,uu~yl..~c.i pol~.,tl.v~-y' ' ethylene glycols and C,o l~-O-(EO/PO)55 80.,.-H.
Nippon Paint Co., U.S. 4,256,601, 1981 discloses a low foam surfactant with very good foam breaking abilities which is thc all para X-Ph-CR~R2-Ph-O(AO)320H. This material is mentioned in, ~ with nonionic substances that have a cloud point less than 40C such as alcohol clLu~y' , ~Lkyl~ .ol ethoxylates and block CUIJVI~ of the (EO)--(PO)--(EO) type. The weight ratio of the above compound to the noniorlics is given as a range of 1.0 to 0.05 up to 1.0 to 5Ø
Sandoz Ltd. patent (Abstracts of GB 2204321-B, 1991 and GB 2204321-A, 1988) discusses l.i.~ detergent . - for cleaning surfaces (metals, plastics, laundry) which in addition to an ;~ --P and l ~ agent include the mixture of a fatty alcohol pol~ glycol ether and a low foaming nonionic surfactant as I~IJlC.~ ,d by:C".22-O-(EO)525H(2-35%)andC~22-O-(EO),.,2(PO),.5H(0.5-5.0%),-~ Iy. According to GB æO4321-A, 1988, the preferred mixture in the surfactant ~ . was C,2_,6--O--(EO)5_,2H and C,~-O-(EO),-(PO),H. In Example 2 thereof, laboratory glassware ' with dried blood, brain substance and albumirl was immersed in a solution containing from 3 to 5% by weight of a ~.. ,...-:~;..,. contairling 12% by weight C,2"5--O--(EO),--H and 1% by weight C,2-O~EO),-(PO),-H for 2 to 3 hours at 80C. or 12 hours at room ~ There w~c no mention of lûw foam nor defoaming with this cv., ~ The remaining examples dealt with laundry detergents (continuous working HOU03: 124033.- -5-215~370 process through wash tunnel) and cleaning electronic ll~;u~u~,;lu~lib (immersion) and watch cases (ultrasorlic treatment).
Henkel published patent application WO 91/03536, 1991 discloses foa~-inhibiting additives for low foaming cleansers. These additives are: C,2 20-O-(EO)2 ~H where the alkyl group is from a 2-braQched even alkanol and optionally mixed with CI.,,-O-(EO)26-(PO)3.rH where the alkyl group caQ be branched or liQear. The 2-branched aspect of the ~lh~ y~ ' alcohol is stressed iQ part by seizing on the uu~_-v~liu.. that slight structural changes produce sigr~ificaQt differences in the properties of nonionic surfactants. For exa[nple, DE 3,315,951 and 3,800,493 were compared. The primary differences ih~,.c': .. were the carbon residue of the alcohol used iQ each case. In the first, the carbon residue bad 8 to 18 carbon atoms aQd that of the other had 20 to 28 carbon atoms. Surfactants with highly branched chains generally show lower foam heights thaQ isomeric straight-chaiQ materials, except where the length of the II~L.~,hJbl., group becomes too long for straight-chain -U~ to have adequate water solubility for good defoan~iQg (e.g., greater than 16 carbon atoms at 4ûC). See "SurfactaQts aQd Interfacial PL~..v.n~,.~'' by Milton J. Rosen, p. 212, published by Wiley r..~ . (1978). As , ' '~ ' in this Henkel patent, the branched portioQ of the alkyl group rangGd from 4 to 8 carbon atoms with the straight portion of the alkyl group ranging from 8 to 12 carbon atoms. Accordingly, this Henkel patent teaches away from straight or ~ ' ' ' alkyl groups iQ the ~:LIIUA~Y' ' ' alcohol so as to effect a reduction in its foaming tendencies.
Henkel published patent application ZA 9ûll0,356, 1991 discloses industrial cleaners mainly used for cleaning aQd passivating in spray-cleaning units in the automotive HOW~: 12403a.t -6--2~S6370 . .
industry. The industriai cleaners use a .~, ..1; . '; ~ of surfactants for clearLing hard surfaces and which exhibit low foaming properties from 15C. to 80C. arld excellent wetting properties without leaving spots and stairls. The surfactant .v ~ " contains (a) C6 ,,-O-(EO)2 ,2-H and (b) C6 "-O-(EO)2 ,0 (Po)2J H
where the weight ratio of (a):(b) is within the range of 10:1 to 1:10. The carbon residue of a) and (b) are preferably linear. The surfactant ~ \ may further contain (c) C6 ,,-O-(EO)2 ,2-C-I..-HOW3:12~03~.- 7 21~370 SUMMARY OF THE INVENTION
This invention utilizes a compatible mixture of at least one linear, uncapped CLI~ y' ~ nonionic surfactant and at least one low foam nonionic surfactant capped with propylene oxide, which mixture retains tne properties of the low foam ~ s) while reducing the overall cost of the useful surfactt3nt system(s).
MOK pa~L~.ukul~ there is provided a low foaming d;_~" ' , having:
(a) at least one first nonionic surfactant having a general formula selected from the group consisting of general formula (I) Rl-O-(CH2CH~O)y-H (I) , wherein R' represents a linear alkyl or olefmic group having from about 6 to about 18 carbon atoms and y represents a number ranging from about 3 to about 15, and general formula (II) Np-O-(CH,CH2O)~-H (II) , wherein Np is the carbon residue of ~ l,' ' or u~,L~ and z rcpresents a number ranging from about 4 to about 200; and (b) at least one second nonionic surfactant having a general formula selected from the group consisting of general formula (III) R2-O-(CH2CH20)m-A'-H (111) ,wherein R2 represents a linear or branched alkyl or olefnic group having from about 6 to about 16 carbon atoms, m represents a number ranging from about 3 to about 15, and A' represents a group having the formula ~(CH2~CH(CH3)-O)q~~ -(CH(CH3)-CH~-O),- or a ....1~1...A~ thereof with q and r each .el,.c ~ a number ranging from 0 to about 30 and H~U03:12~031.1 -8-. .
the sum of q and v represents a numbcr ranging from about 4 to about 30, and general formula ([V) R3-o-A2-(CH2CH2o)c-A3-H (IV) , wherein R3 represents a linear or brarlched alkyl or olefinlc group having from about 6 to about 18 carbon atoms, n represents a number rangirlg from about 10 to about 25, A2 representC a group having the formula -(CH2-CH(CH3 )-O)t-, -(CH(CH3)-CH2-O)U- or a thereof with t and u each l~.c ~ a number ranging from 0 to about 15 and the sum of t and u represent_ a number ranging from about 2 to about 15, and A3 represents a group having the formula -(CH2-CH(CH3)-O)V-, -(CH(CH3)-CH3-O)W- or a .i.. l.. ~,.. ~
thereof with v and w each l~ l~g a number ranging from 0 to about 55 and the sum of v and w represents a number rangirlg from about 10 to about 55, wherein the ~---r ' a and b above are compatible with each other.
('~7mrn.ontc a arld b are preferably present in a mole ratio a:b ranging from about 95:5 to about 60:40.
S~ hlxl.~ tbis invention maintains the low foam and defoaming ~ r needed for a number of low foam ~1." (e.g. automatic dishwasher detergenb, rinSe aids) while ~ '~ '.~ reducing the cost of the surfactants which form the major functional .(S) of the product~ used in these rr DES~RIPTION OF THI~ PREFFRR~n F.MRODIM~.~T
The Sl-t f~ror~t l'. . ~ of the invention contain from about 2% to about 5%, preferably from about 2% to about 3%, by weight of a compatible mixture of (1) uncapped ~LLu~y' HOU03:~2tO3~.~
2i~6370 .~ .
nonionic surfactants and (2) typical propylerle oxide capped low foarlung surfactants for use as automatic dishwasher detergents. It has oeen found that certain of these compatible mixtures perform in automatic dishwasher detergents without the loss of food soil removal and with a~ ly little loss of defoaming I r Mixtures of this type ai~lir~ ly reduce the overall cost of the surfactants useful for thes~ al~p~
We have ~ 51.Y found that compatible mixed nonionic surfactant systems (where at least one surfactant is the typical alcohol-~llw~.~' ylu~.u..~y' or alcohol-I"VI~U~Y' ~ lu~.y' -UlU~U~y' IOW foam type and at least one is the typical alcohol-ethoxylate of a moderate-to-high foam generation) afford dishwasher 1~ cc , in the area of film generation, equal to or superior to that of the low foam (defoaming) surfactant when used alone. It is further surprising that mixtures of surfactants that contain a major arnoumt of a typical ~ u~y' ' alcohol retain the low foam and defoaming properties of the more expensive capped low foaming surfactants and thus show equivalent or superior ~- 1.. - .-in r~ like automatic dishwasher detergents.
Nonionic surfactants can be broadly defined as ~ ---r- ~ prepared by well-known methods of adding an alkylene oxide compound to an alcohol a shown for example in U.S. 2,677,700; 3.956,401; 4,223,163; and 4,226,736, which are hereby u~,ul~ by reference. This process is also known as aLIwAy' A. Fthn~lated Alivhatic ~Irnhnlc Generally, the ~ . ' (I) may be prepared by reacting a primary, linear, IllOllOll.rll;c alcohol having an aLlcyl or olefinic group having from about 6 to about 18 carbon atoms, preferably from about 10 to about 16 carbon atoms, with ethylene oxide in amounts HOU03:124038.~ -IU-- = ~
~1~6370 such that the ethylene oxide residue i.e., -(CH2-CHz-O~-, content is on average about 3 to about 15 moles of ethylene oxide per mole of alcohol, as well as mixtures thereof. The reaction is carried out at an elevated L~ aLulc in the presence of alkaline catalysts such as the salts or hydroxides of the alkali metals or the alkaline earth metals, for example, KOH. A mixture of such alcohols may be used and this is generally true when using ,. ~,;al alcohols which are often available as a blend of several alcohols. ~ , the number of carbon atoms in the alcohol is referred to as an average nurnber. Al ~.ly, the number of carbon atoms in the alcohol mixture may be referred to, for example, C~0"z. The C~ z d~ign~tion, for example, means a mixture primarily having . , ~vith carbon residues having 10 and 12 carbon atoms with small amounts of r~ 1- having carbon residues of different carbon lengths. Useful surfactants of this type include those "~, available from Huntsman Chemical ~ n~ n, Austin, Texas, under the ~ ~iL - ;-- ~ L610-3; L10-3; L1270-2; L12-3;
L12-6; L24-1.3; L24-2; L24-3; arld L244.
