[go: up one dir, main page]

WO1996006878A1 - Composes de polyester derives et leurs utilisations - Google Patents

Composes de polyester derives et leurs utilisations Download PDF

Info

Publication number
WO1996006878A1
WO1996006878A1 PCT/US1995/010789 US9510789W WO9606878A1 WO 1996006878 A1 WO1996006878 A1 WO 1996006878A1 US 9510789 W US9510789 W US 9510789W WO 9606878 A1 WO9606878 A1 WO 9606878A1
Authority
WO
WIPO (PCT)
Prior art keywords
hair
compound
skin
formula
polyester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1995/010789
Other languages
English (en)
Inventor
David J. Grillo
Rocco V. Burgo
Robert W. Siegfried
Anna M. Howe
Thomas Grebenar, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Inolex Investment Corp
Original Assignee
Inolex Investment Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Inolex Investment Corp filed Critical Inolex Investment Corp
Priority to AU33724/95A priority Critical patent/AU3372495A/en
Publication of WO1996006878A1 publication Critical patent/WO1996006878A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/85—Polyesters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/74—Biological properties of particular ingredients
    • A61K2800/75—Anti-irritant

Definitions

  • the invention generally relates to polyester resins and formulations thereof. More specifically, the invention is directed to polyester resins derivatized with various functional groups, and to hair-care and skin-care formulations incorporating the derivatized polyester resins. BACKGROUND OF THE INVENTION
  • ingredients may either perform a specific function on the hair and skin such as
  • polymers of many types have been used over the past twenty years to perform some of these functions. These polymers include polyvinyl pyrrolidone derivatives, hydroxyl ethyl cellulose copolymers and derivatives, polysaccharides, polyethers and derivatives, and many others.
  • Polyester polyols have historically had limited use in personal care formulations. This is at least partly because most polyesters have limited performance properties in personal care product formulations, and they can be difficult to incorporate into stable formulations
  • Polyester polyols are used for non-personal care applications such as the diol component in polyurethanes, plasticizers for industrial applications and specific polymer additives including adhesion promoters, carrier vehicles and stabilizers. Though some classes of polyester polyols have been introduced for personal care application, they have not been derivatized in the ways disclosed herein, nor have efforts been made to derivatize polyester polyols specifically for the personal care applications as disclosed herein.
  • the invention is directed to compounds of the formula
  • R 1 is -N(R 5 ) (R 6 ) or -OR 7 ;
  • R 2 is independently C 2 -C 10 aliphatic;
  • R 3 is independently C 2 -C 10 aliphatic having 0-5 oxygen atoms as ether groups;
  • R 4 is R 1 ;
  • p is an integer between 3-100, inclusive;
  • R 5 is H or C 1 -C 10 aliphatic;
  • R 6 is -R 8 -N(R 9 ) 2 (R 1. ),
  • R 14 or -CH 2 CH (OH) CH 2 -NH-polysiloxane R 14 ;
  • R 11 is R 12 or C 1 -C 22 ;
  • R 12 is lithium, sodium, calcium, magnesium, ammonium monoalkylammonium, dialkylammonium, trialkylammonium, or
  • R 13 is C 1 -C 22 aliphatic
  • R 14 is halide, sulfate, phosphate, citrate, lactate, malate, fatty carboxylate or polymeric carboxylate
  • R 15 is C 1 -C 22 hydrocarbon
  • n is an integer between 1 and 5, inclusive
  • a further aspect of the invention is the product resulting from the reaction between at least one of a botanical derivative, an essential oil or a polysiloxane, and the polyester of the formula
  • R 1 is -OH or -O-R 3 -OH;
  • R 2 is independently C 2 -C 10
  • polyesters By derivatizing the polyesters with various functional moieties, they can be altered into materials which have wide- ranging physical and performance properties. Physical propertie can be varied widely in terms of solubility, viscosity, melting point, HLB value, hydrophilicity/hydrophobicity, hydrolytic stability, emulsion stability, surfactancy and others.
  • Performance properties of the derivatized polyesters include film-forming, moisture retention, emolliency, adhesion,
  • the derivatized polyesters can also be used to delive other functional ingredients with enhanced efficacy, where these properties are valued in skin-care and hair-care formulations.
  • compositions of the invention include derivatized polyester molecules and formulations comprising those derivatize polyester molecules, particularly in hair-care and skin-care formulations.
  • the polyester molecule of the invention terminates with endgroups, designated R 1 and R 4 , that contain functional groups, where the R 1 or R 4 groups are also known as functionalized endgroups, as described in detail below.
  • R 1 or R 4 groups are also known as functionalized endgroups, as described in detail below.
  • the preferred R 2 and R 3 groups are aliphatic, and not aromatic.
  • the polyesters of the invention having a polyester chain and functionalized endgroups are denoted herein as derivatized polyesters.
  • Preferred derivatized polyesters of the invention have the formula (II)
  • the derivatized polyesters have functional groups present only as part of the endgroups, as shown in Formula (II). However, in another embodiment of the invention, functional groups may be additionally present at one or more points along the polyester chain. In a preferred embodiment,
  • the polyester chain is linear, e.g., there are no crosslinks present, as shown in formula (II).
  • crosslinks may be present which provide for the joining together of two or more polyester chains through R 2 and/or R 3 groups.
  • Formula (Ila) represents a polyester resin of the invention which clearly indicates, with groups R 1S and R 18 , that the derivatized polyesters may have functional groups along the polyester chain, or cites for
  • an R 2 group of the invention has between 2 and 10 aliphatic carbon atoms, inclusive, where said aliphatic carbon atoms are present in a linear, branched and/or cyclic arrangement.
  • the R 2 group is a hydrocarbon, that is, it contains only hydrogen and carbon atoms.
  • the R 2 groups may additionally contain oxygen atoms, where said oxygen atoms are present in the form of one or more ether
  • R 2 group contains one or more oxygen atoms
  • Any of the exemplary R 2 hydrocarbon groups listed below may additionally contain not more than 5 oxygen atoms.
  • Exemplary hydrocarbon R 2 groups have molecular formulas selected from the group C 2 H 4 , C 3 H 6 , C 4 H 8 , C 5 H 10 , C 6 H 12 , C 7 H 14 , C 8 H 16 , C 9 H 18 and C 10 H 22 .
  • the carbon atoms are arranged in a straight chain, that is, R 2 is selected from the group having the formula (-CH 2 -) a , wherein a is 2 to 10,
  • An especially preferred straight chain R 2 group is butyl, -CH 2 -CH 2 - CH 2 -CH 2 -.
  • R 2 may also be a branched chain hydrocarbon group, where exemplary, non-limiting branched chain hydrocarbon groups include 1-methylethyl (-CH (CH 3 ) -CH 2 -), 1-methylpropyl (-CH(CH 3 )- CH 2 -CH 2 -), 2-methylpropyl ( -CH 2 -CH (CH 3 ) -CH 2 - ), 1, 2-dimethylethyl (-CH(CH3) -CH(CH3)-), 1-ethylethyl (-CH (CH 2 CH 3 ) -CH 2 - ), 1- methylbutyl (-CH(CH 3 ) -CH 2 -CH 2 -CH 2 - ), 2-methylbutyl (CH 2 -CH (CH 3 ) - CH 2 -CH 2 -), 1-ethylpropyl (-CH (CH 2 CH 3 ) -CH 2 -CH 2 -), 2-ethylpropyl (-CH 2 CH 3 ) -CH
  • R 2 may also contain a cyclic hydrocarbon group, where exemplary non-limiting R 2 groups with a cyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl groups.
  • R 2 may also contain one or more bicyclic arrangement of carbon atoms.
  • a single R 2 group may contain both a cyclic arrangement of carbon atoms and acyclic carbon atoms.
  • R 2 group may be substituted with m R 18 groups, where m is up to 5, and where the R 18 substituent is attached to the R 2 group in lieu of one of the hydrogen atoms otherwise present in the R 2 group.
  • the R 3 group of the invention has between 2 and 10 aliphatic carbon atoms, inclusive, and between 0 and 5 oxygen atoms, inclusive, and may have any of the atomic arrangements previously set forth for the R 2 groups.
  • Preferred R 3 groups include butyl (-CH 2 -CH 2 -CH 2 -CH 2 -), hexyl (-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - CH 2 -), 2-methylpropyl (-CH 2 -CH (CH 3 ) -CH 2 -), 1-methylethyl
  • Ethylene oxide derivatives are a preferred R group of the invention, where said ethylene oxide derivatives are recognized by having a formula corresponding to
  • R 3 group may be substituted with n R 16 groups, where n is up to 5, and where the R 16 substituent is attached to the R 3 group in lieu of one of the hydrogen atoms otherwise present in the R 3 group.
  • the addition of functionality to the polyester chain o the invention provides for a molecule having unique and desirable properties which are particularly valuable in hair-care and skin- care formulations.
