United States Patent
`
`1191
`
`[11] Patent Number:
`
`5,037,818
`
`[45] Date of Patent:
`Aug. 6, 1991
`Sime
`
`[54] WASHING COMPOSITION FOR THE HAIR
`Stuart J. Sime, South Wirral, United
`Kingdom
`.
`
`Inventor:
`
`[75]
`
`[73] Assignee:
`
`Chesebrough-Pond’s USA Co.,
`Division of Conopco, Inc.,
`Greenwich, Conn.
`
`[21] Appl.No.: 225,605
`
`[22] Filed:
`
`Jul. 26, 1988
`
`4,470,982
`
`9/1984 Winkler ............................... 424/245
`
`FOREIGN PATENT DOCUMENTS
`
`406375 11/1968 Australia ............................. 252/106
`.. 252/106
`18717 11/1980 European Pat. Off.
`.. 424/245
`0034846 9/ 1981 European Pat. Off.
`.. 252/106
`60611
`9/1982 European Pat, Off.
`.. 424/245
`0093541 11/1983 European Pat. Off.
`55-116800 9/1980 Japan ............................ 252/106
`2107586
`5/1983 United Kingdom ................ 424/245
`
`
`
`OTHER PUBLICATIONS
`
`Related US. Application Data
`
`Norda Briefs, No. 464, Feb. 1975.
`
`[63]
`
`Continuation of Ser. No. 07/038,435, Apr, 13, 1987,
`abandoned, which is a continuation of Ser. No.
`06/488,513, Apr. 25, 1983, abandoned.
`
`Foreign Application Priority Data
`[30]
`Apr. 30, 1982 [GB] United Kingdom ................. 8212687
`
`[51]
`
`Int. Cl.5 ......................... A61K 7/06; A61K 9/08;
`A61K 31/33; A61K 31/395
`[52] US. Cl. .................................... 514/183; 252/106;
`252/ 107; 252/542; 424/70; 424/78; 424/80;
`514/881
`
`[58] Field of Search ................... 424/245, 70; 514/183
`
`[56]
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`3,489,686
`1/1970 Parran, Jr.
`.......................... 424/245
`
`3,549,546 12/1970 Moore .............. 252/542
`
`...... 252/106
`3,580,853
`5/1971 Parran
`.............. 252/106
`3,761,417
`9/1973 Parran
`
`.............. 252/106
`3,761,418
`9/1973 Parran
`
`1/1974 Grand .............. 424/245
`3,785,985
`1/1975 Furia et a1.
`.......................... 424/245
`3,862,151
`
`Prima'ry Examiner—Dale R. Ore
`Attorney, Agent, or Firm—Milton L. Honig
`
`ABSTRACT
`[57]
`The invention concerns a washing composition for
`washing a surface to deposit thereon substantially wa-
`ter—insoluble particles. The aqueous washing composi-
`tion of the invention comprises an anionic surfactant,
`the particulate substance to be deposited and a water-
`soluble cationic non-cellulosic polymer which enhances
`the deposition of the particulate substance onto the
`surface but which cationic polymer does not form in the
`composition a water-insoluble complex with the anionic
`surfactant, the cationic charge density of the polymer
`being from 0.0001 to 0.0017; the concentration of the
`cationic polymer in the washing composition being
`from 0.0001%_to 0.01% by weight; and the concentra-
`tion of the surfactant in the washing composition being
`from 0.01% to 5% by weight.
`'
`
`1 Claim, 3 Drawing Sheets
`
`50
`
`L0
`
`302
`
`Q2
`
`:U1
`
`‘
`
`8E
`
`S 20
`._.
`
`Z ‘
`
`15o:
`if
`
`10
`
`-l+
`
`-3
`
`'2
`
`-1
`
`1.0610(91'1 JAGUAR c-13-S)
`
`UNL 1028
`
`1
`
`

`

`US. Patent
`
`Aug. 6, 1991 ‘
`
`Sheet 1 of3
`
`5,037,818 E
`
`Fig. 7.
`
`DEPOSITION
`
`PERCENT
`
`L0(310(gl'1 JAGUAR C-13-S)
`
`2
`
`

`

`US. Patent
`
`.
`
`Aug. 6, 1991
`
`Sheet'20f3
`
`5,037,818
`
`DEPOSITION
`
`PERCENT
`
`-2
`
`-1
`
`LOG10 (MOLAR CONCENTRATION SODIUM LAURYL SULPHATE)
`
`3
`
`

`

`US. Patent
`
`Aug. 6, 1991
`
`Sheet 3 of 3
`
`5,037,818 .
`
`Fig.3.
`
`50
`
`U.)C
`
`
`PERCENTDEPOSITION NO
`10
`
`-3
`
`-2
`
`-I
`
`LOG10 IMOLAR CONCENTRATION SURFACTANTI
`
`4
`
`

`

`5,037,818
`
`1
`
`WASHING COMPOSITION FOR THE HAIR
`
`This is a continuation application of Ser. No. 038,435
`filed Apr. 13, 1987, which is a continuation of Ser. No.
`488,513, filed Apr. 25, 1983 both now abandoned.
`This invention relates to a washing composition for
`washing a surface to deposit thereon water-insoluble
`particles, such as particles of a solid antimicrobial sub-
`stance or the liquid particles of an emulsified oil. In
`particular the invention relates to an aqueous washing
`composition comprising an anionic surfactant, the wa-
`ter-insoluble particles and a cationic polymer which
`serves to enhance the deposition and retention of the
`particles on the said surface.
`for example shampoos,
`Detergent compositions,
`comprising an anionic surfactant, water-insoluble parti-
`cles and a cationic polymer have been described in U.S.
`Pat. No. 3,580,853 (Parran). In the detergent composi-
`tions described in that patent the cationic polymers are
`water-soluble cationic nitrogen-containing polymers
`having a molecular weight within the range from 2,000
`to 3,000,000 and have a cationic charge density greater
`than 0.001 in aqueous solution. The “cationic charge
`density” of a polymer as that term is used in said U.S.
`Patent, and as used herein, refers to the ratio of the
`number of positive charges on a monomeric unit of
`which the polymer is comprised to the molecular
`weight of said monomeric unit. The cationic charge
`density multiplied by the polymer molecular weight
`determines the number of positively charged active sites
`on a given polymer chain. The Parran patent states that
`the cationic polymer can be employed in the detergent
`composition at a concentration within the range from
`about 0.1% to about 10% by weight, preferably from
`about 0.25% to about 4.0% by weight.
`'
`The Applicant has investigated the mode of action of
`the enhancement of deposition from liquid detergent
`compositions of the Examples of the Parran patent con-
`taining an anionic surfactant and it appears that the
`enhancement is dependent upon the precipitation upon
`dilution of the detergent composition to form an aque-
`ous washing composition of a complex formed between
`the anionic surfactant and the cationic polymer. The
`formation of complexes between cationic polymers and
`anionic surfactants is well-known and is described in
`Norda Briefs, No. 464, February 1975. This article men-
`tions that such complexes may be solubilised at
`in-
`creased surfactant levels and also refers to the deposi-
`tion of the water-insoluble complex onto the hair during
`the shampooing process. The Norda Briefs article refers
`in particular to- those complexes formed using the qua-
`ternary nitrogen-substituted cellulose ether derivatives
`(available commercially under the trade name Polymer
`JR) which the Parran patent states are particularly effi-
`cacious for enhancing the deposition of particulate sub-
`stances. Applicant’s experiments have indicated that in
`the Parran formulations comprising an anionic surfac-
`tant, complexes between the cationic polymer and ani-
`onic surfactant precipitate, or separate upon dilution
`during use and that it is essential for this to occur if an
`enhancement in the deposition of the particulate sub-
`stance is to be obtained from the Parran compositions
`containing an anionic surfactant. While precipitation of
`the complex and its deposition onto the hair may give a
`benefit in its own right, for such deposition leads to
`improved hair condition, more particularly improved
`ease of combing, such deposition of substantial amounts
`
`5
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`15
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`
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`
`65
`
`2
`of cationic polymer is not always desired by the user. It
`is known for example from European Patent Applica-
`tion No. 80300940 (Publication No. 0 018 717) that
`deposition of a cationic derivative of a polygalactoman-
`nan gum onto the hair during shampooing gives condi-
`tioning effects.
`Applicant has now found that the presence of certain
`cationic polymers in aqueous washing compositions
`comprising an anionic surfactant can enhance the depo-
`sition of water-insoluble particles in the absence of the
`precipitation of a cationic polymer-anionic surfactant
`complex.
`According to the invention there is provided an aque-
`ous washing composition for washing a surface to de-
`posit
`thereon substantially water—insoluble particles
`comprising an anionic surfactant, the particulate sub-
`stance and a water-soluble cationic non-cellulosic poly-
`mer for enhancing the deposition, of the particulate
`substance onto the surface but does not form in the
`composition a water-insoluble complex with the anionic
`surfactant, wherein the cationic charge density of the
`polymer is from 0.0001 to 0.0017; the concentration of
`the cationic polymer in the washing composition is
`from 0.0001% to 0.01% by weight; and the concentra-
`tion of the surfactant in the washing composition is
`from 0.0% to 5% by weight.
`The cationic polymer employed in the washing com-
`position of the invention is a non-cellulosic polymer
`having a cationic charge density of from 0.0001 to
`0.0017 in aqueous solution. In the detergent composi-
`tions of the Parran patent the polymers employed have
`a cationic charge density greater than 0.001 and the
`lowest specific cationic charge density mentioned is
`0.002 for the cellulosic polymer employed in Example
`XII of that patent. It is to be noted in particular that
`non-cellulosic polymers having a cationic charge den-
`sity of 0.0001 to 0.001 are useful in washing composition
`of this invention but are excluded from the Parran in-
`vention. The cationic polymers employed in this inven-
`tion have a molecular weight within the range from
`about 2,000 to about 3,000,000 as in the Parran inven-
`tion.
`The non-cellulosiccationic polymers employed in the
`washing composition of the present invention are pres-
`ent in a concentration of from 0.000% to 0.01% by
`weight. Below 0.0001% a less satisfactory degree of
`deposition is obtained and above about 0.01% it may
`not be possible to avoid the separation of a polymer-sur-
`factant complex. We have found that the amount of
`particulate substance deposited onto the substrate is
`dependent upon the concentration of the polymer in the
`aqueous washing composition.
`The preferred cationic polymer for use in the wash-
`ing composition of the invention is a cationically-sub-
`stituted galactomannan gum. The gum occurs naturally
`as guar gum, the principal component of the seed ofthe
`guar plant, cyamopsis tetragonalobus. The guar mole-
`cule is essentially a straight chain mannan branched at
`quite regular intervals with single membered galactose
`units on alternative mannose units. The mannose units
`are linked to each other by means of beta (1—4) glyco-
`sidic linkages. The galactose branching is accomplished
`through an alpha (1—6) linkage. Thecationic derivatives
`are obtained by reaction between the hydroxyl groups
`of the polygalactomannan and reactive quaternary am-
`monium compounds. The degree of substitution of the
`cationic groups is sufficient to provide a cationic charge
`density of 0.0001 to 0.0017. The quaternary ammonium
`
`5
`
`

`

`3
`compounds which can be used for preparing the cati-
`onic agents employed in this invention are those of the
`general formula
`
`4
`bon atoms in the alkyl group. The ether sulphates may
`contain an average of from 1 to 10 oxyethylene groups
`in the molecule. These can be used in the form of their
`
`5,037,818
`
`RI
`1
`R4fNT—R2
`3,;
`
`2‘
`
`where R], R2 and R3 are methyl or ethyl groups and R4
`is an epoxyalkyl group of the formula
`
`
`H3C
`
`\/
`0
`
`CH-RS—
`
`or halohydrin group of the formula
`
`X—CHz—(IJH-Rs-
`on
`
`where R5 is a C1—C3 alkylene group and X is chlorine
`or bromine, Z being an anion such as C1—, BR‘, 1‘ or
`HSO—4.
`These reagents would lead to the formation of a ga-
`lactomannan derivative of the formula
`
`Rl
`l
`R—O—CHz-CH—R5—T+—Rl
`OH
`R3
`
`2“
`
`where R represents guar gum.
`An example of a suitable quaternary ammonium de-
`rivative is hydroxypropyltrimethylammonium guar
`gum of the formula
`
`R~O—CH1—CH—CHZl ' *tCH3)3Cl_
`IOH
`
`l0
`
`15
`
`20
`
`25
`
`30
`
`35
`
`Such a material is available commercially from Cela-
`nese-Stein Hall, U.S.A. under thename JAGUAR C-13-
`S; the word JAGUAR is a trade mark. This material 45
`also has the CTFA designation Guar Hydroxypropyl-
`trimonium Chloride. JAGUAR C-13-S has a cationic
`
`charge density of 0.0008. Another suitable material is
`that known as JAGUAR C-l7 which is similar to JAG-
`UAR C-13-S but has a higher degree of substitution of
`cationic groups and has a cationic charge density of
`0.0016. A further example of a suitable guar derivative
`is
`the hydroxypropylated cationic guar derivative
`known as JAGUAR C-l6 which as well as containing
`the above cationic quaternary ammonium groups also
`contains hydroxypropyl (—CH3CH(OH)CH3) substitu-
`ent groups. JAGUAR C-16 has a cationic charge den-
`sity of approximately 0.0008, the degree of substitution
`of the hydroxypropyl groups being 0.8-1.1.
`Other suitable cationic polymers are copolymers of
`dimethylaminoethylmethacrylate and acrylamide and
`copolymers of dimethyldiallylammonium chloride and
`acrylamide in which the ratio of the cationic to neutral
`monomer units has been selected give a copolymer
`having a cationic charge density in the required range.
`Suitable anionic surfactants for use in the aqueous
`washing compositions of the invention include alkyl
`sulphates and alkyl ether sulphates having 8 to 20 car-
`
`50
`
`55
`
`60
`
`65
`
`sodium, potassium, ammonium or lower alkanolamine
`(eg mono-, di- or triethanolamine) salts.
`Further suitable anionic surfactants include the so-
`
`dium or potassium alkyl benzene sulphonates, in which
`the alkyl group contains from about 9 to about 15 car-
`bon atoms; sodium alkyl glycerol ether sulphonates;
`sodium coconut oil fatty acid monoglyceride sulphates
`and sulphonates; sodium salts of sulphuric acid esters of
`the reaction product of one mole of a higher alcohol
`(tallow or coconut oil alcohols) and about 3 moles of
`ethylene oxide; the sulphosuccinates; and the water~sol-
`uble salts of condensation products of fatty acids with
`sarcosine. Conventional soaps may also be used as the
`anionic surfactant.
`
`Other types of surfactants may be optionally included
`in the washing composition of the in‘ventidn. Such other
`surfactants include the amphoteric and non-ionic sur-
`factants.
`
`Amphoteric surfactants are a well known class of
`surfactants which includes the alkyl beta-iminodipro-
`pionates RN(C2H4COOM)2 and the alkyl beta-amino-
`propionates RNHCH4COOM where the alkyl group R
`contains 8 to 18 carbon atoms in both formulae and M is
`a salt-forming cation such as the sodium ion. Further
`examples are the long chain imidazole derivatives, for
`example the di-sodium salt oflauroyl—cycloimidinium-l-
`ethoxy-ethionic acid-Z-ethionic acid, and the substituted
`betaines such as alkyl dimethyl ammonio acetates where
`the alkyl group contains 12 to 18 carbon atoms.
`Suitable non-ionic surfactants include the polyox-
`yethylene-polyoxypropylene condensates, which are
`sold under the trade name “Pluronic”; polyoxyethylene
`condensates of alkyl phenols; polyoxyethylene conden-
`sates of aliphatic alcohols having 8 to 18 carbon atoms,
`e.g. coconut alcohol/ethylene oxide condensates hav-
`ing from 10 to 30 moles of ethylene oxide per mole of
`coconut alcohol; polyoxyethylene condensates of sorbi-
`tan fatty acids; alkanolamides, such as the monoalk-
`anolamides, dialkanolamides and the ethoxylated al-
`kanolamides, for example coconut monoethanolamide,
`lauric isopropanolamide and lauric diethanolamide; and
`amine oxides, for example dodecyldimethylamine ox-
`ide.
`
`In the aqueous washing composition of the invention
`the formation of a water-insoluble complex between
`the cationic polymer and anionic surfactant is avoided.
`The maintenance of such a soluble system is favoured
`by the use of cationic polymers of low cationic charge
`density, use of low polymer concentrations and use of
`high surfactant concentrations. Satisfactory combina-
`tions of cationic polymer and anionic surfactant are
`readily found within the ranges set forth above and if,
`with a given combination of cationic polymer and ani—
`onic surfactant within these ranges a complex tends to
`separate out, variation of the polymer and/or surfac-
`tant, for example variation of their relative concentra-
`tions, will readily ensure that the combination meets the
`requirements of the present invention. Generally it is
`only necessary to avoid the use of the lower surfactant
`concentrations with the higher concentrations of the
`more cationic polymers.
`The nature of the water-insoluble particles employed
`in the aqueous washing composition is not critical and a
`wide variety of materials can be deposited onto various
`
`6
`
`

`

`5
`substrates from washing compositions in accordance
`with the invention. The essential requirement is that the
`material of the particles should be insoluble or at most
`onl'y sparingly soluble in water. Materials which it is of
`practical benefit to deposit on substrates are mentioned
`in the Parran patent and these can also be employed in
`the aqueous washing compositions of this invention.
`These include substances having an average particle
`diameter of from about 0.2 to about 50 microns and they
`may be anti-microbial agents, sunscreens, fabric bright-
`eners, and various substances that create a favourable
`skin feel after washing. One class of particulate sub-
`stances mentioned in the Parran patent that are of spe-
`cial interest are the salts of pyridinethione (also known
`as 2-pyridinethiol-l-oxide). The water-insoluble or spar-
`ingly water-soluble substance may be employed in the
`washing composition in an amount of from 0.001% to
`about 1% by weight.
`The washing composition of the invention may take
`the form of a shampooing composition for the shampoo-
`ing of hair on the head wherein the water—insoluble
`particles comprise particles of an anti-microbial agent,
`particularly a pyridinethione salt, especially zinc pyri-
`dinethione or zirconium pyridinethione. However,
`other shampooing compositions may include particles
`of a water~insoluble oil having hair conditioning attri-
`butes, such oil being emulsified in the composition with
`the aid of suitable emulsifying agents. The washing
`composition of the invention may also be one suitable
`for the washing of fabrics, where the aqueous washing
`composition comprises particles of a fabric conditioning
`or treating agent, for example an acrylic latex; or for the
`washing of hard-surfaces where the aqueous cleaning
`composition may comprise a germicide, as in, for exam-
`ple, compositions for the cleaning of toilets, or it may
`comprise a polymer latex designed to leave a polymer
`film on the cleaned surface, for example to provide a
`glossy appearance to the surface, or it may comprise a
`perfume oil. The washing composition of the invention
`may also find application in the field of oral hygiene
`where the deposition during use of an oral treatment
`composition of particles consisting of or comprising an
`active compound for the care of the oral cavity, includ-
`ing the teeth, may be beneficial.
`In the use of the washing composition according to
`the invention the measure of the enhancement of the
`deposition of the particulate material is dependent on a
`number of factors. For a given cationic polymer and a _
`given anionic surfactant,
`the degree of deposition is
`dependent on both the concentration of the polymer
`and on the concentration of the surfactant. There will
`be a wide range of conditions over which the enhance-
`ment is obtained and by simple experimentation those
`conditions favouring optimum deposition can readily be
`determined. This variation is illustrated with reference
`to specific washing compositions given hereinafter. It is
`believed that the cationic polymer forms, at certain
`surfactant concentrations above the critical miscelle
`concentration,- a coating on the surface of the water-
`insoluble particles which does not lie close to the sur-
`face of the particles but has loops which extend into the
`detergent solution and that these loops, because of the
`positive charges along the polymer chain, provide brid-
`ges for attachment to negative sites on the substrate. It
`should be noted however that the particles will have a
`net negative charge due to the presence of the anionic
`detergent. This fact is readily demonstrated by the mi-
`croelectrophoresis technique. However, the Applicant
`
`5
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`
`65
`
`5,037,818
`
`6
`has discovered that in spite of the net negative charge
`the cationic polymer can substantially enhance the de-
`position of the particles onto a negatively charged sub-
`strate within the range of conditions described herein.
`With regard to the above it has to be pointed out that
`the belief expressed in the Parran patent that the cati-
`onic polymer imparts a net positive charge to the in-
`volved particles is incorrect in the case of those compo-
`sitions where the detergent comprises an anionic deter-
`gent as in the shampoo compositions described in the
`Parran patent.
`According to another aspect of the invention there is
`provided a shampoo for washing hair on the head
`which upon dilution 10 times with water furnishes an
`aqueous washing composition for washing hair in ac-
`cordance with the invention and comprising the anionic
`surfactant in a concentration of 0.8 to 2.5% by weight.
`The surfactant of the shampoo is preferably an alkyl
`sulphate or alkyl ether sulphate, present in the shampoo
`in an amount of 8 to 25 % by weight. As the particulate
`substance, an antimicrobial substance is preferably used,
`especially zinc or zirconium pyridinethione in an
`amount of 0.1 to 3 % by weight.
`According to a further aspect of the invention there is
`provided a detergent composition for cleaning fabrics
`which upon dilution 250 times with water furnishes an
`aqueous washing composition for washing fabrics in
`accordance with the invention,
`the particulate sub-
`stance consisting of a fabric conditioning or treating
`agent.
`The invention also relates to a method of washing a
`surface to deposit thereon substantially water-insoluble
`particles which comprises contacting the surface with
`an aqueous washing composition in accordance with
`the invention.
`.
`The following experiments illustrate the invention.
`Percentages are by weight.
`The following description includes accounts of ex-
`periments involving the deposition onto various sub-
`strates of particles of polystyrene from a polystyrene
`latex and particles of zinc pyridinethione, respectively,
`from an aqueous washing composition containing the
`respective particles. Methods that were used for deter-
`mining the degree of deposition of these particles will
`first be described.
`
`In these experiments there was used either a polysty-
`rene latex comprising polystyrene particles of diameter
`about 0.5 micron and having a solids content of 10%, or
`a 50% aqueous suspension of zinc pyridinethione parti-
`cles. Adsorption of particles onto a substrate was moni—
`tored by observing their depletion from the treatment
`medium using a visible spectrophotometer at a wave
`length of 410 nm. Deposition of these particles onto hair
`was carried out by the following procedure.
`Hair switches of 10 cm length and about 4 grams
`weight were made from virgin Italian ‘Blue String ’
`hair. The hair was not degreased but was extensively
`rinsed in running deionized water and combed to re-
`move easily detachable cuticle scales before use. A
`series of such hair switches which ‘had been stored in
`deionized water were blotted dry with clean cotton
`fabric. Each switch was placed in a 10 cm Petri dish
`with a lid. 5 mls of an aqueous washing composition
`containing the particles were added from a burette and
`the switch briefly probed to distribute the liquid and to
`make sure that it was all taken up into the fibre bundle.
`The suspension was left in contact with the switch for 2
`minutes and then withdrawn slowly with a plastic sy-
`
`-
`
`7
`
`

`

`5,037,818
`
`8
`thione) and remain so upon dilution demonstrating that
`no complex separates.
`EXPERIMENT 2
`
`Experiments were conducted with three other tri-
`methyl ammonium hydroxypropyl guars having cati-
`onic charge densities different from that of Jacquar
`C-13-S, namely 0.0004, 0.0016 and 0.0018. The shame
`poos tested had the following compositions:
`
`
` %
`
`___.____Shm_z____
`D
`E
`F
`G
`14.4
`4.2
`14.4
`14.4
`——
`0.01
`—
`—
`
`Ingredient
`Sodium lauryl sulphate
`Trimethylammonium
`hydroxypropyl guarl
`Trimethylammonium
`hydroxypropyl guarZ
`Trimethylammonium
`hydroxypropyl guar3
`‘— qs —>
`Polystyrene latex“
`
`Water «— to 100 —>
`
`—
`
`—
`
`—
`
`—
`
`0.01
`
`—-b
`
`——
`
`0.01
`
`101‘ cationic charge density 0.0004
`301‘ cationic charge density 0.0016 (Jaguar 017)
`3of cationic charge density 0.0018
`4sufficient latex was present to give a convenient absorbance reading
`
`The shampoos were diluted 10 times with water to
`form the aqueous washing compositions used to treat
`the hair switches in the manner described above.
`
`The results are given in Table 2.
`TABLE 2
`
`Shampoo
`‘70 Deposition
`D _
`0 -_+‘ 6
`E
`27 i 5
`F
`31 i 6
`G
`O 1‘ 3
`
`The results show that the guar derivatives having
`cationic charge densities of 0.0004 and 0.0016 were
`effective in enhancing deposition, whereas that of
`charge density 0.0018 was not effective in enhancing
`deposition.
`None of the shampoos E, F and G when diluted with
`water to give the washing compositions used to treat
`the hair switches formed an insoluble complex of the
`polymer and the surfactant.
`EXPERIMENT 3
`
`In this experiment cationic polymers other than guar
`derivatives were employed. These were the following:
`Polymer A - a quaternised copolymer of dimethylami-
`noethyl methacrylate and acrylamide having a cati—
`onic charge density of 0.0002.
`Polymer B - a dimethyldiallylammonium chloride/a-
`crylamide copolymer having a cationic charge den-
`sity of 0.0015.
`Polymer C - poly(dimethyldiallylammonium chloride)
`having a cationic charge density of 0.006.
`The following shampoos were used in this experiment.
`
`
`
` %
`
`H
`14.4
`—
`—
`
`Shampoo:
`I
`J
`14.4
`14.4
`0.01
`——
`—
`0.01
`
`K ‘
`14.4
`-—
`——
`
`Ingredient
`Sodium lauryl sulphate
`Polymer A
`Polymer B
`
`7
`ringe. The absorbance of the liquid that was withdrawn
`was then measured. The switches were cleaned by
`combing vigorously under running deionized water. It
`was demonstrated that this procedure was adequate to
`remove the adsorbed particles from the hair. The 5
`switches were stored in deionized water before reuse.
`The percentage deposition of the particles is given by
`the expression (Ao-A)>< lOO/Ao where A0 is the initial
`absorbance of the washing composition used to treat the
`hair and A is the absorbance of the treatment composi-
`tion after contact with the hair.
`
`10
`
`In those cases where the aqueous washing composi-
`tion contained both zinc pyridinethione and a suspend-
`ing agent so that where there was a co-deposited second
`phase, the extent of deposition was determined by de-
`pletion from the analysis for pyridinethione present in
`the liquid withdrawn from the treated hair switch.
`For the avoidance of doubt, it is to be understood that
`in the compositions described hereinafter references to
`zinc pyridinethione as an ingredient thereof refer to the
`50% aqueous suspension of zinc pyridinethione, and
`references to a polystyrene latex as an ingredient refer
`to the polystyrene latex comprising polystyrene parti-
`cles having a diameter of about 0.5 micron and having a
`solids content of 10%.
`
`15
`
`20
`
`25
`
`EXPERIMENT 1
`
`In this experiment the following shampoo composi-
`tions were used.
`30
`‘7c
`Shampoo:
` Ingredient A B C
`
`
`
`Sodium lauryl ether sulphate (2E0)
`11.3
`11.3
`11.3
`Zinc pyridinethione (50%)
`2.0
`2.0
`0.4
`Jaguar C-13-S
`—
`0.08
`0.04
`ZnSOi.7I-110
`0.1
`0.1
`0.1
`NaCl
`2.0
`2.0
`2.0
`Water
`~— to 100.0 —->
`
`35
`
`These shampoos were each diluted 10 times with 40
`water to form aqueous washing compositions which
`were used to treat hair switches in the manner described
`above, except
`that
`in order to obtain absorbancies
`within the range of the spectrophotometer shampoos A 45
`and B were diluted a further 10 times after deposition of
`the zinc pyridinethione and before measurement. The
`results are given below in Table 1.
`TABLE 1
`
`Amount of deposit
`relative to deposit
`_
`from Shampoo A
`% Deposition
`Shampoo
`1
`11 i 4 '
`A
`7.2
`79 -+_‘ 6
`B
`0.98
`54 t 7
`C
`55
`
`50
`
`The data show that deposition of the zinc pyridine-
`thione was considerably enhanced by the inclusion of
`the cationic polymer Jaguar C-13-S. In particular the
`results show that Shampoo C containing the cationic 60
`polymer but containing only one-fifth of the amount of
`the zinc pyridinethione present in Shampoo A depos-
`ited substantially the same amount of the particulate
`zinc compound onto the treated hair switches as did
`Shampoo A.
`Neither Shampoo B or C on dilution gave rise to a
`precipitate of a polymer—surfactant complex. The sys-
`tems are clear (in the absence of the zinc pyridine-
`
`65
`
`8
`
`

`

`5,037,818
`
`10
`
`-continued
`
`‘70
`Shampoo:
`
`Ingredient
`H
`I
`J
`K
`Polymer C
`——~
`—
`—
`0.004
`Polystyrene latexl
`<— qs —->
`
`Water ‘- to 100.0 —-v
`lsufficient latex was present to give a convenient absorbence reading.
`
`The shampoos were diluted 10 times with water to
`form the aqueous washing compositions used to treat
`the hair switches.
`
`The results are given in Table 3.
`TABLE 3
`
`
`Shampoo
`% Deposition
`H
`O i- 6
`I
`29 i 5
`J
`27 i 5
`
`K —3 i 4
`
`10
`
`15
`
`20
`
`______—___________———
`%
`_.ML09;_.
`_______—________._——————
`N
`O
`Ingredient
`Triethanolamine lauryl sulphate
`16.6
`16.6
`Lauryl isopropanolamide
`3.5
`3.5
`Ethylene glycol monostearate
`3.0
`3.0
`Jaguar C-13-S
`—
`0.04
`Zinc pyridinethione (50%)
`0.4
`0.4
`ZnSO4.7H20
`0.1
`0.1
`NaCl
`2.0
`2.0
`
`to 100.0Water to 100.0
`
`
`The shampoos were diluted 10 times with water to
`form the aqueous washing compositions used to treat
`the hair switches in the manner described above.
`The deposition of the zinc pyridinethione was deter-
`mined by analysis for pyridinethione of the liquid with-
`drawn after treatment of the hair switches since in this
`experiment the cationic polymer also enhanced deposi-
`tion of the ethylene glycol monostearate.
`‘
`The results are given in Table 5.
`TABLE 5
`
`25
`
`% Deposition of Zinc Pyridinethione
`Shampoo
`11 i 5
`N
`
`O 50 i 3
`
`3O
`
`Shampoo 0 did not give rise to the separation of a
`polymer-surfactant complex when it was diluted with
`water to give the aqueous washing composition used to
`treat the hair switches.
`
`EXPERIMENT 6
`
`The results again show that the cationic polymers of
`cationic charge density above 0.0017 are not effective in
`enhancing deposition.
`None of the shampoos I,J and K gave rise to the
`separation of a polymer-surfactant complex when di-
`luted with water to form the aqueous washing composi-
`tions used to treat the hair switches.
`
`EXPERIMENT 4
`
`The following shampoos were used in this experi-
`ment.
`
`
`‘70
`Shampoo:
`
`Ingredient
`L.
`M
`Sodium lauryl ether sulphate (3E0)
`100
`—-
`Lauryl triethoxy monosulphosuccinate
`—
`5.0
`Jaguar C-l3-S
`0.01
`0.01
`Polystyrene latex1
`~— qs —>
`
`Water ~— 100.0 —>
`Isufficient latex was present to give a convenient absorbance reading
`
`The shampoos were diluted 10 times with water to
`form the aqueous washing compositions used to treat
`the hair switches in the manner described above.
`The deposition from each shampoo was compared
`with that from the corresponding shampoo obtained by
`omitting the cationic polymer. These shampoos are
`referred to below as shampoos L' and M’, respectively.
`The results are given in Table 4.
` TABLE 4
`Shampoo
`% Deposition
`L(L’)
`60 i 3 (10 t 4)
`
`MtM') 44 z 3 (8 i 2)
`
`The effect of variation in the concentration of cati-
`onic polymer in the aqueous washing composition is
`shown by the curve of FIG. 1 of the drawings.
`The vertical axis represents the percentage deposition
`and the horizontal axis is the logarithm to the base 10 of
`the concentration in grams per liter of the cationic poly-
`mer which was Jaguar 013-5.
`The curve relates to the deposition of the polystyrene
`latex (as used in the eXperiments described previously)
`from a surfactant solution of constant concentration of
`5><10—2 moles, the surfactant being sodium lauryl sul-
`phate.
`In this experiment no separation of a polymer-surfact-
`' ant complex from the washing compositions occurred.
`EXPERIMENT 7
`
`35
`
`4O
`
`45
`
`50
`
`55
`
`The effect of varying the surfactant concentration in
`the washing composition at constant concentration of
`the cationic polymer (lO—Zgl—l) is shown in FIG. 2 of
`the accompanying drawings.
`The vertical axis is the same as that of FIG. 1 and the
`horizontal axis is the logarithm to the base 10 of the
`molar concentration of the surfactant which was so-
`dium lauryl sulphate. The curves were obtained from
`experiments in which the particles being deposited onto
`hair were those of a polystyrene latex as described
`above.
`The curves were obtained using different cationic
`polymers as follows:
`curve I~Jaguar C-l3-S
`II-Polymer A of Experiment 3
`III—Polymer B of Experiment 3.
`In this experiment no separation of a polymer-surfact-
`ant complex from the washing compositions occurred.
`
`The results show that in each case the presence of the
`cationic polymer resulted in an improvement in deposi-
`tion.
`
`Neither of shampoos L and M gave rise to the separa-
`tion of a cationic polymer-surfactant complex when
`diluted with water to form the aqueous washing compo-
`sition used to treat the hair switches.
`
`65
`
`EXPERIMENT 5
`
`The following shampoos were formulated.
`
`9
`
`

`

`5,037,818
`
`12
`-continued
`
`11
`In the absence of a cationic polymer the deposition of
`the polystyrene particles was about 1%.
`EXPERIMENTS 8
`
`This experiment concerns the eff