B. F~h~lyvlated Alkvl Ph~-nnlc ~ ,.n r~ (Il) may be prepared by rcactlng in similar fashion alkyl phenols having an alkyl group containing from about 8 to about 12 carbon atoms in either a straight chain or branched chain c Ci_ with ethylene oxide in amounts such that the ethylene oxide residue content is on average from about 4 to about 200 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such .- . j.~. -.-l~ may be derived from JUI.y~ ,d propylene, d;i~ubu~yl~ , octene or nonene for example. Preferred alkyl phenols include nu..~l~ll..lol and OC~I,U~ OI. Useful surfactants of this type include those ~IOU0~:12103S.B -I 1-~ 21~637~
~,u~ ially available from Huntsman Chemical Corporation, Austin, Texas, under the ~ir~i~n~tir,n~ N--120, N--100 and N--40.
C. Ell~u~Y'a ~ PIU~JU~Y' ' Alinh~tir Alcohol Generally, the . . ' (lIl) may be prepared by reacting in similar fashion a primary, linear or branched, ~llullull~ , alcohol having an alkyl or olefinic group having from about 6 to about 18 carbon atoms with ethylene oxide in amounts such that the ethylene oxide residue, i.e., -CH2-CH2-O-, content is on aYerage about 3 to about 15 moles of ethylene oxide per mole of alcohol, as well as mixtures thaeof. Following this, proxylene oxide is added in the desired amounts using the same conditions to obtain an alcohol-pul~u"~ ,u~,-polyu,~ylu~ . reaction product. The propylene oxide residue, i.e., -CH2-CH(CH,)-O-and/or -CH(CH3)-CH2-O-, content ranges from 0 to about 30 for each type of such residue with the total averaging from about 4 to about 30.
Useful low foam, nonionic surfactants of this type include structures having the formula: R-(~O)~-(PO)y~H where x is on average from about 3 to about 15 with from about 5 to about 15 preferred, y is on average from about 4 to about 30 with from about 5 to about 15 preferred, and R is a linear or branched alkyl or olefinic group having from about 6 to about 18 carbon atoms with from about 6 to about 14 preferred. Useful surfactants of this type include those cùnl ~ y available from Huntsman Chemical ('r~lr~tirn, Austin, Texas, under the ' e LF--37, LF-17 and JL--80X; and from BASF Corporation, Parsippany, New Jersey, under the l- ~.~;.. ;.... DW-5.
HOU03 1Z~03~ ~ -12-21~637~
D. PropoxYlated-EthoxYlated P~v~u~.vL.~ irh~ lrnhrl Generally, the ~.,,.,I u , l~ (IV) may be prepared by reacting in similar fashion a primary, linear or branched, I.~u..vl..~L;., alcohol having an alkyl or olefinic group having from about 8 to about 18 carbon atoms with propylene oxide in amounts such that the propylene oxide residue, i.e., -CHrCH(CH3)-O- and/or-CH(CH3)-CH,-O-, content ranges from 0 to about 15 for each type with the total averaging from about 2 to about 15 moles of propylene oxide per mole of alcohol, as well as mixtures thereof. Following this, ethylene oxide is added in the desired amounts using the same conditions to obtain an alcohol-,vlupu~' cthoxylate reaction product. The ethylene oxide residue content is on average from about 10 to about 25 moles of ethylene oxide per mole of alcohol. Following this, propylene oxide is again added in the desired amoumts using the same conditions to obtain an ' ' -' ~u,vv~ v~y' -l~v~u~y` reaction product. This propylene oxide residue content ranges from 0 to about 55 for each type with total averaging from about 10 to about 55 moles of propylene oxide per mole of alcohol.
Useful low foam, nonionic surfactants of this type include structures having the formula: R-~PO)s-(EO),~-(PO),-H where z i5 on average from about 2 to 15 with from about 3 to 15 preferred, x is on average from about 10 to about 25 with from about 11 to about 20 preferred, y i5 on average from about 10 to about 55 with from about 13 to about 25 preferred, and R is a linear or branched alkyl or olefnic group having from about 6 to about 18 carbon atoms with from about 6 to about 14 preferred.
Useful surfactants of this tYpe include those cu .. ,.. "y available from Huntsman Chemical C~ . Austin, Texas, under the ~L~ n~ n LF-0312A and from HVU03:12403~,~ 13 21~6370 Olin Corporation, New Haven, C~nnP~tic~t ssnder the ~1~ci~natil~n Poly-Tergent SLF-18 which according to U.S, 4,464,281 and U.S. 4,973,419 has the structure C6 lo~(PO)3~(EO)lz--(P)16-H
A preferred ....1 ,ùJ;., ....1 of t~ise present invention includes a compatible surfactant mixture of (a) about 39 to about 42 wt.% Clo"2-O-(EO),-(PO)9.5-H and (b) about 58 to about 61 wt.% C,2"4-0-(E0)4-H.
Deters~ ncv 13uilder MAt~ri~l C~ of the invention cont_in from about 20% to about 95%, preferably from about 40% to about 90%, by weight of detergency builder ,- . t, or mixtures thereof, said ~ being determined on an arhydrous basis a'sthough the builders can be hydrated.
The detergency builder materia. can be any of t se detergent builder materia'Ss cnown in the art which include trisodium phosphate, t~ hwl" l~yll .' . ' , sodium sliuulyl ~ ' , sodium I , ' . ' . sodium silicates having SiOz:NazO weight ratios of from about 1:1 to about 3.6:1, sodium carbonate, sodium hydroxide, sodium citrate, borax, sodium ethylenediaminetetraacetatc, sodium nitrolotriacetate, sodium ,~Svu~ll._~l-..,.~ ' , sodium ~SVU~ IYIUA~ ' polyl' .' polymeric Ca~S~u~y' such as ~I~Iy' and mixtssres tLsereof. Preferably, ' organic detergency builder materia s comprise not more t,~3an about 10% of the ~ by weight.
Preferred detergency builder materiass have the ability to remove meta'S ions other than aka'si meta's ions from wasilsing solutions by ~ ., which as defsned herein includes chelation, or by ~!lc ." reactions. Sodium tripolyl' .' is a s.~~ d~ly ISOUo3 1Z403~.. 3 -14-~ 21563~û
preferred detergency builder material which is a ~-1 .t ;..~ agent. Sodium carbonate is a preferred IJIC . ' '- detergency builder, ~li._ul~ly when it is desirable to reduce the total pl.o~ .)lulls level of the c-~ c of the invcntion. ('1-~ ' trisodium Vl ll-U, ' . ' can act as both a chlorine bleach and a 1~ detergency builder material.
The inclusion of water-soluble silicates, especially sodium silicates having SiO2:Na20 weight ratios of from about 1:1 to about 3.6:1 is a ~ ul~ly preferred .... I.u.l:.. 1 of the invention. Such silicates are a source of alkalinity useful in the automatic di~ w!~lg process and also act to inhibit the corrosion of aluminum, glassware and ceramic glazes.
rcUli~ukul.~ preferred . , of the invention contain from about 15% to about 50% sodium h;~ulyl h . ' , from about 5% to about 40% of sodium silicate solids as described h~ r and from 0% to about 40% sodium carbonate by weight.
Rl ' ~D~nts A wide variety of bleaching agents may be employed for use in the ~ .u~
of the present invention. Both halogen and peroxygen type bleaches are . . ' by this invention. Such bleaches are well-known. See for example U.S. 4,188,305; 4,464,281; and 4,601,844, which are hereby . ' by reference.
Among the suitable halogen donor bleaches are k~t.,.u~.~.' N-bromo and N-chloro imides such aS l.;.,Llc,~ ;hl~ .~ dibromo- and ~.' ' ' ~ . acids, and salts thereof with water-;ol-~bil Ig cations such as potassium and sodium. An example of the hydrated ~' '' ~.UI i~, acid is Clearon CDB56, a product, r ~:.i by Olin Corporation. Such bleaching agents may be employed in admixtures comprising two or more HOu03 l2qO3~.~ -15-~ 2156370 distinct chlorine donors. An exarnple of a commercial mixed system is one available from the Monsanto Chemical Comparly under the trademark ~ cign~tinn "ACL-66" (ACL signifying "available chlorine" and the numerical ~,~cien~inn "66" irldicatirlg the parts per pound of available chlorine) which comprises a mixture of potassium dh,hl~lu; ,o~ (4 parts) and U;~ VlU;lu~.1 ' aeid (I part).
Other N-bromo and N-chloro imides may also be used such aS N-brominated and N- ' ' ~ ~ ~ ' . phthalmide arld l~ h ~ Other cv~l~vullds include the 11.~' such as 1,3-dibromo arld 1,3-dichloro-5,5-dihl~~ ~.' N-~vllucllulu-5,5-~' ~L,.' Il.. ,ihyl~ N-bromo-5,5-dimethylhydantoirl); 1,3-dibromo and 1,3-dichloro 5,5-isvl,..~ LItù~, 1-3,dibromo and 1,3-dichloro 5-methyl-5-n-1L~d~ vhl~ and the like. Further useful hypohalite liberatirlg agents comprise L~;VI~ -' ' and tl;~,llul~ ' Dry, particulate, water-soluble anhydrous inorgarlic salts are likewise suitable for use herein such as lithium, sodium or calcium L.~ and L.~ulllul~ e.
The hypohalite liberatirlg agent may, if desired, be provided irl a form of a s~able solid complex or hydrate. Examples include sodium p- ' -salru-l,l-.. :~- h;l.J.' sodium benzene-sulfo~ dihydrate, calcium l..~t,uL,., t~,LI L,~.' calcium hypochlorite i ' ~.' , ete. r ' and chlorinated trisodiurn phosphate formed by the reaction of the cvll~ sodium hypohalite solution with trisodium phosphate (and water if necessary) likewise comprise efficaeious materials.
Other sources of available chlorine which can be used are: N,N'-di~,lllvlv~l~vyl~ urea; I ' .r .~ lvlv ,............................ 1;. r, N,N'-HOW3:12403~ ~ -16-2~5637Q
vi-' ' .._ ' I,ull~u,lide; N-~:LIVIUG~ YI urea; N,N'-dichlorobiuret; and chlorinated d;~,~/auv,iallliv~.
Preferred hlvl;~ldt;llg agents include potassium and sodium v~iulllùlv;~vu~r~al~
dihydrate,, ' ' ' trisodium phosphate and calcium ll.yl - ~.' raLLi.,ul .1~ preferred are the organic chlorine bleaches such as sodium and rotassium ViUIIIUIU~ ic~.huly sodium or potassium vi~,llulu;~ dihydrate.
