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Publication numberUS3429822 A
Publication typeGrant
Publication dateFeb 25, 1969
Filing dateOct 11, 1965
Priority dateOct 9, 1964
Also published asCA803475A, DE1467638A1
Publication numberUS 3429822 A, US 3429822A, US-A-3429822, US3429822 A, US3429822A
InventorsGrunewald Helmut, Waag Ake
Original AssigneeMo Och Domsjoe Ab
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Detergent compositions
US 3429822 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,429,822 DETERGENT COMPOSITIONS Helmut Grunewald, Goteborg, and Alrewifig, Stenungsund, Sweden, assignors to M0 och Domsjo Aktielsiolaget, Ornskoldsvik, Sweden, :1 limited company of we en No Drawing. Filed Oct. 11, 1965, Ser. No. 494,900 Claims priority, application Sweden, Oct. 19, 1964, 12,155/64; Jan. 16, 1965, 598/65 US. Cl. 252--99 19 Claims Int. Cl. Clld 1/72, 3/20 ABSTRACT OF THE DISCLOSURE A water-soluble surface active detergents are provided which have a low foaming tendency and good cleansing power, containing (A) a water-soluble surface-active ethylene oxide adduct having good cleansing power and a high foaming tendency and (B) a water-insoluble waterdispersible surface-active dialkylphenol-ethylene oxide adduct having a low-foaming tendency and relatively poor cleansing power, in an amount to reduce the foaming tendency of (A) without substantially adversely affecting the cleansing power of (A).

This invention relates to a washing and cleansing composition having low foaming tendency and high detersive power.

Detergents used for washing in modern washing machines are required to show in addition to good detersive power also a very low foaming tendency within the entire temperature range (20-100 C.) used in machine washing, since otherwise there will be the risk of overfoaming which may damage the washing machine. This latter property is of particular importance in connection with certain detergents at lower washing temperatures, i.e., at temperatures below 60 C., and when the laundry to be washed is only very slightly soiled. The foam proper does not contribute to the washing effect of the detergent either.

It is previously known to incorporate in detergents as an active component water-soluble alkylene oxide adducts of hydroxy group containing substances, such as monoor dialkylphenols, oxo alcohols or fatty alcohols, or mixtures thereof. Such alkylene oxide adducts have also been mixed with dlhylniyl sn-lphonates-aniwith-soapfln-which case the soap acts mainly as a foam reducing agent. There are alseo previously known particularly low foaming water-soluble alkylene oxide adducts obtained by adding ethylene oxide and propylene oxide to various hydroxy group containing substances. Due to their high price these adducts have not been used to a greater extent, however. None of the known compositions renders the desired low foaming tendency without at the same time substantially reducing the detersive power.

The present invention relates to a low-foaming washing and cleansing composition which does not show the aforesaid disadvantages but produces very little foam within the entire temperature range used in machine washing at the same time as a highly satisfactory detersive power is obtained. The washing and cleansing composition according to the invention comprises as a surface-active component a water-soluble mixture of (A) a water-soluble surface-active ethylene oxide adduct of a polypropylene glycol having a minimum molecular weight of 1000, a primary or secondary straight or branched chain aliphatic alcohol having 8 to 24 carbon atoms, or a mono-, dior tri-substituted alkylphenol having a total of 8 to 24 carbon atoms in the alkyl portion, in combination with 3,429,822 Patented Feb. 25, 1969 Dotcmcmonn wherein R and R are straight or branched chain alkyl substituents having 8 to 12 carbon atoms, and n is a figure indicating the number of ethylene oxide units up to which the product is water-insoluble but water-dispersible. The combination of the substances A and B above has surprisingly proved to bring about the effect that component B which is only water-dispersible, extremely low foaming and of poor detersive power becomes water-soluble while maintaining its low-foaming properties at the same time as the detersive power of the resulting mixture becomes good and usually better than the detersive power of each individual component A or B.