  • the functionality is added to one or both of the ends of the polyester chain.
  • An R 2 or R 3 group closest to an end of the polyester chain will be denoted herein as a terminal R 2 or R 3 group, while all other R 2 and R 3 groups will be denoted as internal R 2 or R 3 groups.
  • functionality is preferably identical.
  • the functionality at each end the
  • the polyester chain is joined to functionality at one or more sites other than, or in addition to, the ends of the polyester chain.
  • the polyester molecules of the invention may have functional groups appended to the polyester chain at sites along the chain. More specifically, any R 2 and/or R 3 group of the polyester chain may be joined to one or more functional groups of the invention. In instances where at least one functionality is appended to at least one internal R 2 or R 3 group, then the polyester chain may terminate at both ends with either carboxylic acid or hydroxyl groups.
  • the polyester molecules of the invention necessarily have at least one functional group, where said functional groups will be described next.
  • the functional groups of the invention are selected to result in polyester derivatives having nonionic, anionic, cationic and zwitterionic character.
  • functional groups groups are hydrocarbon groups, which may be saturated or unsaturated.
  • Other exemplary nonionic groups come from essential oils, botanical extracts or have a polysiloxane structure.
  • exemplary anionic groups include the carboxylate, sulfonate and sulfate groups, which have associated therewith a neutralizing group of opposite charge, i.e., a counterion.
  • Exemplary cationic groups include ammonium, sulfoxonium and phosphonium, which have associated therewith a neutralizing group of opposite charge, i.e., a counterion.
  • Exemplary zwitterionic groups have both positively and negatively charged moieties present as part of the functional group.
  • zwitterionic group is the - + N(R 9 ) 2 - (CH 2 ) 1-3 -COO- group, where the nitrogen atom bears a positive charge and the carboxylate group bears a neutralizing negative charge.
  • Another functional group is the amine oxide functional group, represented by -N(R 9 ) 2 -O.
  • the amine terminus of the polyamino acid chain is joined to the polyester chain, and the carboxyl terminus is present as either a carboxylate salt or carboxylic ester.
  • an exemplary nonionic endgroup is a hydrocarbon chain.
  • Said hydrocarbon chain may have from 1 to 22 aliphatic carbon atoms, joined together by single and/or double bonds.
  • Preferred hydrocarbon chains have none or minimal branching, and are available as the hydrocarbon portion of natural or synthetic fatty acids.
  • the condensation of a fatty acid with a hydroxyl group from the polyester chain of the invention provides a convenient means of providing for polyester molecules having nonionic endgroups that comprise a hydrocarbon chain.
  • Exemplary fatty acids which may be used to introduce exemplary nonionic hydrocarbon endgroups to the polyester
  • molecules of the invention include fatty acids available from, for example, tallow, coconut oil, palm oil, palm kernel oil, canola oil, soybean oil, tall oil, peanut oil, cottonseed oil, rapeseed oil, cod liver oil, castor oil, sunflower oil, olive oil, safflower oil and carobseed oil.
  • Polyester chains may be reacted with essential oils or botanical extracts to provide derivatized polyesters of the invention.
  • An exemplary reaction between an essential oil or a botanical extract and a polyester chain may be conducted by contacting the reactants, optionally in the presence of a catalyst, and heating until at least some condensation reaction has occurred between the reactants.
  • the polyester chain and/or the essential oil or botanical extract may be chemically modified so as to provide a preferred means of linking the polyester chain to the functional group.
  • Exemplary essential oils are obtained from, for example, camphor, vanilla bean, mint, eucalyptus, pine, rose, jasmine, garlic, orange, lemon, lime, grapefruit, mandarin, almond, anise, avocado, bayberry, bergamot, mace, nutmeg, menthol, turpentine, gardenia, lilac, clove, and ylang ylang.
  • Exemplary botanical derivatives are extracts of, for example, comfrey, chamomile, algae, cucumber, arnica, nettle, kelp, hypericum, mimosa bark, hawkweed, myrtle, English oak, horsetail, spiraea, quince, rosemary, pansy, yeast, sage,
  • Polyester chains may be reacted with polysilicone and/or polysiloxane incorporating materials, to provide a
  • polysiloxane incorporating materials include the repeating unit - (Si(R) 2 O)-, where a preferred R group is C 1 -C 4 alkyl, and
  • a convenient polysiloxane material for preparing polysiloxane derivatized polyesters of the invention have a primary amine terminus, e.g., amodimethicone, having the structure HO [Si (CH 3 ) 2 -O] - [Si (OH) (CH 2 CH 2 -NH-CH 2 CH 2 -NH 2 ) ] x -H, where x is a positive integer ⁇ 1.
  • the polysiloxane materials may also have hydroxy termination to enable them to enter into
  • R 12 exemplary, non-limiting, positively charged counterions R 12 include sodium (Na + ), lithium (Li * ), calcium
  • RNH 3 + dialkylammonium (R 2 NH 2 + ), trialkylammonium (R 3 NH + ) and tetraalkylammonium (R 4 N + ) wherein an alkyl group R attached to a nitrogen atom of an alkylammonium group has from 1 to 20 carbon atoms, inclusive, and has 0-3 hydroxyl groups, inclusive.
  • said cationic endgroup which may be present in the derivatized polyesters of the invention, said cationic endgroup is characterized in having a positive charge, and is preferably selected from the group consisting of ammonium (including mono-, di- and trialkylammonium), sulfoxonium (-S(R) 2 -O + ) sulfonium (-S(R) 2 + ) and phosphonium (-P(R) 3 + ).
  • the R groups which are bonded to the N, S or P atom of the ammonium, sulfonium or phosphonium group, respectively, may have from 1 to 22 carbon atoms, where those carbon atoms may be present in aliphatic or aromatic arrangements, and where those R groups may additionally contain hydroxyl functionality.
  • R groups bonded to a nitrogen atom of an ammonium group preferably have 1 to 3 carbon atoms, and 0-3 hydroxyl substituents.
  • R 14 Exemplary, non-limiting, negatively charged counterions R 14 include organic and inorganic counterions, where inorganic counterions include halide (specifically fluoride, chloride, bromide or iodide), sulfate and phosphate, and where organic counterions include carboxylates such as citrate, lactate, malate, fatty acid carboxylate and carboxylates bonded to polymeric materials.
  • inorganic counterions include halide (specifically fluoride, chloride, bromide or iodide), sulfate and phosphate
  • organic counterions include carboxylates such as citrate, lactate, malate, fatty acid carboxylate and carboxylates bonded to polymeric materials.
  • said zwitterionic endgroup is characterized in having a positively charged site covalently bonded to a negatively charged site, in other words, the zwitterionic group is
  • An exemplary zwitterionic functional group is the betaine group, where an exemplary betaine is (- + N(R 9 ) 2 - (CH 2 ) 1 - 3 -COO-).
  • the group which links the cationic ammonium group to the anionic carboxylate group preferably has 1 carbon, so as to form - + NR 2 -CH 2 -COO-, however additional carbon atoms may be present.
  • the R groups which are bound to the ammonium nitrogen atom, i.e., the R 9 groups are independently selected from alkyl groups having 1 to 3 carbon atoms, where those carbon atoms may be optionally substituted with up to 3 hydroxyl groups.
  • Another exemplary endgroup is the amine oxide group (- + N(R 9 ) 2 -O-), where the R groups bonded to the nitrogen atom of the amine oxide are independently selected from alkyl groups having 1 to 3 carbon atoms, where those carbon atoms may be optionally substituted with up to 3 hydroxyl groups.
  • Another exemplary functional group is a polyamino acid chain.
  • a convenient source for a polyamino acid chain is
  • polyamino acid chain through its amine terminus, i.e., its terminal -NH 2 group, to the polyester chain.
  • the other end of the polyamino acid chain i.e., the carboxyl terminus, may be in the carboxylic acid, carboxylate or
  • the esterifying alcohol has from 1 to 22 carbon atoms.
  • the pH of the formulation into which the derivatized polyester having a polyamino acid chain is
  • the polyamino acid chain may have one or more positively or negatively charged groups.
  • proteins include, for example, keratin, collagen, silk, wheat, oat bran, zein, pea, milk, lentil, tobacco, egg yolk, soy, elastin, gelatin, and fibronectin.
  • polyester chain Preferably, a linear aliphatic dicarboxylic acid molecule , HOOC-R 2 -COOH, which may be simply called the diacid, is reacted with an excess of a dihydric compound, HO-R 3 - OH, which may be simply called the diol, under thermal conditions to form a polyester polyol. More specifically, the diacid is added to the diol and the mixture heated to between about 140°C and 240°C to form the polyester chain by condensation