Desirably, at least 0.1% availablo chlorine based on the weight of the detergent IC should be used. It has been found that automatic .1;~ . which have a source of available chlorine in an amount sufficient to provide available chlorine preferably equal to about 0.1% to about 5%, more preferably from about 0.5% to about 4%, by weight of the c.~...p~ . is used. A more preferred level is from about l.Z5% to about 3% by weight of the ~ Hypohalite liberating ~----r- ' may generally be employed in automatic d;~h.. -- ~ detergents at a level of from 0.5 to 5% by weight, preferably from 0.5 to 3%. A high level of available chlorine provides improved cleaning, especially on starch soils, and improved ~,uuLL~ Lllil~
For granular . , an inorganic chlorine bleach ingredient such as ' ' ' trisodium phûsphate and organic chlûrine bleaches such as the ~hIUIV~ can be utilized. Sodiurn h~ ' ' and other alkali metal 1~ ' ' can be used in aqueûus liquid or gel ~
Methods of 1 ~ .. :.. -g "available chlorine" for ~ - - illl,vl,uvlaLillg chlorine bleach materials such as 1.~ ' ' and ~hIUIUCY are well known in the art.
Available chlorine is the chlorine which can be liberated by ^ ~ of a solution of H0CJC3: 1 2~031.~ - I 1-2~637a ~ yu~ ' ' ions (or a material that can form l-~yO~,IIluliL~ ions in solution) and at least a molar equivalent amount of chloride ions. A ~u~ iu~l analytical method f ~ &
available chlorine is addition of an excess of an iodide salt and titration of the liberated free iodine with a reducing agent.
Althûugh it is preferred to have a source of available chlorine present, acceptable products can be formulated without any such source. In the cæ of peroxygen bleaching agents, it is desirable to have enzymes present. Among the oxygen bleaches which may be included in the invention are alkali metal and salts of inorganic peroxygen c.. ,~ such as perborates, ~..,~ persulfates, ~ andthe like. Generally the inorganic oxygen compound will be used in with an activator such as TAED
(tetraacetyl ethylene diamine), sodium benzoyl u~b_~.._ sulfonate or choline ~ulruyh~
carbonate or a catalyst such as mangarlese or other transition metal, as is well known in the bleaching art. Insoluble orgarlic peroxides such as liy.,lu~ '~ ' acid (DPDA) or lauroyl peroxide may also be used. Generally, the peroxygen . ' are present at a level of from 0.5 to 20% by weight, 0.005 to 5% catalyst and I or 0.5 to 30% activator.
~l~yl r~- F~-r The automatic L~l.. ' _ . of the invention can optionally contain up to about 50%, preferably from about 2% to about 20%, based on the weight of cl~w~,y' ' nonionic surfactant of alkyl phosphate ester or mixtures thereof and wherein the alkyl preferably contains from about 16 to about 20 carbon atoms.
Suitable alkyl phosphate esters are disclosed in U.S. 3,314,891 issued to Schmoka et al., i . ' herein by reference.
HOU03:12403~ 18-The preferred aikyi phosphate esters contain from 16-20 carbon atoms. Highly preferred aikyl phosphate esters are ll~ul~uat~yl acid phosphate and monooleyl acid phosphate, or saits thereof, ~ aikaii metai saits, or mixtures thereof.
The alkyl phosphate esters of the invention have been used to reduce the sudsing of detergent C ~ suitable for use in automatic i;~l.w~'~.g machines. The esters are .ui~l~ effective for reducing the sudsing of . , comprising nonionic surfactants which are heteric ~:~Lu~y' ' E~lu!~u~yl...~,l or block polymers of ethylene oxide and propylene oxide.
Oth-~r Tnore~li,.nte In addition to the above Ul~y. ~' ', it may be desirable, if the product sudses too much, to ~ one of the many suds-~u~l. 3 ingredients disclosed in the above mentioned patents which have been r ' ~ by reference at a level of from about û.001%
to about 10%, preferably from about 0.05% to about 3%. The preferred suds ~ ;llg materiais are mono- and distearyl acid I ' ~ ' the seif-emuisified siloxane suds s..~
for example, as disclosed in U.S. 4,136,045 issued to Gauit et ai., and mixtures thereof. In generai, lower amounts of, or no, suds-~ q.~ are preferred. Less tban 0.2%, preferably less than 0.1% is desirablc, more preferably none for best spot/fiim, long term.
Enzymes are aiso desirable in c r "' which do not contain a source of available c_iorine. Suitable enzymes are those disclosed in U.S. 3,519,379 issued to Blomeyer et ai.; 3,655,568 issued to Zaici et ai.; 4,101,457 issued to Place et ai.; and 4,188,305 issued to Haias, ail of said patents being h~,v~ ' herein by reference.
HOU03 1 Z403~ ~ - ¦ 9--21~6370 Cbina protecting agents including sodium or potassium ~IIlrninnci 31 ' , etc. may be present in amounts of from about 0.1% to about 5%, preferably from about 0.5% to about 2%.
Filler materials can also be present including sucrose, sucrose esters, sodium chloride, sodium sulfate, etc. in amounts of from about 0.001% to about 60%, preferably from about 5% to about 30%.
Hydrotrope materials such as sodium benzene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, etc. can be present in minor amounts.
Dyes, perfurnes, crystal modifiers and tne like can also be added in minor amounts.
5~mllor f~
The: . - of the invention are not restricted as to manner Of r~er ~inn The granular c ....~ can be prepared in any manner, including d~y mixing, that results in formation of a granular product for~n. The process described in U.S. 2,895,916, issued to Milenkevich d al., and variations thereof, are ~ti~.ul~l~r suitablc. Also suitable are the processes described in U.S. 4,077,897, issued to Gault; U.S. 4,169,806, issued to Davis et al.;
U.S. 4,182,683, issued to Irvinc et al.; U.S. 4,207,197, issued to Davis d al.; and 4,427,417, issued to Parasilc. These six patents are ~cvlL ' herein by reference.
I,iauid C~
Liquid c~ , are disclosed in U.S. 4,116,851, issued to Rupe et al.; U.S.
4,226,f36, issued to Bush et al.; U.S. 4,431,559, issued to Ulrich; U.S. 4,511,487, issued to Pruhs et al.; U.S. 4,512,908, issued to Heile; Canadian Pat. No. 1,031,229--Bush et al.;
HOU03:12~03~.~ 20 ` ~ 215~370 European Patent Application No. 0130678--Heile, published January 9,1985; European PatenL
Application 0176163--Robinson, published April 2, 1986; U.K Patent Application GB
No. 2,116,199A--Julemont et al., published September 21, 1983; U.K. Patent Application GB
No. 2,140,450A--Julemont et al., published November 29, 1984; U.K Patent Application GB
No. 2,163,447A--Colarusso, published February 26, 1986; and U.K Patent Application GB No.
2,164,350A--Lai et al., published March 19, 1986. All of said patents and said published are il~ull ' herein by reference.
Such aqueous thickened ~....,,..~:';..,.~ comprise:
(I) from about 0.1% to about 5%, preferably from about 0.1% to about 2.5%
of a bleach-stable, compatible surfactant mixture of tne present invention;
(2) from about 5% to about 40%, preferably frûm about 15% to about 30%
of a detergency builder, especially a builder selected from the group consisting of sodium tripolyl' ,' , sodium carbonate, potassium ~y~ u~ , and mixLures thereof;
(3) a IIY~V~ ' ~ bleach to yield available chlorine in an amount from about 0.3% to about 20.0%, preferably from about 0.5% to about 1.5%;
(4) from about 0.1% to about 10%, preferably from about 0.5% to about 5%
of a thickening agent, preferably a clay thickening agent or a ~IU.~ d vater insoluble pol~ ' agent;
(5) aLkali metal silicate to provide from about 3% to about 15%, preferably from about 5% to about 12.5% of SiO2;
The: . - of the invention are not restricted as to manner Of r~er ~inn The granular c ....~ can be prepared in any manner, including d~y mixing, that results in formation of a granular product for~n. The process described in U.S. 2,895,916, issued to Milenkevich d al., and variations thereof, are ~ti~.ul~l~r suitablc. Also suitable are the processes described in U.S. 4,077,897, issued to Gault; U.S. 4,169,806, issued to Davis et al.;
U.S. 4,182,683, issued to Irvinc et al.; U.S. 4,207,197, issued to Davis d al.; and 4,427,417, issued to Parasilc. These six patents are ~cvlL ' herein by reference.
I,iauid C~
Liquid c~ , are disclosed in U.S. 4,116,851, issued to Rupe et al.; U.S.
4,226,f36, issued to Bush et al.; U.S. 4,431,559, issued to Ulrich; U.S. 4,511,487, issued to Pruhs et al.; U.S. 4,512,908, issued to Heile; Canadian Pat. No. 1,031,229--Bush et al.;
HOU03:12~03~.~ 20 ` ~ 215~370 European Patent Application No. 0130678--Heile, published January 9,1985; European PatenL
Application 0176163--Robinson, published April 2, 1986; U.K Patent Application GB
No. 2,116,199A--Julemont et al., published September 21, 1983; U.K. Patent Application GB
No. 2,140,450A--Julemont et al., published November 29, 1984; U.K Patent Application GB
No. 2,163,447A--Colarusso, published February 26, 1986; and U.K Patent Application GB No.
2,164,350A--Lai et al., published March 19, 1986. All of said patents and said published are il~ull ' herein by reference.
Such aqueous thickened ~....,,..~:';..,.~ comprise:
(I) from about 0.1% to about 5%, preferably from about 0.1% to about 2.5%
of a bleach-stable, compatible surfactant mixture of tne present invention;
(2) from about 5% to about 40%, preferably frûm about 15% to about 30%
of a detergency builder, especially a builder selected from the group consisting of sodium tripolyl' ,' , sodium carbonate, potassium ~y~ u~ , and mixLures thereof;
(3) a IIY~V~ ' ~ bleach to yield available chlorine in an amount from about 0.3% to about 20.0%, preferably from about 0.5% to about 1.5%;
(4) from about 0.1% to about 10%, preferably from about 0.5% to about 5%
of a thickening agent, preferably a clay thickening agent or a ~IU.~ d vater insoluble pol~ ' agent;
(5) aLkali metal silicate to provide from about 3% to about 15%, preferably from about 5% to about 12.5% of SiO2;
(6) about 0.1 to about 0.5% of a physical stabilizer such as a fatty acid or soap; and HOU03:111C35.8 -2 1-21S~3~0 ' ' (7) the balance an aqueous liquid.
Hard surface cleaning c ~ of all types which contain dyes can be formulated including granular and liquid scouring cleansers of the type described in U.S.
