ll~S~ J~ 138 SURFACTANT COMPOSITIONS
The presen~ invention relates to surfactant composit~ons.
5 More particularly, this in~ention relates to conditioning and cleansing sur~actant compositions which are mild and, if used as cosmetic ~ormU~ations,non-irritating to the skin and eyes.
10 The cleaning or shampooing of hair is known to cause difficulty in its after-shampoo arrangement and management.
That is, shampooing can produce tansled hair and can cause the buildup of static electricity on the hair, thus causing generally unattractive appearance and "flyaway"
lS hair.
In order to combat these problems in the shampooing o~
hair, many conditioning products have been introduced for application to the hair after shampooing. These products 20 generally ~acilitate detanyling of the hair and reduce static charge, thus making the hair more manageable and attractive. While these after-shampoo conditioners are effective in their canditioning of hair, they also have several disad~antages. It is necessary to apply the 2S after-shampoo conditioner in a separate step from the shampooing operation itself, which is both expensive and time consuming. Furthermore, these prior art ater-shampoo conditioners cover the hair shaft with a thick sticky coating and thus greatly decrease the perceived 30 cleanliness of the hair. As a result of this latter disadvantage, it is necessary to shampoo hair condi~ioned in this fashion more often than unconditioned hair~
There are also a number of prior art conditioning 35 shampoos, which combine the washing and conditioning steps ~' ; r~ g into a single shampooing operation. While t~e~e condi~
tioning ~hampoos do simplify the process of obtaining clean, conditioned hair, the resulting haix is still thickly coated with a s~icky ~aterial and still has a low 5 degree of perceived cleanliness. Moreover, these condi-tioning shampoos are often irritating ~o the eyes. A
typical prior art condi~ioning shampoo is ~hat shown on page 112 of the September 1974 issue of Soap, Cosmetics, Chemical Specialties.
It should be noted that it has been round that perceived cleanliness and conditioning are not obtaina~le simultaneously, either from separate shampooing and conditioning products or from products which perform 15 both functions immediately.
It is thus an object of the present invention to provide surfactant compositions which are effective for ~le cleansing and/or conditioning of the hair in a single 20 application.
It is another object of the present invention to provide surfactant compositions which are ml}d and non-irritating to the skin and eyes.
It is a still further object of the present invention to provide suxfactant compositions which are mild and can be utilized as textile cleansers and softenersO
~0 These and other objects o~ ~he present invention will become apparent to one skilled in the art from the detalled description given hereinafter.
Summary of the Invention This invention encompasses surfactant composiki.ons compris-ing as the active ingredient a cationic triester of phos-phoric acid as a surfactant, and preferably at least one other surfactant selected from the group conslsting of anionic, nonionic, cationic and amphoteric detergents. ~he balance of the compositions can comprise vario~s detergency and cleansing adjuncts, fillers, carriers and the like which are well known in the art.
Detailed Description of the Invention The cleansing and conditioning surfactant compositions of the present invention comprise as the active ingredient a cationic triester of phosphoric acid and preferably at least one other surfactant.
The cationic triesters of phosphoric acid which are useful in the present invention are novel compounds described and claimed in Canadian Patent No. 1,126,750, which issued on June 29, 1982.
These compounds are of the formula (I) R 6~1 R163 _ 0 _ p = o 3X
O
_ _ wherein Rl, R2 and R3 are the same or different and can be represented by the following formulae:
(II) r 6 l (III) r R8 l~
~ 5 ~ and L4 C N -(CH2)n- ~ -R
wherein R4, R5 and R6 are the same or di~ferent and are alkyl, alkenyl, hydroxyalkyl, arylalkyl or polyoxyalkylated ether, containing from 1 to about 22 carbon atoms with the proviso that at least one of R4, R5 and R6 contains at least 8 carbon atoms. Further, R5 and R6 taken with the nitrogen to which they are attached can form a heterocyclic structure such as morpholine, thiomorp~holine, indole and the like, R7 is alkylene or mono- or polyoxyalkylene of from 2 to 12 carbon atoms which may be substituted with alkyl, alkoxy, hydro~y or hydroxyalkyl groups of up to about 10 carbon atoms, R8 is hydrogen, alkyl, hydroxyalkyl, alkenyl or cycloalkyl, of up to 7 carbon atoms or polyoxyalkylated hydroxyalkyl of up to 10 carbon atoms; n is an integer from about 1 to 10 and X is an anion such as Cl , Br or the like.
The triesters of phosphoric acid described above can be prepared in accordance with the processes described in Canadian Patent No. 1,126,750~
Representative triesters of phosphoric acid useful in the present invention include compounds having the following structures:
(A) OH ~ CIH3 _ ~-t+
~H - CH CH2 -N ~ C18 37 O CH3 3C1~3 l 1H C~13 ~ ~T
5 ~3 OH CH
(B) CH2 - C~ - CH2 - INCl2EI25 O C~3 3Cl~
CH 2 - CH - CH 2 - ~ C 12 2 5 (C) fH2 - CH - CH2 - ~ - Ra +~+
O = I - OCH2 - CH - CH2 ~ ~ Ra 3C1 1H2 ~ CI H ~ CH2 - ~ - Ra wherein Ra is a mixture of CzoH4l ar~d C~2~I45 (D) C~2-CH-C~2~-CH2-CH2-C~I2-N-C C17~35 O C~I 3 H O
I C~I2 CH C~Iz ~l~CH2-cEI2-cH2-N-c-cl7E~35 3C13 CH2-cH-cH2-N~-cH2-cH2~ N-c-cl7EI3s 6 116~6~9 JBP 133 (E) OH C2HSH O
CH2-CH C~2- N -CH2-CH2 N C ~17~35 1 2 CH CH2 ~ --cx 2CH2 -N--C--C1 7H3 5 3Cl CH2--fH--CH2-~ --cH2-c~2 - N - c-cl7H35 ( F ) r 3 ~++
CH2-CHz-~~C18H37 P- 1 -0-CH2CH2-~ C18H37 3Clg CH2-CH2-~1 ~18~17 ( G ~r ,C~I 3 ~++
¦ CH3 o=P-ocHzcH2-~-cl2~25 3Cl9 _ CH2CH2 -0~ -Cl 2H 2 5 l 5 ~ S ~
(H)~C2H5 H 1l ¦ 2H5 ' = ~ -CH2c~2- ~ -CH2c~2- ~-C-C17H35~ 3Cl~
CH2 C~2 -~ - CH2 CH2 - N- C- Cl 7 H3 5 C2H5 .
me cationic triesters of phosphoric acid can be present in the detergent compositions of the present invention in a range of from 0.5 to 10% by weight of the total compo-sition when such compositions are utilized as cleansing and conditioning compositions and from 1 to 5% when such compositions are utilized as textile softeners.
The cationic triesters of phosphoric acid disclosed above have been found to be compatible with other known surfactants. me fact that the cationic triesters of phosphoric acid are readily compatible with other sur-factants in general and the anionic surfactants in parti-cular to form various detergent compositions is unexpected since cationics are generally not readily compatible with other surfactants and processing difficulties would be e~pected.
Such is, however, not the case with the triesters of phosphoric acid disclosed hereinabove and in Canadian Patent No. 1,126,750.
This unexpected compatibility between the specific triesters of phosphoric acid disclosed herein and the anionic surfac-tants results in very desirable conditioning and cleansing compositions since the anionic surfactants are good cleansing and foaming compounds.
. j ., ~ .
5 ~ S ~
Preferred embodim~n~s of the present invention relate to cleansing and conditioning detergent compositions con-taining a triester of phosphoric acid and at least one other surfactant selected from the group consisting of amphoteric, nonionic, anionic and cationic detergents.
The amphoteric surfactants which may be used in the present invention include betaines, sultaines, phospho-betaines, phosphitaines, n-alkylamino propionates and n-alkylimino dipropionates. The betaine and sultaine surfactants use~ul in this invention are described in U.S. Patent No. 3,950,417 issued April 13, 1976.
The phosphobetaines and phosphitaines useful in this invention are described in Canadian Patent No. 1,110,640, which issued on October 13, 1981. The n-alkylamino propionates and n-alkylimino dipropionates are sold under the tradename Deriphats by General Mills.
The preferred betaine amphoteric surfactants include the alkylbetaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethyl- ~-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, lauryl-_is-(2-hydroxyethyl) carboxymethylbetaine, oleyldimethyl-gamma-carboxypropylbetaine, lauryl-bis-(2-hydroxypropyl) ~-carboxyethylbetaine, and the like, the sultaines,such as cocodimethylpropylsultaine, stea.ryl-dimethylpropylsultaine, lauryl-bis-(2-hydroxyethyl) propyl-sultaine and the like, and the amidosultaines such as cocoamidodimethylpropylsultaine, stearylami~odimethyl propylsultaine, laurylamido-bls-(2-hydroxyethyl) propyl-sultaine, and the like.
~ .,, ~S~ JBP 138 The preferred phosphobetaines include lauric myristi~
amido 3-hyd~oxy~ropyl phosphobetaine, coc~mido disodium 3-hydroxypropyl phosphobetaine, lauric myristic amido disodium 3-hydroxypropyl phosphobetaine, lauric myristic 5 amido glyceryl phosphobetaine, lauric myristic amido carboxy disodium 3-hydrox~propyl phosphobetaine, and the like. The preferred phosphitaines include oocoamido propyl monosodium phosphitaine, lauric myrlstic amido propyl monosodium phosphitaine and the like.
The preferred n-alkylamuno propionates and n-alkylimino dipropionates include those o~ the ~ollowing structures:
and ~ CH2 - C~2 - coo~3 R - ~N
H CH2 - CH2 - COO Na wherein R is from about 8 to 22 carbon atoms and mixtures thereof. The ampho~eric detergents may be present in an 15 amount from about 2 to 10% by weight of the total compo-sition.
It is envisioned that any anionic surfactant may be used in the compositions of the invention such as, for example, 20 an alkyl sulfate of the foxmula R-C~2-OS~3X, an alkylether sulfate of the formula R(OCH2CH2)-OSO3X, an alkyl~ono-glyceryl ether sulfonate of the formula R-OCH2-CH-CH2-SO3X, OH
an alkylmonoglyceride sulfate of the formula5 RCOaCH2-CH-C~2OSO3X, an alkylmonoglyceride sul~onate of OH
the formula RCOQCH2CX-CH2SO3X, an alkyl sulfonate of the OH
11~56$~.3 ~BP 138 formula RSO3X, an alkylaryl sulfonate of the formula R
~ _ SO3X
an alkyl ulfosuccinate o~ the for~ula O O
R-C~2-O-C-C~-CH2-~-OX, an alkyl sarcosinate of the formula ~O3X
O CH
l 1 3 R-C-N-C~2-CQOX, an acyl isethionate of the formula 5 R-C-O-CH2CH2S03X, an alkyl methyl tauride of the foxmula O C~
Il 1 3 R-C-N CH2-CH2-SO3X, a fatty acid protein condensate of the o R' O R"
Il I ~1 1 ~
formula RC~(N~-C~-C-~H-~)r-COOX, an alcohol ether carboxy-late of the ~ormula RO(CEI2CHzO)q~CH2CO2X and the like, wherein R is higheralkyl having from 7 to 17 carbon atoms;
10 R' and ~" are m~mbers each selec~ed from the group con-sisting of hydrogen, loweralkyl, hydroxyloweralkyl, thioloweralkyl, carboxyloweralkyl, am~noloweralkyl, benæyl, and p-hydroxybenzyl; ~ is a me~ber selected from the group consi$ting of alkali metal ions, alkaline ear~h 15 metal ions, ammonium ions, and am~onlum ions substituted with fxom 1 to 3 loweralkyls; p is an integer ~rom about 3 to about 6; q is an integer from 2 to 6 and r i5 an integer from 2 to 10.
20 The preferred t~pe of a~ionic surfactant is an alkyl ether sulfate, more preferably sodium tridecylalcohol ether sulfate i~ which p is 1 to 5. The anionic detergent may be present in anamount of from about 2 to 10~ by weight of the total composi~ion.
1~5~9 J~P 138 Nonionic detergents which are u~eful include the alkylene oxide ethers of phenols, ~atty alcohols, and alkyl mercaptans; the alkylene oxide esters of fatty acid amides;
the condensation products of e~hylene oxide with par~ial S fatty acid esters, and mixtures thereof. The polyoxy-alkylene chain in such agPnts may contain from 5 to 100 alkylene oxide uni~s in which each alkylen~ unit has from
2 to 3 carbon atoms.
10 The preferred nonionic surfac~ant in the composi~ions of the invention i5 a water-soluble polyoxye~hylene derivative of a hydrophobic base, said derivative being a member of the group consisting o ~he reaction products of 9-20 carbon atom fatty acid monoesters of aliphatic polyhydric 15 alcohols, which polyhydric alcohols con~ain at least 3 hydroxyls, with at least 10 moles of ethylene oxide, and preferably with from about 10 to about 100 moles of ethylene oxide.
20 The nonionic surfactant may be present in an amount of from about 2 to 30~ by weight of the total composition.
Cationlc surfactants suitable in these compositions include ~o- and bis-quaternary ammonium halides such as 25 stearyldimethylbenzylamm~nium chloride, cetyltrimethyl-ammonium chloride, N,N-dioctadecyl-~,N,~ '-tetramethyl~
1,5 (3 oxapentylene~di ammonium bromide; ter~iary amine salts such as cocamidopropyldimethylamine hydrochloride stearylamidopropyldimethylamlne citrate; cationic polymers 30 such as hydroxyethyl cellulose reacted wi~h epichloro-hydrin and then guaternized with trimethylamine.
(Polymers of this type are sold by Union Carbide under ~he tradename Polymex JR.) The cationic surfac~ants should be present in an amount of fro~ about 1 to 5% by weight of the 35 total composition.
~ 5~5g J3~ 138 The total amount of the act've sur~actant ingredients in the present in~ention should no~ be greater than about 50% by weight of the ~otal composition in order to avoid ocular irritation probLems, preferably from about 10 to 5 30% by weight of the ~otal composition wi~h the proviso that the total amount of anionic surfactant and ampho-teric surfactant should not exceed 15% by weight of the total composition.
lO In addition, other ingredien~s conventionally added to sur-fa^tant compositions for personal use, such as dyes, preservatives, perfumes, thickeners, opacifiers, condi-tioners, emollients, bufering ag~nts, and ~he like, may be added in minor amounts. Ingredients such as dyes, 15 preservatives and perfumes together usually constitute less than 2% by weight of the total composition and thickeners may be added to the composition in an amount of from about 1 to about 3% by weight of the total composition.
20 The cleansing and conditioni~g ~urfactant compositions of the presen~ invention may be concentrate compositions which are subsequently modified by dilution with water or other diluents to provide the u}timate compositions for use ox they may be the ultimate cleansing compositions to be 25 employed without modification. The compositions of the ~resent in~ention are use~ul ir. con~.itionins ~ompositions, shampoo and conditioning formulations and cr~me rinses and they may also be used as liquid soaps and cleansers such as baby bath compositions, in bubble bath compositions, 30 as well as in compositions suitable for cleansing animals and inanimate o~jects.
The aforementioned clea~sing and conditioni~g sur~actant compositions are prepared by admixing the triesters of phosphoric acid with the other sur~actant(s), i~ utilized, at room temperature or slightly elevated temperatures (about 50C) and then sufficient deionized water is added to ~ring th~ composition to about three-quarters of its intended wei~ht. The pH is adjusted to within the range of ~ to 9, pre~erably 6 ~O 8 , by adding s~rony acid, e.g., ~Cl, or strong base, e.g., ~aOH, as needed~
' O
Other ingredients such as viscosity builders, preserva-tives, dyes, perf~umes and the like are incorporated prior to adjusting the pH and adding the remainder o~ the water.
The cleansing and conditioning suxfactant co~positions of the present invention can be tested for ocular irritation by the following modified Draize Tes~ ~J.R. Draize et al., Toilet Goods Assn. No. 17, May 1952, No. 1~ Proc. Sci.
Sect.).
An O.1 ml. sample of a neutral composition under test is dropp~d into one eye of an albino rabbit r the other eye serving as a control. Six rab~its are employed for each composition. Obs~rvations are made after 1, 24, 48, 72 and 96 hours and 7 days after ini~ial instillation; second and third instillations are made after the 24 and 48 hour readingsO Results may ~ary from substantially no change or only a slight irritation in the appearance of the rabbit's eye after 7 days to severe irrita~ion ~nd/or complete corneal opacity. Ocular lesions are scored for the cornea~ iris and conjunctiva with a higher number indicating grea~er ocular irritation and the scores are added to give a total numerical value for each reading for six rabbits and a~eraged. 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 b~.
~ $ ~ 5 9 ~T~P 138 The conditioning properties of wet comb out, hair manage~
ability, 1US~QX~ body and dry hair feel can be evaluated in salon studies o~ the following nature.
A panelist's haix is rinsed and divided into two equal parts starti~g from the center of the forehead to the center of the nape of the nec~. A specific amoun~ of the test composition is applied to one po~tion of the hair and an equal amount of a control composition is lO applied to the other portion af the hair. The compositions are worked into the hair and characteristics noted and then carefully rinsed insuring that the water from one portion of the hair does not mix with the other portion of the hair. The rinseabili~y characteris~ics are noted.
15 The wet combability is e~aluated by passing a separate comb through each portion of the hair from the center part to the ends of the hair shafts. After the hair is dried, dry combability, flyaway control, hair manageability, lustre, body and dry hair feel are all e~aluated.
All of these properties are subject7vely evaluated on a scale of 1 (very poor) to 7 (excellent) by trained and experienced evaluators.
25 Specific embodiments of the cleansing and con~itioning compositions prepared in accordance with the present invention are illustrated by the following representative exa~ples. It will be understood, however, that the invention is not confined to the specific limitations s~t 30 foxth in the individual examples, but rather to the scope of the appended claims.
EXAMPLE I
A conditioning creme rinse com~osition is pre-35 pared by charging 200 grams or deionized water to a vesselequipped with a mechanical stirrer to whicn 10 grams of ` 1~65~5~ J~P 13~
hydroxyethyl cellulose are the:n added and the mixture is then heated to 70C. 20 grams of Compound A are then added followed by 5 grams o~ stearyl alcohol and 0.2 grams of dye. ~he mixture is ~ooled ~o 35C and the pH
is adjusted to 5.0 with citxic acid. 2 grams of fragrance and sufficient deionized water to bring the total mixture to 1000 grams are then added resulting in a composition consisting of the following ingredients:
% w/w 10 Compound A 2.00 stearyl alcohol.50 hydroxyethyl cellulose 1.00 dye .02 fragrance .20 deionized water q.s. to 100%
pH adjusted to 5.0 with citric acid Salon studies show this composition to be a good condi-tioning creme rinse composition with enhanced wet comb-out.
EXAMPLE II
. . _ A conditionïng shampoo composition is prepared in accordance with the general pr~cedure of EX~MPLE I and consists of the following ingredients:
% wt/wt Compound B 0.10 Compound A 2.00 sodium lauryl ether sulfate 12.00 lauric diethanolamide 4.00 dye .01 fragrance .20 deionized waterq.s. to 100 pH adjusted to 7.5 with HCl Salon studies show this composition to be a good condition-ing shampoo composition exhibiting good foaming, cleans-3s ing and conditioning.
:l ~656~9 EXAMPLE IIIA creme rinse shampoo composition is prepared in accor-dance with the general procedure of EXAMPLE I and con-sists oE the following ingredie~ts:
% W/W
Compound C 3.00 Polymer JR-400 (Union Carbide's .50 trademark for water soluble cationic cellulose ethers having a chain of anhydro glucose units with side groups containing quaternary ammonium substituents amidobetaine S.00 sodium tridecyl (4) ether sulfate 5.00 dye .02 Dowicil 200 (Dow Chemical Company's .20 trademark for the cis isomer of 1~ t3-chloroalkyl)-3,5,7-triaza-1-azoneadamantine chloride) fragrance .20 deionized water q.s. to 100%
pH ad~usted to 6.5 with citric acid.
Salon studies show this composition to provide good cleansing and detangling of the hair.
EXAMPLE IV
A pour-on creme rinse conditioner compo~ition ls prepared in accordance with the general procedure of EXAMPLE I and consists of the following ingredients:
~.~65~ J~ 138 ~ ~/w Compound C 1.10 ethyl, n,n-dihydroxypropyl- 0.55 4-aminobenzoate benzyl alcohol 0.55 stearyl alcohol 0.88 isostearyl alcohol 0~33 hydroxyethyl celluLose 0.88 sodium hydroxide 0.02 deionized water q.s. to 100%
The above composition when ~ested for ocular irritation in accordance with the previously described m~dified Draize test is found to be a slight irritant.
EXAMPLE V
~ fine fabric detergent and softener composition is pre-pared consisting of the following ingredients:
~ w/w linear dodecylb~nzene sulfonate 8.00 Compound G 3.00 coconut monoethanolamide 2.00 citric acid 10.00 optical brightener.50 isopropanol 1.00 dye .02 fragra~ce .10 deionizad waterq.s. to 100%
pH adjust~d to 5. a with citric acid.
The composition of EXAMPLE V:is evaluated for deterg~ncy and softening properties u~ilizing the following procedure:
Standard soiled wool ~abric, from Test Fabrics, Inc., i~
35 used to evaluate the relative cleansing ~bility of a given 116~59 J3P 138 composition~ A Texg-O-Tometer, ~odel 7243, is used to simulate the cleansing action. The conditions are controlled as follows:
1. washing time (5 minutes) 2. was~ing speed (lO0 ~pm.)
3. rinsing time (5 minutesj
4. rinsing speed (lO0 rpm)
5. wash and rinse temperature (105F) The test cloth is made ~rom wool challi and comes i~ ten-yard rolls. A ~oil mix~ure, con~is~ing mainly of lamp ~lack, oils and commercial solvents, is appli~d ~o the clo h with a printing roll 50 that only half of the 8 inch wide cloth becomes soiled.
lS This ~est cloth is cut into 4 x 8 inch strips so that half of each strip is soiled and half unsoiled. A Gardner Color Difference Meter i~ used to ob~ain the initial color value (degree of white~ess) for both thé soiled and unsoiled portion of each strip~ Three of these strips along with three 4 x 8 inch cotton filler strips are placed in the Terg-O-Tometer beaker containing lO00-ml. of a 10~ ~queous solution of the te~t compositio~. Prior to this, ~he . solution is agitated for two mlnutes and allow~d to equilibrate at 105~. The samples are agita~ed ~or ~i~e munutes, removed, squeezed out, and returned to the agi~a~ing bea~ex containing 1000 ml. of clean 105F tap water. After five mlnutes o~ agitating, the strips are removed, squeezed ou~ nd laid flat to dry. When dry, they are again evaluated usi~g the rolor Difference Meter to determinQ how mllch æoil has been remo~ed as well as how much soil has been deposited on ~he unsoiled por~ion of the cloth. The relati~e cleansing effecti~eness is indicated by the spread between the initial and fin~l whiteness measuremen~s which is chaxacterized ~5 a R.
A /\R of two uni~s is considered signi~icant. To ~ 9 3BP 138 19.
determin2 ssftness, panelists are asXed to choose the fabrics which are softer to the hand from paired groups containing fabrics treated with the test composition and fabrics treated with the control composition.
When the composition of this examplQ is e~aluated as above, it is found ~o pro~ide good cleaning and softening to the test fabrics.
EX~MPLE YI
A ~ild shampoo and conditioning composition i~ prepared consisting of the ~ollowing ingredients ~ '~7/W
Compound E 1.00 Polymer JR-400.20 betaine 5.00 sodium lauryl (3) ether sulfate 5.00 polyoxyethylene 80 SML10.00 Dowicil 200 .10 dye .02 fragrance .30 ` deionized waterq,s.tO 100%
p~ adjusted to 7.0 with citric acid The above composition is ~ound to be a good shampoo and conditioning composition.
EXAMPLE VII
A mild gel shampoo and conditioning composition is 30 prepared consisting of he following ingredients:
~ 56~ J~P 138 .~
~mldo sultai~e 5.0 betaine 5.0 tridecyl (4) ether sul~ate10.0 S polyoxyehtylene (80) sorbitan monopalmita~e 20.0 dye, preservative Compound ~ 1.0 Compound D 1.0 Dowicil 200 .10 dye .02 fragrance .20 deionized water g.s. to 190%
pH adjusted to 7.0 wi~h citric acid The above composition ~s found to be a good shampoo and conditioning composition.
Various other features and e~bodimenks of the present invention not speci~ically enumerated will be obvious to those skilled in the art, all of which may be achieved without departi~g from the spirik and the scope of the invention as defined ~y the following claims.