  • a strong acid such as toluenesulfonic acid or methanesulfonic acid, or an organometallic compound, such as an organotin compound, may be added to catalyze the reaction.
  • condensation reaction is continuously separated from the forming polyester according to distillation techniques well known in the art.
  • polyester The number average molecular weight of the polyester chain, after its synthesis and before being
  • derivatized polyesters preferably ranges from about 2,000 to about 10,000.
  • a convenient means to quantitatively monitor the progress, or extent, of the reaction is to periodically pull aliquots of the reaction mixture and measure the acid number, or acid value, of the aliquots. It is preferred for the preparation of many of the derivatized polyesters of the invention that the polyester chain having a low acid number, preferably less than 2.
  • Acid numbers also known as acid values, may be determined as follows. 2-10 g of a sample is weighed and placed into a 200 to 300 mL Erlenmeyer flask, and an ethanol/benzene (1/1) mixture is added to dissolve the resin. If the resin is not readily dissolved, a small amount of acetone may be added. The resultant solution is titrated with a preliminarily
  • the above-mentioned KOH solution is prepared as follows. First, 1.5 g of KOH is dissolved in about 3 mL of water, and 200 mL of alcohol are added thereto, followed by stirring. After standing, a uniform clear solution is formed.
  • the concentration of the KOH solution is determined by titration with a standardized 1/10 N HCl solution.
  • Diacid molecules which may be employed to prepare the polyester chain of the invention include succinic acid, methylmalonic acid, fumaric acid, maleic acid, acetylene dicarboxylic acid, glutaric acid, ethylmalonic acid,
  • dimethylmalonic acid methylsuccinic acid, citraconic acid, glutaconic acid, itaconic acid, mesaconic acid, 2,2- dimethylsuccinic acid, 2-methylglutaric acid, trans-beta- hydromuconic acid, trans-trans-muconic acid, pimelic acid, butylmalonic acid, diethylmalonic acid, 2, 2-dimethylglutaric acid, 2 -ethyl-2-methylsuccinic acid, 3-methyladipic acid, cyclopentanedicarboxylic acid, suberic acid,
  • cyclohexanedicarboxylic acid azelaic acid, 5-norbornene-2, 3- dicarboxylic acid, sebacic acid, camphoric acid, 1,1- cyclohexanediacetic acid, cyclohexylsuccinic acid, benzylmalonic acid, undecanedioic acid, 1,10-decanedicarboxylic acid, and trans-traumatic acid.
  • Diol molecules which may be used to prepare the polyester chain of the invention include compounds with the molecular formulas C 2 H 6 O 2 , e.g., 1, 2-ethanediol (HO-CH 2 -CH 2 -OH); C 3 H 8 O 2 , e.g., 1,2-propanediol and 1,3-propanediol; C 4 H 10 O 2 , e.g., 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2 -methyl-1,3-propanediol; C 4 H 8 O 2 , e.g., 2-butene-1,4-diol, 2- methylene-1,3-propanediol; C 4 H 6 O 2 , e.g., 2-butyne-1,4-diol;
  • C 5 H 12 O 2 e.g., 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol;
  • C 5 H 10 O 2 e.g., 1,2-cyclopentanediol (cis and trans), 1, 3-cyclopentanediol (cis and trans);
  • C 6 H 14 O 2 e.g., 3,3- dimethyl-1, 2 -butanediol, 2 -ethyl-2-methyl-1,3-propanediol, 1,2- hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2- methyl-2,4-pentanediol, 2, 3-dimethyl-2, 3-butanediol;
  • C 6 H 12 O 2 e.g., 1,
  • C 9 H 20 O 2 e.g., 2 -butyl-2-ethyl-1, 3-propanediol, 1,2-nonanediol;
  • C 9 H 14 O 2 e.g., 5-norbornene-2, 2-dimethanol;
  • C 10 H 22 O 2 e.g., 1,2- decanediol, 1,10-decanediol;
  • C 10 H 18 O 2 e.g., 1,5-decalindiol, trans, trans-2, 6-methyl-2, 6-octadiene-1, 8-diol, 3,6-dimethyl-4- octyne-3, 6-diol, trans-p-menth-6-ene-2, 8-diol, 1,2,3,5- pinanediol;
  • C 10 H 16 O 2 e.g., (2-endo-3-exo-)-bicyclo [2.2.2] oct-5- ene-2,
  • diol compounds contain at least one ether group in the chain of atoms which link the two hydroxyl groups of the diol.
  • exemplary ether containing diols include ethylene glycols of the general formula HO- (CH 2 - CH 2 -O-) b CH 2 -CH 2 -OH, where b is between 1 and 5.
  • a preferred diol with an ether group is diethylene glycol.
  • polyester chain In the preparation of the polyester chain, one may use a single isomeric diol, or one may use a mixture of diols. For example, one may use diethylene glycol in admixture with ethylene glycol. In addition, if a partially crosslinked polyester chain is desired, then one may add some polyol, i.e., a polyhydric molecule, i.e.,. a molecule with at least three hydroxyl groups, to the reaction mixture which will additionally comprise diol and diacid.
  • a polyhydric molecule i.e.,. a molecule with at least three hydroxyl groups
  • Exemplary polyols include glycerol, 1,2,4-butanetriol, 1,1,1-tris (hydroxymethyl) ethane, 2 -ethyl-2- (hydroxymethyl)-1,3- propanediol, 1,2,3-trihydroxyhexane, 1,2,6-trihydroxyhexane, 1, 2, 3 -heptanetriol, erythritol, threitol, pentaerythritol, adonitol, arabitol, xylitol, dulcitol, iditol, mannitoi, sorbitol and dipentaerythritol.
  • the polyol contributes less than 20% of the hydroxyl functionality present in the reaction mixture used to prepare the polyester chain.
  • polyol contributes more than about 20% of the hydroxyl functionality, then an unacceptable portion of the product is an insoluble gel, ill-suited for use in skin-care and hair-care formulations.
  • polyols may also be employed in the
  • polyesters having functional groups bonded to internal R 2 or R 3 groups it is typically necessary to protect those additional hydroxyl groups, that is, those hydroxyl groups other than the two hydroxyl groups necessary for the formation of the polyester chain.
  • a protected hydroxyl group it is meant a hydroxyl group which has been chemically modified so that it will not enter into condensation polymerization reactions.
  • Protecting groups for hydroxyl functionality are well known in the art, and are
  • deprotecting the hydroxyl group so that the hydroxyl group is susceptible to functionalization so as to allow the formation of a derivatized polyester having functionality along the chain rather than, or in addition to, functionality at the termini of the chain.
  • Methods for deprotecting hydroxyl groups are well- known in the art.
  • polycarboxylic acid compounds i.e., molecules having more than two carboxylic acid groups, may be employed to introduce either crosslinking or internal functionality to the polyester chain. It is generally preferred to use polyhydric rather than
  • polycarboxylic acid compounds merely because a greater array of polyhydric compounds are readily available at a reasonable cost.
  • the polyester polyol In the preparation of the derivatized polyesters of the invention, it is convenient to react a low acid number polyester chain, hereinafter the polyester polyol, prepared as described above, with a diamine (III) to provide an intermediate polyester amidoalkylamine.
  • a polyester amidoalkylamine is very readily converted to the derivatized polyesters of the invention.
  • the polyester polyol preferably having an acid number or value of less than 2
  • R 8 having two amine groups linked with a chain, designated R 8 , where R 8 has 1 to 3 carbon atoms, hereinafter "the diamine”.
  • One of the two amine groups of the diamine is a tertiary amine group, where the tertiary amine is, in addition to being covalently bonded to the R 8 group, is bonded to two groups R 9 .
  • Each R 9 group is independently selected from the group consisting of C 1 -C 3 radicals having 0-3 hydroxyl
  • R 9 radicals include methyl, ethyl, propyl, hydroxymethyl, 2 -hydroxyethyl and 3-hydroxypropyl .
  • the other of the two amine groups of the diamine is either a primary or secondary amine group, represented by the formula H- N(R 5 )-R 8 , wherein R 5 can be hydrogen or a C 1 to C 10 radical.
  • the diamine of formula (III) can be represented as shown below:
  • the preparation of the derivatized polyesters of the invention preferably proceeds through a polyester amidoalkylamine intermediate of formula (IV), prepared by the condensation reaction of (I) and (III):
  • reaction to prepare the intermediate (IV) is preferably carried out by adding the diamine to the polyester polyol in a ratio such that the desired average degree of
  • polyester amidoalkylamine polymerization of the product polyester amidoalkylamine.
  • 3 moles of diamine are added to one mole of polyester polyol which has a number average molecular weight of 5,000, a mixture of one mole polyester polyol and three moles of polyester amidoalkylamine is obtained, where the
  • molecular weight of the polyester amidoalkylamine is (number average molecular weight of the polyester polyol + molecular weight of the diamine) / (moles of polyester polyol + moles of diamine), or in the instant case, (5,000+ MW of diamine) / (1+3).