3,583,922, issued to McClain et al.; U.S. 4,005,027, issued to Hartman; U.S. 4,051,055, issued to Trinh et al.; and U.S. 4,051,056, issued to Hartman, all of said patents being i hercin by reference.
r. for cleaning toilets including automatic products such as disclosed in U.S. 4,208,747, issued to Dirksing, il r ' ~ herein by reference, can be ' F,XAMPLF.!i;
Comparative testing of the surfactants and mixtures thereof was carried out according to the testing procedure mentioned in "Deposition on Glassware During ~' ' ' Di~L.. ' ,," CSMA Designation DCC-05A December 1981 as published in Detergents Division Test Methods Cl A ~', Second Edition, December 1985 by the Chemical Specialties ~ r ' ~ ", Inc. except that we carried out our testing in both machines to minimiæ machine to machine differences.
In the examples, a WIN occurs wnen one test ~ ' better film or spot r r ~ than the . it is being compared against. This test method helps to clearly d;lf,.. ~ results.
FOOD S )rT. COMPOSITION A~ PRFPARAI~ON
A. Cook, for five minutes after the mixture starts to boil, a mixture of drv wheat cereal (90 g. of Hodgson Mill All Natural Ul.~ d Wheat Bran) and 310 g. of HOU03:12403~ 22-deionized water. After the five minute boil, let the cooked mass cool, and remove the exceSs water by filtration through a iarge Buchner funnel.
B. Into the stainiess steel mixing bowl of a Hobart mixer, slice ~ / 900 g. (a two pound box of margarine sticks) of margarine. Place the bowl into a 37-39C. water bath in order to melt the margarine.
C. After the margarine has melted (about 90 minutes) remove the bowl from the water bath and add to the melted margarine 225.8 g. of non-fat, instant powdered miik.
Mix the milk into the melted margaritle. Next add 167.0 g. of the cooked wheat cereai to the powdered milk mixture. Mix the liquified food soil with the Hobart mixer untii it becomes slightly stiff from cooling.
D. For storage, transfer the test soil to aluminum foil cups (aiuminum weighing boats). Into each cup place 40-41 g. of the soil mixture. Place the individuai cont~uners onto a tray and place the tray into a ~ for storage.
SPOT/F~I.M TEST PRO~F.nURE
1. The Pr~i, of Test Gl~ses A. Load as many glasses as possible in the top rack of automatic liall ~1...1~ machine No. I and set the cycle selector to "LighVChina."
1. Wash the glasseâ with Cascade by filling each of the two machine detergent cups with the Cascade.
2. After tne Cascade wash, wash with citric acid by addin8 to each machine detergent cup 60 g. of citric acid.
~iOU03: 124038 ~ -23-~ 21~637~
3. Add a small amount of ha~d water only during tne first wash and the main wash of each "Light/China" cycle.
B. Select the twenty best glasses for use in the test run.
C. Do a baseline spotlfilm evaluation on the twenty selected glasses. Then using the baseline scores, distribute the test glasses between the two automatic d;~l.. ' ~
machines in such a manner that will insure that the SpotlFilm baseline totals for the two machines will match within one unit for the spot category and for the film category.
II. Test Run; Initil~tion of Round I
Remove the food soil from the " r '_ ' To preheat the system and machines, stagger start both machines on the lightlchina settirLg. Let each machine run through at least the main wash period before stopping them. Use only the deionized water from the hot water system for tbis warm-up. This operation warms up the l; ~.. ' , the dishes etc. in the machines and equalizes the t~ , in the hot water system.
~ . Start operations with machine No. 1. Spread the food soil, about 40 g.
to 41 g. per run, placing an rrF ~~ 'y equal amount on each of six dinner plates.
E~. Add tbirty-eight grams of test detergent " I" to the machine door detergent cup that will be closed (the closed cup) and tbirty grams of test detergent "I" to the machine door detergent cup that will remain open (the open cup). Close and latch the machine door.
C. Set machine No. I cycle selector to the light/china setting, D. Start the test and record the data on the run data sheet.
HOU0~:12403~ 4-21~637~
E. While machine No. I is running in its main test wash period, prepare machine No. 2 for operation. Apply the food soil as before to six diMer plates from machine No. 2 and add test detergent "2" samples to the d~tergent cups in the door of machine No. 2.
F. After machine No. I has completed all wash and rinse periods, start machine No. 2.
G. Start machine No. 2 on the light/china settirlg and record all data on the run data sheet.
H. Open machine No. 1, after it has been on the dry period for at least ten minutes, and switch the test glasses within the upper rack as follows:
00~
1. During the main wash period of machine No. 2, prepare machine No. I
for its second run of this round by adding new food soil to the diMer plates and fresh test detergent "I" to the detergent cups in the machine door according to the above methods.
J. When machine No. 2 finishes its first run of this round:
HOU03 12403~ 25-~ 21~6370 1. Start machine No. I in a like manner as above for its second run of this round.
2. Make machine No. 2 ready for operation in a like manner as above.
K. When maclune No. I fnishes its second run, start mæhine No. 2 for the second, and last, time of this round.
L. After machine No. 2 finishes the second run, open both machines and let all glasses air dry for one to two hours.
M. Plæe the test glasses 1-10 in a mixed order, five from each machine, into a light box for evaluation. Note: the use of a light box, which is constructed with fluorescent lights to give edge lighting of the glasses, is made for critical ~ for spots and film.
Place glasses 11-20 on top of the light box, five from each mæhine in the same order by machine as those in the light box. All glasses are now out of the two machines.
N. Evaluate the glasses on a scale of 0 to 10. Each glass is individually scored for both spot and film formation. A scor~ of 0 means no spots or no film. A score of 10 means complete and heavy coverage of the glass by spots or film O. Rour~d I is now complete.
m. Setup for Round 2 A. Switch glass and dish sets from machine No. I to mæhine No. 2 and vice versa. Switch detergents also as the detergent used stays with the same glass/dish set throughout the entire test.
HOU0~:12~03t.~ -26-B. With the glasses (and silverware if desired) removed from the machines, stagger stârt both machines on the light/china setting for a warm-up cycle. Use deioni.~d water only, and use no detergent.
IV. Initi~lte Round 2 After 30 minutes, stop the machines if they have not yet stopped on their own.
A. Return the glasses (and silverware if it was removed) to the ~u machine.
B. Make machine No. 1 ready to go as described above.
C. Run two runs for each machine as described above in Round 1.
D. Let the glasses dry in the machines as above.
V. Round 2 E~ nd Round 3 Initiation A. Remove tne glasses from the machines and place tnem into the light box in a like manner as described abovc. Complete the evaluation of the glasses. Round 2 is now complete.
1. While evaluatmg the glasses, run both machines to preheat them and equilibrate the system. Use only deionized water for tbis procedure and set the machines for a staggered start on the lightlchina setting.
B. After all of tne glasses have been evaluated and after any machine drain cyclc, shut off both machines.
C. Switch glass racks, silverware racks, and dish sets from machine No. I
to machine No. 2 and vice versa.
~iOU03:12~03~ 27-~ 21S6370 D. Replace the glasses into their appropnate machine, ~ the switch that needs to be made.
E. Proceed as stated above until round 3 and round 4 have been completed.
Vl. Test Conclusion A. Make the last evaluation of the test glasses.
AUTOMATIC DISHWASEIING DETERGENT PREPARATION
In each of the following Examples, the identified surfactant(s) were formulated into an automatic 1;,h~ detergent prepared as follows.
Into a mixer bowl place in the order listed the following materials:
1. Sodium Carbonate, lite, granular 76 g.
2. Sodium Sulfate, anhydrous, granular 287 g.
3. STPP H~O, granular 150 g.
4. STPP, anhydrous, granular 375 g.
5. Britesil C-24 105 g.
6. Test Surfactant or surfactant mixture 31 g.
Britesil C24 is an anhydrous sodium polysilicate having a silica-to-alkali (SiO~:Na2O) weight ratio of 2.4 and is available from The PQ Cnrrnr~inn, Valley Forge, rc~.~ . STPP is sodium II;~,vl.~
The surfactant is spread on top of the mixed powders (1-5) using a dropper and then mixed into the powders using a spatula or a large spoon. Place the bowl onto a mixer and mix the bowl contents for about 15 minutes.
Next, to the above mixture add 315 grams of Silicate M~ solution. Silicate M3 solution is a sodium silicate solution available from The PQ Corporation, Valley Forge, rc~ ufi~.. Perform the addition slowly in a dropwise fashion.
During the addition, constantly mix the bowl contents with the mixer.
~10U03:12~03~ ~ -28--- 21~6370 When the Silicate M~ solution addition is finished, stop mixing, scrape the bowl sid~ l blades and break up all lumps that have formed. Resume mixing for five to ten minutes.
Finally, add to the test automatic di~w~lfulg detergent r.,..,..~
89 grams of deionized water. Add the deionized water in a dropwise fashion, with mixing in a fashion similar to that used to add the Silicate M solution above.
Layer the mixture onto a large plastic tray and leave it at ambient conditions overnight to d~y. After drying, remove the large lumps of detergent before use in tne testing procedure by using a No. 8 sieve (ASTM-II spec. screen).
To the test detergent prepared as described above, CDB ClearonD compound is added at a rate of 0.042 grams per gram of test detergent (1.25 g. of CDB ClearonD compound per 30 g. of test detergent or 1.60 g. of CDB ClearonD compound per 38 g. of test detergent).
This CDB Clearonr compound post addition is best , ' ' tbe day of tbe test. CDB
ClearonD compo~md is a sodium dichloro-s-i ~ dihydrate available from Olin Corporation.
Test F ' ' Sodium Carbonate 76 g. (5.3%) Sodium Sulfate 287 g. (20.1%) STpp-H2o 150 g. (10.5%) STPP, anhydrous 375 g. (26.3%) Britesil C-24 105 g. (7.4%) Test Surfactant or Surfactant Mixture 31 g. (2.1%) Silicate M 315 g. (22.1%) Deionized Water 89 g. (6.2%) CDB ClearonD Post Add HOU0~:12403~ 29--- ~1563~0 As used herein, all ~ 7 parts and ratios are by weight unless otherwise stated.
~ Vhere indicated, the following nor~ionic surfactants (Table 1) were used in the following Examples:
T~BLE I
Mol. Alcohol ,~ Structure Used A C6/,o-(EO)3-H 276 B Clo-(E~3~H 290 11 C C,2-(EO)2-H (70%) 326 111 D Clo"2-(EO)3-H 395 IV
E C~o/~2-(Eo)6-H 436 IV
F C,o/,2-(EO),-H 524 ~V
G C~v~-(EO), 3-H 255 V
H C~v~-(EO)2-H 286 V
C~v~4-(EO)3-H 330 V
J C,2"~-(EO)~-H 372 V
K Clvl~-(Eo)6 5-H 484 V
L Clv~-(EO)7-H 487 . V
M C~v~4~EO)9-H 575 V
N Clvl4-(Eo)l2-H 707 V
O C~V~6-(Eo)rH 532 Vl P Clo/12-(Eo)4-(po)l s-(EO)4-H 603 IV
Q Np-(EO),2-H 748 NpOH
R Np-(EO)lo-H 660 NpOH
S Np-(EO)~-H 57Z NpOH
HOU03 124035.5 -30-2~5637~
.~, , .
Surfactant Structure Mol Alcobol Wei~bt Used TCloll2-o-(Eo)8-(pohs-H 1036 IV
UC6,,0-o-(po)3-(Eo)l2-(po)2~-H 2006 r VC12 ~-O-(EO)9-(POh-H 111~ V
WCl2"~-O-(EO)~-(PO)~-H 783 V
The foregoing surfactants were prepared by aL~Iul '~/ alkoxylating the following alcûhûls using KOH as a catalyst.
TABLE II
Typical Alcûhol Cl . by Weight %
Alcûhol Cullll 1....;.,11 Used Avaiiable as' C6 C, C,0 C,z C,~ Cl6 C,, EPAL-610 4.3 42 53.6 0.1 -- -- --Il EPAL-10 99.4~
III EPAL-12/70 -- -- 0.5 69.5 29 IV EPAL 1012 0.2 1.8 75 22.8 0.2 V EPAL 1214 -- -- -- 66.3 26.6 7.1 Vl EPAL 1416 -- -- -- 0.3 62.4 35.9 1.4 ~ Culllll~ ,;all.~ available linear alcohols from Ethyl Corporation, Baton Rouge, LA.
b No other _~ ~ ~ iden'dfied.
"NpOH" stStnds for ~h_..JI. Np is t~.te carbon residue of llu~
The following Examples illustrate the nattlre of the invention and facilitate its ~ ,~1- .~1 .\.1;,.~ but are not intended to be limitative. Reference is also made to the foregoing surfactants by tlteir ~,UII~ r ~- ~ letter ~ tif~n HOU03: 124039 t -31-21~637~
. ~ , EXAMPL~S 1-6 U vs. U+E
The test ratio of U: E was 1:0.87 wt ratio which is a 20: 80 mole ratio. In the ability to defoam the test soil mixture, surfactant U was a bett~r defoamer by 3.3 to 11.0%
(depending upon the dishwasher used for the evaluation). The average defoaming difference was 5.6 to 9.2% favoring surfactant U. Surfactant U won a total of eleven (Il) ~v~lualivl~
when both categories of spot and film were evaluated while the mixture U+E won fifteen (15) c.~ iv~ls. The results of the spoVfilm tests are given in Table III.
HOU03:12J0~ 32-~ 215~370 TABLE
U MIXTURE (U+E~
Example Film Spot Film Spot 296.5 242.5 216.0 245.5 2186.5 188.0 121.0 132.5 3306.0 305.5 367.5 340,5 4432.0 371.0 364.5 352.0 5329.5 287.5 339.0 293.5 6408.5 359.0 423.0 357.5 Total 1959.0 1753.5 1831.0 1721.5 Avg.lglass 2.8 2.5 2.7 2.5 FxAlvlpLE 7 IJ v~. U+E
The test ratio of U:E was a 1:2.1 weight ratio which is a 9.5:90.5 mole ratio.
As Table IV depicts, the mixture was of equal ~ r. ..- -- ~ to surfactant U. The mixture (U+E) had lost about 10% in defoaming.
TABLE IV
U MIXTURE (U+E) Example Film Spot Film Spot 7128.5 131.5 144.0 144.0 Avg./glass 1.6 1.6 1.8 1.8 Fx~lpLEs 8-12 T v~. T+E
The test ~atio of T:E was a 1:1.7 weight ratio (or 31.3 and 62.7 wt%
i~ly) which is a 20: 80 mole ratio. In the ability to defoam the test soil mixture, HOU03:12403~,1 33 -'~ 2156370 surfactant T was a better defoamGr by 5 to 7% (average values) than the mixture. The lower cost mixture of surfactants T and E (20 mole %: 80 mole%) afforded equivalent spot/film ,. . r.".,.~.,. c to surfactant T. C( ~ ' ~ both the spot and film categories, surfactant T won 9 evaluation sessions, while the mixture (T+E) won 13 evaluation sessions. The spotlfilm test results are given in Table V.
TABLE V
T IvlIXTURE (T+E) Example Film Spot Film Spot 8392.5 419.5 400.0 347.0 9260.0 234.0 3 12.5 254.0 10345.0 325.5 333.0 350.5 I 1387.0 333.0 344.5 351.0 12436.0 362.0 311.0 271.5 Total 1820.5 1674.0 1701.0 1574.0 Avg./glass 3.1 2.9 3.0 2.8 F.X~fPt.F..~ lS
T v~. TIL
The mixture ratio of surfactant T to surfactant L was a 1:1..9 weight ratio (or 33.4 and 66.6 wt% l~.ot~ lJ) which equals a 20: 80 mole ratio. Although the mixture was equivalent to surfactant T for the prevention of spots, it was inferior to surfactant T for the prevention of film formation.
Surfactant T ~ , ' ' the mixture in the area of defoaming by 16-19% (based on spray arm IG~. ~ '- ), This was a noticeable drop in defoaming I'` lr(~ .e.
HOU03: 121031.~ -34 . ~ . 21~637a It WflS also very obvious to the naked eye that the defoaming ~ rf~ e of the mixture was inferior to that of surfactant T. When the dishwasher door was opened during a wash cycle, the machine using tf~fe mixture was full of foam while the machine using surfactant T contained little foam. Thus, it was not surprising that the clearLing E~ r~"". f for this mixture was at a lower level. The spot/film test results are given in Table Vl.
TABLE Vl T MIXI'[JRE (T+L) Example Film Spot Film Spot 13427.5 453.5 627.0 484.0 14271.0 266.5 324.0 216.0 15511.5 421.5 551.5 482.5 Tota'f 1210.0 1141.5 1502.5 1182.5 Avg./glass 3.2 3.0 4.0 3.1 ~XAMPLE 16 T v~f. T+L
The mixture ratio of surfactant T to surfactant L was a 1:1.9 weight ratio (or 33.4 and 66.6 wtf/o ~ lJ) which equa'fs a 20: 80 mole ratio. In this f~Yrf~rf~f~ nt an even more severe test of defoafning ability was performed. It was carried out under heavy stress conditions including hif~h food soil and high foaming food soils. For this test, tf fe food soils consisted of our usuaf miYture plus a heavy charge of oatmeal with mixed greerfs and one-haff of a raw medium egg (per wash cycle). Under these test conditions, the defoaming ability of surfactant T fell only 11%. Thus, the surfactant T was a better defoamer than the mixture (T+L) by a level of 24-33% under these test conditions.
HOUOJ I~fO3t.t -35-21~6370 .
During this more severe test, the ability of both surfactant T and the mixture (T+L) to prevent spot and film formation fell by a large amount. But now surfactant T clearly . . r." ,.,. ~ the mixture in both spot and film prevention. The spoVfilm test results are given in Table VII.
TABLE Vll T MIXIURE (T+L) Example Film Spot Film Spot 16 179.5 232.0 219.0 275.5 Avg./glass 4.5 5.8 5.5 6.9 F.~AMPI,F..~ 17-18 T v~. T+L
The mixture ratio of T:L was 66.7: 33.3 weight ratio or 50: 50 mole ratio. After 240 evaluations, we concluded tbat the l) r~ for tne mixture (T+L) was definitely inferior. The defoaming ~.. r- ... .. - was much better than that noted previously for the 20: 80 mole mixture. However, surfactant T still had a better defoaming score by 2.6-6.8%.
This was not a significant difference. The foam observed in tbe machines dropped ~i,S.. r..~ y, relative to that observed for the 20: 80 mole ratio mixture. Machine foam generation was now back near that of surfactant T alone. The spoVfilm results are given in Table Vlll.
I~Q~ L~ -36-21~6370 . .
TABL~: Vlll T MIXTURE (T+L) Example Film Spot Film Spot ~7391.0 432.0 641.0 519.5 18462.0 362.5 532.5 410.5 Total 835.0 794.5 1173.5 930.0 Avg.lglass 3.6 3.3 4.9 3.9 F,XA.MP~ 19 Two mixtures within the scope of the present invention were prepared and compared to each other. The first surfactant mixture was T:E. The second surfactant mixture was W:E. The test molar ratio was 20:80. The spotlfilm test results are given in Table IX.
TABLE IX
MIXTURE I (T+E) MIXTURE 2 (W+E) Example 19 Film Spot Film Spot Avg./glass 2.9 2.5 2.7 2.4 The two mixturos afforded equivalent 1~ r l;~XAMPl.F..~ 20_21 T VS. T+J
The mixture ratio of T:J w~s about 40:60 wt. rado or 20:80 mole ratio. As seen by the following film and spot results, the mixture (T+J) ~ tl r. ,....1 or was equivalent to surfact~nt T. However, surfactant T still had a beffer defoaming score by 1.8-7.8% in Example 20 and 6.9-7.4% in Example 21. This was not a sigluficant difference. The spot/film test results are given in Table X.
HOU~3:124~38.8 -37-21~6370 .~, TABLE X
T MIXTURE (T+~) Example Film Spot Film Spot 20447.0 361.5 250.0 250.0 Avg./glass 3.7 3.0 2.1 2.1 21552.0 596.0 595.5 41 1.5 Avg./glass 3.1 3.3 3.3 2.3 F~,MP~lF~ 22 CQMPATlRI ~ ~IXTURES
The "compatible" rnixtures of nonionic surfactants useful in the present invention are rlPtPrmin-(l by mixing at ambient conditions 20 mole% of a propylene oxide capped nonionic surfactant (structures III and IV) and 80 mole% of an ~IL~ ' ' nonionic surfactant (structures I and II). For each sample, total sample ~eight was about lO0 grams. In the present disclosure and appended claims, if such a mixture is clear, the rnixture of such surfactants is . ''- If the rnixture is cloudy, contains ~ ., or l~ll.J;~
surfactant (if solid), the mixture is not within the scope of the present invention.
