NZ199856A - Non-zwitterionic amphoteric-fatty acid complexes and detergent compositions - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number 1 99856 r1998 56 O- -» ~,V <-»• Priority uaSv^u?: Compteta SoQci«€3l£SJi Fssod: Ca^s-b -co i c<53 co-tcj^■, Class: .CQTf.^l.7. sbfscsiion Deris: ...>••••••••• Pub'' P.O. Joitrns!, tto: '26 ( ■ 2 $>2. a • ■ a M ^ ga*" Patents Form No. 5 Number PATENTS ACT 1953 Dated COMPLETE SPECIFICATION DETERGENT COMPOUNDS AND COMPOSITIONS l?We JOHNSON & JOHNSON BABY PRODUCTS COMPANY, a corporation organized under the laws of the State of New Jersey, United States of America, located at 501 George Street, New Brunswick, New Jersey, United States of America do hereby declare the invention for whichxJ/we pray that a Patent may be granted to kk/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - 1 - (followed by page la) 1998 JBP 183 Background of the Invention The present invention relates to amphoteric-fatty acid complexes. More specifically, the invention relates to amphoteric-fatty acid complexes which exhibit unexpected foam properties and low ocular irritancy. The invention further relates to detergent compositions containing the 10 novel amphoteric-fatty acid complexes in combination with other surfactants and/or detergent components.

Nonirritating detergent compositions have been known in the art and have been in use for some time. United States 15 Patent Nos. 3,299,069 and 3,055,836 are merely two representative examples of such prior art nonirritating detergent compositions. Likewise, amphoteric compounds have been well known in the art and have been disclosed in use with various other detergent compounds. United States 20 Patent No. 2,528,380, discloses a ring structured amphoteric compound with a fatty acid attached to the ring nitrogen. None of the disclosures in the prior art disclose the amphoteric-fatty acid complexes of the present invention nor the advantages provided by same.

It is an object of the present invention to provide novel detergent compounds. 109856 Summary of the Invention This invention encompasses non-zwitterionic, amphoteric-fatty acid complexes of the formula 0 II RiC-0 G ro—n' I H *1 'A2 0 wherein R]_, R2, A^ and A2 are as defined below, Detailed Description of the Invention The present invention relates to novel non-zwitterionic, amphoteric-fatty acid complexes of the formula ' O II R]_C-0 © r2-n I H \ ,Ai A2 0 wherein R]_ is alkyl or substituted alkyl containing from 6 to 18 carbon atoms and mixtures thereof; R2 is alkyl containing from 8 to 18 carbon atoms and mixtures thereof or alkyl amido of the formula 1 3 ©APR 1984 19D858 0 2 11 I |r3-C-n-y« wherein R3 is alkyl containing from about 8 to 18 carbon atoms, Z is H or lower alkyl containing from 1 to 4 carbon atoms; and Y is lower alkyiene containing from 1 to 4 carbon atoms; hi and A2 are the same or different and are selected from the group of anionic salt moieties consisting of the following: 4ch2ch2-coox]n -£ch2-coox]n 4ch2choh-ch2-so3x]n -fch2-choh—ch2—opo3x] n when x is divalent, €.ch2-ch0h-ch2-0p03x2i n when x is monovalent wherein X is a water-soluble cation such as Na + , K+, Ca++, Mg++ and the like and n is an integer of 1 or 2 with the proviso that if only one of Ajl and A2 are selected from the anionic salt moieties above the other can be hydrogen lower alkyl or lower hydroxyalkyl containing from 1 to 4 25 carbon atoms.

The non-zwitterionic, amphoteric compounds which are useful in the complexes of the present invention are of the formula: *1 R2-N r*2 H © wherein R2, A^ and A2 are as defined above. 1998 56 These compounds can be prepared in accordance with the teachings of the art, see for example, United States Patent No. 2,970,160, which is incorporated herein by reference.

The fatty acid compounds which are useful in the complexes of the present invention are of the formula. 0 " II r]_-c-0 © wherein is as defined above. These compounds are readily available commercially from numerous sources such as the fatty acids available from Emery Industries Inc. Cincinnati, Ohio Procter & Gamble, Cincinnati, Ohio and various other commercial suppliers.

The amphoteric-fatty acid complexes of the present 20 invention can be prepared by admixing a suitable non-zwitterionic amphoteric and a suitable fatty acid, utilizing heat, if necessary, to facilitate the blending and adding water, if needed. The ratio of fatty acid to amphoteric can be in the range of about 0.5:1 to 1.5:1, 25 preferably about 1:1. The pH of the resulting complex should be within the range of 6.5-8.5, preferably within the range of 7.0-7.5, to minimize potential irritation problems.

Specific examples of the novel amphoteric-fatty acid complexes of the present invention include: © 0 1© oh c2h4oh "I / (A) Ri-C-0 C, H -C-N(CH2)2-Nn 11 '3 |NCH2COOK H wherein R]_ is a C11H23 - C18H37 mixture. 199856 40 (B) ■ O * II rl-c-0 0 1© /CH2CH2COONa Cl4H29-NN h CH2CH2COONa wherein R^ is derived from an 80%/20% tallow coconut mixture.

© (C) o II R^-C-0 0 o ch3 II / r2-c-n-(ch2)2x ch2chohch2so3k CH2CH0HCH20P03Na2 wherein Ri is derived from tallow and R2 is a C11H23~C17H25 mixture.

(D) O II r^c-0 © 0 y CH2CH0HCH2S03 c18h37-N\ I CH-CHOHCH-SO,^ h 2 23 wherein Rj_ is derived from a 70%/30% mixture of lauric and myristic acids. © 0 ii 0 h | (e) rlc-0 c12h25-n~ch2ch2-coona 1 ™■ h wherein R^ is derived from tallow. 0 " || © (f) ci2h25c-0 c14**29~ (G) O II R^C-0 0 c12h25~N\ H^CH2CH2COONa' ^CH 2 CH 2 COON a J © CH2CH2COONa 0 H CH2CH2COONa wherein R^ is a CgHj^ - Ci8H37 mixture. 3 ">i.: 190856 The amphoteric-fatty acid complexes of the present invention exhibit excellent surfactant properties. In particular, these complexes exhibit good foam properties and low ocular irritancy. The good foam properties are unexpected because fatty acids do not normally exhibit such properties. It has further been found within the pH range of 7.0-7.2 that the amphoteric-fatty acids complexes exhibit unexpected foam synergism.

These complexes can be utilized in detergent compositions either alone or in combination with other surfactants in a range of from about 1.0 to 50.0% by weight of the total compositions.

The amphoteric surfactants which may be used in the present invention include betaines, sultaines, phosphobetaines, phosphitaines, n-alkylamino propionates, n-alkylimino dipropionates and imidazolines. The betaine and sultaine surfactants useful in this invention are described in U.S. Patent No. 3,950,417 issued April 13, 1976, which is incorporated herein by reference. The phosphobetaines and phosphitaines useful in this invention are described in New Zealand Patent No. 190,363 which is incorporated herein by reference. The n-alkylamino propionates and n-alkylimino dipropionates are sold under the tradename Deriphats by General Mills. The imidazolines which are useful in the compositions of this invention are described in U.S. Patent No. 2,970,160, which is incorporated herein by reference.

The preferred betaine amphoteric surfactants include the alkylbetaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethylcarboxy-ethylbetaine, cetyldimethylcarboxymethylbetaine, lauryl-bis-(2-hydroxyethyl) carboxymethylbetaine, 3 0 APR 1984 199 8 5 6 oleyldimethyl-qamma-carboxypropylbetaine, lauryl-bis-(2-hydroxypropyl)-carboxyethylbetaine, and the like; the sultaines such as cocodimethylpropylsultaine, stearyldi-methylpropy1su1taine, lauryl-bis-(2-hydroxyethy1) propylsultaine and the like; and the amidosultaines such as cocoamidodimethylpropylsultaine, stearylamidodimethyl-propylsultaine, laurylamido-bis-(2-hydroxyethyl) propylsultaine, and the like.

The preferred phosphobetaines include lauric-myristic-amido-3-hydroxypropylphosphobetaine, cocamidodisodium-3-hydroxypropylphosphobetaine, lauric-myristicamido-disodium-3-hydroxypropylphosphobetaine, lauric-myristic-amidoglyceryl-phosphobetaine, lauric-myristicamidocarboxy-disodium-3-hydroxypropylphosphobetaine, and the like. The preferred phosphitaines include cocoamidopropylmonosodium-phosphitaine, lauric-myristicamidopropylmonosodium-phosphitaine and the like.

The preferred n-alkylamino propionates and n-alkylimino dipropionates include those having the following structures: © © R - NH2CH2CH2COO and @ 0 ^CH 2CH-2 COO r - nh \ CH2CH2COO Na wherein R is from about 8 to 22 carbon atoms and mixtures thereof.

The amphoteric detergents may be present in an amount from about 2 to 10% by weight of the total composition. 1998 56 It is envisioned that any anionic surfactant may be used in the compositions of the invention such as, for example, an alkyl sulfate of the formula R-CH2-OSO3X, an alkylether sulfate of the formula R(OCH2CH2)p-OSO X, an alkylmonoglyceryl ether sulfonate of the formula R-OCH2-CH-CH2-SO3X, I OH an alkylmonoglyceride sulfate of the formula RC00CH2-CH-CH20s03x I OH an alkylmonoglyceride sulfonate of the formula RC00CH2CH-CH2S03X I OH an alkyl sulfonate of the formula RSO3X and an alkylaryl sulfonate of the formula wherein R is alkyl having from 7 to 17 carbon atoms; X is selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, and ammonium ions substituted with from 1 to 3 lower alkyls and p is an integer from 1 to 6.

The anionic detergent may be present in an amount of from about 2 to 10% by weight of the total composition.

Nonionic detergents which are useful include the alkylene oxide ethers of phenols, fatty alcohols, and alkyl mercaptans; the alkylene oxide esters of fatty acid amides; the condensation products of ethylene oxide with partial fatty acid esters, and mixtures thereof. The polyoxyalkylene chain in such agents may contain from 5 to 100 alkylene oxide units in which each alkylene unit has from 2 to 3 carbon atoms. 199856 The nonionic surfactant may be present in an amount of from about 1 to 30% by weight of the total composition.

Cationic surfactants suitable in these compositions 5 include mono-and bis-quaternary ammonium halides, such as stearyldimethylbenzylammonium chloride, cetyltrimethyl-ammonium chloride, N,N-dioctadecyl-N,N,N' ,N'-tetramethyl-1,5-(3-oxapentylene)di-ammonium bromide; tertiary amine salts such as cocoamidopropyldimethylamine hydrochloride 10 stearylamidopropyldimethylamine citrate; cationic polymers such as hydroxyethyl cellulose reacted with epichloro-hydrin and then quaternized with trimethylamine (Polymers of this type are sold by Union Carbide under the tradename Polymer JR) and specific triesters of phosphoric acid. 15 The specific triesters of phosphoric acid are described in New Zealand patent No. 194,289 which is incorporated herein by reference. The cationic surfactants should be present in an amount of from about 0.-5 to 3.0% by weight of the total composition.

The total amount of the active surfactant ingredients in the present invention should not be greater than about 50% by weight of the total composition in order to avoid 25 ocular irritation problems, preferably from about 5 to 20% by weight of the total composition with the proviso that the total amount of anionic surfactant and amphoteric surfactant should not exceed 20% by weight of the total composition. In addition, other ingredients convention-30 ally added to surfactant compositions for personal use. such as dyes, preservatives, perfumes, thickeners, opacifiers, conditioners, emollients, buffering agents, and the like, may be added in minor amounts. Ingredients such as dyes, preservatives and perfumes together usually 35 constitute less than 2% by weight of the total composition and thickeners may be added to the composition in an 3 ©APR 1984 1998 56 amount of from about 1 to about 3% by weight of the total composition.

The detergent compositions of the present invention should 5 have a pH in the range of about 6.5 to 8.5, preferably from about 7.0-7.5.

Liquid detergent compositions utilizing the complexes of the present invention can be prepared by admixing the 10 amphoteric-fatty acid complex with the other surfactant(s) at room temperature or slightly elevated temperatures (about 50°C) and then sufficient deionized water is added to bring the composition to about three quarters of its-intended weight. Other ingredients such as various 15 detergency adjuncts, fillers, carriers, perfumes, preservatives, gelling agents and the like are added as required followed by the balance of the water. The pH is then adjusted to within the desired range by the addition of strong acid, e.g., HC1, or strong base NaOH, as 20 needed.

Detergent bar compositions utilizing the complexes of the present invention can be prepared by admixing the amphoteric - fatty acid complex with the other 25 surfactant(s) in a steam jacketed rotary mixer at temperatures within the range of 60-80°C. Fillers, whitening agents and processing oils can be added, as needed, to the hot slurry. After adequate mixing to assure homogeneity and moisture balance the product is 30 chill rolled or drum dried into flakes. Dyes and fragrances are added to the flakes in a standard amalgamator together with additional water to provide proper bar formation. After adequate mixing the flakes are milled and plodded into logs which are then cut into 35 blanks prior to stamping into bar form. 1998 56 -ll- The detergent compositions of the present invention can be tested for ocular irritation by the following modified Draize Test (J.H. Draize et al. , Toilet Goods Assn. No. 17, May 1952, No. 1, Proc. Sci. Sect.).

An 0.1 ml. sample of a neutral composition under test is dropped into one eye of an albino rabbit, the other eye serving as a control. Six rabbits are employed for each composition. Observations are made after 1, 24, 48, 72 and 96 hours and 7 days after initial instillation, second and third instillations are made after the 24 and 48 hour readings. Results may vary from substantially no change or only a slight irritation in the appearance of the rabbit's eye after 7 days to severe irritation and/or complete corneal opacity. Ocular lesions are scored for the cornea, iris and conjunctiva with a higher number indicating greater ocular irritation and the scores are added to give a total numerical value for each reading for six rabbits and averaged. The averaged score is an indication of the irritation potential of the composition under test. Based on the averaged score, descriptive irritation evaluation may be given, e.g., none, slight, moderate, severe, as the case may be.

Detergent compositions of the invention provide high foam volume and moreover outstanding foam stability as measured by an adaption of the well-known Ross-Miles foam test principle "Oil and Soap" 18.9-102 (1941) ; Lanolin, anhydrous, cosmetic grade is mixed with dioxane (technical grade) in the proportion of 2.5 grams lanolin and 100 grams of dioxane. The lanolin is first mixed with 25 cc. of dioxane. This mixture is heated over a steam bath to 45°C in order to dissolve the lanolin in the dioxane. The remainder of the dioxane is then added and mixed. This lanolin dioxane solution, which is stored in 1998 5 an amber bottle, should be prepared fresh on the day that the tests are run.

The composition to be tested is diluted by adding 376 cc. of distilled water to 4 grams of the composition, and then by adding 20 cc. of the lanolin-dioxane solution described above while mixing. Heat is produced when the lanolin-dioxane solution is added to the solution of the composition in water and care must be taken in adjusting 10 the temperature of this solution to 24°-25°C. Both of these intermediate solutions should therefore be adjusted to 23°C before mixing. The cooling of the lanolin-dioxane solution should be gradual in order to avoid precipitation of the lanolin. This will produce a final solution with a 15 temperature of 24°-25°C.

The final solution of the composition to be tested, water, dioxane and lanolin described above, is then run in a modified Ross-Miles foam column in the usual way. All 20 tests are conducted in duplicate, and the average of the two results is taken. Foam stability is determined by measuring the decay in foam height after two minutes, expressed as a percentage of the original height.

Specific embodiments of the present invention are illustrated by the following representative examples. It will be understood, however, that the invention is not confined to the specific limitations set forth in the individual examples, but rather to the scope of the 30 appended claims. 19 9 8 5 6 Example I 320.2 grams (.19g/moles) of a 24% active solution of an amphoteric of the formula © 0 H C2H4OH II I / CHH23C-N-<CH2>2-Nv J"L " |XCH2COOK H _ are mixed with 47 grams (.24 g/moles) of premelted coconut fatty acids of the following chain length percentage distribution: Cg-0.3, Cg-7.3, Ciq-6.5, Ci2~50.7, C14-I8.9, C^g-8.6, C^g-7.7.

The resulting product is an opaque, viscous slurry containing 34% solids with a pH of 7.1 and is an amphoteric-fatty acid complex of the structure shown as compound G in the specification. The complex foams 20 copiously in both soft and hard water and is a slight ocular irritant.

Example II The slurry obtained in Example I is freeze-dried by known 25 procedures to yield about 95% solids. The solids are ground to a slightly tacky powder which can be utilized to form a bar soap and is a slight to moderate ocular irritant.

Example III Following the procedures of Example I, the amphoteric of Example I is mixed with stripped hydrogenated coconut fatty acids of the following chain length percentage distribution: C9-I, C]_q-1, Cj_2~56, 0^4-24, C]_(>-12.5 and Cis-5; to form an amphoteric-fatty acid complex shown as compound A in the 19 9 8 5 6 specification. The resultant dried powder is found to be a slight ocular irritant.

Example IV Following the procedures of Example I, 227 grams (.15 g/moles) of a 22% active solution of tetradecyl -iminodicarboxylate are dissolved in 450 grams of deionized water at a temperature of about 50°-60°C. 30 grams (.15 g/moles) of the coconut fatty acid of Example I are added to form the resulting amphoteric-fatty acid complex which is a moderate irritant and is of the following structure: 0 1 R^C-0 0 / C14H29-N\ H CH2CH2COONa CH2CH2COONa © wherein is a CgHx3-CisH37 mixture, EXAMPLE V 300 grams (0.07 g./moles) of an 11.1% active solution of an amphoteric of the formula O C2H40H II H | I C11H23"C"N-(CH2)2-N-CH2CH0HCK2S03Na H 0 are mixed with 14.1 grams (0.07 g./moles) of premelted coconut fatty acids having the alkyl chain length distribution sot forth in Example I. The resulting product is a hazy solution containing 15% solids, having a 1 9.9 8 5 € pH of 7.3 and is an amphoteric-fatty acid complex of the formula: 0 c2h4oh c2h4oh © EXAMPLE VI 360 grams (0.19 g./moles) of a 19.1% active solution of an amphoteric of the formula wherein Ri has an alkyl chain length percent distribution 20 as follows: C^q-2, Cj_2-53/ 0^4-24, C15-II Ci8~10' are mixed with 40 grams (0.19 g./moles) of premelted coconut fatty acids having the alkyl chain length distribution set forth in Example I. The resulting product is a thin, opaque slurry containing 27% solids 25 having a pH of 7.5 and is an amphoteric fatty acid complex of the formula.

-,© R1 " .

J ^CH2COONa H 0 Ri - s: - o © CH2COONa © CH2COONa 1998 Example VII A clear gel hair care product is prepared as follows: 200 grams of deionized water are charged to a vessel equipped 5 with an agitator and steam. 50 grams of a phosphate ester hydrotrope are added and the pH is adjusted to 7.0. 150 grams of Compound A are added and the solution is mixed until clear. 20 grams of polyethylene glycol 6000 aistearate are added and heat is applied to the solution 10 to 70°C for twenty minutes. The solution is cooled to 25-30°C and 1.0 grams of preservative, 2.0 grams of fragrance and sufficient deionized water is added to bring the total weight to 1000 grams.

The resulting product has the following compositions: wt./wt.% Compound A 15.00 phosphate ester hydrotrope 5.00 polyethylene glycol 6000 distearate 2.00 preservative 0.10 fragrance 0.20 deionized water q.s. to 100% Example VIII An opaque liquid soap is prepared having the following formulation: wt./wt.% Compound A 15.00 Compound C 15.0 0 Cabosil (tradename for colloidal silica, 3.50 available from Cabot Corp., Boston, Mass.) isopropanol 0.10 fragrance 0.30 deionized water q.s. to 100% 1998 56 The pH of the above formulation is adjusted to 6.5 with citric acid.

Example IX A clear, liquid hair cleanser composition is prepared having the following formulation: wt./wt.% Compound A 5.00 polyoxyethylene 80 sorbitan monolaurate 10.00 Deriphat (tradename for salt of N-alkyl 5.00 beta-iminopropionic acid available from General Mills Inc., Kankekee, Illinois) polyethylene glycol 6000 distearate 2.00 benzyl alcohol 0.10 Dowicil 200 (tradename for the cis isomer 0.10 of l-(3-chloroalkyl)-3,5,7-triaza-l-azoniaadamantine chloride) fragrance 0.20 deionized water q.s. to 100% The above formulation is adjusted to a pH of 7.1 with 15% HC1 and has a viscosity of 413 cps. at 25°C and is a slight ocular irritant. The formulation also exhibits 25 good foam properties.

Example X A detergent bar composition is prepared as follows: 50 parts of Compound A are mixed with 20 parts of Deriphat in 30 a steam jacketed mixer at a temperature of 70°C. After the slurry is homogeneous, 10 parts of polyoxyethylene (80) sorbitan monopalmitate are added followed by the addition of 10 parts each of talc and dextrin. The batch is mixed 20 minutes, cooled, milled into ribbons and pressed into 35 detergent bars. 199 The resulting bars have the following formulation. wt./wt.% Compound A 50.00 Deriphat 20.00 polyoxyethylene (80) 10.00 sorbitan monopalmitate talc 10.00 dextrin 10.00 100.00 and has a pH of 7.0. This product is a moderate irritant and exhibits excellent foaming properties.

EXAMPLE XI In order to demonstrate the synergism of the amphoteric-fatty acid complexes of the present invention with respect to foam characteristics, compounds A and B, the amphoteric portion thereof and the coconut fatty acid portion thereof were individually tested in accordance with the modified Ross-Miles foam test set forth here inbefore.

The results are shown in Table I below: -19- TABLE I 199 Initial foam Height (mm) Normal Water Hard Water Compound % Active and Grease 200 ppm CaCQ^ amphoteric of compound A 5.0 295 343 coconut fatty acid 5.0 0 0 compound A 5.0 353 358 amphoteric of compound B 5.0 - 295 coconut fatty acid 5.0 - 0 compound B 5.0 - 360 In addition to the preferred embodiments described herein, other embodiments, arrangements and variations within the spirit of the invention and the scope of the appended claim will occur to those skilled in the art. 190856 JBP 183

Claims (10)

WHAT WE CLAIM IS:

1. A non-zwitterionic amphoteric-fatty acid complex of the formula R^C-0 0 R2-N< I ^ A2 H © wherein Ri is alkyl or substituted alkyl containing from 6 to 18 carbon atoms and mixtures thereof; R2 is alkyl containing from 8 to 18 carbon atoms and mixtures thereof or alkyl amido of the formula 0 Z II I b C-N-Y' wherein R3 is alkyl containing from 8 to 18 carbon atoms; Z is H or lower alkyl containing from 1 to 4 carbon atoms; and Y is lower alkylene ccntainiaig frcm 1 to 4 carbon atoms; 25 Ai and A2 are the same or different and are selected from the group of anionic salt moieties consisting of the following: ■£CH2CH2~C00X] n 3 0 -fCH2-COOX]n -£CH2CHOH-CH2-SC>3X] n -tCH2-CH0H-CH2-0P03X] n when X is divalent -£CH2-CH0H-CH2-0P03X^ n when X is monovalent wherein X is a water soluble cation and n is an integer of 35 1 or 2 with the proviso that if only one cf A^ and A2 is selected from the anionic salt moieties above, 109856 -21- the other can be hydrogen, lower alkyl or lower hydroxyalkyl containing from 1 to 4 carbon atoms.

2. The complex of claim 1 wherein COO~ is derived from a coconut fatty acid mixture.

3. The complex : of claim 1 wherein R2 is Ci4H2g. 10

4. The complex ; of claim 1 wherein R2 is C^2H25' 15

5. The complex of claim 1 wherein R^ COO" is derived •from a tallow fatty acid mixture.

6. The complex of claim 1 wherein Aj_ and A2 are fCH2COOX)n. 20 25

7. The complex- of claim 1 of the formula 0 II Rl-C-0 © 0 H / C2H40H :11H23-C-N(CH2)2-NNcHf COOK © wherein R^ is a C]_iH23 - Ciqh37 mixture, 30 35

8. The complex of claim 1 of the formula O II RlC-0 -.© c12h25-N H CH2CH2C00Na ^CH2CH2COONa © wherein R^ is a CgHi3 " C18H37 mixture Q W.2. „ 30 APR 1984 REC51V,ii7 190856 -22-

9. The complex of claim 1 of the formula 0 II CllH23C-° o H^CH2CH2COONa c14h29"n \ CH2CH2COONa ©

10. A detergent composition wherein the active ingredient comprises from 1 to ;50% by weight of the total composition of at least one complex of the formula of claim 1. WEST-WALKER. MCCABE p®r: ATTORNEYS FOR the ap.-.jcant 3 0 APR received W.2. f>", 30APR PM