The water-soluble surface-active ethylene oxide adduct comprised in the composition according to the invention may be an ethylene oxide adduct of a polypropylene glycol having a minimum molecular weight of 1000 and the general formula wherein a, b and 0 have such values that the ethylene oxide content in the adduct amounts to 20-90%. Examples are the products sold by Wyandotte Chemical Corporation under the name Pluronic Other suitable water-soluble surface-active ethylene oxide adducts which may be used in the composition according to the invention are adducts of ethylene oxide and primary or secondary, straight or branched chain aliphatic alcohols having a total of 8 to 24 carbon atoms in the molecular chain, for example ethylene oxide adducts of the fraction of fatty alcohols which is obtained at the hydrogenation of oils, such as coconut oil, or tallow, or by hydrolizing whale fat, or ethylene oxide adducts of dodecyl alcohol, cetyl alcohol, oleyl alcohol and stearyl alcohol, or 0x0 alcohols, such as tridecyl alcohol, hexadecyl alcohol and the like, or mixtures thereof. A suitable amount of ethylene oxide to be added to the fatty alcohol are 5-100 moles per mole of fatty alcohol.

Other suitable water-soluble surface-active ethylene oxide adducts are adducts of ethylene oxide and mono-, dior trisubstituted alkylphenols having a total of 8 to 24 carbon atoms in the alkyl portion, such as octylphenol, dioctylphenol or trioctyl phenol, nonylphenol, dinonylphenol, dodecylphenol, didodecylphenol, tributylphenol, methyldibutylphenoh.

A suitable amount of ethylene oxide to be added to the alkylphenol are 7-100 moles per mole of alkylphenol. Examples of such products are the products sold under the names Triton X- (Rohm & Haas), Lissapol N (ICI), Igepal (Antara), Hostapal (Hoechst), LANCO (Berol).

The water-insoluble but water-dipersible component is an ethylene oxide adduct having the general formula wherein R and R are straight or branched chain hydrocarbon substituents having 8 to 12 carbon atoms, and n is a figure indicating the number of ethylene oxide units up to which the product is water-insoluble. A water-insoluble but water-dispersible product is in this connection to be understood such, that the product in question when being diluted with water of 18 C. to an 1% concentration shall result in a dispersion, i.e. not a clear solution but a turbid liquid. The suitable number of ethylene oxide 4 Example 1 75 parts by weight of a water-insoluble dinonylphenol ethylene oxide adduct containing 12 moles of ethylene oxide and the alkyl chains originating in propylene trimer f a d th b 5 were mixed with 25 parts by weight of a tallow fatty z i i 1 2 3: alcohol ethylene oxide adduct containing 30 moles of g a g??? 0 5 t ethylene oxide. The resulting mixture was water-soluble.

p y g? era g; {if 15 parts by weight of the mixture were mixed with a Oxlde i Sum p 953 3 f builder and with water to form a detergent having the water'insou e m water" e yp mo e 10 following composition and being suitable for machine ene oxide adducts are the following, the amount of added washin ethylene oxide (E0) being indicated within parenthesis: I Percent dinonylphenol (9 to 14 moles of E0) wherein the nonyl Adduct mixture 15 portion originates in propylene trimer, dialkylphenol (9 Sodium tnpolyphosphate 35 to 15 moles of EO) wherein the alkyl portion originates 15 Anh drous sodium carbonate 15 linear alpha-olefin mixture having 8 to 12 carbon o m a Sodium silicate 38/40 Be. Nap/510 :1125 15 atoms (straight chain), branched chaln dioctylphenol 1010 14 moles of E0) didodec 1 henol (1410 moles Swim Sulphate 8 of E0) y p SOdlUm carboxymethylcellulose (Cellufix LB) 2 The ratio by weight of component A to component B 20 watar ""5 T in the washing and cleansing composition according to The 505mm Pefbofaie (bleachlng agent) Whlch h invention i fro 1;9 to 1;1 f bl f 1;3 normally would have been comprised in the formulation to 1:2. was exchanged against water, so that the washing effect Furthermore it has been found according to the inven- Could be at ributed only to the adduct mixture used. tion that the foaming capacity can be reduced still more The foammg'capaclty 0f detergent at C and while maintaining or im ovin th detergent power by C. was determ ned accordlng to the so-called shake test adding (C) a further water-insoluble but water-dispensible a! a concemrailon and 300 P-P- ether addu t havi g the general f ul water hardness. The foam determination according to this method is carried out such, that a 500 ml. cylinder is XO(cH2CH20)nH filled with 200 m1. of detergent solution of the indicated wherein X designates a monoalkyl group having 8 to 24 temperature and concentration whereupon shaking is carbon atoms, a monoalkylaryl group having 8 to 16 effected by rotation causing the cylinder to make 10 carbon atoms in the alkyl chain, a dialkylaryl group havrevolutions in 15 seconds. The foam level in the cylinder ing a total of 12 to 24 carbon atoms in the alkyl chains is read off immediately and after 5 minutes. or a trialkylaryl group having a total of 8 to 24 carbon In addition, the detersive power was determined in a atoms in the alkyl chains, and n designates the number TergO-Tometer, at 85 C. using an artificially soiled of ethylene oxide units up to which the product is watercotton fabric at a concentration of 2.5 g./l. and 300 p.p.rn. insoluble but water-dispersible. The addition of this third water hardness. The reflectance of the fabric before and componentCis particularly advantageous for the washing after the washing was determined in a refiectometer. at lower temperatures, such as between and C. 40 Corresponding determinations were made individually Compounds having the above formula which are parwith the water-insoluble and water-soluble adduct in comticularly suitable are alkylether adducts having straight or bination with the builders. branched chains and 12 to 22 carbon atoms in the alkyl The results obtained appear from Table 1 below. (In chain, for example ethoxylated fatty alcohols, monoalkylthis and the following tables DNF designates dinonyl phenol ethylene oxide adducts, dialkylphenol ethylene 45 phenol, TFA designates tallow fatty alcohol and DAF oxide adducts and trialkylphenol ethylene oxide adducts. designates dialkylphenol. E0 designates ethylene oxide The suitable amount of ethylene oxide to be added in and the figure preceding E0 is the number of moles of order to obtain a water-insoluble but water-dispersible ethylene oxide units added to the nonylphenol or tallow product varies from 2 to 25 moles and is to be determined fatty alcohol.)

TABLE 1 Adduet mixture Foamlevelinmm., Increase Water-insoluble adduct Water-soluble adduct 75 0. int reflec- Type Percent 0min. 5min. perc iit by wt.

TFA,30 E0.... 25 15 10 84.0

FA,30EO-. 100 so 15 81.9

in each individual case. Examples of such suitable waterinsoluble but water-dispersible ether adducts are nonylphenol+4 E0, didecylphenol+14 E0, tallow fatty alco 6 E etc.

When component C is used in the compositions according to the present invention the amount of component A in relation to the total amount of components B and C should be from 1:9 to 1:1, preferably from 1:3 to 1:2.

The invention is illustrated by the following examples. The alkylphenols indicated in the examples were prepared by reacting phenol with olefins using boron trifluoride as a catalyst. The addition of ethylene oxide was effected in Examples 2-6 In the same manner as in Example 1 the foaming capacity and the detersive power were determined for detergents, the adduct mixture of which was composed of a water-insoluble dinonylphenol ethylene oxide adduct and a water-soluble ethylene oxide adduct in such an amount that this mixture became water-soluble. The results are a known manner in the presence of an alkaline catalyst. indicated in Table 2. As from Example 1 it appears from 3,429,822 5 6 Examples 2-6 that according to the invention a detergent is obtained having substantially reduced foaming capacity Examp 16S 11 and at the same time as the high detersive power of the watersoluble ethylene oxide adducts is maintained or improved.

A water-insoluble dialkylphenol ethylene oxide adduct (DAF) with 14 moles of ethylene oxide and side chains TABLE 2 Adduct mixture Ex. Foam levellnmm., Increase No. Water-insoluble adduct Water-soluble adduct 75 C. in reflectence, Type Type Percent min. min. percent by wt 15 5 69. 7 2 DNF, Non lphenol plus 50 E0. 30 20 82. 8 o. 100 75 75.7 3 Nonylphenol plus 12 E0. 30 10 80.6 do. 100 80 10 81.4 4 {DNR 12 E Leuryl alcohol plus 15 150---. 25 10 82. 4 l ..d0 1 100 B5 10 81.1 Block polymer of 20% poly- 10 10 78. 3

propylene glycol M.W. 1,750 5 grist; 80% E0 plus Pluronlc -410----..-...-.. I00 75 75.0 DNF, 14 E0.. 100 20 10 78.5 6 DNF, 14 E0... 20 15 82.6 65 15 80.7

Examples 7-10 In the same manner as in Example 1 the foaming capacity and detersive power were determined at 40 C. for detergents, the adduct mixture of which was composed of a water-insoluble dinonylphenol ethylene oxide adduct originating in a straight chain alpha-olefin mixture containing 8 to 12 carbon atoms was investigated with respect to foaming capaicty at C. and with respect to deter- O sive power at C. in the same manner as in Example 1.

The results are shown in Table 4.

TABLE 4 Adduct mixture Ex. Foam level in mm., Increase No. Water-insoluble adduct Water-soluble adduct 75 C. in reflectnnce, Type Percent Type Percent 0 min. 5 min. percent by wt. by wt. DAY, 14 130.-.. 15 5 71.0 n DAF, 14 E0 75 @methyl-iG-dibutylphenol 25 20 0 80. 5

----- Elus 12 E0.

100 55 20 80, 0 DAF,14 130.... 100 15 5 71.0 12. DAF,14 150.... 75 25 20 10 80. 0 100 65 50 79. 3

and a water-soluble ethylene oxide adduct in such an amount that this mixture became water-soluble. For the determination of the detersive power at this low temperature 4 g./l. of the detergent were used. The results appear from Table 3.

The examples show that the invention may be applied 50 also to unbranched dialkylphenol derivatives originating in alpha-olefins and that the same advantageous results are obtained.

TABLE 3 Adduct mixture Ex. Foamlevelinmm., Increase N o. Water-insoluble adduct Water-soluble adduct 75 C. lntreflecance, Type Percent Type Percent 0 min. 5 min. percent by wt. by wt. DNF, 12 1510--.. 15 5 30. 9 7 DNF, 12 20 10 40.8 2 i8 32-; NF 12 E0.. 5 8

e0 5 21.0 DNF, 12 120..-. 20 10 as. a 9 .do 65 15 40. 9 as? a .2 a; 1 i e5 40 42. s

The examples show that detergents composed according to the invention render the desired foam reduction even at low temperature, while maintaining or improving the washing effect.

Examples 13-18 The following further experiments were carried out to show the effect of adduct mixtures containing at most 20% of alkylphenol ,adducts and the remainder fatty alco- 75 hol adducts.

TABLE Percent Foam level in mm. Sol] removal, percent Ex. No. DNF, DNF, DNF, DNF, TFA, DNF, TFA, 40 C. 60 C.

9130 E0 12 E0 14 E0 0 4E0 EOEO 40 C. 60 C.

0 min. 5 min. 0 min. 5 min.

1; 50 30 25 45 40 57.6 82. 4 14 50 2O 35 57. 7 84. 1 1s 20 50 25 30 30 58.4 82. 5 16 20 60 40 40 68.0 84. 5 17 40 30 30 30 25 30 25 60.7 87.7 is 100 B0 20 85 25 56. 4 81.0

The foam tests were carried out at 300 p.p.m.=17.6

dH; cone. 4.75 g./l. at 40 C. and 75 C.

dH; cone. 5 g./l. at 40 C.; 3 g./l. at 85 C.

From Examples 1316 it thus appears that even with a content of up to 20% of biologically hard surface active substances (dinonylphenol adducts) low foam levels are obtained without the washing capacity being materially lowered.

om sition used in the foam tests: Percent C xiduct mixture 10 The use of an adduct mixture containing the three Na tripolyphosphate 35 components A, B and C mentioned above is illustrated by Nafcarbonate 15 20 the following examples in which the detergents used were Na su1phate 8 composed as follows:

Na-CMC 2 Percent gag? glass Surface active components (A, B, C) 15 25 Sodium polyphosphate 35 Composition used in the washing tests: Percent Anhydrous sodium carbonate 15 Adduct mixture 10 Sodium silicate 38/40 B. Na O/SiO,=l:2.4 15 Na-tripolyphosphate 35 Sodium sulphate 8 Na-carbonate 15 Sodium carboxymethylcellulose (Cellufix LB) 2 Na-sulphate 9 30 Water 10 Na-CMC 2 Water glass 14 Water 10 The results obtained appear from the Tables 6, 7 and 8.

I TABLE 6 [Foam level at 75 C. and detersive power at 85 0.] Water-insoluble Water-soluble Foam level in Incressen EX. N0. mm., 75 C. reflectance Type Percent Type Percent Type Percent in percent,

by wt. by wt. by wt. 0 min. 5 min. 85 C. 100 20 5 73.5 19 40 NF 1 plus 4 E0 30 TFA plus E0 30 20 1o 32. 2

-.do 100 65 15 80.7 20 ..{DN 5 40 NF plus 4 E0 3o DNF lus 21 E0- 30 15 10 as. a 100 75 70 82.7 D plus 12 E0..- 100 15 5 69.7 21 .-do e0 DDF I plus 14 130..-- 20 TFA plus to E0 50 25 10 79.4 o... 100 65 15 80.7 22 ..{DNF plus 12 E0 30 TFA plus 6 E0 20 012-01; alcohol plus 7 E0..- 25 10 81. 0 0.... 100 70 10 82.4

DNF=dinonylphenol; NF=nonylphenol; DDFzdldecylphe nol; TFA=ta1low fatty alcohol; EO=ethylene oxide unit.

1 Foam level 0 deterslve power very low. 1 Foam level 0 deterslve power very low.

TABLE 7 [Foam level at 40 C. and detergent power at 40 0.]

Adduct mixture Foam level in Increase mm., 40 C. in reflec- Ex. No. tanee in Water-insoluble Water-soluble psint,

0 min; 5 min. 40 Type Percent Percent Type Percent by wt. by wt. by wt. 23 DNF plus 14 E0........ 100 15 10 33 8 -do.. 40 NF plus 4 E0.-...-..- 30 TFA plus 50 E0 30 20 10 40 9 do 100 10 40 9 2L -.{DNF plus 14 EO- 40 NF plus 4 EO...-.-- 30 NF plus 10 E0... 30 15 10 4s 6 n 100 35 42 3 TABLE 8 [Foam level at 40 C. and 60 0.; detergent power at 40 C. and 60 0.]

Adduct mixture Increase in reflectance Ex. No. Water-insoluble Water-soluble Fom level in mm. in percent T P t T P 'r P t 6000' 40C 600 e ereen ype ereeu ype ereen W by wt. bywt. bywt. 0min. 5min. 0min. 5min. 25 NF plus 14 130...- 70 NF lus 10 E0 30 45 35 20 15 51.5 79.2 .do 40 NF plus 4 EO..-.- 30 o 30 16 10 15 10 52.3 81.6

The Examples 19-25 show that the addition of the third component C substantially reduces the foaming capacity at the same time as the detersive power of the composition is maintained or improved. Example 25 shows a comparative test with a composition having a two-component adduct mixture and a composition having a three-component adduct mixture at low temperatures (40 and 60 C.). It appears from this example above all that at such a low temperature as 40 C. the immediate foam formation is reduced to Va by the addition of the third water insoluble but water-dispersible component C.

What we claim is:

1. A water-soluble surface-active detergent having a low foaming tendency and good cleansing power, consisting essentially of (A) a member selected from the group consisting of water-soluble surface-active ethylene oxide adducts of a polypropylene glycol having a molecular weight of at least 1000, the ethylene oxide content in the adduct being within the range from about 20 to about 90%, primary and secondary aliphatic alcohols having from about eight to about twenty-four carbon atoms containing from about 4 to about 100 moles of ethylene oxide, and alkylphenols having from about eight to about twenty-four carbon atoms in the alkyl group and from one to three alkyl groups containing from about 7 to about 100 moles of ethylene oxide, in combination with (B) a water-insoluble water-dispersible surface-active dialkylphenol-ethylene oxide adduct having the formula cnlonzonn wherein a, b, and c are sufficiently large to provide an ethylene oxide content in the adduct within the range from about to about 90% of the adduct.

3. A detergent composition having low foaming tendency and good cleansing power consisting essentially of a water-soluble surface-active combination in accordance with claim 1 and water.

4. A detergent composition in accordance with claim 1 containing, in addition, an inorganic builder.

5. A detergent composition 111 accordance'withclaim"' 1 containing, in addition, sodium perborate as a bleaching agent.

6. A water-soluble surface-active detergent in accordance with claim 1 wherein (A) is a tallow fatty alcoholethylene oxide adduct (B) is a dinonylphenol-ethylene oxide adduct.

7. A water-soluble surface-active detergent in accordance with claim 1 wherein (A) is a nonylphenol-ethylene oxide adduct and (B) is a dinonylphenol-ethylene oxide adduct.

8. A water-soluble surface-active detergent in accordance with claim 1 wherein (A) is a lauryl alcoholethylene oxide adduct (B) is a dinonylphenol-ethylene oxide adduct.

9. A water-soluble surface-active detergent in accordance with claim 1 wherein (A) is a block polymer comprising 20% polypropylene glycol of molecular weight 1750 and 80% ethylene oxide and (B) is a dinonylphenol-ethylene oxide adduct.

10. A water-soluble surface-active detergent in accordance with claim 1 wherein (A) is a 3-methyl-4,6-dibutylphenol-ethylene oxide adduct containing 12 moles of ethylene oxide and (B) is a dialkylphenol-ethylene oxide adduct containing 14 moles of ethylene oxide and side chains originating in a straight chain alpha olefin mixture containing from eight to twelve carbon atoms.

11. A water-soluble surface-active detergent in accordance with claim 1 wherein (A) is a dodecyl-phenolethylene oxide adduct containing 13 moles of ethylene oxide and (B) is a dialkylphenol-ethylene oxide adduct containing 14 moles of ethylene oxide and side chains originating in a straight alpha olefin mixture containing from eight to twelve carbon atoms.

12. A water-soluble surface-active detergent in accordance with claim 1 containing, in addition, (C) a waterinsoluble water-dispersible ethylene oxide ether adduct having the formula wherein X is a member selected from the group consisting of alkyl groups having from about eight to about twenty-four carbon atoms, alkylphenyl groups having from about eight to about sixteen carbon atoms in the alkyl chain, dialkylphenyl groups having a total of from about twelve to about twenty-four carbon atoms in the alkyl chains, and trialkylphenyl groups having a total of from about eight to about twenty-four carbon atoms in the alkyl chains, and n is a number within the range from about two to about twenty-five sutficient to provide water-insolubility and water-dispersibility.

13. A water-soluble surface-active detergent in accordance with claim 12 wherein (C) consists essentially of an ethoxylated fatty alcohol having from about twelve to about twenty-two carbon atoms in the alkyl group.

14. A water-soluble surface-active detergent in accordance with claim 12 wherein (C) consists essentially of an ethylene oxide adduct of a monoalkylphenol having from about eight to about fifteen carbon atoms in the alkyl chain.

15. A water-soluble surfaceactive detergent in accordance with claim 12 wherein (A) is a tallow fatty alcoholethylene oxide adduct containing 50 moles of ethylene oxide, (B) is a dinonylphenol-ethylene oxide adduct containing 14 moles of ethylene oxide and (C) is a nonylphenol-ethylene oxide adduct containing 4 moles of ethylene oxide.

16. A water-soluble surface-active detergent in accordance with claim 12 wherein (A) is a dinonylphenolethylene oxide adduct containing 21 moles of ethylene oxide, (B) is a dinonylphenol-ethylene oxide adduct containing 14 moles of ethylene oxide and (C) is a nonylphenol-ethylene oxide adduct containing 4 moles of ethylene oxide.

17. A water-soluble surface-active detergent in accordance with claim 12 wherein (A) is a tallow fatty alcoholethylene oxide adduct containing 50 moles of ethylene oxide. (B) is a dinonylphenol-ethylene oxide adduct containing 12 moles of ethylene oxide and (C) is a dodecylphenol-ethylene oxide adduct containing 14 moles of ethylene oxide.

18. A water-solublesurface-active detergent in accordance with claim 12 wherein (A) is a fatty alcohol containing from about twelve to about eighteen carbon atomsethylene oxide adduct containing 7 moles of ethylene oxide, (B) is a dinonyl phenol-ethylene oxide adduct containing 12 moles of ethylene oxide and (C) is a tallow fatty alcohol-ethylene oxide adduct containing 6 moles of ethylene oxide.

19. A water-soluble surface-active detergent in accordance with claim 12 wherein (A) is a nonylphenolethylene oxide adduct containing 10 moles of ethylene oxide, (B) is a dinonylphenol-ethylene oxide adduct containing 14 moles of ethylene oxide and (C) is a nonylphenol-ethylene oxide adduct containing 4 moles of ethylene oxide.

(References on following page) 11 12 References Cited FOREIGN PATENTS UNITED STATES PATENTS 838,975 1/1960 Great Britain.

3,034,839 5/1962 Michaels 252-435 3 20 949 9 19 5 Rosnati 252 109 MAYER WEINBLATI Primary Examine"- 3,215,633 11/1965 Grefo 252-152 9 US. Cl. X.R.

3,255,117 6/1966 Knapp et al 25299 252-89, 135

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 822 Dated February 25. 1969 Inventm-(Q Helmut Grunewald and Ake Waag It: is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 15 "A water" should be Water line 50, "alseo" should be also.

Column 2, line 31, A period should be inserted at the end of the line.

Column 3, line 27, "dispensible" should be dispersible Column 4, line 16, "1:25" should be 1:2.4

Column 6, Table 4, "3-methyl-4, G-dibutylphenol Elus 12 E0."

should be 3-methyl-4, G-dibutylphenol plus 12 E0.

Column 8, Table 6, last heading, "Increasen" should be Increase in Column 9, line 59 (Claim 6), "and" should be inserted after "adduct";

line 67 (Claim 8), "and" should'be inserted after "adduct".

Column 11, line 3, (References cited) "3, 034, 839 should be line 5, "Grefo" should be Grifo SIGNED AND SEALED MAR101970 Axum;

Edward M. Fletcher, Ir. WILLIAM E. SGHUYIER, Attesting Officer Oomissioner of Patents

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
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US3208949 *Oct 30, 1961Sep 28, 1965Lever Brothers LtdLiquid detergent composition
US3215633 *Dec 11, 1953Nov 2, 1965Gen Aniline & Film CorpLow foaming detergent
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GB838975A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3948819 *Jun 18, 1973Apr 6, 1976Minnesota Mining And Manufacturing CompanyCleaning composition
US4234443 *Mar 24, 1978Nov 18, 1980Michael A. CanaleComposition and a method useful for making a fountain solution for lithographic printing operations
US4340509 *Apr 16, 1980Jul 20, 1982Michael A. CanaleComposition, concentrate and fountain solution for lithographic printing operations
US4374036 *Nov 19, 1980Feb 15, 1983Michael A. CanaleComposition and concentrate useful for making a fountain solution for lithographic printing operations
US4588516 *Dec 26, 1984May 13, 1986Schwartz Lenore FCleaning liquid and process of using same
US4689082 *Oct 28, 1985Aug 25, 1987Basf CorporationPolyether block copolymer and alkyl phenol ethoxylate
US5286300 *Aug 12, 1992Feb 15, 1994Man-Gill Chemical CompanyA nonionic polyoxyalkylene glycol and an alkoxy derivative thereof; treating metal surfaces
EP1259586A1 *Jan 29, 2001Nov 27, 2002Amechem Inc.Multipurpose, multifunctional complex cleaning and washing agent
Classifications
U.S. Classification510/317, 510/471, 510/506, 510/378, 510/356, 510/360
International ClassificationC11D3/00, C11D1/722, C11D1/72, C11D1/825
Cooperative ClassificationC11D1/72, C11D1/8255, C11D3/0026, C11D1/722
European ClassificationC11D3/00B5, C11D1/825B, C11D1/722