HOU03:12~03~.t -38-21~6370 TABLE Xl COMPATIBILI IY TEST
80 Mole% Surfactant With 20 Mole% Surfactant T
Surfactant Clear Cloudy B X
C X
D X
E' X
G X
H X
r x L~ XX
Mb X
Nb X
ob X
P X
R X
Dishwasher Tested b Solid at Ambient T,.~.,~.al~
HOU03:12~03~ 39-, ~, 21~370 The c~mr~tihility test is indicative of the combinations of nonionic surfactantssuitable in the present invention. For example, a mixture of surfactants T and J was clear and performed ~ r~ . On the other hand, a mixture of surfactants T and L was cloudy and did not perfonn - ~;~r~. t""1~
HOU03: ~403-.- -40-
Hard surface cleaning c ~ of all types which contain dyes can be formulated including granular and liquid scouring cleansers of the type described in U.S.
3,583,922, issued to McClain et al.; U.S. 4,005,027, issued to Hartman; U.S. 4,051,055, issued to Trinh et al.; and U.S. 4,051,056, issued to Hartman, all of said patents being i hercin by reference.
r. for cleaning toilets including automatic products such as disclosed in U.S. 4,208,747, issued to Dirksing, il r ' ~ herein by reference, can be ' F,XAMPLF.!i;
Comparative testing of the surfactants and mixtures thereof was carried out according to the testing procedure mentioned in "Deposition on Glassware During ~' ' ' Di~L.. ' ,," CSMA Designation DCC-05A December 1981 as published in Detergents Division Test Methods Cl A ~', Second Edition, December 1985 by the Chemical Specialties ~ r ' ~ ", Inc. except that we carried out our testing in both machines to minimiæ machine to machine differences.
In the examples, a WIN occurs wnen one test ~ ' better film or spot r r ~ than the . it is being compared against. This test method helps to clearly d;lf,.. ~ results.
FOOD S )rT. COMPOSITION A~ PRFPARAI~ON
A. Cook, for five minutes after the mixture starts to boil, a mixture of drv wheat cereal (90 g. of Hodgson Mill All Natural Ul.~ d Wheat Bran) and 310 g. of HOU03:12403~ 22-deionized water. After the five minute boil, let the cooked mass cool, and remove the exceSs water by filtration through a iarge Buchner funnel.
B. Into the stainiess steel mixing bowl of a Hobart mixer, slice ~ / 900 g. (a two pound box of margarine sticks) of margarine. Place the bowl into a 37-39C. water bath in order to melt the margarine.
C. After the margarine has melted (about 90 minutes) remove the bowl from the water bath and add to the melted margarine 225.8 g. of non-fat, instant powdered miik.
Mix the milk into the melted margaritle. Next add 167.0 g. of the cooked wheat cereai to the powdered milk mixture. Mix the liquified food soil with the Hobart mixer untii it becomes slightly stiff from cooling.
D. For storage, transfer the test soil to aluminum foil cups (aiuminum weighing boats). Into each cup place 40-41 g. of the soil mixture. Place the individuai cont~uners onto a tray and place the tray into a ~ for storage.
SPOT/F~I.M TEST PRO~F.nURE
1. The Pr~i, of Test Gl~ses A. Load as many glasses as possible in the top rack of automatic liall ~1...1~ machine No. I and set the cycle selector to "LighVChina."
1. Wash the glasseâ with Cascade by filling each of the two machine detergent cups with the Cascade.
2. After tne Cascade wash, wash with citric acid by addin8 to each machine detergent cup 60 g. of citric acid.
~iOU03: 124038 ~ -23-~ 21~637~
3. Add a small amount of ha~d water only during tne first wash and the main wash of each "Light/China" cycle.
B. Select the twenty best glasses for use in the test run.
C. Do a baseline spotlfilm evaluation on the twenty selected glasses. Then using the baseline scores, distribute the test glasses between the two automatic d;~l.. ' ~
machines in such a manner that will insure that the SpotlFilm baseline totals for the two machines will match within one unit for the spot category and for the film category.
II. Test Run; Initil~tion of Round I
Remove the food soil from the " r '_ ' To preheat the system and machines, stagger start both machines on the lightlchina settirLg. Let each machine run through at least the main wash period before stopping them. Use only the deionized water from the hot water system for tbis warm-up. This operation warms up the l; ~.. ' , the dishes etc. in the machines and equalizes the t~ , in the hot water system.
~ . Start operations with machine No. 1. Spread the food soil, about 40 g.
to 41 g. per run, placing an rrF ~~ 'y equal amount on each of six dinner plates.
E~. Add tbirty-eight grams of test detergent " I" to the machine door detergent cup that will be closed (the closed cup) and tbirty grams of test detergent "I" to the machine door detergent cup that will remain open (the open cup). Close and latch the machine door.
C. Set machine No. I cycle selector to the light/china setting, D. Start the test and record the data on the run data sheet.
HOU0~:12403~ 4-21~637~
E. While machine No. I is running in its main test wash period, prepare machine No. 2 for operation. Apply the food soil as before to six diMer plates from machine No. 2 and add test detergent "2" samples to the d~tergent cups in the door of machine No. 2.
F. After machine No. I has completed all wash and rinse periods, start machine No. 2.
G. Start machine No. 2 on the light/china settirlg and record all data on the run data sheet.
H. Open machine No. 1, after it has been on the dry period for at least ten minutes, and switch the test glasses within the upper rack as follows:
00~
1. During the main wash period of machine No. 2, prepare machine No. I
for its second run of this round by adding new food soil to the diMer plates and fresh test detergent "I" to the detergent cups in the machine door according to the above methods.
J. When machine No. 2 finishes its first run of this round:
HOU03 12403~ 25-~ 21~6370 1. Start machine No. I in a like manner as above for its second run of this round.
2. Make machine No. 2 ready for operation in a like manner as above.
K. When maclune No. I fnishes its second run, start mæhine No. 2 for the second, and last, time of this round.
L. After machine No. 2 finishes the second run, open both machines and let all glasses air dry for one to two hours.
M. Plæe the test glasses 1-10 in a mixed order, five from each machine, into a light box for evaluation. Note: the use of a light box, which is constructed with fluorescent lights to give edge lighting of the glasses, is made for critical ~ for spots and film.
Place glasses 11-20 on top of the light box, five from each mæhine in the same order by machine as those in the light box. All glasses are now out of the two machines.
N. Evaluate the glasses on a scale of 0 to 10. Each glass is individually scored for both spot and film formation. A scor~ of 0 means no spots or no film. A score of 10 means complete and heavy coverage of the glass by spots or film O. Rour~d I is now complete.
m. Setup for Round 2 A. Switch glass and dish sets from machine No. I to mæhine No. 2 and vice versa. Switch detergents also as the detergent used stays with the same glass/dish set throughout the entire test.
HOU0~:12~03t.~ -26-B. With the glasses (and silverware if desired) removed from the machines, stagger stârt both machines on the light/china setting for a warm-up cycle. Use deioni.~d water only, and use no detergent.
IV. Initi~lte Round 2 After 30 minutes, stop the machines if they have not yet stopped on their own.
A. Return the glasses (and silverware if it was removed) to the ~u machine.
B. Make machine No. 1 ready to go as described above.
C. Run two runs for each machine as described above in Round 1.
D. Let the glasses dry in the machines as above.
V. Round 2 E~ nd Round 3 Initiation A. Remove tne glasses from the machines and place tnem into the light box in a like manner as described abovc. Complete the evaluation of the glasses. Round 2 is now complete.
1. While evaluatmg the glasses, run both machines to preheat them and equilibrate the system. Use only deionized water for tbis procedure and set the machines for a staggered start on the lightlchina setting.
B. After all of tne glasses have been evaluated and after any machine drain cyclc, shut off both machines.
C. Switch glass racks, silverware racks, and dish sets from machine No. I
to machine No. 2 and vice versa.
~iOU03:12~03~ 27-~ 21S6370 D. Replace the glasses into their appropnate machine, ~ the switch that needs to be made.
E. Proceed as stated above until round 3 and round 4 have been completed.
Vl. Test Conclusion A. Make the last evaluation of the test glasses.
AUTOMATIC DISHWASEIING DETERGENT PREPARATION
In each of the following Examples, the identified surfactant(s) were formulated into an automatic 1;,h~ detergent prepared as follows.
Into a mixer bowl place in the order listed the following materials:
1. Sodium Carbonate, lite, granular 76 g.
2. Sodium Sulfate, anhydrous, granular 287 g.
3. STPP H~O, granular 150 g.
4. STPP, anhydrous, granular 375 g.
5. Britesil C-24 105 g.
6. Test Surfactant or surfactant mixture 31 g.
Britesil C24 is an anhydrous sodium polysilicate having a silica-to-alkali (SiO~:Na2O) weight ratio of 2.4 and is available from The PQ Cnrrnr~inn, Valley Forge, rc~.~ . STPP is sodium II;~,vl.~
The surfactant is spread on top of the mixed powders (1-5) using a dropper and then mixed into the powders using a spatula or a large spoon. Place the bowl onto a mixer and mix the bowl contents for about 15 minutes.
Next, to the above mixture add 315 grams of Silicate M~ solution. Silicate M3 solution is a sodium silicate solution available from The PQ Corporation, Valley Forge, rc~ ufi~.. Perform the addition slowly in a dropwise fashion.
During the addition, constantly mix the bowl contents with the mixer.
~10U03:12~03~ ~ -28--- 21~6370 When the Silicate M~ solution addition is finished, stop mixing, scrape the bowl sid~ l blades and break up all lumps that have formed. Resume mixing for five to ten minutes.
Finally, add to the test automatic di~w~lfulg detergent r.,..,..~
89 grams of deionized water. Add the deionized water in a dropwise fashion, with mixing in a fashion similar to that used to add the Silicate M solution above.
Layer the mixture onto a large plastic tray and leave it at ambient conditions overnight to d~y. After drying, remove the large lumps of detergent before use in tne testing procedure by using a No. 8 sieve (ASTM-II spec. screen).
To the test detergent prepared as described above, CDB ClearonD compound is added at a rate of 0.042 grams per gram of test detergent (1.25 g. of CDB ClearonD compound per 30 g. of test detergent or 1.60 g. of CDB ClearonD compound per 38 g. of test detergent).
This CDB Clearonr compound post addition is best , ' ' tbe day of tbe test. CDB
ClearonD compo~md is a sodium dichloro-s-i ~ dihydrate available from Olin Corporation.
Test F ' ' Sodium Carbonate 76 g. (5.3%) Sodium Sulfate 287 g. (20.1%) STpp-H2o 150 g. (10.5%) STPP, anhydrous 375 g. (26.3%) Britesil C-24 105 g. (7.4%) Test Surfactant or Surfactant Mixture 31 g. (2.1%) Silicate M 315 g. (22.1%) Deionized Water 89 g. (6.2%) CDB ClearonD Post Add HOU0~:12403~ 29--- ~1563~0 As used herein, all ~ 7 parts and ratios are by weight unless otherwise stated.
~ Vhere indicated, the following nor~ionic surfactants (Table 1) were used in the following Examples:
T~BLE I
Mol. Alcohol ,~ Structure Used A C6/,o-(EO)3-H 276 B Clo-(E~3~H 290 11 C C,2-(EO)2-H (70%) 326 111 D Clo"2-(EO)3-H 395 IV
E C~o/~2-(Eo)6-H 436 IV
F C,o/,2-(EO),-H 524 ~V
G C~v~-(EO), 3-H 255 V
H C~v~-(EO)2-H 286 V
C~v~4-(EO)3-H 330 V
J C,2"~-(EO)~-H 372 V
K Clvl~-(Eo)6 5-H 484 V
L Clv~-(EO)7-H 487 . V
M C~v~4~EO)9-H 575 V
N Clvl4-(Eo)l2-H 707 V
O C~V~6-(Eo)rH 532 Vl P Clo/12-(Eo)4-(po)l s-(EO)4-H 603 IV
Q Np-(EO),2-H 748 NpOH
R Np-(EO)lo-H 660 NpOH
S Np-(EO)~-H 57Z NpOH
HOU03 124035.5 -30-2~5637~
.~, , .
Surfactant Structure Mol Alcobol Wei~bt Used TCloll2-o-(Eo)8-(pohs-H 1036 IV
UC6,,0-o-(po)3-(Eo)l2-(po)2~-H 2006 r VC12 ~-O-(EO)9-(POh-H 111~ V
WCl2"~-O-(EO)~-(PO)~-H 783 V
The foregoing surfactants were prepared by aL~Iul '~/ alkoxylating the following alcûhûls using KOH as a catalyst.
TABLE II
Typical Alcûhol Cl . by Weight %
Alcûhol Cullll 1....;.,11 Used Avaiiable as' C6 C, C,0 C,z C,~ Cl6 C,, EPAL-610 4.3 42 53.6 0.1 -- -- --Il EPAL-10 99.4~
III EPAL-12/70 -- -- 0.5 69.5 29 IV EPAL 1012 0.2 1.8 75 22.8 0.2 V EPAL 1214 -- -- -- 66.3 26.6 7.1 Vl EPAL 1416 -- -- -- 0.3 62.4 35.9 1.4 ~ Culllll~ ,;all.~ available linear alcohols from Ethyl Corporation, Baton Rouge, LA.
b No other _~ ~ ~ iden'dfied.
"NpOH" stStnds for ~h_..JI. Np is t~.te carbon residue of llu~
The following Examples illustrate the nattlre of the invention and facilitate its ~ ,~1- .~1 .\.1;,.~ but are not intended to be limitative. Reference is also made to the foregoing surfactants by tlteir ~,UII~ r ~- ~ letter ~ tif~n HOU03: 124039 t -31-21~637~
. ~ , EXAMPL~S 1-6 U vs. U+E
The test ratio of U: E was 1:0.87 wt ratio which is a 20: 80 mole ratio. In the ability to defoam the test soil mixture, surfactant U was a bett~r defoamer by 3.3 to 11.0%
(depending upon the dishwasher used for the evaluation). The average defoaming difference was 5.6 to 9.2% favoring surfactant U. Surfactant U won a total of eleven (Il) ~v~lualivl~
when both categories of spot and film were evaluated while the mixture U+E won fifteen (15) c.~ iv~ls. The results of the spoVfilm tests are given in Table III.
HOU03:12J0~ 32-~ 215~370 TABLE
U MIXTURE (U+E~
Example Film Spot Film Spot 296.5 242.5 216.0 245.5 2186.5 188.0 121.0 132.5 3306.0 305.5 367.5 340,5 4432.0 371.0 364.5 352.0 5329.5 287.5 339.0 293.5 6408.5 359.0 423.0 357.5 Total 1959.0 1753.5 1831.0 1721.5 Avg.lglass 2.8 2.5 2.7 2.5 FxAlvlpLE 7 IJ v~. U+E
The test ratio of U:E was a 1:2.1 weight ratio which is a 9.5:90.5 mole ratio.
As Table IV depicts, the mixture was of equal ~ r. ..- -- ~ to surfactant U. The mixture (U+E) had lost about 10% in defoaming.
TABLE IV
U MIXTURE (U+E) Example Film Spot Film Spot 7128.5 131.5 144.0 144.0 Avg./glass 1.6 1.6 1.8 1.8 Fx~lpLEs 8-12 T v~. T+E
The test ~atio of T:E was a 1:1.7 weight ratio (or 31.3 and 62.7 wt%
i~ly) which is a 20: 80 mole ratio. In the ability to defoam the test soil mixture, HOU03:12403~,1 33 -'~ 2156370 surfactant T was a better defoamGr by 5 to 7% (average values) than the mixture. The lower cost mixture of surfactants T and E (20 mole %: 80 mole%) afforded equivalent spot/film ,. . r.".,.~.,. c to surfactant T. C( ~ ' ~ both the spot and film categories, surfactant T won 9 evaluation sessions, while the mixture (T+E) won 13 evaluation sessions. The spotlfilm test results are given in Table V.
TABLE V
T IvlIXTURE (T+E) Example Film Spot Film Spot 8392.5 419.5 400.0 347.0 9260.0 234.0 3 12.5 254.0 10345.0 325.5 333.0 350.5 I 1387.0 333.0 344.5 351.0 12436.0 362.0 311.0 271.5 Total 1820.5 1674.0 1701.0 1574.0 Avg./glass 3.1 2.9 3.0 2.8 F.X~fPt.F..~ lS
T v~. TIL
The mixture ratio of surfactant T to surfactant L was a 1:1..9 weight ratio (or 33.4 and 66.6 wt% l~.ot~ lJ) which equals a 20: 80 mole ratio. Although the mixture was equivalent to surfactant T for the prevention of spots, it was inferior to surfactant T for the prevention of film formation.
Surfactant T ~ , ' ' the mixture in the area of defoaming by 16-19% (based on spray arm IG~. ~ '- ), This was a noticeable drop in defoaming I'` lr(~ .e.
HOU03: 121031.~ -34 . ~ . 21~637a It WflS also very obvious to the naked eye that the defoaming ~ rf~ e of the mixture was inferior to that of surfactant T. When the dishwasher door was opened during a wash cycle, the machine using tf~fe mixture was full of foam while the machine using surfactant T contained little foam. Thus, it was not surprising that the clearLing E~ r~"". f for this mixture was at a lower level. The spot/film test results are given in Table Vl.
TABLE Vl T MIXI'[JRE (T+L) Example Film Spot Film Spot 13427.5 453.5 627.0 484.0 14271.0 266.5 324.0 216.0 15511.5 421.5 551.5 482.5 Tota'f 1210.0 1141.5 1502.5 1182.5 Avg./glass 3.2 3.0 4.0 3.1 ~XAMPLE 16 T v~f. T+L
The mixture ratio of surfactant T to surfactant L was a 1:1.9 weight ratio (or 33.4 and 66.6 wtf/o ~ lJ) which equa'fs a 20: 80 mole ratio. In this f~Yrf~rf~f~ nt an even more severe test of defoafning ability was performed. It was carried out under heavy stress conditions including hif~h food soil and high foaming food soils. For this test, tf fe food soils consisted of our usuaf miYture plus a heavy charge of oatmeal with mixed greerfs and one-haff of a raw medium egg (per wash cycle). Under these test conditions, the defoaming ability of surfactant T fell only 11%. Thus, the surfactant T was a better defoamer than the mixture (T+L) by a level of 24-33% under these test conditions.
HOUOJ I~fO3t.t -35-21~6370 .
During this more severe test, the ability of both surfactant T and the mixture (T+L) to prevent spot and film formation fell by a large amount. But now surfactant T clearly . . r." ,.,. ~ the mixture in both spot and film prevention. The spoVfilm test results are given in Table VII.
TABLE Vll T MIXIURE (T+L) Example Film Spot Film Spot 16 179.5 232.0 219.0 275.5 Avg./glass 4.5 5.8 5.5 6.9 F.~AMPI,F..~ 17-18 T v~. T+L
The mixture ratio of T:L was 66.7: 33.3 weight ratio or 50: 50 mole ratio. After 240 evaluations, we concluded tbat the l) r~ for tne mixture (T+L) was definitely inferior. The defoaming ~.. r- ... .. - was much better than that noted previously for the 20: 80 mole mixture. However, surfactant T still had a better defoaming score by 2.6-6.8%.
This was not a significant difference. The foam observed in tbe machines dropped ~i,S.. r..~ y, relative to that observed for the 20: 80 mole ratio mixture. Machine foam generation was now back near that of surfactant T alone. The spoVfilm results are given in Table Vlll.
I~Q~ L~ -36-21~6370 . .
TABL~: Vlll T MIXTURE (T+L) Example Film Spot Film Spot ~7391.0 432.0 641.0 519.5 18462.0 362.5 532.5 410.5 Total 835.0 794.5 1173.5 930.0 Avg.lglass 3.6 3.3 4.9 3.9 F,XA.MP~ 19 Two mixtures within the scope of the present invention were prepared and compared to each other. The first surfactant mixture was T:E. The second surfactant mixture was W:E. The test molar ratio was 20:80. The spotlfilm test results are given in Table IX.
TABLE IX
MIXTURE I (T+E) MIXTURE 2 (W+E) Example 19 Film Spot Film Spot Avg./glass 2.9 2.5 2.7 2.4 The two mixturos afforded equivalent 1~ r l;~XAMPl.F..~ 20_21 T VS. T+J
The mixture ratio of T:J w~s about 40:60 wt. rado or 20:80 mole ratio. As seen by the following film and spot results, the mixture (T+J) ~ tl r. ,....1 or was equivalent to surfact~nt T. However, surfactant T still had a beffer defoaming score by 1.8-7.8% in Example 20 and 6.9-7.4% in Example 21. This was not a sigluficant difference. The spot/film test results are given in Table X.
HOU~3:124~38.8 -37-21~6370 .~, TABLE X
T MIXTURE (T+~) Example Film Spot Film Spot 20447.0 361.5 250.0 250.0 Avg./glass 3.7 3.0 2.1 2.1 21552.0 596.0 595.5 41 1.5 Avg./glass 3.1 3.3 3.3 2.3 F~,MP~lF~ 22 CQMPATlRI ~ ~IXTURES
The "compatible" rnixtures of nonionic surfactants useful in the present invention are rlPtPrmin-(l by mixing at ambient conditions 20 mole% of a propylene oxide capped nonionic surfactant (structures III and IV) and 80 mole% of an ~IL~ ' ' nonionic surfactant (structures I and II). For each sample, total sample ~eight was about lO0 grams. In the present disclosure and appended claims, if such a mixture is clear, the rnixture of such surfactants is . ''- If the rnixture is cloudy, contains ~ ., or l~ll.J;~
surfactant (if solid), the mixture is not within the scope of the present invention.
HOU03:12~03~.t -38-21~6370 TABLE Xl COMPATIBILI IY TEST
80 Mole% Surfactant With 20 Mole% Surfactant T
Surfactant Clear Cloudy B X
C X
D X
E' X
G X
H X
r x L~ XX
Mb X
Nb X
ob X
P X
R X
Dishwasher Tested b Solid at Ambient T,.~.,~.al~
HOU03:12~03~ 39-, ~, 21~370 The c~mr~tihility test is indicative of the combinations of nonionic surfactantssuitable in the present invention. For example, a mixture of surfactants T and J was clear and performed ~ r~ . On the other hand, a mixture of surfactants T and L was cloudy and did not perfonn - ~;~r~. t""1~
HOU03: ~403-.- -40-
Claims (3)
1. A low foaming machine dishwashing composition comprising:
(a) at least one first nonionic surfactant selected from the group consisting of nonionic surfactants having the formula (I) (I) , wherein R1 represents a linear alkyl or olefinic group having from about 6 to about 18 carbon atoms and y represents a number ranging from about 3 to about 15, and the formula (II) (II) , wherein Np is the carbon residue of nonylphenol or octylphenol and z represents a number ranging from about 4 to about 200; and (b) at least one second nonionic surfactant selected from the group consisting of nonionic surfactants having the formula (III) (III) ,wherein R2 represents a linear or branched alkyl or olefinic group having from about 6 to about 16 carbon atoms, m represents a number ranging from about 3 to about 15, and A1 represents a group having the formula -(CH2-CH(CH3)-O)q-, -(CH(CH3)-CH2-O)r- or a combination thereof with q and r each representing a number ranging from 0 to about 30 and the sum of q and v represents a number ranging from about 4 to about 30, and the formula (IV) R3-O-A2-(CH2CH2O)n-A3-H (IV) , wherein R3 represents a linear or branched alkyl or olefinic group having from about 6 to about 18 carbon atoms, n represents a number ranging from about 10 to about 25, A2 represents a group having the formula or a combination thereof with t and u each representing a number ranging from 0 to about 15 and the sum of t and u represents a number ranging from about 2 to about 15, and A3 represents a group having the formula or a combination thereof with v and w each representing a number ranging from 0 to about 55 and the sum of v and w represents a number ranging from about 10 to about 55, wherein the at least one first surfactant and the at least one second surfactant are compatible with each other.
(a) at least one first nonionic surfactant selected from the group consisting of nonionic surfactants having the formula (I) (I) , wherein R1 represents a linear alkyl or olefinic group having from about 6 to about 18 carbon atoms and y represents a number ranging from about 3 to about 15, and the formula (II) (II) , wherein Np is the carbon residue of nonylphenol or octylphenol and z represents a number ranging from about 4 to about 200; and (b) at least one second nonionic surfactant selected from the group consisting of nonionic surfactants having the formula (III) (III) ,wherein R2 represents a linear or branched alkyl or olefinic group having from about 6 to about 16 carbon atoms, m represents a number ranging from about 3 to about 15, and A1 represents a group having the formula -(CH2-CH(CH3)-O)q-, -(CH(CH3)-CH2-O)r- or a combination thereof with q and r each representing a number ranging from 0 to about 30 and the sum of q and v represents a number ranging from about 4 to about 30, and the formula (IV) R3-O-A2-(CH2CH2O)n-A3-H (IV) , wherein R3 represents a linear or branched alkyl or olefinic group having from about 6 to about 18 carbon atoms, n represents a number ranging from about 10 to about 25, A2 represents a group having the formula or a combination thereof with t and u each representing a number ranging from 0 to about 15 and the sum of t and u represents a number ranging from about 2 to about 15, and A3 represents a group having the formula or a combination thereof with v and w each representing a number ranging from 0 to about 55 and the sum of v and w represents a number ranging from about 10 to about 55, wherein the at least one first surfactant and the at least one second surfactant are compatible with each other.
2. The mixture of claim 1, wherein the at least one first surfactant and the at least one second surfactant are present in a molar ratio ranging from about 95:5 to about 60:40.
3. In a machine dishwashing composition, a nonionic surfactant mixture comprising:
(a) at least one first nonionic surfactant selected from the group consisting of nonionic surfactants having the formula (I) (I) , wherein R1 represents a linear alkyl or olefinic group having from about 6 to about 18 carbon atoms and y represents a number ranging from about 3 to about 15, and the formula (II) Np-O-(CH2CH2O)z-H (II) , wherein Np is the carbon residue of nonylphenol or octylphenol and z represents a number ranging from about 4 to about 200; and (b) at least one second nonionic surfactant selected from the group consisting of nonionic surfactants having the formula (III) R2-O-(CH2CH2O)m-A1-H (III) ,wherein R2 represents a linear or branched alkyl or olefinic group having from about 6 to about 16 carbon atoms, m represents a number ranging from about 3 to about 15, and A1 represents a group having the formula -(CH2-CH(CH3)-O)q-, -(CH(CH3)-CH2-O)r- or a combination thereof with q and r each representing a number ranging from 0 to about 30 and the sum of q and v represents a number ranging from about 4 to about 30, and the formula (IV) R3-O-A2-(CH2CH2O)n-A3-H (IV) , wherein R3 represents a linear or branched alkyl or olefinic group having from about 6 to about 18 carbon atoms, n represents a number ranging from about 10 to about 25, A2 represents a group having the formula -(CH2-CH(CH3)-O)t-, -(CH(CH3)-CH2-O)u- or a combination thereof with t and u each representing a number ranging from 0 to about 15 and the sum of t and u represents a number ranging from about 2 to about 15, and A3 represents a group having the formula -(CH2-CH(CH3)-O)v-, -(CH(CH3)-CH2-O)w- or a combination thereof with v and w each representing a number ranging from 0 to about 55 and the sum of v and w represents a number ranging from about 10 to about 55, wherein the at least one first surfactant and the at least one second surfactant are compatible with each other.
(a) at least one first nonionic surfactant selected from the group consisting of nonionic surfactants having the formula (I) (I) , wherein R1 represents a linear alkyl or olefinic group having from about 6 to about 18 carbon atoms and y represents a number ranging from about 3 to about 15, and the formula (II) Np-O-(CH2CH2O)z-H (II) , wherein Np is the carbon residue of nonylphenol or octylphenol and z represents a number ranging from about 4 to about 200; and (b) at least one second nonionic surfactant selected from the group consisting of nonionic surfactants having the formula (III) R2-O-(CH2CH2O)m-A1-H (III) ,wherein R2 represents a linear or branched alkyl or olefinic group having from about 6 to about 16 carbon atoms, m represents a number ranging from about 3 to about 15, and A1 represents a group having the formula -(CH2-CH(CH3)-O)q-, -(CH(CH3)-CH2-O)r- or a combination thereof with q and r each representing a number ranging from 0 to about 30 and the sum of q and v represents a number ranging from about 4 to about 30, and the formula (IV) R3-O-A2-(CH2CH2O)n-A3-H (IV) , wherein R3 represents a linear or branched alkyl or olefinic group having from about 6 to about 18 carbon atoms, n represents a number ranging from about 10 to about 25, A2 represents a group having the formula -(CH2-CH(CH3)-O)t-, -(CH(CH3)-CH2-O)u- or a combination thereof with t and u each representing a number ranging from 0 to about 15 and the sum of t and u represents a number ranging from about 2 to about 15, and A3 represents a group having the formula -(CH2-CH(CH3)-O)v-, -(CH(CH3)-CH2-O)w- or a combination thereof with v and w each representing a number ranging from 0 to about 55 and the sum of v and w represents a number ranging from about 10 to about 55, wherein the at least one first surfactant and the at least one second surfactant are compatible with each other.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MX9600197A MX9600197A (en) | 1995-01-12 | 1996-01-11 | Mixed surfactant systems for low foam applications. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/372,049 US5612305A (en) | 1995-01-12 | 1995-01-12 | Mixed surfactant systems for low foam applications |
| US08/372,049 | 1995-01-12 |
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| Publication Number | Publication Date |
|---|---|
| CA2156370A1 true CA2156370A1 (en) | 1996-07-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002156370A Abandoned CA2156370A1 (en) | 1995-01-12 | 1995-08-17 | Mixed surfactant systems for low foam applications |
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| Country | Link |
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| US (1) | US5612305A (en) |
| CA (1) | CA2156370A1 (en) |
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| US5259963A (en) * | 1989-01-12 | 1993-11-09 | Sandoz Ltd. | Surface active compositions their production and use |
| DE3928604A1 (en) * | 1989-08-30 | 1991-03-07 | Henkel Kgaa | USE OF SELECTED MIXTURES OF POLYGLYKOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM DETERGENTS |
| DE3928601A1 (en) * | 1989-08-30 | 1991-03-07 | Henkel Kgaa | USE OF SELECTED MIXTURES OF POLYALKYLENE DIOLETHERS AS FOAM-PRESSING ADDITIVES FOR LOW-FOAM CLEANING AGENTS |
| DE3935374A1 (en) * | 1989-10-24 | 1991-04-25 | Henkel Kgaa | ALKYLPOLYETHYLENGLYKOLETHER AS FOAM-PRESSING ADDITIVES FOR CLEANERS |
| DE3942727A1 (en) * | 1989-12-22 | 1991-06-27 | Henkel Kgaa | USE OF A COMBINATION OF NONIONIC SURFACES |
| DE4009533A1 (en) * | 1990-03-24 | 1991-09-26 | Henkel Kgaa | LOW-EFFICIENT NON-ionic surfactant mix |
| US5273677A (en) * | 1992-03-20 | 1993-12-28 | Olin Corporation | Rinse aids comprising ethoxylated-propoxylated surfactant mixtures |
| US5498378A (en) * | 1993-11-12 | 1996-03-12 | Lever Brothers Company, Division Of Conopco, Inc. | Process for preparing capsules with structuring agents |
-
1995
- 1995-01-12 US US08/372,049 patent/US5612305A/en not_active Expired - Fee Related
- 1995-08-17 CA CA002156370A patent/CA2156370A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| US5612305A (en) | 1997-03-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |