CA2058361A1 - Compositions and methods for treating hair - Google Patents

Abstract

ABSTRACT
A method for semi-permanently conditioning hair by applying thereto a composition comprising an aqueous oil-in-water emulsion of a mixture of (1) a hydroxy-terminated dimethyl polysiloxane having the general formula where n not less than 500 and (2) a methyl hydrogen polysiloxane having the general formula where n is from about 185-235 and where R is selected from the group consisting of H or CH3, said composition being at an acid pH
and wherein the ratio of polysiloxane (1) to polysiloxane (2) is about 100:1 with the total concentration of said polysiloxanes being from about 0.5% to about 10% by weight of said composition, said polysiloxanes in said composition prior to application to said hair being in an unreacted state, said hair being dried after application of said composition resulting in cross-linking of said polysiloxanes on the hair.

Description

2~83~.

Attorney ' s Docket No . 13 a 6 -U-l 0-13 CIP

COMPO8ITION~ AND ME:T~IOD8 FOX TREATING lIAIR
Related Applisations:
This is a continuation-in-part application of my pending applications identified as follows:
Serial No. 07/383,499 filed July 24, 1989;
Serial No. 07/383,500 filed July 24, 1989;
Serial No. 07/593,580 filed October 9, 19~0, which in turn is a continuation of application S.N.
07/383,509, now abandoned;
Serial No. 07/600,153 filed Octobex 19, 1990, which in turn is a continuation of application S.N.
07/383,501, now abandoned.

Field of the Invention:
The present invention relates to compositions and methods for treating hair and more particularly to compositions containing a blend of a hydroxy-terminated polysiloxane polymer and a reactive methyl hydrogen polysiloxane and methods for treating hair with said compositions whereby crosslinking of said polymers takes place on the hair resulting in long ~asting hair conditioning.

Backqround of the Invention:
Hair in its natural state is rather impervious ~o damage. However, due to environmental conditions as well as the abuse to which it is usually subjected, hair can wear 2~3~

out at abnormal rates, causing its natural shield - the cuticle - to fall out and the cortex to shatter ending in breakage. Hair treating compositions and conditioners in particular, are designed to attempt to prevent or restore this damage. State-of-the-art products achieve these goals with various degrees of success, but all fail at providing the benefit for prolonged periods of time, paxticularly, after shampooing previously treated hair~
A typical high quality hair conditioner is expected to provide benefits to the hair such as detangling and low comb drag, among others, without imparting an unnatural or greasy feel to the hair. The conditioning effect also should not interfere with setting of the hair, i~e., it should not diminish the hair's ability to retain curl or hair style.
Further, a conditioner should not make the hair stringy or dull a few hours after application. The dulling effect of some conditioners can occur by wicking the natural oils from the scalp up the hair shaft or by attracting dirt.
Hair conditioners ~ormulated with ingredients containing functional groups substantive to the hair such as quaternized proteins, quaternized amines, amine oxides or silicone polymers with amino functional groups tend to be substantiva to the hair to varying degrees. In general, hair substantivity for conditioning ingredients increases with more hydrophobic character, higher molscular weight, higher charge densities (with positively charged molecules).

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Most of these ingredients provide acceptable conditioning benefits to varying degrees, but fail to provide a longer-lasting clean feeling while providing long lasting conditioning benefits. As a rule of thumb, it can be stated that the greater the substantivity of the conditioning ingredient, the greater the likelihood it will impart a greasy coated feel to the hair or more generally, an unnatural feel and appearance. With some ingredients, over-conditioning and build-up is the result. The build-up effect is manifested as the inability of the hair to hold a set and/or by having a matted stringy look. Heretofore the difficulty in developing products with residual action and good performance without debilitating negative effects, as described, has limited the ability of hair product formulators and marketers to provide a product the consumer does not have to use every time he or she uses shampoo.
It is therefore an object of this invention to provide methods for treating hair employing a composition containing a blend of two polysiloxane polymers whereby cross-linking of the polymers takes place on the hair.
It is a further object of this invention to provide hair-treating compositions which contain a low viscosity emulsion of a reactive hydroxy terminated dimethyl polysiloxane and a reactive methyl hydrogen polysiloxane, said polysiloxanes being unreacted in the composition.
It is a still further object of this invention to provide hair treating compositions and methods which provide 2~3~ ~

good conditioning benefits for prolonged periods of time, particularly after repeated shampooing.
It is another object of this invention to provide a hair treating composition which i5 highly substantive to hair, and provides long lasting hair conditioning properties without build-up or over conditioning.

Summary o~ the ~nventio~
The foregoing objectives and others are accomplished by treating the hair, preferably following shampooing, with a composition including a low viscosity oil-in-water emulsion of a mixture of two polysiloxane polymers, that is, a hydroxy terminated dimethyl polysiloxane and a methyl hydrogen polysiloxane, the composition being at an acid pH.
It is a feature of this invention that the polysiloxane polymers in the hair-treating composition are in an unreacted or non-crosslinked state. However, after the composition is applied to the hair, the crosslinking of the two polysiloxane polymers takes place on the hair resulting in a semi-permanent conditioning effect. Although some crosslinking of the polymers will occur while drying the treated hair at room temperatures, increased crosslinking oCcurC when the hair is blow dried using heated air.

Detai~ed Descr~pti~ of the ~ ntion The hair treating compositions of this invention include a low viscosity oil-in-water emulsion of a mixture 2~3~

of a hydroxy terminated dimethyl polysiloxane having the general formula:
~A) HO - Si - O - ~Si O - Si - OH
CH3 CH3 n CH3 where n is not less than 500, and more specifically ranging from about 530 to about 675 and having a molecular weight of from about 40,000 to about 50,000 and a methyl hydrogen polysiloxane having the general formula:
(B) _ _ IH3 R ~H3 CH3 - Si - O - Si - - Si - CH3 CH3 _H3 _ n CH3 where n is from about 185-235 and having a molecular weight ranging from about 12,800 to about 17,000 and where R=H or CH3 and further where the ratio of R=H to ~=CH3 is about 1: 3.
The aforementioned polymers, although reactive, are maintained in the composition in an unreacted state and the crosslinking of the two polymers does not occur until the composition is applied to the hair and drying has taken place. Th~ ratio of the poly~ers in the composition ranges from about 1 part of polymer A to about 1 part of polymer B
(1:}) to about 100 parts of A to 1 part of B ~100:1) with a preferred ratio of about 10 parts of A to 1 part of B
(10:1). The total concentration of polymers in the composition is from about 0.5% to about 10% by weight. Very 2 0 ~

effective compositions are provided having a total concentration ranging from about 1% to about 5% by weight with a most preferred composition at about 4.4% and wherein the ratio of polymer A to polymer B is about 10:1. It is important that the composition have an acid pH, that is a pH
ranging from about 2 to 6, preferably about 4. The pH may be adjusted in the usual manner with organic or inorganic acids which are customarily employed in toiletries, such as oitric acid.
As previously noted, the compositions are in the form of an oil-in-water emulsion and thus the compositions include water and an appropriate emulsifier. Ethoxylated fatty alcohols having a chain length of C12 to C20 work well and are present in an amount ranging from about .10 to about 1% by weight. The composition may also include ingredients to enhance the substantively of the polymers to the hair, thickeners, colorants, perfumes, preservatives and the like.
In incorporating perfume into the composition it is possible that perfume separation may result due to incomplete emulsification of the perfume oil. This can be remedied by ensuring that a sufficient level of emulsifier is included in the composition.
The hydroxy terminated dimethyl polysiloxane and methyl hydrogen polysiloxane are available as commercial products from Sandoz Chemicals Cnrporation under the trademarks "Sandoperm FE'I and "Sandoperm FV" r~spectively. Sandoperm FE has a total solids level of 49% +/-3% with the level of 2~3~

hydroxymethyl polysiloxane at about 45%. Sandoperm FE also contains about 5~ of cl2 - C20 branched chain ethoxylated fatty alcohol as well as from about 1% to about 2% of Amodimethicone (CTFA name) for added substantively.
Sandoperm FV has a total solicls level of about ~0% +/-3%, about 35% of methyl hydrog~n polysiloxane and about 5% of an ethoxylated polyethylene glycol monyl phenyl alcohol as an emulsifier.
In order to demonstrate the effectiveness of the compositions and methods, the hair conditioning effects of the composition of Example I below, were quantified by frictional force measurements on hair tresses, using a model Instron universal testing instrument manufactured by the Instron Corporation. Hair tresses made with natural human hair (30cm long weighing 2.5 +/-.2 gms) were treated by soaking them for one minute, in the composition of Example I, followed by squeezing out the excess material prior to drying~ The hair treating composition was not rinsed out, although it may be rinsed out without adversely affecting the conditioning effect or its permanency. A ~imilar set of tresses was treated with a leading commercial hair conditioner available under the trademark "Flex" (Regular Conditioner), with the product being rinsed out of the hair tresses prior to drying, as is customary with that type product.
The Instron instrument was fitted with a 0.5kg load cell for the test and the test was conducted at a crosshead 2Q~83~1 speed of 200mm/minute, using a comb 15mm wide with average interteeth separations. All measurements were conducted on wet hair.
Referring to Fig. 1, average data is plotted, with the force in grams on the y-axis and the distance travelled by the comb down the hair shaft, on the x-axis. Fig. 2 shows the degree of damage to the hair which is plotted versus the number of washings. It was found that combing force measurements made under equal conditions, after the tresses were shampooed once with a commercial shampoo for normal hair, show force differences between the test product (i.e., Example I) and the untreated hair and hair treated with the commercial product of greater than ten fold in some regions of the hair shaft, particularly at the ends. The single dashed line shown in Fig. 1 reveals that for hair treated with a composition of this invention, the force required to comb the tresses barely exceeds O.Olkg for the greater portion of the length of the hair. The noise in the signal (or lack thereof), is associated with the roughness of the hair surface. The curve for hair treated with the composition of this invention was marked by that with no significant undilations. This indicated the polysiloxane composition left the hair smooth. In contrast, plots for the untreated control and the tresses treated with the commercial product after one shampoo are average envelope curves representing extremely jagged curves hard to reproduce in a diagram. These curves show that, after one 2 ~

shampooing, the hair treated with a leading commercial competitive product is just about as difficult to comb as combing hair that has not been treated. The conditioning treatment is washed out, while the treatment using a composition of this invention remains. The conditioning effect of the instant composition was measured after each of six consecutive shampooings, although Fig. 1 shows only the data for the first, second and sixth treatments.
In further tests, a statistically designed half head salon test was conducted with 20 subjects, mimicking the protocol used in the force measurement study previously described and shown in Fig. 1. The commercial product and a product of this invention were applied randomly to the left and right sides of the subject's head and compared for three wet hair performance attributes before blow drying and twelve dry hair performance attributes after blow drying.
In addition, seven of the twelve dry hair attributes were re-evaluated twenty-four hours after the treatment.
Furthermore, the subjects were given questionnaires focussing on six dry hair evaluations and one overall preference rating.
The results of this study are best understood by reviewing the data shown in Tables 1, 2 and 3. The ratings correspond ~o a three point scale as follows: 0 = no difference, 1 = small difference, 2 = obvious difference and 3 = great difference. Significant differences at the 80%, 90% and 95~ confidence level are marked with appropriate ~836~

superscripts. As used herein "test product" shall mean the product of Ex. I.
The data in Table 1 show that when the products were first applied the test product rated significantly (95%) better than the commercial control for three key dry hair conditioning attributes: "fewer snarls", "less comb drag"
and "smoother feel". All other dry attributes were essentially at parity except for "manageability" for which the commercial control product was found better at the 80%
confidence level. Of the wet hair conditioning attributes, the test product was rated better than the commercial control for "less comb drag" at the 80% confidence level, but just directionally better for "wet detangling".
After the first shampoo when neither one of the products was reapplied (i.e., day 2) the test product was found superior in several wet and dry conditioning attributes at the 95% confidence level. (See the second column marked Day 2 in Table 1). These data are in agreement with the Instron force measurements discussed earlier.

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OPERATOR'S RATINGS
STANDARD ~RE- ANp POST-TREATMENT FVA~UATION
(After Initial Application With No Reapplication of Products) Ratina Differences; Test Product Minus (-~ C~ommercial Product WET EVALUA~Q~S
Attribute Day 1 Day 2 Dav 3 Day 4 DaY 5 Detangling (Wet) .35 1.30* .85 .85* .55*
Less Comb Drag (Wet) .55~ 1.15* .85* .70* .30*
Cleaner Feel (After Rinse) -.10 -.05 -.05 .05 .05 DRY EVALUA~ONS
Fewer Snarls (Dry) .85* 1.35* .75* .60* .25#
hess Comb Drag (Dry) .75* 1.35* .55* .60* .25#
Less Static -.25 .30@ -.05 .10 .00 Less Flaking .00 .00 .00 .00 .00 More Luster .20@ .15 .05 .20~ .05 More Bulk/Fullness -.05 .20Q .10 -.10 .00 More BouncejSpring -.05 .50* .40* .35* .05 More Body .00 .30* .25# .25* .00 More Manageability -.25Q .45* .05 .05 .00 Cleaner Feel (Dry) -.25 -.10 .00 .05 .00 Le~s Tackiness .00 .00 .00 .00 .00 Smoother Feeling .70* .85~ .40* .25# .30#

2 ~

Q, # and * - difference significant with 80%, 90% or 95%
confidence, respectively. Values given are the differences in the ~eauticians ratings of the test product minus the commercial product.

OP~RATOR'S RATINGS

Ratina Differences, Test Product Minus f-~ Commercial Product Attribute Day 2 E~Y_~ Dav 4 Day S
Fewer Snarls .~o* .35# . .50~ .50*
Less Comb Drag . B5* . 45* .30* .30*
More Bulk/Fullness .20 .05 .00 -.10 More Bounce/Spring .30# .20 .10 .00 Less Greasy/Cleaner Feel -.15 -.10 .05 .00 More Curl Retention .25# .25~ .2Q@ .00 Better Appearance .15 .10 .20@ -.05 f~, # and * - difference significant with 80%, 90% or 95%
confidence, respectively.

SUBJECT'S SELF-EVALUATIONS
AMONG SUBJECTS WITH A PREFERENCE (I.E. IGNORING "NO PREF"
RESPONSES), THB TABLE ENTRIES ARE THE PERCENT OF SUBJECTS
CHOOSING THE TEST PRODUCT OVER THE COMMERCIAL PRODUCT FOR
THE LISTED ATTRIBUTES
%_Choosin~ Test Product over Commercial Product INo Diff = 50~) After Running Co~b/Brush Through Hair:
Att~ibute Initial Day 2 Day 3 Day 4 Day_5 Stay in Place Better 55 50 63 71@ 56 Looks Fuller/Thicker 55 ~5~ 61 89* 56 After Running Fingers Through Hair:
Stay in Place Better 50 50 53 71# 59 Looks Fuller/Thicker 55 56 40 82* 53 Hair Feels Better 44 35Q 62 62 45 Healthier-Looking 56 53 64 62 64 Prefer Overall 55 61 55 72# 65@

~, ~ and * - difference from 50% significant with 80%, 90 or 95% confidence, respectively. The percentage of subjects choosing Test Product over Commercial Product in the Table is calculated ignoring ties, which nu~ber from 0 to 9 of the 20 subjects.
As further shown in Table 1, for days 3 and 4 these differences persist (after 2 and 3 shampooings) but the significance of the difference wanes by the fourth shampoo (Day 5), except for wet detangling and wet comb drag which 2~36~

is still superior at the 95% confidence level and for the dry attributes of fewer snarls and less comb drag. Again these data are in agreement with the Instron data shown in Fig. 1.
The evaluation after 24 hours shown in Table 2 clearly demonstrates one of the attributes of the present invention, that is, superior, long-lasting curl retention properties.
This attribute is originally seen, in Table 1, as composite of two attributes "more bounce/spring" and "more body". The ratings shown in Table 2 for more curl retention correlate with the ratings for fewer snarls (as hair curls fallout while sleeping and the hair gets snarled);
particularly taking into consideration that the panelists were not allowed to touch-up their hairdos.
Another attribute of the present invention is the delivery of conditioning benefits over a longer period of time without making the hair feel coated, greasy or stiff.
In Tables 1 and 2, the ratings for cleanliness are consistently at parity with the side which was not treated any further after the first shampoo, i.e., the residue on the hair is equal to freshly shampooed hair.
The subjects were requested to do a preference evaluation by running the comb or brush through their hair once (without setting it or rearranging the set) for a visual and a tactile evaluation, for five conditioning attributes. As shown in Table 3, the subj ects overall pre~erence was for the test product over the five days of 2~$~g ~

the test. It is noteworthy that the number of patrons preferring the test product grew to a maximum at day 4. The difference over a split ~50/50), was significant at the 90%
confidence level, at this point 72% versus 28%.
This trend is borne out in every attribute tested, e.g., the preference for "looks fuller/thicker" increased from a 55%/45% split to 89%/11% at day 4. This difference is significant at the 95% confidence level. A similar result was obtained whether the evaluation was done by combing through the hair or by running the fingers through it.
The number of subjects preferring the test product for "(hair) stays in place better, i.e. holding the set" also increased from a 50/50 split to 71% preferring the test product, a significant difference.
The fact that the number of subjects preferring the side of their head treated with the test product increased with the number of shampooings, perhaps can be explained as a hair protecting mechanism against the harshness of shampooing every day, i.e. as the untreated hair gets stripped further and further by the washing action, the differences between the treated versus the untreated hair increases, until the fourth day on the third shampooing after treatment. In reality, both sides of the head are being "damaged" by shampooing, but at different rates.
This is best understood by again examining the diagram of Fig. 2 wherein the degree of damage to the hair is 2~

plotted against th~ number of washings. At day 1 thP hair treated with the test product is perceived to be equal in condition or slightly better than the side treated with the commercial product, i.e., Yl is small. After washings one and two the difference between the treatments increases,( Y2 & y3) ~ut the differences are not numerically significant. After the third washing ( Y4) the dif ference is maximum and also numerically significant; thereafter the difference begins to narrow ( ~5), ( Y6) etc.
The following specific Examples disclose useful hair treating compositions according to the`present invention.

Example I
IngFedient % by Weiqht Hydroxy Dimethyl Polysiloxane2.000 Methyl Hydrogen Polysiloxane 0.156 Emulsifying Surfactant; 2.244 Ethoxyla~ed fatty alcohol (cetyl/lauryl) Water, DI 95.600 1~0. ooo pH adjus~ed with citric acid (30%) to 4 Example II

(Product with improved static control) Ingredient% by Weight Sandoperm FE 4.00 Sandoperm FV 0.40 Antistatic Agent0.50 (Stearyldimethylbenzyl ammonium chloride) Fragrance 0.10 Water, DI 95 00 100. O
pH adjusted to 4 with 30%
citric acid Example_III
Ingredient% by Weight A B
Sandoperm FE .50 1.00 Sandoperm FV 0.50 0.10 *Polyurethane QW 4019 2.00 4.00 SD 40 190 77.00 64.90 Water, DI ~0.00 30.00 100 . 00 100 . 00 The a~ove compositions A and B are useful as hair holding compositions. The pH of the mixture is adjusted with citric acid (30%) to pH 4.0 *obtained from Grace Chemicals 2~36~

Example_~
Inaredient % by Weiaht Sandoperm FE 4.00 Sandoperm FV o.40 Water, Deionized 95.60 Adjust pH to 4.0 with 30% citric acid/cold blend by adding polysiloxanes to water.
This composition is useful as a conditioner, as such, or in a pump spray package.

Example V
Innredient % by Wei~ht Sandoperm FE 4.00 Sandoperm FV 0.40 Fragrance 0.30 Dye D&C Green #5 (0.1% in DI. Water) 0.30 Carbopol 1342* 0.50 Water, DI 94.50 Adjust pH to 4.0 with 10% TEA. Viscosity :193.lK cps LVT sp.TC, @ 12rpm.
ThiC composition is useful as a semi-permanent hair conditioner or creme rinse.
*Carbopol 1342 is a copolymer of acrylic acid and a long chain alkyl methacrylate and available from B.F. Goodrich Company. It functions as a thickener and can serve as an emulsifier for oil-in-water emulsions.

2Q~3~

Example vI
Inaredient % by Weight Sandoperm FE 4.00 Sandoperm FV o.40 Fragrance 0.30 Dye D~C Green #5 (0.1% in DI. Water) 0.30 Xanthan Gum Keltrol Food Grade 0.50 Water, DI 94.50 Adjust pH to 4.0 with 30% Citric Acid. Viscosity 820 cps. LVT sp. #2@ 30 rpm.
This composition is useful as a semi-permanent hair conditioner or creme rinse.
Further tests were conducted as follows:

~nalysis Co~ined Over Hairtype -A study was made to compare the test product to a commercial hair conditioner in a 5-day, "half-head" study in which the test product was applied only on the first day while the commercial product was applied on each of the 5 days of the study. The purpose was to determine the number of days until the conditioning benefits imparted by a single application of the test product would decline to the level of daily applications of the commercial conditioner. The results of this study are shown in Tables 4-6. The ratings correspond to the following scale:

0 - no difference 1 = small difference 2 = obvious difference 3 = great difference 2~'3~

It should be noted that the salon operators were blinded to the treatments when evaluating but the subjects were not blinded to the treatments on days 2 through 5 since they experienced treatment application on only one side of the head during those days. Thus, a placebo effect may partly account for the fact that the subject's self evaluations tended to favor the commercial product on days 2, 3 and especially 4. Their evaluations seem to indicate that "reality" took over by day 5 and the test product was again indicated as superior.

Table 4 OPERATOR'S RATINGS
STANDARD PRE- AND ~OS~TREATMENT EVALUATION

Treatment Diffe~ences: (Tçst Produc~_~i~u,s~ ommerc;al P~oduct WET EVALUATIONS
A~t~i~u~_ Initial ~ 2 ~Day 3 Day 4 Day 5 Detangling (Wet) .62* 55*1.10* 1.02* .76*
Less Comb Drag (Wet) .54* .78* 1.10* 1.19* .76*

Cleaner Feel (After Rinse) .00 .12~.04 .00 .00 .DRY EVALUATIONS
Fewer Snarls (Dry) .86* .74* .83* .64* .64*
Less Co~b Drag ~Dry) .83* .88* .83* .74* .70*

L ss Static .07 .11 .05 .00 .08 Better Overall Appearance .30* .44* .43* .33# .49*

2~36~.

More Luster .00 .15 .20* .04 .23*
More Bulk/Fullness .03 .46* .11 .10 .42*
More Bounce/Spring .15 .53* .41* .14 .38*
More Body .15 .59* .33* .24~ .38*
More Manageability .10 .49* .23* .12 .24@
Cleaner Feel (Dry) -.01 .01 .00 .00 .00 More Curl Retention -.09 .37* .12# -.04 .16 Smoother Feel .17# .25# .35* .29* .21Q

@, # and * - difference significant with 80%, 90% or 95%
confidenc , respectively.

Table 5 OPFRATOR'S RATINGS
"MORNING AF~ER" EV~LUATION
Treatment ~ifferences: (Test Product Minus (-) Commercial Product Attribute Day 2 Day 3 Day 4 Dav 5 Fewer Snarls .53* .55* .66* 1.10*
Less Comb Drag .67~ .55* .73* 1.10*
Less Static .00 .00 -.05 .00 More Bulk Fullness -.01 .22@ .29* .19 More Bounce/Springiness .48*~40* .23* .25 More Manageability .37* .31* .08@ .02 Less Greasy (Cleaner Feel) -.05 -.13~ .00 -.01 More Curl Retention .35* .15# .04 -.03 Better Appearance .25 .56* .34* .36#

@, # and * - difference significant with 80%, 90% or 9 confidence, respectively.

Table 6 SUBJECT'S SELF-EVALURTIONS
Among Subjects With a Preference (I.E. Ignoring "No Pref"
Responses) the Table Entries are the Percent of Subjects Choosing the Test Product over Commercial Conditioner for the Listed Attribute.

% Choosina Test Pxoduct over Commercial Product lNo Diff = 50~L
Attribute Initial ~ay 2 ~a~ 3 Day 4 Day 5 After Running Comb/Brush Through Hair:
Stays in Place Better 52 56 48 36@ 52 Looks Fuller/Thicker 40 48 48 35~ 50 After Running Fingers Through Hair:
Stays in Place Better 52 67@ 40 35@ 52 Looks Fuller/Thicker 42 54 46 35Q 48 Hair Feels Better 50 54 46 43 64@
Healthier-Looking 36@ 57 32# 32# 50 Prefer Overall 48 64@ 40 40 54 @, # and * - difference from 50% significant with 80%, 90%
or 95% confidence, respectively. The percentage choosing test product over commercial conditioner is calculated ignoring ties, which number from 0 to 9 of the 20 subjects.

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Analysis bv Hair_type Tables 7 and 8 summarize a statistical analysis comparing the 2 hair types, "dry" vs. "normal", in terms of the relative performance of the test product and the commercial conditioner. Hair classified as dry is generally colored and/or permed hair and is considered to have some damage. Only the Hair Salon Operator Ratings were analyzed in this way; self-evaluations were not analyzed by hair type since to do so would have produced an overly scarce contingency ta~le (see below).

Table 7 OP~RATOR'S RATINGS
STANDARD.PRE- AND POST-~EATMENT EVALUA~ON ~_H~ TYpE
Treatment Differences: fTest Product Minus ~-) Commercial Produçt) WET EVALUATIONS

Attribute HairType Initial Day 2 DaY 3 Day 4 Day S

Detangling (Wet1 Dry .79 .641.291.14 .71 Nor~al .46 .45.91 .90 .80 Less Co~b Drag Dry .86Q .941.291.07 .71 Normal .22 .65.91 1.30 .80 Cleaner Feel Dry .00 .14.07 .00 .00 Normal .00 .09.00 .00 .00 3 ~ ~

DRY EVALUATIONS
Fewer Snarls tDry) Dry 1. 21* ~ 93 ~ 93~ 57 ~ 29#
Normal .50 ~56 ~73~70 ~99 Less Comb Drag (Dry) Dry1 ~ 14# ~ 93 ~ 93~ 79 ~ 43 Normal~ 52 ~ 83 ~ 73~ 70 ~ 96 Less Static Dry ~14 ~21 ~00~00 ~00 Normal .00 .00 .09.00 ~ 17 Better Gverall Appear. Dry . 64* ~ 71# ~ 57~ 36 ~ 64 Normal ~~05 ~18 ~27~30 ~34 More Luster Dry ~ 07 ~ 29 ~ 21~ 07 ~ 29 Normal ~~07 ~02 ~18~00 ~18 More Bulk/
FullnessDry . 36* ~ 50 ~ 21~ 00 ~ 43 Normal ~~30 ~43 ~01~20 ~41 ~ore Bounce/
Spring Dry .50* .79# ~ 64@ ~ 07 ~ 43 Normal-~20 o27 ~18~20 ~33 More Body Dry .50* . 92* ~ 57# ~ 29 ~ 43 Normal -.20 ~25 ~09~20 ~33 More Manage-ability Dry ~ 42* 710 ~ 28~ 14 ~ 14 Normal -~22 ~26 ~18~10 ~33 Cleaner Feel Dry ~14 ~~07 ~00~00 ~00 Normal -~17 ~08 ~00~00 ~00 More Curl Retention Dry .14 ~ 57# ~ 14 ~ ~ 07 ~ 07 Normal -~31 ~16 ~09~00 ~26 Smoother Feel Dry ~ 13 ~ 22 ~ 42~ 28 ~ 14 Normal .19 ~28 ~27~30 ~27 Q, # and * - Dry vs. Normal Hair types significantly different with 80%~ 90% or 95~ confidence, respectively Table 8 OPERATOR'S R~T~NGS
"MO~NING AFTER" EVAL~ATION
Treatment Differences: LTest Product Minus (-) Commercial Conditioner) AttributeHair Type Dav 2 Day 3 ~y_~ Day 5 Fewer SnarlsDry .50 .86 .42# 1.42*
Normal .55 .25 .88 .75 Less Comb Drag Dry .64 .86* .50* 1.42*
Normal ~ .70 .25 .97 .7S
Less Static Dry .00 .O0 .00 .00 Normal .00 .00 -.09 .00 More Bulk/
Fullness Dry .30 .36 .21~36 Normal -.31 .08 .37 .02#
More Bounce/
Spring Dry .71@ .64Q .28 .50#
Normal .25 .17 .18 .01 More Manage-ability Dry .71* .50@ .07 .14 Normal .03 .11 .09 -.10 Less Greasy Dry -.07 .. 07* .00 .00 Normal -.03 -.33O00 -.01 More Curl Retention Dry .57# .21 .07 .14#
Normal .13 .08 .00 -.17 Better Appearance Dry .50 1.00* .14~ .64Q
No~mal .01 .12 .55 .08 @, # and * - Dry vs. Normal Hair types significantly different with 80%, 90% and 95~ confidence, respectively.

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Statistical Methods The data included the "Standard Pre- and Post-Treatment Evaluations" by the salon operators, "Morning After"
Evaluations by the salon operators and "Sel~-Evaluations" by the subjects. All operators' ratings were analyzed using an analysis of variance which accounted for variation due to differences among hair types, differences among subjects within hair types, differences in side of head, differences between the treatments and the interaction of treatments with hair types. Subjects' Self-Evaluations were paired choice responses where the subject chose which side had morP
of each attribute. These data were analyzed using a 2-by-2 table which tabulated subjects by Preferred-Side-of-Head (left V6. right) and Treatment/Side-Assignment (A=>Left/~=>Right V8. B->Left/A=>Right). Subjects' Self-evaluations were not analyzed by hair type since to do so would have produced an overly sparce contingency table:
cross classification of 20 subjects by 8 categories (Preferred-Side-of-Head) (Left vs Right), Treatment/Side-Assignment (A->Left/B=>Right vs B+>Left/A=>Right) and Hair type (Dry vs Normal).
The following examples disclose additional useful compositions for treating hair.

2~3~1 Example VII
Inaredient % bv Weiaht Sandoperm FE 4.000000 Sandoperm FV o.400000 Fragrance 05-10 0.300000 Dye Green #5 0.1% in H20 0.300000 Hydantoin 55 0.500000 Methyl Paraben 0.150000 Propyl Paraben 0.050000 Xanthan Gu~1.0% in Water 50.000000 Water,- DI , i . 44.300000 Adjust pH to 4.0 with 30% Citric Acid Hydantoin, Methyl Paraben and Propyl Para~en used as a - preservative Example VIII
Inaredient % by Weiaht Sandoperm FE 4.000000 Sandoperm FV 0.400000 Fragrance 05-lO 0.300000 Dye Green #5 0.1% in Water0.300000 Hydantoin 55 0.500000 Water, Deionized 94.500000 Adjust pH to 4.Q with 30% Citric Acid a~ueous.
Low viscocity product.

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Exampl~e IX
Inaredient % by Weiqht Sandoperm FE Liquid 4.000000 Sandope~m FV Liquid 0.400000 Fragrance 06-37 0.150000 FD&C Green #5 0.000300 DMDM Hydantoin (55%~ 0,500000 Water, Deionized 94.9497C0 Adjust pH to 4.0 +/- .5 with 30% citric acid Inqredient % bY Weiaht Sandoperm FE Liquid 4.000000 Sandoperm FV Liquid 0.400000 Fraqrance 06-37 0.075000 FD&C Green #5 0.000300 DMDM Hydantoin (55%) 0.500000 Water, Deionized 95.024700 Adjust pH to 4.0 +~- .5 with Citric Acid (30% Aq.) 2 ~
Exam~le XI
Inaredient % by Weiaht Sandoperm FE Liquid 2.000000 Sandoperm FV Liquid 0.200000 Fragrance 06-37 0.075000 FD&C Green #5 0.000300 DMDM Hydantoin (S5%) 0.500000 Water, Deionized 970224700 Adjust pH to 4.0 +/- .5 with Citric Acid (30% Aq.) Exam~le XII
Inaredie~~ ~ by Weiqht Sandoperm FE Liquid 1.000000 Sandoperm FV Liquid O.lOQ000 Fragrance 06-37 0.075000 FD~C Green #5 0.000300 DMDM Hydantoin (55%) 0.500000 Water, Deionized 98.324700 Adjust pH to 4.0 +/- .5 with Citric Acid (30% Aq.) Exa~ple XILI
. Inqredient % by Weiaht Sandoperm FE Liquid 1.000000 Sandoperm FV Liquid 0.100000 Fragrance 06-37 0.075000 DMDM Hydantoin (55%) 0.500000 Water, De~onized 98.325000 Adiust pH to 4.0 +/- 0.5 with Citric Acid (30% Aq.) 2~83~1 Fxample XIV
Inaredisnt % bv Weiaht Sandoperm FE Liquid 2.000000 Sandoperm FV Liquid 0.200000 Fragrance 06-37 0.075000 DMDM Hydantoim (55~) 0.500000 Water, Deionized 97.225000 Adjust pH to 4.0 +/- 0.5 with Citric Acid (30% Aq.~.

Examp~ç ~
Ina~edient % by Weiaht Sandoperm Fe Liquid -- 4.000000 Sandoperm FV Liquid o.400000 Fragrance 06-37 0.075000 DMDM Hydantoin (55%) 0.500000 Water, Deionized 95.025000 Adjust pH to 4.0 1/- 0.5 with Citric Acid (30% Aq.) Example XVI
Inqredient % by Weiaht Sandoperm FE Liquid 4.000000 Sandoperm FV Liquid 0.400000 Fragrance 06-37 0.075000 DMDM Hydantoin 0.500000 Water, Deionized 94.950000 ~he level of active Kathon CG is 11.25 PPM adjust pH to 4.0 +/- with Citric Acid ~30% Aq.~.

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Example XVII
Inaredie~t % by Weiaht Sandoperm FE Liquid 1.000000 Sandoperm FV Liquid 0.100000 Fragrance 06-37 0.075000 Dantoin DMDMH-55 0.500000 Kathon CG (as sold~ 0.075000 Water, Deionized 98.250000 The level of active Kathon CG i8 11 ~ 25 P~M. Adjust pH
to just under 4.0 with Citric Acid (30% Ag.).

Example XVIII
Inqrediçn~ ~ by Weight Sandoperm FE Liquid 4.000000 Sandoperm FV Liquid 0.400000 Fragrance 06-37 0.075000 Dantoin DMDMH-55 0.500000 Kathon CG (as sold) 0.050000 Methylparaben USP/NF 0.200000 EDTA.NA2 0.100000 Water, Deionized 94.675000 The level o~ active Kathon CG is 7.5 PP~. Adjust p~ to ~ust under 4.0 with Citric ~cid (30% Aq.).

2 ~
Exam~le XIX
I~gredient ~ bY Weiqht Sandoperm FE Liquid 1.000000 Sandoper~ FV Liquid o.lOOOOO
Fragrance 06-37 0.075000 Dantoin DMDMH-55 0.500000 Kathon CG (as sold3 G.050000 Methylparaben USP/NF 0.100000 Water, Deionized 97.975000 The level of active Kathon CG is 7.5 PPM. ~djust pH to just under 4.0 with Citric Acid (30% Aq.~.

To use the conditioning compositions, the hair may be shampooed and towel dried. Thereafter the composition is applied to the hair followed by working in the hair with the fingers. The treated hair may then be combed and dried in the customary manner. Blow drying with heated air gives longer lasting conditioning. For users who want to style their hair, any one of the following procedures will give acceptable results.
1~ After shampooing the hair is air dried.
~hereafter the conditioner is applied and then the h~ir is curled while still damp.
2) Application of the conditioning composition after shampooing, then placing the hair on rollers while still wet followed by blow drying.

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3) Application of the conditioning composition to the hair followed by drying. Thereafter the hair is rewetted slightly, placed on rollers or a curling iron may be used and thereafter tha hair is dried.
4) The hair is treated wi~h the conditioning composition, then blow dried until slightly moist to the touch and then placed on rollers or curled in the customary way.
In the foregoing, a styling mousse or gel may also be applied .to the hair after applying the conditioning composition.

Claims (14)

1. A method for semi-permanently conditioning hair by applying thereto a composition comprising an aqueous oil-in-water emulsion of a mixture of (1) a hydroxy-terminated dimethyl polysiloxane having the general formula where n is not less than 500 and (2) a methyl hydrogen polysiloxane having the general formula where n is from about 185-235 and where R is selected from the group consisting of H or CH3, said composition being at an acid pH and wherein the ratio of polysiloxane (1) to polysiloxane (2) is about 100:1 with the total concentration of said polysiloxanes being from about 0.5% to about 10% by weight of said composition, said polysiloxanes in said composition prior to application to said hair being in an unreacted state, said hair being dried after application of said composition resulting in cross-linking of said polysiloxanes on the hair.

2. The method of claim 1 wherein said hair is dried by application of heat following application of said composition.

3. The method of claim 2 wherein said drying by application of heat is at a temperature greater than room temperature and less than 100°C.

4. The method of claim 3 wherein the value of n in polysiloxane (1) is from about 530 to about 675 and wherein the ratio of polysiloxane (1) to polysiloxane (2) is about 10:1.

5. The method of claim 4 wherein the concentration of said polysiloxanes in said composition is from about 1% to about 5% by weight.

6. The method of claim 5 wherein said pH of said composition is from about 2 to about 6.

7. The method of claim 6 wherein said pH is about 4.

8. The method of claim 7 wherein said composition additionally includes an ingredient to enhance the substantivity of said polysiloxanes to hair.

9. A composition for semi-permanently conditioning hair comprising an aqueous oil-in-water emulsion of a mixture of (1) a hydroxy-terminated dimethyl polysiloxane having the general formula where n is not less than 500 and (2) a methyl hydrogen polysiloxane having the general formula where n is from about 185-235 and where R is selected from the group consisting of H or CH3, said composition being at an acid pH and wherein the ratio of polysiloxane (1) to polysiloxane (2) is about 100:1 with the total concentration of said polysiloxanes being from about 0.5% to about 10% by weight of said composition, said polysiloxanes in said composition prior to application to said hair being in an unreacted state.

10. The composition of claim 9 wherein the value of n in polysiloxane (1) is from about 530 to about 675 and wherein the ratio of polysiloxane (1) to polysiloxane (2) is about 10:1.

11. The composition of claim 10 wherein the concentration of said polysiloxanes is from about 1% to about 5% by weight.

12.The composition of claim 11 wherein said pH of said composition is from about 2 to about 6.

13. The composition of claim 12 wherein said pH is about 4.

14. The composition of claim 13 additionally including an ingredient to enhance the substantivity of said polysiloxanes to hair.