  • amidoalkylamine intermediate of formula (IV) is typically less than the value of p for the starting polyester.
  • the intermediate (IV) typically has a number average molecular weight of between about 500 and 5,000.
  • the diamine may be added to the polyester polyol with stirring under an inert atmosphere, for example, under a nitrogen or argon atmosphere, and the mixture may be heated to between about 100°C and 160°C. This reaction temperature is maintained until it has been determined that the diamine has been
  • the determination is made by titration of an aliquot of the reaction mixture.
  • the polyester amidoalkylamine intermediate (IV) is readily converted to derivatized polyesters of the invention.
  • the intermediate (IV) can be combined with water and heated to a temperature between about 60°C and 90°C to provide a dispersion.
  • approximately one mole of proton acid, HR 14 is slowly added to the dispersion for each mole of intermediate (IV), until a clear solution or a turbid dispersion is obtained.
  • HR 14 proton acid
  • the intermediate (IV) is also a convenient precursor to cationic polyester derivatives having terminal trialkylammonium groups.
  • the intermediate (IV) may be dissolved or
  • the resulting quaternary ammonium compound has the formula (II) wherein R 1 is -N(R 5 ) (R 6 ), R 6 is -R 8 -N (R 9 ) 2 (R 10 ), R 10 is -R 9 R 14 , and R 4 is R 1 or -OR 7 .
  • the intermediate (IV) is also a convenient precursor for the preparation of zwitterionic polyester derivatives.
  • the intermediate (IV) may be dissolved or dispersed in a solvent, preferably water and/or propylene glycol.
  • R 6 is -R 8 -N(R 9 ) 2 (R 10 )
  • R 10 is -CH 2 -COO-
  • R 4 is R 1 or -OR 7 .
  • the intermediate (IV) can be reacted with
  • the intermediate (IV) wherein R 14 is preferably a halide, is dissolved in water and/or propylene glycol and heated to between about 40°C and about 90°C.
  • the secondary intermediate (V) has the formula shown below:
  • polyamino acid refers to a chain of amino acids, having one terminal -NH 2 group and one terminal -COOH group, as occurs naturally in, for example, protein.
  • a protein hydrolysate derived from animal or vegetable sources is slowly added, with stirring, to an aqueous solution of the secondary intermediate (V) maintained at a temperature of about 40°C to about 90°C.
  • the amine terminus of the protein hydrolysate reacts with terminal -CH 2 -Cl group of the intermediate (V) so as to displace the chloride group with the amine group, and thus join the polyamine acid chain of the protein hydrolysate to the polyester chain.
  • the product of this reaction has the formula (II) wherein R 1 is N(R 5 ) (R 6 ), R 6 is -R 8 -N(R 9 ) 2 (R 10 ), and R 10 is -CH 2 -CH (OH) -CH 2 -polyamino acid-COO-.
  • the protein hydrolysate is preferably reacted with R 15 - OH prior to its reaction with the secondary intermediate (V).
  • the secondary intermediate (V) is also a convenient precursor to derivatized polyesters having polysiloxane
  • an aqueous solution or dispersion of the intermediate (V) is heated to between about 40°C and 90°C, and slowly treated with an amine functionalized silicone-containing molecule.
  • a representative amine functionalized silicone is amodimethacone.
  • Additional representative amine functional silicones have the formula H 2 N- (Si (CH 3 ) 2 -O) g -H wherein g is an integer from about 2 to about 50.
  • the polysiloxane derivatized polyesters so made have the formula (II) wherein R 1 is N(R 5 ) (R 6 ), R 6 is -R 8 -N(R 9 ) 2 (R 10 ), and R 10 is CH 2 -CH (OH) -CH 2 -NH-polysiloxane R 14 .
  • the first step consists of the reaction of a diol with an excess of diacid, with heating and stirring, to form a polyester diacid, i.e., a polyester chain having carboxylic acid endgroups.
  • the diacid is added to the diol and the two component are reacted together at a temperature of about 140°C to about 240°C.
  • the water of reaction is continuously removed by
  • a strong acid such as toluenesulfonic acid or methanesulfonic acid, or an organometallic catalyst such as a tin catalyst, may be added to further drive the reaction.
  • the pressure is then reduced in the reaction vessel, and the reaction mixture maintained at about 240°C until titration of an aliquot of the reaction mixture indicates that the acid number has reached the theoretically desired acid value.
  • the number average molecular weight of the polyester diacid so obtained is approximately about 2,000 to about 10,000.
  • the polyester acid is neutralized with two equivalents of base.
  • bases for the neutralization include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, monoalkylamine such as ethanolamine, dialkylamine such as diethanolamine, and trialkylamine such as triethanolamine.
  • the polyester diacid is combined with water at a temperature of about 60°C to about 90°C to provide a solution or, more
  • the product of this reaction has the formula (II) wherein R 1 is -OR 7 , R 7 is R 12 , and R 12 is selected from the group consisting of sodium, lithium, calcium, magnesium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium and
  • tetraalkylammonium wherein an alkyl portion of an ammonium group has 1-20 carbon atoms and 0-3 hydroxyl groups.
  • nonionic polyester derivatives of the invention two alternative schemes may be followed.
  • diacid and diol are reacted as previously described for the preparation of polyester diol, however the reaction is conducted in the presence of at least one monocarboxylic acid having the formula R 13 -COOH.
  • R 13 is a C 1 to C 22 , saturated or unsaturated, straight chain or branched hydrocarbon group.
  • R 13 examples include methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl and decyl through behenyl.
  • Additional, non-limiting examples of R 13 -COOH include the fatty acids obtained from the splitting of coconut, palm, soy and other natural oils. Where the R 13 -COOH is derived from natural oils, the R 13 radical may be substituted with one or more hydroxyl groups.
  • R 13 -COOH may also be a silicone carboxylic acid, having a polysiloxane chain terminated with one or more carboxylic acid groups.
  • At least one diacid and at least one monoacid are added to at least one diol, and the mixture heated to about 140°C to about 240°C.
  • the water of reaction, produced by the resulting condensation reaction is continuously removed by distillation.
  • a strong acid such as toluenesulfonic acid or methanesulfonic acid, or an organometallic catalyst such as a tin catalyst, may be added.
  • the pressure is then reduced until a derivatized
  • polyester having an acid value of less than 2 is obtained.
  • the product has a number average molecular weight of about 2,000 to about 10,000.
  • a mixture of diacid, diol and a natural triglyceride are prepared.
  • exemplary, non-limiting natural triglycerides include coconut oil, palm oil, soy oil and other natural oils.
  • the reaction temperature and course of the reaction are identical to that previously described in connection with the first approach to the preparation of the nonionic derivatized polyesters of the
  • polyester resins according to the present invention provides unique materials that are useful in skin-care and hair-care formulations.
  • Compounds described within this disclosure may be used in hair-care and skin-care
  • Hair-care and skin-care systems utilizing compounds described within this disclosure as formulation aids may include, for example: surfactant systems; oil-in-water cream and liquid emulsions; water-in-oil cream and liquid emulsions; aqueous, hydro-alcoholic and alcoholic gel systems; aqueous, hydro-alcoholic and alcoholic suspension systems; solid suspension or emulsion systems; and aerosol systems.
  • Hair care formulations utilizing compounds described within this disclosure may include, for example: cleansing, rinsing, conditioning, styling, bleaching, coloring and setting compositions such as gels, liquids, mousses, sprays, lotions, glazes, creams, hydro-alcoholic systems and shampoos.
  • formulations utilizing compounds described within this disclosure may include, for example: facial, hand and body moisturizing creams, liquids, pastes, and lotions; facial and body sunscreen creams, lotions, solids, pastes and liquids; facial treatment creams, lotions, pastes and liquids; underarm antiperspirant and deodorant sprays, liquids, creams and solids; facial, body and hand cleansing creams, gels, lotions, liquids and mousses;
  • foaming bath gels liquids, salts, oils and powders
  • aqueous, alcoholic and hydro-alcoholic toners astringents pre-shaves, after-shaves and after-bath products
  • eyelash and mascara lip color sticks and glosses
  • liquid and cream foundation make-up preparations aqueous, alcoholic and hydro-alcoholic toners, astringents pre-shaves, after-shaves and after-bath products.
  • foam volume texture and endurance enhancement are achieved upon incorporation of amine oxide and betaine functionalized polyester resins into skin-care and hair-care formulations.
  • Detergency in skin, hair, hand and body cleansing systems is provided by the incorporation therein of anionic, zwitterionic and polyamino acid containing derivatized polyesters.
  • mitigation of the irritation potential of primary surfactants can be achieved by incorporation of nonionic and zwitterionic derivatized polyesters.
  • the viscosity of skin- and hair-care formulations can be adjusted through the addition of
  • zwitterionic, nonionic and polyamino acid derivatized polyester compounds An enhancement in the electrolyte tolerance of primary surfactants is observed upon incorporation of anionic or zwitterionic polyesters into hair- and skin-care formulations having primary surfactants. Improved wetting and dispersion of particulate matter is provided to skin- and hair-care
  • a modification in the cloud point or critical micelle concentration of a nonionic surfactant, and/or a modification in the critical micelle concentration of an ionic surfactant, including an anionic surfactant, in a hair-care or skin-care formulation is provided by the addition thereto of a zwitterionic or nonionic derivatized polyester.
  • Improved solubilization of lipophilic materials is imparted to hair-care and skin-care formulations by incorporating therein either nonionic or a betaine derivatized polyester of the invention.
  • Nonionic, anionic, and cationic derivatized polyesters provide
  • improved hair shine and tactile feel enhancement is provided to hair-care formulations by the addition of a derivatized polyester having nonionic,
  • cationic, betaine, polysiloxane or polyamino acid functional groups An improvement in hair manageability is observed upon incorporation of cationic, anionic, nonionic, polysiloxane or polyamino acid functionalized polyester into a hair-care
  • quaternary ammonium groups, nonionic, polysiloxane and polyamino acid derivatized polyesters into hair-care formulations provides products that, when applied to hair, impart enhancement of hair body, greater perceived thickness, improvement of wet and dry combability, enhancement of hair styling ability and style retention.
  • Another aspect of the invention is the neutralization of static charge on hair with less hair flyaway due to combing, which is observed upon application of hair-care formulations incorporating cationic, and particularly quaternary ammonium containing, derivatized polyesters. Dry and damaged hair moisture normalization is observed upon application to hair of a hair-care product incorporating polyesters with cationic, nonionic and polyamino acid functional groups.
  • Repair of hair split ends may be achieved by applying to hair having spit ends a hair-care product incorporating polyester molecules of the invention having cationic, and particularly quaternary ammonium groups, nonionic, polyamino acid or polysiloxane functional groups.
  • skin-care sensory enhancement through contribution of a moist, soft tactile feel and visual smoothness is provided to skin having applied thereto a skin-care formulation that incorporated derivatized polyester compounds having cationic, nonionic, anionic, polysiloxane or polyamino acid functional groups. Normalization of the moisture content of the stratum corneum of skin, and enhancement in the ability of the stratum corneum to retain moisture is observed when a skin-care product having cationic, nonionic or polyamino acid derivatized polyester compounds incorporated therein is applied to the skin.
  • nonionic derivatized polyester compounds to topical skin-care preparations confers water resistance barrier properties to the topical skin-care
  • a sufficient amount refers to an amount of the referred to compound which can provide the indicated performance property to the skin-care or hair-care formulation. This amount will vary, depending on the derivatized polyester employed and the hair- or skin-care properties desired.
  • the amounts of the derivatized polyester generally present in the skin-care and hair-care formulations of the invention are indicated in the following Table A.
  • the invention provides a method for improving the endurance and volume of foam, and modifying the texture of foam, by the addition of a sufficient amount of polyester betaine and/or polyester amine oxide (see Examples 6 and 13 for the preparation of betaine and amine oxide functionalized polyesters, respectively) as a modifier of the foaming characteristics of primary anionic surfactant systems when aerated during use in systems designed to function, for example, as human hair
  • the invention provides a method of providing detergent cleansing function to systems designed to function as human hair shampoos, body cleansers, bubble baths, hand cleansers and facial skin cleansers through the addition of a sufficient amount of polyester betaine, polyester dicarboxylate, polyester protein derivative and/or polyester amine oxide (where representative examples thereof may be prepared according to Examples 6, 9, 11 and 13, respectively) so that particulate debris, skin oils, body sweat and make-up residue can be wetted, emulsified and rinsed from relevant body surfaces.
  • the invention provides a method to mitigate and minimize the irritating effects of primary anionic surfactant systems upon human skin and eyes through addition of a sufficient amount of polyester betaine polyester dicarboxylate, polyester protein derivative and/or polyester amine oxide (where
  • representative examples thereof may be prepared according to Examples 6, 9, 11 and 13, respectively) to systems designed to function as human hair shampoos, body cleansers, bubble baths, hand cleansers and facial skin cleansers.
  • the invention provides a method to modify the viscosity and rheology of aqueous systems, aqueous phases of emulsion systems and/or surfactant systems through the addition of a sufficient amount of polyester betaine, polyester/botanical condensate, polyester dicarboxylate, polyester amine oxide and/or a nonionic polyester alkylate (where representative examples thereof may be prepared according to Examples 6, 7, 8, 13 and 14, respectively) to systems designed to function, for example:
  • shampoos body cleansers, bubble baths, hand cleansers, facial skin cleansers, facial moisturizers, body moisturizers, hand barrier and moisturizing preparations, and make-up preparations.
  • the invention provides a method for extending the concentration of electrolytes which can be combined with primary anionic surfactant systems before foaming, detergent, stability or viscosity characteristics of the primary anionic surfactants are adversely affected.
  • the method comprises the addition of a sufficient amount of polyester betaine, polyester dicarboxylate and/or polyester amine oxide (where representative examples of which may be prepared according to Examples 6, 9 and 13,
  • surfactant systems designed for use, for example, as human hair shampoos, body cleansers, bubble baths, hand cleansers, hair conditioners, and facial skin cleansers.
  • the invention provides a method for wetting and/or dispersing particulate matter in aqueous systems, aqueous and oil phases of emulsion systems and anhydrous systems through addition of a sufficient amount of polyester betaine, polyester
  • dicarboxylate, polyester amine oxide and/or nonionic polyester alkylate where representative examples thereof may be prepared according to Examples 6, 9, 13 and 14
  • This method would apply, for example, to systems designed for use as human hair shampoos, body shampoos, facial and body masks, facial and body moisturizers, make-up preparations, bath and body oils, antiperspirant and deodorant systems, sunscreen preparations and bubble baths.
  • the invention provides a method for reducing the concentration at which primary anionic surfactants may change from a spherical or micellar gel structure to lamellar gel structure or otherwise become visually hazy (or reach their critical micelle concentration) by addition of a sufficient amount of polyester betaine, polyester dicarboxylate and/or polyester amine oxide (where representative examples thereof may be prepared according to Examples 6, 8 and 13, respectively) to systems designed for use as human hair shampoos, body cleansers, bubble baths, hand cleansers and facial skin cleansers.
  • the invention provides a method for solubilizing lipophilic materials into aqueous systems, surfactant systems, or aqueous phases of emulsion systems so that the lipophilic
  • micro emulsion which is clear and/or
  • polyester betaine polyester dicarboxylate and/or nonionic polyester alkylate
  • the invention provides a method of emulsifying or aiding in the emulsification of lipophilic materials into water or hydrophilic materials, or emulsifying or aiding in the
  • the method involves addition of a sufficient amount of polyesteramine, polyesteramine salt, polyester ammonium salt, polyester betaine, polyester dicarboxylate and/or nonionic polyester alkylate (where representative examples thereof may be prepared according to Examples 2, 3, 4, 5, 6, 7, 8 and 14, respectively) to a system designed to perform, for example, as human hair conditioner or rinse, body or facial moisturizer, hand protectant or moisturizer, suncare or skin protectant
  • the invention provides a method of enhancing or adding visual shine to hair and/or enhancing the tactile feel of hair to the extent that it is perceived as healthy, moist and attractive through the addition of a sufficient amount of polyesteramine, polyester ammonium salt, polyester betaine, polyester/botanical condensate, polyester/protein condensate, polyester/silicone condensate and/or nonionic polyester alkylate (where
  • representative examples thereof may be prepared according to Examples, 2, 3, 4, 5, 6, 7, 8 and 14) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
  • the invention provides a method of improving hair manageability through the deposition and/or attachment on hair and/or through addition of a sufficient amount of polyesteramine, polyester ammonium salt, polyester/botanical condensate,
  • polyester/protein condensate, polyester/silicone condensate and/or nonionic polyester alkylate (where representative examples thereof may be prepared according to Examples 2 or 4, 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
  • the invention provides a method of enhancing the tactile sense that hair has body and/or perceived thickness through the deposition and/or attachment on hair of, or addition of a sufficient amount of polyesteramine, polyester ammonium salt, polyester/botanical condensate, polyester/protein
  • polyester alkylate (where representative examples thereof may be prepared according to Examples 2 or 4 , 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
  • the invention provides a method of improving the wet and dry combability of hair through the deposition and/or attachment on hair, or addition of a sufficient amount of polyesteramine, polyester ammonium salt, polyester/botanical condensate, polyester/protein condensate, polyester/silicone condensate and/or nonionic polyester alkylate (where
  • representative examples thereof may be prepared according to Examples 2 or 4 , 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
  • the invention provides a method of incorporating the capability of forming hair into specific configurations or styles and/or retaining the configuration or style when formed by providing a means for individual hairs to adhere to one another at locations of contact through addition of a sufficient amount of a polyesteramine, polyester ammonium salt, polyester/botanical condensate, polyester/protein condensate, polyester/silicone condensate and/or nonionic polyester alkylate (where
  • representative examples thereof may be prepared according to Examples 2 or 4 , 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair oils, hair sprays, hair gels or hair creams.
  • the invention provides a method to neutralize the static electrical charge on hair and "fly-away” or repulsion of individual hairs as a result of static electrical charge build-up on hair through the deposition and/or attachment on hair, or addition of a sufficient amount of polyesteramine and/or polyester ammonium salt (where representative examples thereof may be prepared according to Examples 2 or 4, and 5,
  • the invention provides a method to normalize the moisture content or moisture absorbed onto hair keratin through the deposition and/or attachment on hair of, or addition of a sufficient amount of polyesteramine, polyester/botanical
  • polyester alkylate (where representative examples thereof may be prepared according to Examples: 2 or 4, 7, 11 and 14,
  • the invention provides a method of repairing hair split ends or temporarily facilitating the adhesion of hair tips that have separated into visibly differentiated segments within the area roughly approximating the tip of a hair through the
  • polyesteramine terephthalate
  • polyester ammonium salt terephthalate
  • polyester/botanical condensate polyester/protein condensate
  • polyester/silicone condensate and/or nonionic
  • polyester alkylate (where representative examples thereof may be prepared according to Examples 2 or 4 , 5, 7, 11, 12 and 14, respectively) to systems designed to function, for example, as human hair shampoos, hair conditioners, hair rinses, hair gels, hair creams, hair hot oil treatments, hair ambient temperature oil treatments or hair sprays.
  • the invention provides a method of contributing a moist soft tactile feeling on skin and/or visual skin smoothness through the deposition and/or attachment on the surface of skin, or addition of a sufficient amount of polyesteramine,
  • polyesteramine salt polyester/botanical condensate, polyester dicarboxylate, polyester/protein condensate, polyester/siloxane condensate and/or nonionic polyester alkylate (where
  • moisturizers suncare preparations, antiperspirant preparations or deodorant preparations.
  • the invention provides a method of normalizing the moisture content of the stratum corneum of human skin through deposition and/or attachment on the surface of skin, or addition of a sufficient amount of polyesteramine, polyesteramine salt, polyester/botanical condensate, polyester dicarboxylate,
  • polyester/protein condensate, polyester/siloxane condensate and/or nonionic polyester alkylate (where representative example thereof may be prepared according to Examples 2 or 4, 3, 7, 9, 11, 12 and 14, respectively) to systems designed to function, for example, as human facial moisturizers, body moisturizers, make-up preparations dusting powders, after-bath veils, facial masks, body masks, facial scrubs, body scrubs, facial cleansers, body cleansers, hand protectants and moisturizers, suncare
  • the invention provides a method of modification of the application characteristics or the apparent relative friction on the surface of skin during application and rub-in and/or the relative tactile impression of wetness, dryness and/or sliminess during rub-in of products designed to function as human facial moisturizers, body moisturizers, make-up preparations, dusting powders, after-bath veils, facial masks, body masks, facial scrubs, body scrubs, facial cleansers, body cleansers, hand protectants and moisturizers, suncare preparations,
  • polyesteramine polyesteramine salt, polyester/botanical condensate, polyester diacid, polyester dicarboxylate and/or polyester alkylate (where representative examples thereof may be prepared according to Examples 2 or 4, 3, 7, 8, 9 and 14, respectively).
  • the invention provides a method to confer resistance to rinse off or wash off by water or human perspiration of
  • formulation ingredients or entire formulations through deposition and/or attachment on the surface of skin or inclusion in a formulation or part, or parts of a formulation of a sufficient amount of polyester/botanical condensate and/or nonionic
  • polyester alkylate (where representative examples thereof may be prepared according to Examples 7 and 14, respectively) to systems designed to function, for example, as human sunscreen
  • polyester/silcone condensates are particularly desirable components in skin-care and hair-care products because the condensates do not build up on skin or hair with repeated usage of skin- and hair-care formulations incorporating the polyester/silicone condensates.
  • Example 2 Into an apparatus like the one used in Example 1, 4500 g (0.9 moles) of the polyester of Example 1 and 408.5 g (4.0 moles) of dimethylaminopropylamine (DMAPA) were placed. The mixture was heated under atmospheric pressure with nitrogen purge to 120°C and held for twelve hours at these conditions. The pressure was then reduced to 5 mm Hg and 0.1 grams per hour of steam was sparged through the mixture (stripping) for four hours to remove any residual amine and trace odor compounds. After stripping, the mixture was brought to atmospheric pressure and 4900 g (4.9 moles) of poly (propylene glycol adipate) amidopropyldimethylamine with a number average molecular weight of 1000 were obtained.
  • DMAPA dimethylaminopropylamine
  • Example 2 Into an apparatus like the one used in Example 1, 4900 g (4.9 moles) of the polyester of Example 2 and 4575 g of pure water were placed. The mixture was heated to 60°C and 470 g of 31% by weight of aqueous hydrochloric acid (4 moles) was slowly added over a one-hour period. Additional hydrochloric acid was then added as necessary to bring the pH of the solution to 6.0 at 25°C. About 5000 g of poly (propylene glycol
  • Example 2 Into an apparatus like the one used in Example 1, 4500 g (0.9 moles) of poly (diethylene glycol adipate) diol with a molecular weight of 5000 (obtained in a manner similar to the procedure set forth in Example 1) and 1038 g (10.2 moles) of dimethylaminopropylamine (DMAPA) were placed. The mixture was heated under atmospheric pressure with nitrogen purge to 120°C, and held for twelve hours at these conditions. The pressure was then reduced to 5 mm Hg and 0.1 grams per hour of steam was sparged through the mixture for four hours to remove any residual amine and odor bodies. After sparging, the mixture was brought to atmospheric pressure and 5500 g (11.0 moles) of
  • poly (diethylene glycol adipate) amidopropyldimethylamine with a number average molecular weight of 500 was obtained.
  • MCH monochlorohydrin
  • Example 2500 g (5.0 moles) of the polyesteramide product of Example 4 4575 g (60 moles) of propylene glycol and 612 g (5.25 moles) of sodium monochloroacetate (SMCA) were added. The mixture was heated to 90°C and held at that temperature for six hours. The product was then vacuum-filtered through a bed of diatomaceous earth. This removes some of the sodium chloride that was formed as a byproduct of the reaction. About 10,500 g of poly (diethylene glycol adipate) amidopropylbetaine were obtained.
  • SMCA sodium monochloroacetate
  • Example 2 Into an apparatus like the one used in Example 1, 5,000 g (1.0 mole) of the polyester of Example 1 and 439 g (0.5 moles) of olive oil (a botanical extract) were placed. The mixture was heated to 220°C and held at that temperature for sixteen hours. The mixture was then cooled to 120°C. The pressure was then reduced to 5 mm Hg and 0.1 grams per hour of steam was sparged through the mixture for four hours to remove any residual odor bodies. About 5400 g of derivatized polyester containing some glycerin crosslinks and olive fatty acid termination were
  • Example 2 Into an apparatus like the one used in Example 1, 5,000 g (1.0 mole) of the polyester of Example 1 and 292 g (2 moles) of adipic acid were placed. The mixture was heated with nitrogen purge to 220°C and held at these conditions for sixteen hours. The pressure was then reduced and the mixture was heated under vacuum for 20 hours until 36 g (2 moles) of water were distilled off. 5256 g of poly (propylene glycol adipate) diacid with a molecular weight of 5250 were obtained.
  • Example 8 Into an apparatus like the one used in Example 1, 5256 g (1.0 mole) of the derivatized polyester product of Example 8 were placed. The polyester was heated to 120°C. The pressure was then reduced to 5 mm Hg and 0.1 grams per hour of steam was sparged through the polyester for four hours to remove any residual odor compounds. Then 5000 g of pure water and 110 g (2 moles) of a 30% by weight solution of ammonia were added with stirring. This resulted in the formation of 10,300 g of a 50% by weight aqueous solution of ammonium poly (propylene glycol adipate) dicarboxylate.
  • Example 2 Into an apparatus like the one used in Example 1, 5000 g (10 moles) of the polyester of Example 4, 5000 g of propylene glycol (65.8 moles), and 1177 g (10 moles) of 31% by weight aqueous hydrochloric acid were placed. The mixture was heated with stirring to 60°C and held under these conditions for one hour until the neutralization of the polyester of Example 4 was complete. 925 g (10 moles) of epichlorohydrin were added and the mixture was held at 60°C for 5 hours.
  • Example 2 Into an apparatus like the one used in Example 1, 4900 g (4.9 moles) of the polyester of Example 2 and 4575 g of pure water were placed. The mixture was heated to 60°C and 272 g of 50% by weight aqueous hydrogen peroxide (4 moles) was slowly added over a one-hour period. About 9,500 g of poly (propylene glycol adipate) amidopropyldimethylamine oxide were obtained.
  • Example 2 Into an apparatus like the one used in Example 1, 5000 g (1.0 moles) of the polyester of Example 1 and 416 g
  • Legends A through Y represent polymer names
  • Legends AA through GG represent trade names with corresponding supplier's addresses.
  • Polyesters which are liquids at room temperature were agitated to ensure homogeneity. Polyesters which are solid at room temperature were warmed above their melting point (ca. 50°C) and agitated until homogeneous. Into 1.5 oz. screw-top glass jars, polyester (solute) and solvent (water, ethanol or
  • isopropanol were weighed in amounts required to provide 20 grams in each vial of mixtures at concentrations of 5, 25, and 50 percent by weight.
  • the jars were capped with polyethylene lids, warmed to 30°C, and shaken vigorously for thirty to sixty
  • the specific gravity of the derivatized polyesters was determined by using a Gardner gallon weight cup. Polyesters which were liquid at room temperature were agitated to ensure
  • Derivatized polyesters which were liquid at room temperature were agitated to ensure homogeneity, and their pH measured using a Brinkmann 632 pH-Meter equipped with combination glass electrode. Solid polyesters were warmed above their melting point (ca. 50°C), agitated until homogeneous, and then diluted to 10% by volume in deionized water, before measuring their pH. All measurements were carried out at 25°C, with the results provided in TABLE V.
  • the viscosity of selected derivatized polyesters was measured at various temperatures using a Brookfield RV coaxial cylinder viscometer (No. 24 spindle, RPM adjusted as necessary).
  • the sample chamber was fitted with a small sample adapter, which was jacketed, and through which flowed heat transfer fluid from a controlled temperature bath. The viscosity measurement so obtained are recorded in TABLE VI.
  • polyesters Approximately a 10% w/w mixture was made of respective polyesters in deionized water. The polyester was mixed into the water using an electric rotating stirrer equipped with a
  • Worsted wool challis (6" x 2.75") (Test Fabrics, Inc.)
  • Polyesters M, B, U and V and Polyester I appear to perform on a competitive level with ingredients commonly used for their ability to adhere to skin and hair.
  • Polyester I appears to retain moisture on leather comparatively better than other film forming agents typically used in skin- and hair-care applications. Polyesters M and V appear to be similar in their moisture retention ability as other film forming agents commonly used in skin- and hair-care
  • polyesters U and V When applied to leather, polyesters U and V appear to absorb moisture from the atmosphere comparatively better than other film forming agents typically used in skin- and hair-care applications.
  • Polyesters M and I appear to improve the visual shine of hair tresses and perform better than competitive ingredients used in hair-care products for that purpose.
  • PROCEDURE
  • Rate resistance on a scale of 1 to 10 (with 1 being optimum, or least resistant to combing). After 2 hours of drying at ambient temperature and humidity, pass comb through tress 20 times making a comparative evaluation of relative resistance to combing. Rate resistance on a scale of 1 to 10 (as before). While dry combing, make a comparative
  • Polyesters B and I appear to improve the combability of hair tresses to the same extent as competitive ingredients typically utilized in hair conditioning preparations for
  • Polyester M appears to perform better than many competitive additives as far as providing good hair tress combability.
  • section "3" material polyyester O
  • the resulting product is a clear, high foaming conditioning shampoo which conditioned without causing build-up of conditioner on hair.
  • Polyester O is a conditioning agent which adds body to hair and improves its manageability.
  • the resulting product is a cleansing gel for direct use on skin.
  • the resulting product provides moderate hold utilizing minimal volatile organic compounds (VOC).
  • VOC minimal volatile organic compounds
  • the resulting product is an after-shampoo leave-on conditioner for sun and wind damaged hair.
  • Polyester S boosts foam, mitigates the irritation potential of TEA lauryl sulfate and helps build viscosity.
  • Polyester Q enhances detergency while minimizing irritation .
  • the resulting product is a thin lotion that would be compatible for use in a glass bottle.
  • the inclusion of Polyester V adds a moist emollient feel to the skin following application and is expected to increase the substantivity of the alpha hydroxy acid. Polyester V is also expected to act as a buffer for lactic acid, thereby increasing the efficacy of the AHA and mitigating it's irritation potential.
  • the resulting product is a thixotropic lotion which leaves a non-greasy and moist feeling on the skin following application and has good body.
  • Polyester B adds a moist
  • the resulting product is a light cream which leaves a non-greasy and perceptible moist film on the skin following application.
  • Polyester U adds a substantive moist film on the skin.
  • the resulting product is a viscous lotion which leaves a non-greasy and moist feeling on the skin following application.
  • Polyester U adds a moist emollient skin feel.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Chemical & Material Sciences (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

L'invention concerne des résines de polyester obtenues à partir d'acide dicarboxylique aliphatique et de composés de dialcool, modifiées pour donner des polyesters dérivés comportant des groupes fonctionnels. Ces groupes fonctionnels comprennent des dérivés anioniques, cationiques, d'ammonium quaternaire, de chaîne d'acide de polyamine, zwitterioniques, non ioniques, d'huiles essentielles, botaniques ou des polymères à base de silicone. Ces polyesters dérivés s'utilisent sous forme d'auxiliaires de formulation et d'agents de conditionnement dans les produits de soins des cheveux et de la peau.
PCT/US1995/010789 1994-08-26 1995-08-24 Composes de polyester derives et leurs utilisations Ceased WO1996006878A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU33724/95A AU3372495A (en) 1994-08-26 1995-08-24 Derivatized polyester compounds and uses thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US29682794A 1994-08-26 1994-08-26
US296,827 1994-08-26

Publications (1)

Publication Number Publication Date
WO1996006878A1 true WO1996006878A1 (fr) 1996-03-07

Family

ID=23143743

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/010789 Ceased WO1996006878A1 (fr) 1994-08-26 1995-08-24 Composes de polyester derives et leurs utilisations

Country Status (2)

Country Link
AU (1) AU3372495A (fr)
WO (1) WO1996006878A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5833961A (en) * 1996-06-25 1998-11-10 Inolex Investment Corporation Polyester-based suncreen formulations
US5989527A (en) * 1998-01-26 1999-11-23 Inolex Investment Corporation Compositions and methods for improving the performance of chemical exfoliating agents, sunless tanning agents, skin lightening agents and insect repellents
FR2831430A1 (fr) * 2001-10-26 2003-05-02 Oreal Composition cosmetique et/ou de soin contenant un polyester-siloxane filmogene, non reticule
FR2873570A1 (fr) * 2004-08-02 2006-02-03 Oreal Composition cosmetique de soin et/ou de maquillage comprenant au moins un polymere polyester amide
WO2006013200A1 (fr) * 2004-08-02 2006-02-09 L'oreal Soins cosmétiques et/ou composition de maquillage comprenant au moins un polymère polyestérimide
US8163274B2 (en) 2004-04-07 2012-04-24 Rocco Burgo Personal care products containing high refractive index esters and methods of preparing the same
US20160244853A1 (en) * 2013-09-30 2016-08-25 Rhodia Poliamida E Especialidades Ltda Chrome tanning process
US20160244854A1 (en) * 2013-09-30 2016-08-25 Rhodia Poliamida E Especialidades Ltda Tanning process for obtaining leather
US10272026B2 (en) 2017-07-31 2019-04-30 L'oreal Water-in-oil emulsion compositions suitable for altering the color of hair

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1426289A (fr) * 1963-12-16 1966-01-28 Monsanto Co Nouveaux polyesters à groupes méthylol-aminés, leur préparation et leurs applications
EP0229400A2 (fr) * 1986-01-08 1987-07-22 Hoechst Aktiengesellschaft Polyesters modifiés par des acides gras, procédé pour leur préparation et leur utilisation pour l'augmentation de la viscosité dans des préparations contenant des tensioactifs
US5164471A (en) * 1992-02-19 1992-11-17 Siltech Inc. Fluorine containing silanol polyester waxes
US5210133A (en) * 1992-06-15 1993-05-11 Siltech Inc. Silicone polyester polymers as delivery systems
EP0551749A2 (fr) * 1991-12-20 1993-07-21 Unilever Plc Composition pour le traitement des cheveux

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1426289A (fr) * 1963-12-16 1966-01-28 Monsanto Co Nouveaux polyesters à groupes méthylol-aminés, leur préparation et leurs applications
EP0229400A2 (fr) * 1986-01-08 1987-07-22 Hoechst Aktiengesellschaft Polyesters modifiés par des acides gras, procédé pour leur préparation et leur utilisation pour l'augmentation de la viscosité dans des préparations contenant des tensioactifs
EP0551749A2 (fr) * 1991-12-20 1993-07-21 Unilever Plc Composition pour le traitement des cheveux
US5164471A (en) * 1992-02-19 1992-11-17 Siltech Inc. Fluorine containing silanol polyester waxes
US5210133A (en) * 1992-06-15 1993-05-11 Siltech Inc. Silicone polyester polymers as delivery systems

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5833961A (en) * 1996-06-25 1998-11-10 Inolex Investment Corporation Polyester-based suncreen formulations
US5989527A (en) * 1998-01-26 1999-11-23 Inolex Investment Corporation Compositions and methods for improving the performance of chemical exfoliating agents, sunless tanning agents, skin lightening agents and insect repellents
FR2831430A1 (fr) * 2001-10-26 2003-05-02 Oreal Composition cosmetique et/ou de soin contenant un polyester-siloxane filmogene, non reticule
US8163274B2 (en) 2004-04-07 2012-04-24 Rocco Burgo Personal care products containing high refractive index esters and methods of preparing the same
FR2873570A1 (fr) * 2004-08-02 2006-02-03 Oreal Composition cosmetique de soin et/ou de maquillage comprenant au moins un polymere polyester amide
WO2006013200A1 (fr) * 2004-08-02 2006-02-09 L'oreal Soins cosmétiques et/ou composition de maquillage comprenant au moins un polymère polyestérimide
US20160244853A1 (en) * 2013-09-30 2016-08-25 Rhodia Poliamida E Especialidades Ltda Chrome tanning process
US20160244854A1 (en) * 2013-09-30 2016-08-25 Rhodia Poliamida E Especialidades Ltda Tanning process for obtaining leather
US10731230B2 (en) * 2013-09-30 2020-08-04 Techpolymers Industria E Comercio Ltda Tanning process for obtaining leather
US10844445B2 (en) * 2013-09-30 2020-11-24 Techpolymers Industria E Comercio Ltda Chrome tanning process
US10272026B2 (en) 2017-07-31 2019-04-30 L'oreal Water-in-oil emulsion compositions suitable for altering the color of hair

Also Published As

Publication number Publication date
AU3372495A (en) 1996-03-22

Similar Documents

Publication Publication Date Title
KR100656739B1 (ko) 양쪽이온성 실록산 중합체 및 그로부터 제조된 이온적으로 교차결합된 중합체
JP6484438B2 (ja) ポリグリセロール部分エステル、その製造および使用
CN101155575B (zh) 毛发化妆品
CN103946444A (zh) 用于纤维处理的氨基官能化有机硅乳液
JP5723986B2 (ja) アミノ官能性シリコーンのエマルション
AU2015255686B2 (en) Non-petrochemically derived cationic emulsifiers, related compositions and methods
CN1071109C (zh) 护发产品
WO1996006878A1 (fr) Composes de polyester derives et leurs utilisations
JP7332352B2 (ja) 表面処理粉体及び表面処理粉体を含有する化粧料
JPS627883B2 (fr)
CN109476921A (zh) 包含季铵基团的低粘度聚有机硅氧烷、其制造方法和用途
JPH0532364B2 (fr)
JP3880186B2 (ja) 毛髪処理剤
KR100490706B1 (ko) 비이온성계면활성제및이를함유하는조성물,화장품및피부외용제
JP3483984B2 (ja) 化粧料
JP2530758B2 (ja) 毛髪化粧料
JP2010013406A (ja) 毛髪化粧料
JPH0436222A (ja) 乳化毛髪化粧料
JPS61129187A (ja) エステル化生成物およびこれらを配合してなる化粧料
WO2021173954A1 (fr) Compositions comprenant des protéines hydrolysées
WO2008112200A1 (fr) Polymères protéine-silicone cationiques
CN115590778B (zh) 一种氨基酸头皮毛发护理组合物及含该组合物的头皮毛发护理产品和制备方法
JP3888595B2 (ja) 毛髪処理剤
JP2004026781A (ja) ヒドロキシ脂肪酸ジアルキルアミノアルキルアミドの毛髪処理剤としての利用
WO2025010139A1 (fr) Compositions et utilisation des compositions dans le cadre de soins personnels

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AM AT AU BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IS JP KE KG KP KR KZ LK LR LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TT UA UG UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE MW SD SZ UG AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase