US009610237B2
`
`a2) United States Patent
`US 9,610,237 B2
`(0) Patent No.:
`Apr. 4, 2017
`(45) Date of Patent:
`Burgo etal.
`
`(54) NATURAL SILICONE REPLACEMENTS FOR
`SILICONE FLUIDS IN PERSONAL CARE
`FORMULATIONS
`
`(56)
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`(71) Applicant: INOLEX INVESTMENT
`CORPORATION, Wilmington, DE
`(US)
`
`(72)
`
`Inventors: Rocco Burgo, Mullica Hill, NJ (US);
`Daniel Winn, Kingston, NJ (US);
`Kimberly Burch, Trenton, NJ (US)
`
`(73) Assignee:
`
`Inolex Investment Corporation,
`Wilmington, DE (US)
`
`(*) Notice:
`
`Subject to any disclaimer, the term ofthis
`patent is extended or adjusted under 35
`US.C. 154(b) by 0 days.
`
`(21) Appl. No.: 14/276,788
`
`(22)
`
`Filed:
`
`May13, 2014
`
`(65)
`
`Prior Publication Data
`
`US 2014/0356303 Al
`
`Dec. 4, 2014
`
`Related U.S. Application Data
`
`application
`of
`(63) Continuation
`PCT/US2012/065052, filed on Nov. 14, 2012.
`(Continued)
`
`No.
`
`(51)
`
`Int. Cl.
`A6IK 8/85
`A61K 8/37
`
`(2006.01)
`(2006.01)
`(Continued)
`
`(52) U.S. Cl.
`CPC vieeeceectsnees AG6IK 8/85 (2013.01); A61K 8/37
`(2013.01); A61Q 1/04 (2013.01); A61Q 5/12
`(2013.01); A61Q 19/00 (2013.01); AOIK
`2800/34 (2013.01)
`
`(58) Field of Classification Search
`CPC wo. A61K 2800/34; A61K 8/37; A61K 8/85
`See application file for complete search history.
`
`4,366,100 A * 12/1982 Naskar oe A61K 8/375
`554/164
`IL/1991 Walz wo BOLD 19/0404
`516/131
`
`4,988,463 A *
`
`(Continued)
`
`FOREIGN PATENT DOCUMENTS
`
`JP
`JP
`
`2000-212049 A
`2004-262783 A
`
`8/2000
`9/2004
`
`(Continued)
`
`OTHER PUBLICATIONS
`
`International Search Report and Written Opinion dated Mar. 12,
`2013 (8 pages).
`
`(Continued)
`
`Primary Examiner — Aradhana Sasan
`(74) Attorney, Agent, or Firm — Flaster/Greenberg P.C.
`
`(57)
`
`ABSTRACT
`
`Described herein is a silicone replacement for use in a
`personal care formulation comprising a mixture ofat least
`one polymeric ester and at least one non-polymeric ester.
`The polymeric ester is an esterification reaction product of
`(i) at least one first dicarboxylic acid, (ii) at least one first
`monofunctional alcohol or monofunctional carboxylic acid
`and (iii) glycerin or derivatives thereof. The non-polymeric
`ester is an esterification reaction product of (i) at least one
`second dicarboxylic acid and(ii) at least one second mono-
`functional alcohol, wherein the replacementis substantially
`free of silicone. As described is a personal care formulation
`that is substantially free of silicone, wherein the formulation
`comprises a silicone replacement consisting substantially of
`a mixture of at least one polymeric ester as described above,
`and a non-polymeric ester as described above. Related
`methods are also described.
`
`14 Claims, 16 Drawing Sheets
`
`
`
`
`
`~s3- Nig
`
`
`
`
`
`18 othinone 26UcSt
`
`
`dim 3 nin StH
`
`
`
`NiSQ
`
`Petitioner Dr. Squatch
`Ex. 1026
`
`Petitioner Dr. Squatch
` Ex. 1026
`
`

`

`US 9,610,237 B2
` Page 2
`
`FOREIGN PATENT DOCUMENTS
`2011-506556 A
`3/2011
`JP
`
`(60) Provisional application No. 61/559,266, filed on Nov. 2005/097044 Al—10/2005WO
`
`WO
`2010/019939 Al
`2/2010
`14, 2011.
`
`Related U.S. Application Data
`
`(51)
`
`(56)
`
`Int. Cl.
`A61Q 19/00
`A6IQ 1/04
`A61Q 5/12
`
`(2006.01)
`(2006.01)
`(2006.01)
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`OTHER PUBLICATIONS
`Supplementary European Search Report dated Apr. 17, 2015 (9
`page).
`First Swiss Office Action dated Sep. 30, 2014 (2 pages).
`Response to First Swiss Office Action dated Dec. 24, 2014 (14
`pages).
`Second. Swiss Office Action dated Feb. 27, 2015 (2 pages).
`Response to Second Swiss Office Action dated May 26, 2015 (1
`page).
`7/2001 Kahre etal.
`2001/0006652 Al
`Third Swiss Office Action dated Sep. 30, 2015 (2 pages).
`2004/0241200 Al=12/2004 Winnetal.
`Response to Third Swiss Office Action dated Apr. 6, 2016 (14
`2004/0258642 Al
`12/2004 Calello et al.
`pages).
`2005/0260150 Al* 11/2005 Burgo wc A61K 8/375
`Freeman Organic Chemistry, “Carboxylic Products in Nature” pp.
`424/70.11
`133-134 (3 pages).
`Japanese Office Action dated Nov. 1, 2016 in Application No.
`2014-541417 (counterpart of U.S. Appl. No. 14/276,788)
`(10
`pages).
`
`2005/0288478 Al
`2008/0051470 Al
`2009/0123398 Al
`2010/0068162 Al
`2011/0020258 Al
`2011/0064685 Al
`
`12/2005 Burgo
`2/2008 Issberneretal.
`5/2009 Labaetal.
`3/2010 Greenberg et al.
`1/2011 Lorant
`3/2011 Jordan
`
`* cited by examiner
`
`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 1 of 16
`
`US 9,610,237 B2
`
`FIGURE |
`
`
`
`Wet
`
`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 2 of 16
`
`US 9,610,237 B2
`
`FIGURE 2
`
`
`
`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 3 of 16
`
`US 9,610,237 B2
`
`FIGURE 3
`
`
`
`votes Dimethinone 200¢St oe N3S0
`
`ome WO
`
`oe Dimethicone 10 cSt
`
`N20
`
`a. Bimethicone 20 0St
`
`some DESO
`
`Bimathiogne 80 oSt
`
`nates N106
`~~ Dimethicone 100 oSt
`
`wooIGG
`
`ie. Dhnethicone 350¢St
`
`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 4 of 16
`
`US 9,610,237 B2
`
`
`
`
`
`
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`
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`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 5 of 16
`
`US 9,610,237 B2
`
`
`
`
`
`
`
`
`
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`
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`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 6 of 16
`
`US 9,610,237 B2
`
`
`
`SURVEY
`
`FIGURE 5
`
`
`We are studyi cloant will receive&set of two saraples for
`
`
`
`
`2 the atiutessetaa series ofnew nahwal emollionis. Each par
`
`
`
`
`vected and record evaluation of products below.
`
`Product Al
`
`Product B:
`
`4,
`Howdoes iothon feel when apoled?
`
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`i
`2
`3
`
`4
`
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`b
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`i
`2
`3
`
`
`
`&.
`
`Howloug does H iake for the prodnct io be absorbed?
`ven ee eee Long
`
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`
`
`
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`
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`
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`
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`
`ve Rag
`
`ow
`does your skin feel bumediaivly afer apo
`
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`2
`i
`
`
`
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`e.
`Mo Residual oo eee
`i5
`a
`us
`
`sreasy, SHiey,
`
`t
`5
`
`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 7 of 16
`
`US 9,610,237 B2
`
`Light vs. Rich
`5,
`By
`
`—~- Dimethicone 10cs
`et N10
`
`FIGURE 6A
`
` FIGURE 6C
`
`Olliness
`
`Ve
`
`.
`/
`Absorbtion rate
`
`FIGURE 6B
`
`:
`
`’
`
`5oh,
`
`cee Di
`
`i
`
`Oi
`
`~O® IN20
`
`> Slip vs. Drag
`
`
`
`Light vs. Rich
`ON,
`
`comme Dimethicone 100cs
`
`
`
`\
`Oiliness “rrr~
`
`Mf
`“Absorbtion rate
`
`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 8 of 16
`
`US 9,610,237 B2
`
`FIGURE 6D
`
`
`~——- Dimethicone 200cs
`
`Light vs. Rich
`Sun
`
`
`
`9 Slip vs. Drag
`
`f
`
`
`
`on
`A
`: {
`
`Olliness *
`Absorbtion rate
`
`
`
` “hen 200
`
`
`
`
`
`* Absorbtion rate
`Olliness “-~
`
`
`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 9 of 16
`
`US 9,610,237 B2
`
`FIGURE 7A
`
`BEPOR!a
`E
`an
`ns SS
`SRE ‘
`<
`SS
`
`
`
`
`NX
`
`APTER
`KO°%Lexorez200
`
`
`
`FIGURE 7B
`
`20%NiO NN
`
`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 10 of 16
`
`US 9,610,237 B2
`
`FIGURE 7C
`
`FIGURE 7D
`
`BEFORE \N
`
`APTER
`
`8O%Loxorez200 + 20%N20
`
`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 11 of 16
`
`US 9,610,237 B2
`
`FIGURE 7E
`
`
`FIGURE 7F
`
`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 12 of 16
`
`US 9,610,237 B2
`
`FIGURE 7G
`
`FIGURE 7H
`
`BEFORE
`
`
`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 13 of 16
`
`US 9,610,237 B2
`
`FIGURE71
`
`BEPORE
`
`FIGURE7J
`
`APTER
`80% LexorezZ00+20%N2GG
`
`
`
`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 14 of 16
`
`US 9,610,237 B2
`
`FIGURE 7K
`
`FIGURE 7L
`
`
`20%N350
`
`APTER
`
`2054 Lexorez200 4
`
`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 15 of 16
`
`US 9,610,237 B2
`
`FIGURE &
`
`420,006 -
`
`100,000
`
`20,000 4
`
`> 80,000 4
`3 Ao
`2
`80,000 -
`43,000
`
`2-
`
`
`
`

`

`U.S. Patent
`
`Apr. 4, 2017
`
`Sheet 16 of 16
`
`US 9,610,237 B2
`
`FIGURE 9
`
`
`
`
`
`ecrenseresnemeppepsprmpssopromsonmmmoamon
`
`Silicone Repia
`
`Invenitvi
`8
`cor
`
`TK
`
`
`
`
`
`50c8
`
`406cs
`
`9200s
`
`aa0cs
`
`
`
`

`

`US 9,610,237 B2
`
`1
`NATURAL SILICONE REPLACEMENTS FOR
`SILICONE FLUIDS IN PERSONAL CARE
`FORMULATIONS
`
`CROSS-REFERENCE TO RELATED
`APPLICATIONS
`
`This application is a continuation of International Appli-
`cation No. PCT/US2012/065052, filed Nov. 14, 2011, which
`in turn claims the benefit under 35 U.S.C. §119(e) to US.
`Provisional Patent Application No. 61/559,266, filed Nov.
`14, 2011; the entire disclosures of each of which are incor-
`porated herein by this reference.
`
`BACKGROUND OF THE INVENTION
`
`Silicone fluids are widely used in toiletry, cosmetic, and
`personal care formulations. Most frequently used are the
`dimethicones, the cyclomethicones, and phenyl trimethicone
`(hereinafterall silicone materials collectively refereed to as
`“silicones”). Incorporated into a skin care formulation,sili-
`cone fluids provide a variety of benefits such as improved
`slip, reduction of tack, impartation of emolliency, and other
`modifications of the “feel” characteristics of the formula-
`
`tion, as well as other benefits. Incorporated into hair care
`formulations such as conditioners,
`they can reduce wet
`combing force and increase shine of hair
`Silicone fluids have been considered to be particularly
`useful as they tend to provide the aforementioned benefits
`without contributing to oiliness or greasiness and give what
`many considerto be a “dry” skin feel. This attribute is highly
`desired in toiletry, cosmetic, and other personal care formu-
`lations such as creams,
`lotions, antiperspirants, shaving
`formulations, and make-up formulations. Additional benefits
`are that silicones are excellent dispersing and spreading
`agents, are generally water white in color, low in odor, and
`are resistant to chemical and oxidative attack. These attri-
`butes make them particularly suitable for personal care
`applications. However, the use of silicones in personal care
`formulation comes with drawbacks.
`
`For example, there has been concern about the safety of
`the use of silicone fluids on the skin. In light of potential
`links between silicone and silicone degradation products to
`the development of autoimmune system deficiencies in
`women with silicone breast implants and/or individuals with
`other disorders, these materials have recently come under
`higher scrutiny by the Food and Drug Administration
`(FDA). Although definitive links have not been confirmed,
`many cosmetic formulators have acted to attempt to reduce
`and or eliminate silicone ingredients from formulations. The
`downside of not using silicones is of course that the skin feel
`and formulation benefits are lost.
`
`In addition, silicones have also been implicated as poten-
`tially being harmful to the environment. For example, Envi-
`ronment Canada has published a documents indicating that
`dimethiciones are suspected to be environmental toxins and
`biocumulative.
`
`Accordingly, there exists a need in the art to identify
`alternative non-silicone fluidsthat provide silicone-like ben-
`efits in formulation but do not bring with the real or
`perceived health and environmental risks.
`The industry has madeefforts to respondto this need. For
`example, U.S. Patent Application Publication 2005/0260150
`describes low viscosity esters that may be used as replace-
`ments for low viscosity silicone fluids. United States Patent
`Application Publication 2004/0241200 describes blends of
`certain synthetic esters with volatile hydrocarbons that are
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`2
`useful for the replacementof volatile tetramer and pentamer
`cyclomethicones. United States Patent Application Publica-
`tion 2009/0123398 describes blends of hydrocarbon fluids
`useful for the replacementof volatile tetramer and pentamer
`cyclomethicones. United States Patent Application Publica-
`tion 2011/0064685 describes personal care compositions
`comprising an aqueous dispersion comprising a metallocene
`catalyzed polyolefin and an ethylene acrylic acid copolymer;
`a cationic polymer; and a least one cosmetically acceptable
`surfactant, emollient, or cosmetic active, provided that the
`personal care composition contains less than 0.09 wt % of 15
`silicone, and preferably is substantially free of silicone.
`As the population becomes more aware of the potential
`adverse effects to the body and to the environment associ-
`ated with the use ingredients derived from fossil fuels, the
`personal care industry has rapidly advancedtheir search for
`“natural” ingredients for use in virtually all cosmetic for-
`mulation types and forms. Media has driven this growth by
`popularizing the idca that there may be potential adverse
`effects to the body and to the environmentassociated with
`the use ingredients derived from fossil fuels. The personal
`care industry has rapidly advanced its attempts to identify
`“natural” ingredients for use in virtually all cosmetic product
`types and forms. Notably, although used in marketing mate-
`rials, the term “natural” has not yet been clearly defined
`within this context; efforts are under way by industry trade
`organizations to give the term a more concise and consistent
`meaning.
`It may be sometime before an industry accepted universal
`definition of natural is provided; however,
`it is generally
`recognized that materials derived from renewable and/or
`sustainable, or otherwise non-fossil fuel sources are consid-
`ered to be natural. Petrochemicals are derived from fossil
`fuels and are not considered to be natural. Any derivatives
`of petrochemicals are not considered to be natural. As such,
`silicones are notclassified as natural, as they are petrochemi-
`cally derived. Accordingly, there is a need in the art for
`natural silicone replacements that can be used in lieu of
`silicones in personal care formulations and which provide to
`the consumer the advantageous end properties of silicones.
`
`BRIEF SUMMARY OF THE INVENTION
`
`Described herein is a silicone replacement for use in a
`personal care formulation comprising a mixture ofat least
`one polymeric ester and at least one non-polymeric ester.
`The polymeric ester is an esterification reaction product of
`(i) at least one first dicarboxylic acid, (ii) at least one first
`monofunctional alcohol or monofunctional carboxylic acid
`and (iii) glycerin or derivatives thereof. The non-polymeric
`ester is an esterification reaction product of (i) at least one
`second dicarboxylic acid and (ii) at least one second mono-
`functional alcohol, wherein the replacementis substantially
`free of silicone.
`
`is
`Also described is a personal care formulation that
`substantially free of silicone, wherein the formulation com-
`prises a silicone replacement consisting substantially of a
`mixture of at least one polymeric ester as described above,
`and a non-polymeric ester as described above. Related
`methods are also described.
`
`BRIEF DESCRIPTION OF THE SEVERAL
`VIEWS OF THE DRAWINGS
`
`The foregoing summary may be better understood when
`read in conjunction with the appended drawings. For the
`purpose of illustrating aspects of the invention,
`there is
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`US 9,610,237 B2
`
`3
`shown in the drawings data and embodiments of the inven-
`tion. It should be understood, however, that the invention is
`not limited to the precise arrangements and instrumentalities
`shown.In the drawings:
`FIG. 1 shows the infrared spectrum of an exemplary
`non-polymeric ester of the invention, deheptyl succinate;
`FIG. 2 shows that infrared spectrum of an exemplary
`polymeric ester of the invention, GSC Type 4;
`FIG. 3 shows spread rate of the silicone replacement as
`compared to that of the conventional silicone material in
`graphic form;
`FIG.4 is a table showing the reactant amounts of various
`sample and comparative sample formulations provided to
`human test subjects in a panel evaluation of comparative
`skin feel properties;
`in
`FIG. 5 is a copy of the survey used by the panel
`evaluating the sample and comparative sample formula-
`tions;
`FIG. 6A is a chart presenting the skinfeel data collected
`from a panel of evaluators who compared the skinfeel of an
`embodimentof the inventionto that of a control formulation
`containing a dimethicone;
`FIG. 6B is a chart presenting the skinfeel data collected
`from a panel of evaluators who compared the skinfeel of a
`first additional embodiment of the invention to that of a
`
`control formulation containing a dimethicone;
`FIG. 6C is a chart presenting the skinfeel data collected
`from a panel of evaluators who compared the skinfeel of a
`second additional embodiment of the invention to that of a
`
`control formulation containing a dimethicone;
`FIG. 6D is a chart presenting the skinfeel data collected
`from a panel of evaluators who compared the skinfeel of a
`third additional embodiment of the invention to that of a
`control formulation containing a dimethicone;
`FIG. 6E is a chart presenting the skinfeel data collected
`from a panel of evaluators who compared the skinfeel of a
`fourth additional embodiment of the invention to that of a
`
`control formulation containing a dimethicone;
`FIG. 7A showsa control formulation sample and a sample
`that is an embodimentof the invention before evaluation by
`the cotton ball tackinesstest;
`FIG. 7B showsthe samples of FIG. 7A after evaluation by
`the cotton ball tackiness test;
`FIG. 7C showsa control formulation sample and a sample
`that is a first additional embodiment of the invention before
`evaluation by the cotton ball tackiness test;
`FIG. 7D showsthe samples of FIG. 7C after evaluation by
`the cotton ball tackinesstest;
`FIG. 7E showsa control formulation sample and a sample
`that is a second additional embodiment of the invention
`before evaluation by the cotton ball tackiness test;
`FIG. 7F shows the samples of FIG. 7E after evaluation by
`the cotton ball tackinesstest;
`FIG. 7G showsa control formulation sample and a sample
`that is a third additional embodimentof the invention before
`
`evaluation by the cotton ball tackiness test;
`FIG. 7H showsthe samples of FIG. 7G after evaluation by
`the cotton ball tackinesstest;
`FIG. 71 shows a control formulation sample and a sample
`that is a fourth additional embodiment of the invention
`
`before evaluation by the cotton ball tackiness test;
`FIG. 7J shows the samples of FIG. 7I after evaluation by
`the cotton ball tackinesstest;
`FIG. 7K showsa control formulation sample and a sample
`that is a fifth additional embodimentof the invention before
`
`evaluation by the cotton ball tackiness test;
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`FIG. 7L showsthe samples of FIG. 7K after evaluation by
`the cotton ball tackinesstest;
`FIG. 8 showsthe results of a pigment grind evaluation;
`and
`FIG. 9 showsthe results of a shine (gloss) evaluation of
`hair to which the silicone replacements were applied.
`
`DETAILED DESCRIPTION OF THE
`INVENTION
`
`The invention described herein encompasses silicone
`replacements for use in personal care formulations (such as,
`without limitation, shampoos, cleansers, conditioners, cos-
`metics and lotions) that are substantially free of silicone(s)
`but have substantially equivalent
`tactile and/or end use
`characteristics. Specifically, the applicants have made the
`surprising discovery that by mixing certain types of natural
`(i.e., non-petrochemically-derived) ester
`fluids,
`certain
`desirable characteristics ordinarily imparted to personal care
`formulationsby silicone fluids can berealized, including, for
`example, spreading rate, skin feel, tack reduction, pigment
`dispersancy, and hair shine. Usingthe silicone replacements
`of the invention, one can formulate personal care formula-
`tions, including skin and hair products, that contain natural
`ingredients, are substantially free of silicone, and are per-
`ceived by the human endusers as having the sameor similar
`aesthetic, tactile and/or skinfeel properties of conventional
`silicone containing formulations.
`By “substantially free of silicone,” it is meant that the
`personal care formulations are formulated without the inclu-
`sion of any initial compounds containing silicone groups.
`For example, the formulations of the invention contain less
`than 0.09 wt % ofsilicone, and preferably 0.08% by weight
`orless.
`The invention includes a natural silicone replacement for
`use in personal care formulations that is a mixture ofat least
`one polymeric ester and at least one non-polymeric ester.
`‘The term “natural,” as used herein describing any acids,
`alcohols and/or esters, meansthat all atoms contained in the
`structure(s) of the acid, ester or alcohol that are used to
`prepare the esters are obtained from renewable and/or sus-
`tainable sources. By “renewable and sustainable,”it is meant
`that the carbon is not obtained from petrochemical sources.
`Exemplary carbon sources that are not petrochemical may
`include, but are notlimitedto, plant, agricultural or forestry
`waste biomass.
`Particularly useful in the invention are mixtures or blends
`of non-polymeric and polymeric esters derived from the
`esterification of natural acids and alcohols. The term “esteri-
`fication” is used herein to describe a condensation reaction
`
`between a carboxylic acid group and/or a carboxylic acid
`ester group with an hydroxyl group. An “esterification
`reaction product” is a resultant product of this event. The
`silicone replacements included in the invention are a blend
`of polymeric and non-polymeric esters formed from esteri-
`fication reactions.
`
`Eachof the esters present in the silicone replacement fluid
`is derived from theesterification of at least one dicarboxylic
`acid. In the practice of the invention, the polymeric ester is
`an esterification reaction product of at least onefirst dicar-
`boxylic acid, at least one first monofunctional alcohol or
`monofunctional carboxylic acid and glycerin and/or a
`derivative thereof. The polymeric esters in a given silicone
`replacement may be made from the samefirst dicarboxylic
`acid, first monofunctional alcohol or monofunctional car-
`boxylic acid, and glycerin or glycerin derivative or it may be
`prepared from a mixture of first dicarboxylic acids, first
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`US 9,610,237 B2
`
`5
`monofunctional alcohols and/or monofunctional carboxylic
`acids, and glycerin or glycerin derivatives or any permuta-
`tion of these materials, such that the “polymeric ester”
`includedin the blend/silicone replacementis itself a blend or
`mixture of various polymeric esters.
`The non-polymeric ester of the silicone replacementis a
`reaction productof at least one second dicarboxylic acid and
`at least one second monofunctional alcohol. As with the
`
`polymeric esters, the non-polymeric ester in a given silicone
`replacement may be made from the same second dicarbox-
`ylic acid and a second monofunctional alcohol or it may be
`prepared from a mixture of second dicarboxylic acids and
`second monofunctional alcohols or any permutation of these
`materials, such that the “non-polymeric ester” included in
`the blend/silicone replacementis itself a blend or mixture of
`various non-polymericesters.
`In the case of each of the polymeric ester and the
`non-polymeric ester,
`suitable dicarboxylic acids and/or
`monofunctional alcohols may independently contain carbon
`chains of medium orshort lengths (although the polymeric
`and non-polymeric esters need not be prepared from initial
`materials having the same number of carbon atoms). By
`“short” chain length, it is meant that the compound contains
`about one to about six carbon atoms. By “medium”chain
`length, it is meant that the compound contains about seven
`to about twelve carbon atoms.
`In some embodiments,
`the dicarboxylic acids and/or
`monofunctional alcohols may independently contain chains
`of about 1, about 2, about 3, about 4, about 5, about 6, about
`7, about 8, about 9, about 10, about 11, about 12, about 13,
`about 14, or about 15 carbon atoms. In other embodiments,
`the dicarboxylic acids and/or monofunctional alcohols may
`independently contain chains of about 10 to about 25 carbon
`atoms and/or about 1 to about 10 carbon atoms. In any of the
`embodiments of the invention, one or moreof the dicarbox-
`ylic acids and/or monofunctional alcohols may indepen-
`dently have carbon chains that are independently linear
`and/or branched and/or carbon atomsthat are independently
`saturated and/or unsaturated and/or
`functionalized or
`unfunctionalized. In some embodiments, at least one of the
`carbon atoms of the chain is saturated and the others are
`unsaturated.
`
`Particularly useful acids and/or alcohols may be thosethat
`contain linear, saturated chains containing about three to
`about ten carbon atoms.
`Any dicarboxylic acids known or developed in the art
`may be independently selected for use in the esterification
`reactions, including, without limitation, 1,4-butanedioic acid
`(succinic acid), 1,5-pentanedioic acid (glutaric acid), 1,6-
`hexanedioic acid (adipic acid), 9-nonanedioic acid (azelaic
`acid) and 1,10-decanedioic acid. In some circumstances,
`sebacic acid maybepreferred.
`Any monofunctional dicarboxylic acids known or devel-
`oped in the art may be independently selected for use in the
`esterification
`reaction,
`including, without
`limitation
`hexanoic acid (caproic acid), heptanoic acid, octanoic acid
`(caprylic acid) nonanoic acid, decanoic acid (capric acid),
`and dodecanoic acid (lauric acid.) It some circumstances,
`caprylic acid and capric acid may bepreferred.
`Glycerin or glycerin derivatives are used in the prepara-
`tion of the polymeric ester. Glycerin derivatives include, but
`are not limited to, those derived from the condensation of
`glycerol with itself to higher glycerol ether derivatives,
`knownas polyglycols.
`Any monofunctional alcohols known or developed in the
`art may be used, including, without limitation 1-hexanol,
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`1-heptanol, 1-octanol, 2-octanol, and 1-decanol. Under
`some conditions, 1-heptanol may be preferred.
`the acid(s),
`In each case,
`it may be preferred that
`alcohol(s) and/or polyols (glycerin or is derivatives) are
`natural as defined above.
`
`In the formation of the esters that make up the silicone
`replacements included in the invention from natural reac-
`tants, one or more dicarboxylic acids are esterified with one
`or more monofunctional alcohols and/or one or more mono-
`
`functional carboxylic acid. The esters may be formed by any
`esterification technique known in the art. For example, in a
`first reaction, a non-polymeric ester derived from the esteri-
`fication of one or more monofunctional alcohols with one or
`
`more dicarboxylic acids is prepared. In a secondreaction, a
`polymeric ester derived from one or more dicarboxylic
`acids, one or more monofunctional carboxylic acids, and
`glycerol and/or polyglycerol is prepared.
`To prepare the silicone replacement, non-polymeric and
`polymeric esters are then blended in an identified ratio such
`that the replacement imparts to a personal care formulation
`performance characteristics that correspond the silicone
`fluid that the mixture is intended to replace, such as a
`cyclomethicone and/or dimethicone fluids. “Performance
`characteristics” means the desirable end properties experi-
`enced by the consumer and/or the product formulator that
`silicone fluids impart to personal care formulations, such as
`spread rate, skin feel and other tactile properties (slip or
`drag, feeling of oiliness, residual afterfeel, absorption rate
`into skin, gloss/shine of hair, light- versus heavy-feeling),
`tackiness (stickiness), and the ability to disperse pigments.
`The polymeric and non-polymeric esters may be present
`in the silicone replacementin any ratio desired, so long as
`the performance characteristics are achieved or retained.
`Evaluation of a given blend to ensure it demonstrates
`adequate and desired performance characteristics as a sili-
`cone replacement (as dictated by the end personal care
`formulation) is a matter of routine testing, well within the
`skill of an ordinary formulator. In some cases the ratio by
`weight of polymeric ester to non-polymeric ester may be
`about 1 to about 1 to about 1:to about 50 (that is, ~1:~1 to
`~1:~50).
`In some circumstances, as a matter of formulation con-
`venience, it may be desirable to use an identified ratio of
`polymeric polymer to non-polymeric polymerin the silicone
`replacementthat is adjusted so that the silicone replacement
`has a specific viscosity. (That way, a personal care product
`formulator seeking to substitute a silicone replacement into
`his/her formulation in place of a silicone of a specific
`viscosity will not have to modify his/her formulation in
`other ways,
`increasing the convenience of the silicone
`replacement.) In such circumstances, the indentified ratio
`may determined by measuring the viscosity of the end
`product(the silicone replacement), and adjusting theratio as
`necessary to arrive at the target viscosity. For example, one
`may desire a silicone replacement that has a viscosity of
`about 1 to about 1000 cSt, about 10 to about 500 cSt, about
`20 to about 350 cSt, about 50 to about 200 cSt and/or about
`70 to about 100 cSt. In some circumstances, for ease of
`handling by personal care formulators, it may be desirable to
`prepare silicone replacements having an identified ratio of
`polymeric to non-polymeric esters that results in viscosities
`of about 10, about 20, about 50, about 100, about 200, and/or
`about 350 (all cSt).
`The invention also includes personal care formulations
`that are natural and are substantially free of silicone. The
`personal care formulations include the silicone replacement
`of the invention andat least one more ingredient(that is not
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`7
`a silicone). Any ingredient that can be applied to hair, skin
`or nails may be included, including pharmacological agents.
`Exemplary ingredients may include, without limitation, a
`surfactant, a flavorant, a fragrance, an opacifier, a colorant,
`a wax, an emulsifier, a fat, an oil, a preservative, a UV
`absorbing compound, a detergent, foaming agents, stabiliz-
`ers, pH modifiers, foaming agents, moisturizers, water, an
`alcohol, a urea, a cosmetic active, a pigment, a wetting
`agent, a skin or hair conditioner and a solvent. Others may
`include acetone, water, alcohol, parabens, mineral oil, veg-
`etable oil, olive oil, paraffin, PEG, polyethylene, polyethyl-
`ene glycol, polyoxyethylene, oxynol, petrolatum, sodium
`lauryl sulfate, sodium laureth sulfate, sodium myrethsulfate,
`sodium oleth sulfate, sodium ceteareth sulfate, DMDM
`15
`Analytical properties of the ester are shown below in
`
`hydantoin, sodium hydroxymethylglycinate,—trietha-
`Table 1.
`nolamine,
`cocamide diethanolamine,
`laurimide dietha-
`nolamine,
`linoleamide diethanolamine, oleamide dietha-
`nolamine,
`oxybenzone,
`essential
`oils,
`an emollient,
`octylmethoxycinnamate, titanium dioxide, and zinc oxide.
`The pers