Features

Recent Patent Applications For Hair Care Polymers

By Robert Y. Lochhead, The Institute for Polymer Science, The School of Polymers & High Performance Materials; The University of Southern Mississippi and Institute for Formulation Science | November 3, 2010

At the Institute for Formulation Science, we monitor patents and patenting as part of our current awareness activities for the Partnership for Innovation. In this article, we have selected interesting advances that have recently been reported in U.S. patent applications.

I have reported in previous articles that several polymeric systems have been introduced that enable restyling of hair after the initial application. L’Oréal researchers invented such a system based on polymers with a glass transition temperature less than 10°C and a minimum defined separation force. One such system was based on branched sulfonic polyesters, and in this disclosure Eastman’s AQ resin 1350 (INCI Polyester-5) was particularly preferred.1 Recently, it has been disclosed that when these polymers are applied from alcohol solutions, they are not homogeneously distributed over the hair and the hair feels dry after brushing. It has been demonstrated that these drawbacks can be overcome by including a polysaccharide thickener in the composition.2 The polysaccharides can be chosen from cellulose derivatives or Gellan gums. An example of the improved compositions that confer natural, long-lasting hold is shown in Table 1.

It may be expected that the interaction of anionic polyester-5 and nonionic polysaccharides may be minimal and this would favor their miscibility. However, the interaction between cationic polysaccharides and anionic polyester-5 commonly results in precipitated complexes rather than gels. In this instance it is interesting that Eastman Chemical can make compatible gels containing both Polyquaternium-10 and Polyester-5.3 These clear gels offer the prospect of styling conditioners or conditioning styling agents.

Table 1: Examples of a composition for natural hold from U.S. Patent Application 2010/0236569

AB
Branched sulfonic polyester52
Hydroxypropyl methyl cellulose2.2—
Gellan gum—1
Glycerol31
Propylene glycol1—
Sorbitol—2.7
Sodium chloride—0.25
PEG-40 hydrogenated castor oil0.50.5
Fragrance0.20.2
Preservativesq.s.q.s
Waterto 100to 100

Soft hold can be achieved by combining special polyurethane with PVP homopolymers or copolymers.4

Chitosan derivatives are being applied to enhance long-term hold. Thus, compositions containing chitosan derivatives and elastomeric silicones improve the fullness and long-term hold of hair.5 Long–lasting hold is also achieved by combining chitosan derivatives with a polymer comprising an amino-substituted vinyl unit, a hydrophobic nonionic vinyl unit, an associative vinyl unit, and a semi-hydrophobic vinyl surfactant unit.6

Thornsten Knapp of Henkel took inspiration from the proteins that allow mussels to adhere tenaciously to surfaces even when they are underwater. Blue marine mussel (Mytilus edulis) secretes adhesive proteins containing the amino acid, L-3,4-dihydroxy-L-phenylalanine (DOPA). There is an ample supply of these proteins at the interface between adhesive pads of the mussels and the surfaces to which they adhere.7,8 The o-dihydroxyphenyl (catechol) functional group of DOPA has strong affinity for many surfaces.9 Under oxidizing conditions, the catechol group transforms its chemical structure into a quinone; aqueous gelling agents have been produced by reacting DOPA with thiol end-capped Poloxamer.10 Knapp used copolymers that contained a group shown in Fig. 1.


Fig. 1 : Monomeric unit similar to catechol,
that was used to synthesize adhesive copolymers.


This group is similar to catechol and the copolymers adhere tenaciously to surfaces. However, the mussel proteins and these copolymers do not confer styling on hair. Fortunately, the copolymer readily coats polysilicic acids and this forms a particulate material that adheres to hair and allows recovery of style even when it has been altered by wind or water.11

Permanent waving involves a first step of reducing the cystine bonds within the hair fiber, shaping the hair into the desired style, then re-oxidizing it to restore the S-S bonds in their new configuration. This process is known to damage the hair and the damage is exacerbated by the common practice of heating the hair with perming irons. Many treatments have been applied to mitigate the damage. The application of cationic polymers to the hair surface during the perming process can reduce the damage.12 This is exemplified by a reducing treatment with cysteine and protection from an amodimethicone (Wacker- Belsil ADM).

Thickeners
Frederic Blondel reports that he is surprised that he can thicken aqueous cosmetic formulations with a copolymer of acrylamide and acrylamidomethylsulfonate (INCI Acryloyldimethyltaurate) crosslinked with an amine-based crosslinking agent that includes three allyl groups.13 Polymeric thickeners based on acryloyldimethytaurine and its salts were introduced into the market in the 1990s14 (Aristoflex AVC from Clariant) and they were found to offer better thickening efficiencies than conventional carbomers in acid and salt-containing compositions. The Blondel patent application indicates that the triallylamine crosslinkers resist hydrolysis whereas the more common dimethylacrylamide crosslinker can be hydrolyzed on acid solutions.

Fig. 2. The structure of Acryloyldimethyltaurate
from WO 98/00094


It is reported that in end-product compositions, the concentration of residual acrylamide monomer in such acrylamide copolymers can rise during storage. An inverse emulsion polymerization process has been devised to produce acrylamide/acryloyldimethyltaurate copolymers that maintain acrylamide concentrations below 2ppm upon storage of the final product.15 This was demonstrated by thickening water with the copolymers and heating the resulting gel to 80°C for 48 hours while monitoring the acrylamide monomer concen- tration by high performance liquid chromatography using an ultra-violet detector.

Crosslinked polyelectrolyte thickeners such as carbomers are inherently sensitive to the presence of salt in solution. This property is used to advantage in carbomer delivery systems that collapse upon application to the salt on the surface of skin, to effectively deliver benefit agents. During the 1990s hydrophobically modified versions of carbomers (acrylates/C10-30 alkyl acrylate crosspolymer) were introduced with both emulsifying and rheology-modifying properties.16 These polymeric emulsifiers offered a route to surfactant-free emulsions with triggered oil release upon application to the skin. These new emulsifiers also overcame the tendency of conventionally emulsified products to re-emulsify after the emulsion broke. This led to products such as sports sunscreen that resisted sweat. Now, (meth)acrylic acid/alkyl (meth)acrylate copolymers, crosslinked with allyl ethers of pentaerythritol have been disclosed as thickening systems that maintain aqueous solution viscosity even in the presence of electrolyte.17

Stimuli-responsive systems have piqued our interest for approximately 20 years. Most commonly, these are systems that are soluble at low temperatures and they show gelling or phase separation when the temperature is raised above a critical temperature (the lower critical solution temperature) that is usually called the cloud point. The very name “cloud point” conveys the impression that these systems become translucent or opaque above the critical temperature. In some cosmetic compositions it is desirable to form clear gels when the critical temperature is reached and Florence L’Alloret of L’Oréal announced that she has achieved this goal by grafting random PEG/PPG copolymers to a poly(meth)acrylic acid backbone.18This was achieved by the reaction of amine end-capped random PEG/PPG copolymers (Jeffamine from Huntsman) with sodium poly(meth)acrylate. The polymers could be tailored to gel within a few degrees over a desired temperature range and the transition temperature could be tailored within the limits of about 20°C to about 60°C.

Hydrophobins are small proteins formed by filamentous fungi such as Schizophyllum commune. The purpose of these proteins seems to be to adjust the free energy of multifarious surfaces to the optimum surface free energy for invasion by the fungus. For example, some hydrophobins spontaneously raise the surface free energy of poly(tetrafluoroethylene) and lower the surface free energy of glass to an optimal range for the benefit of the fungus. Hydrophobins form relatively non-viscous aqueous solutions at low concentrations (less than 3%) but gel at higher concentrations.Surfaces coated with hydrophobins have been suggested for use as demulsifiers, evaporation retardants and soiling inhibitors (U.S. Patent Publication 2009/ 0305930). Their use as thickeners and emulsifiers has also been proposed. Apparently, hydrophobins interact synergistically with a wide range of water-soluble polymers to confer synergistic thickening and this could be used to advantage in cosmetic gels, and conditioners and in cleansing compositions such as shampoos.

Superhydrophobicity
The ability of the lotus leaf to repel water and soil from its surface is well known. The lotus leaf achieves this feat by having a regular periodic hydrophobic nanostructure on its surface. In recent years, there has been a fairly large effort to mimic the lotus leaf and to produce regular nanostructured superhydrophobic surfaces that could be self-cleaning. Avon researchers have proclaimed the ability to render hair and skin superhydrophobic by applying a water-in-silicone emulsion that contained a hydrophobic film-forming polymer and hydrophobic particles.19 As shown in Fig. 3 (next page), water contact angles of greater than 140° were realized. In this instance, the hydrophobic film-forming polymer is acrylates/dimethicone copolymer and the hydrophobic particles are hydrophobic fumed silica and iron oxide and triethoxycaprylsilane.

Fig. 3: A water drop on a superhydrophobic surface prepared by treating a glass slide with a water-in-silicone emulsion that contained a hydrophobic film-forming polymer and hydrophobic particles. (Reproduced from U.S. Patent Application 20100266648.)

The patent specification describes that such films could possibly shield the hair from sweat, rain and dirt. Moreover, the researchers suggest that treatment with such a composition could possibly allow the wearer to go swimming and then to spontaneously dry her hair with a mere shake of the head.

BASF researchers have pronounced that they have created ampholytic terpolymers for 2-in-1 shampoos that have a strong affinity for keratin substrates even in the presence of anionic surfactants, can provide conditioning on their own due to the presence of a hydrophobic monomer, form complexes with anionic, fatty amines and cationic surfactants for stimuli-responsive deposition for hair conditioning,andthey form complex coacervates that can act as deposition aids for silicones beneficial agents. An example terpolymer is synthesized from acryloylaminopropyl-N,N,N-trimethylammonium chloride, acrylic acid and diallylamine. These polymers were shown to enhance deposition of silicone from a conditioning shampoo, and reduce the“squeakiness” of hair and lowered the wet and dry combing friction of hair.20

An alternative approach to the use of shampoo is to treat the hair with a leave-in product that makes the hair feel clean and smell fresh. Such an approach is espoused by Unilever researchers who claim that compositions based on clays and cationic polymers do provide hair sprays that both style the hair and leave it feeling and smelling clean.21

Summary
In this short article, we have highlighted some trends that are apparent from an examination of recent published patent applications. In hair styling, the trends are toward restylability and long-lasting soft fixation of style. There is also a continuing improvement in deposition systems exemplified by conditioning shampoos. Sophisticated surface modification is arising as a result of advances in nanoscience. Two of the most notable trends are the move toward natural and biomimetic systems and the trend toward polymer blends.

Polymers are not usually incompatible and this move is interesting insofar as it will require definitive understanding of the systems to achieve goals of compatibility and synergy.

References
1. Rollat, C. Dupuis, H. Samian; “Hairstyling composition capable of being remodelled,” WO Patent 98/38969, Sept 11, 1998, assigned to L’Oreal.
2.J. Gawtrey, C.Bebot, D. Pasquet;“Cosmetic composition comprising a branched sulphonic acid polyester and a thickener and uses in hairstyling.” U.S. Patent Application 2010/0236569, Sept. 23, 2010.
3. Clear conditioning gels with Eastman AQTM 48 polymer and UCARE polymers JR;Eastman Technical Bulletin.
4. S. Dorr, S. Hofacker, S. Viala,“Hair setting composition,” U.S. Patent Application 2010/0215608, Aug. 26, 2010; assigned to Bayer MaterialScience AG.
5. H. Van Flodrop, D. Hentrich; “Cosmetic compositions with chitosan and silicone elastomers,” U.S. Patent Application 2010/0215604, Aug. 26, 2010.
6. M. Loifenfeld; S. Birkel; “Cosmetic composition,” U.S. Patent Application 2010/0215607, Aug. 26, 2010.
7. H. Lee, N. F. Scherer and P. B. Messersmith, Proc. Natl. Acad. Sci. U. S. A., 2006, 103, 12999–13003.
8. H. Lee, S. M. Dellatore, W. M. Miller and P. B. Messersmith, Science, 2007, 318, 426–430.
9. J. H. Waite and M. L. Tanzer, Science, 1981, 212, 1038–1040.
10. Y. Lee, H.J. Chung, S. Yeo, C-H Ahn, H. Lee, P. B. Messersmith, T. G. Park; Soft Matter, 2010, 6, 977-983.
11. T. Knappe, “Styling agent,” U.S. Patent Application 2010/0239623, Sept. 23, 2010.
12. K. Dutheil-Gouret, M. Pallanchard, A. Livoreil; “Method for shaping the hair using at least one reducing composition, at least one care composition, and heating,” U.S. Patent Application 2010/0263683, Oct. 21, 2010.
13. F. Blondel, “Polymeric Thickening Composition,” U.S. Patent Application 2010/0247473, Sept. 30, 2010.
14. C. DuPuis, I. Hansenne, M. Maubru, L. Sebillotte-Arnaud; and R. Lorant, “Use in cosmetics of a cross-linked and at least 90% neutralized poly(2-acryl amido-2-propane sulfonic acid) and topical compositions containing same,” WO 98/00094; Published Jan. 8, 1998. Assigned to L’Oréal.
15. P. Mallo, O. Braun, F. Guy, A. Bonnardel,“Process for the preparation of inverse latex of acrylamide-based polymers and composition comprising said latex”, US Patent Application 20100233108, Sept. 16, 2010, assigned to Scott Bader Company Limited.
16. R. Y. Lochhead, J. Y. Castaneda and W. J. Hemker; “Stable and Quick-Breaking Topical Skin Compositions from Oil-in-Water Emulsions Containing Acrylic Polymers,” European Patent 268164 A2, May 25, 1988; U.S. Patent 5,004,598, April 2, 1991; assigned to BF Goodrich.
17. M. Yoshinaka, Y. Morimitsu, S. Kobayashi, M. Kosugi; “Meth(acrylic acid/alkyl (meth)acrylate ester copolymer and cosmetic preparation containing the same,” U.S. Patent Application20100267845, Oct. 21, 2010, assigned to Sumitomo Seika Chemicals Co.
18. F. L’Alloret, “Polymer compositions comprising water-soluble units and LCST units, and aqueous composition comprising them,” U.S. Patent Application 2010/0190870, July 29, 2010, assigned to L’Oréal.
19. R.A. Ranade, J.R.Glynn, M.S.Garrison, S. Martin, P. Maitra;“Cosmetic compositions for imparting superhydrophobic films,” U.S. Patent Application 2010/0266648, Oct. 21, 2010, assigned to Avon Products.
20. M. Gamez-Garcia, X-Z. Zhou, “Ampholytic terpolymers for use in personal care compositions,” U.S. Patent 2010/0226868, Sept. 9, 2010.
21. C.C.D. Giles, K. Treesilvattanakul;“Hair treatment composition,” U.S. Patent Application 2010/0221206, Sept. 2, 2010.

Related End-User Markets:

Related Raw Materials:

  • Shin-Etsu Updates Sunscreen Toolbox

    October 6, 2011
    Shin-Etsu Updates Sunscreen Toolbox

  • Monday Morning Quarterback

    Monday Morning Quarterback

    Christine Esposito, Associate Editor||February 6, 2017
    Super Bowl commercials are big business. Let’s look at some of personal and household care brands that bought spots this year

  • Discourse on Disclosure

    Discourse on Disclosure

    Tom Branna, Editorial Director||January 6, 2017
    Transparency impacts the cleaning industry.

  • The Top Stories of 2016

    The Top Stories of 2016

    December 26, 2016
    The companies and topics that grabbed headlines and your attention this year.

  • What the Halal  Is Going On?

    What the Halal Is Going On?

    Imogen Matthews , In-Cosmetics||February 2, 2017
    Demand for these beauty products is surging thanks to a fastgrowing Muslim population.

  • Relief for Sensitive Scalps

    Relief for Sensitive Scalps

    Guadalupe Pellon and Annette Mehling , BASF||February 2, 2017
    BASF researchers detail the attributes of the company’s highly effective hair care system focusing on scalp sensitivity.

  • Defining Clean Skin

    Defining Clean Skin

    Nava Dayan PhD, Dr. Nava Dayan LLC||February 1, 2017
    A look at the issues, research and history surrounding this controversial topic.

  • Linked In

    Linked In

    Christine Esposito , Associate Editor||February 1, 2017
    Through virtual reality, apps and connected devices, beauty and personal care brands can strengthen their customer relations

  • On the Edge

    On the Edge

    January 6, 2017
    Expanding beauty brands to watch in 2017

  • A New Contender?

    A New Contender?

    January 6, 2017
    Detergent sales are up, innovation continues and Henkel is determined to make it a dogfight in the segment.

  • Engagement 2016

    Engagement 2016

    January 6, 2017
    CSPA convenes in Fort Lauderdale for annual meeting.

  • Slow & Steady

    Slow & Steady

    Tom Branna, Editorial Director||December 1, 2016
    In a tumultuous environment, steady gains posted in the industrial and institutional cleaning sector are welcomed.

  • The World Comes to Orlando

    The World Comes to Orlando

    Tom Branna, Editorial Director||December 1, 2016
    More than 1,600 chemists traveled to Florida for the IFSCC Congress

  • The Plex Phenomenon

    The Plex Phenomenon

    Denise Costrini, Croda North America||December 1, 2016
    Croda details the hair-protecting qualities of bond multipliers and the company’s new bond-building formulation system.

  • New Hair Care Ingredients

    December 1, 2016
    Check out the latest releases from suppliers.

  • Hair & Now

    Hair & Now

    Melissa Meisel, Associate Editor ||December 1, 2016
    The shampoo and conditioner category is expanding with modern takes on these classic formulations.

  • New Ingredients for  Household Cleaners

    New Ingredients for Household Cleaners

    Tom Branna, Editorial Director||November 2, 2016
    Here are ingredients introduced by suppliers during the past 12 months.

  • A-Okay!

    A-Okay!

    Imogen Matthews, For In-Cosmetics||November 2, 2016
    K-Beauty influences cosmetic development around the world.

  • Shine On

    Shine On

    Melissa Meisel, Associate Editor||November 2, 2016
    Oral care products are rising to the task with innovative components.

  • Change Is in the Air

    Change Is in the Air

    Doreen Wang, BrandZ ||October 3, 2016
    Technology is changing the personal care market

  • Proof Positive

    Proof Positive

    Christine Esposito, Associate Editor||October 3, 2016
    Testing service providers enable companies to back up their claims and stay in compliance with regulations.

  • Back to School

    Back to School

    Tom Branna, Editorial Director||September 1, 2016
    It may be September, but class was in session this summer during the Private Label Manufacturers Association’s Executive Educ

  • How Green Is Your Surfactant?

    How Green Is Your Surfactant?

    Tom Branna, Editorial Director ||September 1, 2016
    Suppliers offer a range of solutions to help household and personal care product formulators develop formulas

  • Special Effects

    Special Effects

    Melissa Meisel, Associate Editor||August 1, 2016
    Fall 2016 color cosmetics reflect light and offer a focus on elements like pigment, slip and wear.

  • Silent Partners

    Silent Partners

    Christine Esposito, Associate Editor||August 1, 2016
    From research & development to logistics to confidentiality, savvy distributors help finished formulators achieve their goals

  • Sustainability is Omnipresent

    Sustainability is Omnipresent

    Christine Esposito , Associate Editor||July 1, 2016
    Industry stakeholders convene in New York City for Organic Monitor’s annual event

  • Perceived Perfection

    Perceived Perfection

    Christine Esposito, Associate Editor||July 1, 2016
    From primers to pressed powders, facial cosmetics help create the illusion of a flawless complexion.

  • Quaternized Guar Is a Natural Solution

    Quaternized Guar Is a Natural Solution

    Tom Schoenberg, Schoenberg Consulting||July 1, 2016
    The polymer has applications in a range of skin and hair care formulas that does not build up on hair with repeated use

  • Take Notice

    Take Notice

    Melissa Meisel , Associate Editor||June 1, 2016
    Packaging trends revolve around trendy artwork, eco-conscious materials—and portability is a plus too!