WO2011015906A1 - Solvent resistant pigments for cosmetic applications - Google Patents

Solvent resistant pigments for cosmetic applications Download PDF

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Publication number
WO2011015906A1
WO2011015906A1 PCT/IB2009/054053 IB2009054053W WO2011015906A1 WO 2011015906 A1 WO2011015906 A1 WO 2011015906A1 IB 2009054053 W IB2009054053 W IB 2009054053W WO 2011015906 A1 WO2011015906 A1 WO 2011015906A1
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WO
WIPO (PCT)
Prior art keywords
chosen
pigments
pigment
acid
mixtures
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Application number
PCT/IB2009/054053
Other languages
French (fr)
Inventor
Rami Ismael
Hélène DE CLERMONT-GALLERANDE
Marie-Rose Darmon
Original Assignee
Chanel Parfums Beaute
Radiant Color N.V.
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.)
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Application filed by Chanel Parfums Beaute, Radiant Color N.V. filed Critical Chanel Parfums Beaute
Priority to PCT/IB2009/054053 priority Critical patent/WO2011015906A1/en
Publication of WO2011015906A1 publication Critical patent/WO2011015906A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C09B67/0008—Coated particulate pigments or dyes with organic coatings
    • C09B67/0013—Coated particulate pigments or dyes with organic coatings with polymeric coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0002—Grinding; Milling with solid grinding or milling assistants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C09B67/0063—Preparation of organic pigments of organic pigments with only macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • C09B67/009—Non common dispersing agents polymeric dispersing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments

Definitions

  • the present invention relates to cosmetic pigments, and especially fluorescent cosmetic colored pigments, suitable for cosmetic formulations in general and specifically for formulations demanding good solvent resistance, such as nail lacquers formulations.
  • the polymers used to make these pigments are either thermoplastic sulfonamide / formaldehyde polymers or thermoset resins which are essentially based on urea / formaldehyde polymers.
  • the dyes may be introduced at any stage during the manufacture of the polymer, for instance before curing the thermoset resin. After grinding, the resulting pigments are introduced into coating compositions where they are said to be insoluble and to be stable against flocking.
  • U.S. Pat. Nos. 5143723 and 5324506 report utilizing the same technology to create pigments or fluorescent pigments to be used in cosmetic compositions. These pigments are said to confer more gloss and clarity of color to the lips or cheeks than the usual lakes, which are made of an insoluble, oil- dispersible aluminum hydroxide substrate on which a dye is absorbed or precipitated.
  • lakes which are made of an insoluble, oil- dispersible aluminum hydroxide substrate on which a dye is absorbed or precipitated.
  • resins including crosslinked polyester resins, the examples provided in this document only use toluene sulfonamide formaldehyde resins. It has now been found that the available polymer embedding technology does not provide suitable cosmetic pigments for solvent resistance demanding applications like nail varnish.
  • the inventors have realized that the above drawback could be overcome by using a specific kind of polymer in a specific process to make the colored pigment .
  • the pigments according to this invention have also been shown to be heat resistant, which render them useful in various make-up products such as lipsticks, lip glosses, cheek blushes and eye shadows.
  • An object of the present invention is thus to provide pigments which are not soluble and do not swell in the solvents used in nail enamels. Another object of this invention is to provide pigments which can be easily grinded and dispersed into cosmetic compositions. Still another object of this invention is to provide pigments which are heat resistant, in that they do not deteriorate until 22O 0 C.
  • the present invention pertains to a pigment which may be obtained according to a process including the steps of:
  • a crosslinked resin chosen from polyester, polyamide or polyesteramide resins from at least one bi-functional monomer Ml chosen from diols and diamines and at least one bi-functional monomer M2 chosen from dicarboxylic acids and acid anhydrides, in the presence of at least one crosslinking agent chosen from tri-functional crosslinkers CL3 and tetra- functional crosslinkers CL4,
  • This invention also pertains to coating compositions, especially cosmetic compositions, comprising said novel pigment.
  • the pigments according to this invention have proved to be stable upon heating and in solvents used to manufacture nail enamels, especially alkyl acetates and acetone and to be easily dispersible in cosmetic media. They also offer a better resistance to pH and light than the usual organic dyes and a newer range of colors which cannot be obtained by means of these dyes.
  • the process according to the present invention comprises the manufacture of a crosslinked polyester, polyamide or polyesteramide resin from bifunctional monomers Ml and M2, trifunctional crosslinkers CL3 and tetra-functional crosslinkers CL4.
  • trifunctional and tetra-functional are intended to refer to compounds including three or four functions, respectively, which may be chosen among hydroxy, carboxyl, epoxy and amino groups.
  • one anhydride group can be used instead of two carboxyl groups .
  • the bifunctional, trifunctional and tetra- functional compounds used in this invention may be linear, branched or cyclic hydrocarbons bearing said functions or may be chosen from heterocyclic or aromatic compounds (preferably including a phenyl moiety) bearing said functions.
  • the monomers Ml include diols, diamines and their mixtures.
  • diols mention can be made of 1,4- cyclohexane dimethanol (CHDM), 1, 4-butanediol (BDO), 1, 5-pentanediol (PDO), 1, 6-hexanediol (HDO), 1,12- dodecanediol (DDO) and their mixtures.
  • diamines mention can be made of para-phenylenediamine (PPD) , isophorone diamine (IPDA), hexamethylenediamine (HMDA), 2-methylpentane-l , 5-diamine (MPMD), diaminododecane (DADD) and their mixtures.
  • PPD para-phenylenediamine
  • IPDA isophorone diamine
  • HMDA hexamethylenediamine
  • MPMD 2-methylpentane-l
  • DADD diaminododecane
  • Examples of monomers M2 are dicarboxylic acids, such as adipic acid (ADA) , dodecanedioic acid (DDA) , methylisophthalic acid (MIPA), isophthalic acid (IPA) and terephthalic acid (TPA) , acid anhydrides bearing one anhydride group, such as phthalic anhydride (PA) , and their mixtures.
  • ADA adipic acid
  • DDA dodecanedioic acid
  • MIPA methylisophthalic acid
  • IPA isophthalic acid
  • TPA terephthalic acid
  • PA phthalic anhydride
  • the trifunctional crosslinking agents CL3 may be chosen from the group consisting of: tris-(2,3- epoxypropyl) isocyanurate (TGIC), trimethylolpropane (TMP) , trimellitic anhydride (TMA) , dimethylolpropionic acid (DMPA) and their mixtures.
  • the tetra-functional crosslinking agents CL4 may be chosen from the group consisting of: pentaerythritol (penta) , tris (hydroxy) aminomethane (THAM), pyromellitic dianhydride (PMDA), 2-amino-2- (hydroxymethyl) - propanediol, ethylenediaminetetraacetic acid (EDTA) and their mixtures.
  • the foregoing monomers and crosslinking agents should be used in specific ratios so as to obtain pigments having enough solvent resistance while avoiding gelling problems during their manufacture and preserving the ability to grind them.
  • D molar content of CL4 More preferably, at least one and optionally all of the following requirements could be satisfied:
  • A/B ranges from 0.6 to 1.4
  • (A+B) /D ranges from 2.2 to 3.5.
  • the above monomers Ml and M2 are polymerized in the presence of the crosslinking agents CL3 and/or CL4 according to any polymerization process well-known to the skilled person, such as bulk polymerization, emulsion polymerization or suspension polymerization.
  • the polymerization is preferably a polycondensation reaction conducted in the presence of a catalyst such as oxalic acid.
  • a material chosen from pigments and dyes and their mixtures is added to the resin either before, during or after its formation, for instance during its polymerization or during its crosslinking.
  • This material usually provides for an optical effect including absorbing, reflecting, transmitting, diffusing and/or refracting any portion of the light spectrum, and especially of the UV and visible wavelengths, such as providing for a color or a soft- focus effect, for instance.
  • the pigment obtained according to this invention is preferably a colored pigment .
  • Examples of such materials include, without any limitation: FD&C Blue No. 1, FD&C Blue No. 2, FD&C Green No. 3, FD&C Red No. 3, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6, D&C Blue No. 4, D&C Blue No. 9, D&C Green No. 5, D&C Green No. 6, D&C Green No. 8, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, D&C Orange No. 17, FD&C Red No. 4, D&C Red No. 6, D&C Red No. 7, D&C Red No. 8, D&C Red No. 9, D&C Red No. 17, D&C Red No.
  • D&C Violet 2 natural dyes such as caramel and coffee, Phosphorescent pigments, Fluorescent pigments, UV-fluorescent pigment, IR-pigments, thermochromic pigments, glitter pigments, aluminium pigments, polyester pigments, iridescent pigments, holographic pigments, pearlescent pigments, glass flakes, metallic pigments, mica, basic dyes, acid dyes, solvent dyes, mordant dyes, disperse dyes, vat dyes, reactive dyes, basic yellow 10, basic violet 11, basic violet 11:1, basic violet 10, basic red 1, basic red 1:1, pigment yellow 144, pigment white 6, Pigment Blue 15, Pigment Blue 60, Pigment Green 7, Pigment Black 2, solvent yellow 135, solvent red 135, Perylene dyes, Rylene dyes, solvent red 196, Acid yellow 250, acid red 50, acid red 52, vat orange 7, Pigment White 6, Biphenyl distyryl compound sodium salt.
  • natural dyes such as caramel and coffee, Phosphorescent pigments, Fluorescent pigments, UV-fluorescent pigment,
  • Optical brighteners or other additives like sunscreen agents may also be added to the resins.
  • sunscreen agents including UV absorbers
  • UV absorbers such as Benzophenone-3 , ZnO, Nano TiO2
  • Fillers like barium sulfate, talc or different Si ⁇ 2 modifications may also be added to the resins.
  • the powder thus obtained has a median particle size between 0.02 ⁇ m and 1000 ⁇ m, preferably between 0.2 ⁇ m and 100 ⁇ m, more preferably between 2 ⁇ m and 10 ⁇ m, for instance from 3 to 5 ⁇ m.
  • the grinding step may be carried out by means of jet milling, high shear dispersing, ball milling or pin or sand milling, for instance .
  • the pigments thus obtained might be mixed in applications to supply a special effect, like being reflective or absorbing only at a narrow range of the visible or invisible light wavelengths, as an example but not limited to, when being reflective or absorbing only between 400 and 500 nm or between 600 and 700 nm or 400 and 460 nm or having a cascading effect as when one colorant fluoresces whereas the other(s) absorb(s). It is easy to the one skilled in the art to find out the percentage of the needed colorant in the targeted special effect mixtures based on the reflection, absorption and emission curves of the single components.
  • targeting a cascading effect at 560 nm might be achieved by 2 pigments, one absorbing at 430 nm and fluorescing at 500 nm and the other absorbing at 500 nm and fluorescing at 560 nm.
  • the pigments are characterized by a high resistance to solvents such as alkyl acetates and acetone. Solvent resistance may be tested by leaving 1 g of the pigment, pulverized to a median particle size of 5 ⁇ m, in 10 ml of said solvent for 30 minutes at 37- 38 0 C or 24h at 4O 0 C.
  • the solvent attack on the pigment indicates the resistance or the solubility of said pigment and it is classified from 5 (insoluble) to 1 (completely soluble) .
  • Pigments are regarded as solvent- resistant in case their grade is 5. Moreover, one checks that the pigment particles remain free flowing in the solvent after applying the test.
  • the pigments of this invention also have a melting point of 210-240 0 C and a decomposition temperature of more than 300 0 C, which enables them to be processed up to a temperature of 22O 0 C.
  • pigments having a good solvent and/or heat resistance can thus be used to color cosmetic or non cosmetic coating products or to provide a color to a substrate onto which these cosmetic or non- cosmetic products are applied.
  • This invention is thus also directed to coating compositions comprising at least one pigment as defined above.
  • Non cosmetic products are among others polymer articles such as PVC, PU or PE films ; modeling clay ; sand ; inks ; spray cans; paints ; LCDs ; textiles ; electronic devices ; electrical devices ; and mechanical devices.
  • the pigments of this invention are included in a cosmetically acceptable medium.
  • a cosmetically acceptable medium By this expression, it is intended to mean a physiologically acceptable medium, which is compatible with the keratin materials such as the skin and/or lips and/or nails and/or hair and which does not provide the consumer with any unacceptable discomfort such as stinging.
  • This cosmetic medium usually includes at least one solvent which may be chosen from water and polar and apolar organic solvents such as alkyl acetates or acetone and oils.
  • oils include: linear or branched hydrocarbons of mineral or synthetic origin, synthetic (poly) esters and (poly) ethers and in particular (poly) esters of C6-C20 acids and of C6-C20 alcohols that are advantageously branched, such as isononyl isononanoate, plant oils, branched and/or unsaturated fatty acids, branched and/or unsaturated fatty alcohols, fluoro oils, and also mixtures thereof.
  • the resulting composition may be anhydrous or it may be in the form of an oil-in-water, water-in-oil or multiple (W/O/W, 0/W/O, etc.) emulsion or in the form of a hydrodispersion (dispersion of oil in a polar phase, especially an aqueous phase, in the absence of emulsifier) .
  • This composition may include from 5 to 20wt. % of the pigments according to this invention. In addition, it may include at least one additive chosen from:
  • dyestuffs chosen from water-soluble or liposoluble dyes, pigments, nacres and lakes;
  • active agents such as humectants and/or anti- oxidants
  • organic and/or inorganic UV-screening agents • active agents such as humectants and/or anti- oxidants; • organic and/or inorganic UV-screening agents; and
  • Example 2 The same pigment as described in Example 1 is prepared, except that D&C Orange 5 is replaced with solvent Yellow 135. Grinding resulted in a fluorescent greenish yellow pigment with particles of 5 ⁇ m median particle size. The pigment has good solvent resistance and high reflection.
  • Example 1 The preparation method of Example 1 is repeated, except that D&C Orange 5 is replaced with 4 g of D&C Red 22 and 3 g D&C Red 17. Grinding results in a fluorescent bluish red pigment with particles of 5 ⁇ m median particle size. The pigment has good solvent resistance and high reflection.
  • Example 1 The preparation method of Example 1 is repeated, except that D&C Orange 5 is replaced with 8 g of D&C Violet 2. Grinding results in a bluish violet pigment with particles of 5 ⁇ m median particle size with good solvent resistance and high reflection.
  • Example 1 The preparation method of Example 1 is repeated, except that D&C Orange 5 is replaced with 8 g of disodium distyrylbiphenyl disulphonate . Grinding results in a white to colorless pigment with particles of 5 ⁇ m median particle size with good solvent resistance and high reflection. The pigment fluoresces and becomes blue when illuminated with UV-light.
  • COS-14 D&C Yellow 7, D&C Orange 5 and D&C Red 28
  • COS-15 D&C Orange 5 and D&C Red 28
  • COS-17 D&C Red 28 and D&C Red 21.
  • pigments were tested for assessing their solvent resistance in various solvents: they were completely insoluble in acetone, MEK, water, isopropyl alcohol, DMF and in mixtures of DIDP/acetone (1/1) and
  • This example illustrates a lipstick composition containing the pigments of this invention.
  • Pentaerythrityl tetraisostearate 5-15%
  • Phenylpropyldimethylsiloxysilicate 4-10%
  • Anti-oxidants 0-1%
  • This example illustrates a pressed powder blush containing a pigment according to this invention.
  • Magnesium myristate 0-5%
  • Magnesium stearate 0-6%
  • Methylmethacrylate crosspolymer 2-8%
  • mice 0-10%
  • Anti-oxidants 0-1%
  • This example illustrates a procedure for making a nail varnish containing a pigment of this invention.
  • trimellitic anhydride copolymer 0-2%
  • a nail varnish is prepared which comprises a pigment according to this invention.
  • nitrocellulose (1Og) is dissolved in a solvent mixture (2Og of ethyl acetate and qs butyl acetate for 10Og) and then 1Og of a plasticizer (Ethyl
  • a thickening agent stearalkonium hectorite
  • other solvents Ig of diacetone alcohol and
  • a gloss is prepared, which is fluorescent when exposed to UV light and vivid colored when exposed to day light. Its formula is the following:
  • Diisostearyl malate 10-20%
  • the pigments of Example 5 0.01-2% The pigments are grinded into the diisostearyl malate and added to the other raw materials already mixed and melted at 8O 0 C. The full composition is mixed for 30 minutes before cooling at room temperature and filled in appropriate containers.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

The present invention pertains to a pigment which may be obtained according to a process including the steps of preparing a crosslinked resin chosen from polyester, polyamide or polyesteramide resins and introducing at least one material chosen from organic dyes or pigments, inorganic pigments and their mixtures, either before, during or after the manufacture of said crosslinked resin. It also relates to coating compositions, especially cosmetic compositions, comprising said pigment and to a cosmetic process for making-up skin (especially cheeks and/or eyelids) and/or lips, comprising the topical application onto said skin and/or lips of this cosmetic composition.

Description

Solvent resistant pigments for cosmetic
applications
The present invention relates to cosmetic pigments, and especially fluorescent cosmetic colored pigments, suitable for cosmetic formulations in general and specifically for formulations demanding good solvent resistance, such as nail lacquers formulations. BACKGROUND OF THE INVENTION
Embedding dyes into polymers to create fluorescent pigments which may be used in paints, for example, has been reported among others under U.S. Pat. Nos. 2938873 and 2498592. The polymers used to make these pigments are either thermoplastic sulfonamide / formaldehyde polymers or thermoset resins which are essentially based on urea / formaldehyde polymers. The dyes may be introduced at any stage during the manufacture of the polymer, for instance before curing the thermoset resin. After grinding, the resulting pigments are introduced into coating compositions where they are said to be insoluble and to be stable against flocking.
Further, U.S. Pat. Nos. 5143723 and 5324506 report utilizing the same technology to create pigments or fluorescent pigments to be used in cosmetic compositions. These pigments are said to confer more gloss and clarity of color to the lips or cheeks than the usual lakes, which are made of an insoluble, oil- dispersible aluminum hydroxide substrate on which a dye is absorbed or precipitated. Although a number of resins are listed, including crosslinked polyester resins, the examples provided in this document only use toluene sulfonamide formaldehyde resins. It has now been found that the available polymer embedding technology does not provide suitable cosmetic pigments for solvent resistance demanding applications like nail varnish. In these applications, a syneresis or/and a gelification of the texture and/or a sedimentation of pigments is observed. Although it is known that crosslinking may result in higher solvent resistance, the degree of crosslinking should be properly adjusted so it is high enough to provide the required solvent resistance, while not being so high as to form a gel which cannot be grinded into a powder in order to be dispersed into cosmetic compositions.
The inventors have realized that the above drawback could be overcome by using a specific kind of polymer in a specific process to make the colored pigment .
Moreover, the pigments according to this invention have also been shown to be heat resistant, which render them useful in various make-up products such as lipsticks, lip glosses, cheek blushes and eye shadows.
An object of the present invention is thus to provide pigments which are not soluble and do not swell in the solvents used in nail enamels. Another object of this invention is to provide pigments which can be easily grinded and dispersed into cosmetic compositions. Still another object of this invention is to provide pigments which are heat resistant, in that they do not deteriorate until 22O0C.
SUMMARY OF THE INVENTION
The present invention pertains to a pigment which may be obtained according to a process including the steps of:
1- preparing a crosslinked resin chosen from polyester, polyamide or polyesteramide resins, from at least one bi-functional monomer Ml chosen from diols and diamines and at least one bi-functional monomer M2 chosen from dicarboxylic acids and acid anhydrides, in the presence of at least one crosslinking agent chosen from tri-functional crosslinkers CL3 and tetra- functional crosslinkers CL4,
wherein :
0.3 < A/B < 1.7
1.5 < (A+B) /C < 3.5
1.7 < (A+B) /D < 4
where A = total molar content of Ml
B = total molar content of M2
C = molar content of CL3
D = molar content of CL4;
2- introducing at least one material chosen from organic dyes or pigments, inorganic pigments and their mixtures, either before, during or after the manufacture of said crosslinked resin;
3- optionally removing any solvent or suspension medium for the monomers, crosslinkers and/or materials, so as to obtain a powder; and
4- grinding said powder.
This invention also pertains to coating compositions, especially cosmetic compositions, comprising said novel pigment.
It is also directed to a cosmetic process for making-up skin (especially cheeks and/or eyelids) and/or lips, comprising the topical application onto said skin and/or lips of such a cosmetic composition.
The pigments according to this invention have proved to be stable upon heating and in solvents used to manufacture nail enamels, especially alkyl acetates and acetone and to be easily dispersible in cosmetic media. They also offer a better resistance to pH and light than the usual organic dyes and a newer range of colors which cannot be obtained by means of these dyes. DETAILED DESCRIPTION OF THE INVENTION
As mentioned above, the process according to the present invention comprises the manufacture of a crosslinked polyester, polyamide or polyesteramide resin from bifunctional monomers Ml and M2, trifunctional crosslinkers CL3 and tetra-functional crosslinkers CL4.
The words "trifunctional" and "tetra-functional" are intended to refer to compounds including three or four functions, respectively, which may be chosen among hydroxy, carboxyl, epoxy and amino groups. Optionally, one anhydride group can be used instead of two carboxyl groups .
The bifunctional, trifunctional and tetra- functional compounds used in this invention may be linear, branched or cyclic hydrocarbons bearing said functions or may be chosen from heterocyclic or aromatic compounds (preferably including a phenyl moiety) bearing said functions.
The monomers Ml include diols, diamines and their mixtures. Among diols, mention can be made of 1,4- cyclohexane dimethanol (CHDM), 1, 4-butanediol (BDO), 1, 5-pentanediol (PDO), 1, 6-hexanediol (HDO), 1,12- dodecanediol (DDO) and their mixtures. Among diamines, mention can be made of para-phenylenediamine (PPD) , isophorone diamine (IPDA), hexamethylenediamine (HMDA), 2-methylpentane-l , 5-diamine (MPMD), diaminododecane (DADD) and their mixtures.
Examples of monomers M2 are dicarboxylic acids, such as adipic acid (ADA) , dodecanedioic acid (DDA) , methylisophthalic acid (MIPA), isophthalic acid (IPA) and terephthalic acid (TPA) , acid anhydrides bearing one anhydride group, such as phthalic anhydride (PA) , and their mixtures.
The trifunctional crosslinking agents CL3 may be chosen from the group consisting of: tris-(2,3- epoxypropyl) isocyanurate (TGIC), trimethylolpropane (TMP) , trimellitic anhydride (TMA) , dimethylolpropionic acid (DMPA) and their mixtures. The tetra-functional crosslinking agents CL4 may be chosen from the group consisting of: pentaerythritol (penta) , tris (hydroxy) aminomethane (THAM), pyromellitic dianhydride (PMDA), 2-amino-2- (hydroxymethyl) - propanediol, ethylenediaminetetraacetic acid (EDTA) and their mixtures.
According to this invention, the foregoing monomers and crosslinking agents should be used in specific ratios so as to obtain pigments having enough solvent resistance while avoiding gelling problems during their manufacture and preserving the ability to grind them.
Specifically, they should satify:
0.3 < A/B < 1.7
1.5 < (A+B) /C < 3.5
1.7 < (A+B) /D < 4
wherein A = total molar content of Ml
B = total molar content of M2
C = molar content of CL3
D = molar content of CL4 More preferably, at least one and optionally all of the following requirements could be satisfied:
A/B ranges from 0.6 to 1.4,
(A+B)/C ranges from 2 to 3,
(A+B) /D ranges from 2.2 to 3.5.
Moreover, in case a mixture of CL3 and CL4 crosslinking agents is used, it is preferred to have: 1.5 < [ (A+B+C) / (A+B+D) ] <4.
In order to prepare the crosslinked resin according to this invention, the above monomers Ml and M2 are polymerized in the presence of the crosslinking agents CL3 and/or CL4 according to any polymerization process well-known to the skilled person, such as bulk polymerization, emulsion polymerization or suspension polymerization. The polymerization is preferably a polycondensation reaction conducted in the presence of a catalyst such as oxalic acid.
A material chosen from pigments and dyes and their mixtures is added to the resin either before, during or after its formation, for instance during its polymerization or during its crosslinking. This material usually provides for an optical effect including absorbing, reflecting, transmitting, diffusing and/or refracting any portion of the light spectrum, and especially of the UV and visible wavelengths, such as providing for a color or a soft- focus effect, for instance. Thus, the pigment obtained according to this invention is preferably a colored pigment .
Examples of such materials include, without any limitation: FD&C Blue No. 1, FD&C Blue No. 2, FD&C Green No. 3, FD&C Red No. 3, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6, D&C Blue No. 4, D&C Blue No. 9, D&C Green No. 5, D&C Green No. 6, D&C Green No. 8, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, D&C Orange No. 17, FD&C Red No. 4, D&C Red No. 6, D&C Red No. 7, D&C Red No. 8, D&C Red No. 9, D&C Red No. 17, D&C Red No. 19, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 34, D&C Red No. 39, FD&C Red No. 40, D&C Violet No. 2, D&C Yellow No. 7, Ext. D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 11, D&C Brown No. 1, Ext. D&C Violet 2, natural dyes such as caramel and coffee, Phosphorescent pigments, Fluorescent pigments, UV-fluorescent pigment, IR-pigments, thermochromic pigments, glitter pigments, aluminium pigments, polyester pigments, iridescent pigments, holographic pigments, pearlescent pigments, glass flakes, metallic pigments, mica, basic dyes, acid dyes, solvent dyes, mordant dyes, disperse dyes, vat dyes, reactive dyes, basic yellow 10, basic violet 11, basic violet 11:1, basic violet 10, basic red 1, basic red 1:1, pigment yellow 144, pigment white 6, Pigment Blue 15, Pigment Blue 60, Pigment Green 7, Pigment Black 2, solvent yellow 135, solvent red 135, Perylene dyes, Rylene dyes, solvent red 196, Acid yellow 250, acid red 50, acid red 52, vat orange 7, Pigment White 6, Biphenyl distyryl compound sodium salt.
Optical brighteners or other additives like sunscreen agents (including UV absorbers), such as Benzophenone-3 , ZnO, Nano TiO2, may also be added to the resins.
Fillers like barium sulfate, talc or different Siθ2 modifications may also be added to the resins.
After the resin has been formed, any solvent used during its formation is usually removed, for instance by evaporation. After grinding, if necessary, the powder thus obtained has a median particle size between 0.02 μm and 1000 μm, preferably between 0.2 μm and 100 μm, more preferably between 2 μm and 10 μm, for instance from 3 to 5 μm. The grinding step may be carried out by means of jet milling, high shear dispersing, ball milling or pin or sand milling, for instance .
The pigments thus obtained might be mixed in applications to supply a special effect, like being reflective or absorbing only at a narrow range of the visible or invisible light wavelengths, as an example but not limited to, when being reflective or absorbing only between 400 and 500 nm or between 600 and 700 nm or 400 and 460 nm or having a cascading effect as when one colorant fluoresces whereas the other(s) absorb(s). It is easy to the one skilled in the art to find out the percentage of the needed colorant in the targeted special effect mixtures based on the reflection, absorption and emission curves of the single components. As an example, but not limited too, targeting a cascading effect at 560 nm might be achieved by 2 pigments, one absorbing at 430 nm and fluorescing at 500 nm and the other absorbing at 500 nm and fluorescing at 560 nm. The pigments are characterized by a high resistance to solvents such as alkyl acetates and acetone. Solvent resistance may be tested by leaving 1 g of the pigment, pulverized to a median particle size of 5 μm, in 10 ml of said solvent for 30 minutes at 37- 380C or 24h at 4O0C. The solvent attack on the pigment indicates the resistance or the solubility of said pigment and it is classified from 5 (insoluble) to 1 (completely soluble) . Pigments are regarded as solvent- resistant in case their grade is 5. Moreover, one checks that the pigment particles remain free flowing in the solvent after applying the test.
Usually, the pigments of this invention also have a melting point of 210-2400C and a decomposition temperature of more than 3000C, which enables them to be processed up to a temperature of 22O0C.
They can thus be used in all applications requiring pigments having a good solvent and/or heat resistance. These pigments may thus be used to color cosmetic or non cosmetic coating products or to provide a color to a substrate onto which these cosmetic or non- cosmetic products are applied. This invention is thus also directed to coating compositions comprising at least one pigment as defined above.
Among cosmetic products, mention can be made of: lipsticks, lip glosses, nail enamels, mascaras, cheek blushes, eye shadows and hair sprays, without limitation. Non cosmetic products are among others polymer articles such as PVC, PU or PE films ; modeling clay ; sand ; inks ; spray cans; paints ; LCDs ; textiles ; electronic devices ; electrical devices ; and mechanical devices.
When used in cosmetic compositions, the pigments of this invention are included in a cosmetically acceptable medium. By this expression, it is intended to mean a physiologically acceptable medium, which is compatible with the keratin materials such as the skin and/or lips and/or nails and/or hair and which does not provide the consumer with any unacceptable discomfort such as stinging.
This cosmetic medium usually includes at least one solvent which may be chosen from water and polar and apolar organic solvents such as alkyl acetates or acetone and oils. Examples of oils include: linear or branched hydrocarbons of mineral or synthetic origin, synthetic (poly) esters and (poly) ethers and in particular (poly) esters of C6-C20 acids and of C6-C20 alcohols that are advantageously branched, such as isononyl isononanoate, plant oils, branched and/or unsaturated fatty acids, branched and/or unsaturated fatty alcohols, fluoro oils, and also mixtures thereof.
The resulting composition may be anhydrous or it may be in the form of an oil-in-water, water-in-oil or multiple (W/O/W, 0/W/O, etc.) emulsion or in the form of a hydrodispersion (dispersion of oil in a polar phase, especially an aqueous phase, in the absence of emulsifier) .
This composition may include from 5 to 20wt. % of the pigments according to this invention. In addition, it may include at least one additive chosen from:
• plant, animal, mineral or synthetic waxes, the latter advantageously possibly being hydrocarbon-based waxes or silicone waxes ; • a pasty fatty substance or a butter characterized by a melting point of between 25 and 450C;
• lipophilic and/or hydrophilic gelling agents;
• film-forming polymers;
• surfactants;
• fillers;
• dyestuffs chosen from water-soluble or liposoluble dyes, pigments, nacres and lakes;
• active agents such as humectants and/or anti- oxidants; • organic and/or inorganic UV-screening agents; and
• their mixtures. Examples of such adjuvants are mentioned especially in the CTFA dictionary (International Cosmetic Ingredient Dictionary and Handbook published by The Cosmetic, Toiletry and Fragrance Association, 11th edition, 2006) .
The invention will now be illustrated by the nonlimiting examples that follow.
EXAMPLES
EXAMPLE 1
8 g D&C Orange 5, 60 g isophoronediamine, 50 g 2- amino-2- (hydroxymethyl ) -1 , 3-propanediol and 170 g of isophthalic acid are added and mixed in 1 liter reactor. The mixture is heated under mixing for 3 hours between 100 and 25O0C. After cooling to room temperature, the mix is crushed and processed via a laboratory jet mill to get fine fluorescent orange pigment with particles of 5 μm median particle size. The pigment has good solvent resistance and high reflection .
EXAMPLE 2
The same pigment as described in Example 1 is prepared, except that D&C Orange 5 is replaced with solvent Yellow 135. Grinding resulted in a fluorescent greenish yellow pigment with particles of 5 μm median particle size. The pigment has good solvent resistance and high reflection.
EXAMPLE 3
The preparation method of Example 1 is repeated, except that D&C Orange 5 is replaced with 4 g of D&C Red 22 and 3 g D&C Red 17. Grinding results in a fluorescent bluish red pigment with particles of 5 μm median particle size. The pigment has good solvent resistance and high reflection.
EXAMPLE 4
The preparation method of Example 1 is repeated, except that D&C Orange 5 is replaced with 8 g of D&C Violet 2. Grinding results in a bluish violet pigment with particles of 5 μm median particle size with good solvent resistance and high reflection.
EXAMPLE 5
The preparation method of Example 1 is repeated, except that D&C Orange 5 is replaced with 8 g of disodium distyrylbiphenyl disulphonate . Grinding results in a white to colorless pigment with particles of 5 μm median particle size with good solvent resistance and high reflection. The pigment fluoresces and becomes blue when illuminated with UV-light.
EXAMPLE 6
Five colored pigments were made according to the preparation method described in Example 1, except that they contained the following colorants: COS-IO: D&C Yellow 7 and D&C Yellow 8
COS-14: D&C Yellow 7, D&C Orange 5 and D&C Red 28
COS-15: D&C Orange 5 and D&C Red 28
COS-17: D&C Red 28 and D&C Red 21.
COS-19: FD&C Blue 1 Lake
These pigments were tested for assessing their solvent resistance in various solvents: they were completely insoluble in acetone, MEK, water, isopropyl alcohol, DMF and in mixtures of DIDP/acetone (1/1) and
Butyl/propyl/ethyl acetates (1/1/1).
EXAMPLE 7
This example illustrates a lipstick composition containing the pigments of this invention.
Octyldodecanol : 10-20%
Pentaerythrityl tetraisostearate : 5-15%
Sucrose tetrastearate triacetate : 5-15%
Dipentaerythrityl/hexahydroxystearate/
hexastearate/hexarosinate : 5-12%
Diisostearyl malate : 5-12%
Hydrogenated polydecene : 4-10%
Phenylpropyldimethylsiloxysilicate : 4-10%
Mica : 2-7%
Polyethylene : 2-6%
Synthetic wax : 2-6%
Preservatives : 0-1%
Anti-oxidants : 0-1%
Fragrance : 0-1% Pigments and pearls : 0-20%
Pigments of Example 6 (COS14) : 0.1-20%
EXAMPLE 8
This example illustrates a pressed powder blush containing a pigment according to this invention.
Talc : 20-75%
Boron nitride : 5-15%
Magnesium myristate : 0-5%
Magnesium stearate : 0-6%
Methylmethacrylate crosspolymer : 2-8%
Mica : 0-10%
PTFE : 0-8%
Nylon-12 : 2-10%
Polymethylmethacrylate : 0-3%
Octyldodecyl neopentanoate : 1-6%
PPG-2 myristyl ether propionate : 1-6%
Preservatives : 0-1%
Anti-oxidants : 0-1%
Fragrance : 0-1%
Pigments of Example 6 (COS15) : 0.1-20%
EXAMPLE 9
This example illustrates a procedure for making a nail varnish containing a pigment of this invention.
Butyl acetate : 25-35%
Ethyl acetate : 23-29%
Nitrocellulose : 11-15%
Styrene / acrylates copolymer : 4-10% Acetyl tributyl citrate : 3-7%
Isophorone diamine / isophthalic
acid / tromethamine copolymer : 3-11%
Phthalic anhydride / trimellitic
anhydride / glycol copolymer : 0-6%
Isoporpyl alcohol : 4-6%
Isobutyl acetate : 0-5%
Adipic acid / neopentyl glycol /
trimellitic anhydride copolymer : 0-2%
Stearalkonium bentonite : 0.1-3%
Stearalkonium hectorite : 0.1-3%
Propylene carbonate : 0.2-2%
Colorants : 0-0.5%
Phosphoric acid : 0.1 %
Silica : 0.2 %
Pigments of Example 6 (COS17) : 0.1-20%
EXAMPLE 10
A nail varnish is prepared which comprises a pigment according to this invention.
Procedure: nitrocellulose (1Og) is dissolved in a solvent mixture (2Og of ethyl acetate and qs butyl acetate for 10Og) and then 1Og of a plasticizer (Ethyl
Tosylamide and/or Adipic Acid/Neopentyl glycol/trimellitic anhydride copolymer) and 5g of a resin (Styrene/acrylates copolymer) are added to the combination. 1.5g of a thickening agent (stearalkonium hectorite), other solvents (Ig of diacetone alcohol and
5g of isopropyl alcohol) and the pigments of Example 4 are added slowly (over 5 minutes) in order to get good wetting while stirring with a spatula and mixing till a homogenous mixture is obtained.
EXAMPLE 11
A gloss is prepared, which is fluorescent when exposed to UV light and vivid colored when exposed to day light. Its formula is the following:
Polybutene: 50-80%
Diisostearyl malate: 10-20%
Octyldodecanol: 5-20%
Glyceryl Behenate/eicosadioate 0.5-5%
Tocopheryl acetate 0.1-1%
The pigments of Example 5 0.01-2% The pigments are grinded into the diisostearyl malate and added to the other raw materials already mixed and melted at 8O0C. The full composition is mixed for 30 minutes before cooling at room temperature and filled in appropriate containers.

Claims

What we claim is:
1. Pigment which may be obtained according to a process including the steps of:
1- preparing a crosslinked resin chosen from polyester, polyamide or polyesteramide resins, from at least one bi-functional monomer Ml chosen from diols and diamines and at least one bi-functional monomer M2 chosen from dicarboxylic acids and acid anhydrides, in the presence of at least one crosslinking agent chosen from tri-functional crosslinkers CL3 and tetra- functional crosslinkers CL4,
wherein :
0.3 < A/B < 1.7
1.5 < (A+B) /C < 3.5
1.7 < (A+B) /D < 4
where A = total molar content of Ml
B = total molar content of M2
C = molar content of CL3
D = molar content of CL4;
2- introducing at least one material chosen from organic dyes or pigments, inorganic pigments and their mixtures, either before, during or after the manufacture of said crosslinked resin;
3- optionally removing any solvent or suspension medium for the monomers, crosslinkers and/or materials, so as to obtain a powder; and
4- grinding said powder. 2. Pigment according to Claim 1, wherein the monomers Ml are chosen from the group consisting of: 1, 4-cyclohexane dimethanol (CHDM), 1, 4-butanediol (BDO), 1, 5-pentanediol (PDO), 1, 6-hexanediol (HDO), 1, 12-dodecanediol (DDO), para-phenylenediamine (PPD), isophorone diamine (IPDA), hexamethylenediamine (HMDA), 2-methylpentane-l, 5-diamine (MPMD), diaminododecane (DADD) and their mixtures.
3. Pigment according to Claim 1 or 2, wherein the monomers M2 are chosen from the group consisting of: adipic acid (ADA) , dodecanedioic acid (DDA) , methylisophthalic acid (MIPA), isophthalic acid (IPA), terephthalic acid (TPA) , phthalic anhydride (PA) and their mixtures.
4. Pigment according to any of Claims 1 to 3, wherein the trifunctional crosslinking agents CL3 are chosen from the group consisting of: tris-(2,3- epoxypropyl) isocyanurate (TGIC), trimethylolpropane (TMP), trimellitic anhydride (TMA), dimethylolpropionic acid (DMPA) and their mixtures.
5. Pigment according to any of Claims 1 to 4, wherein the tetra-functional crosslinking agents CL4 are chosen from the group consisting of: pentaerythritol (penta) , tris (hydroxy) aminomethane (THAM) , pyromellitic dianhydride (PMDA) , 2-amino-2- (hydroxymethyl ) -propanediol, ethylenediaminetetra- acetic acid (EDTA) and their mixtures.
6. Coating compositions, especially cosmetic compositions, comprising the pigment according to any of Claims 1 to 5.
! 7. Cosmetic process for making-up skin (especially cheeks and/or eyelids) and/or lips, comprising the topical application onto said skin and/or lips of the cosmetic composition according to Claim 6.
PCT/IB2009/054053 2009-08-04 2009-08-04 Solvent resistant pigments for cosmetic applications WO2011015906A1 (en)

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Publication number Priority date Publication date Assignee Title
WO2014135915A1 (en) 2013-03-08 2014-09-12 Chanel Parfums Beaute Non bleeding and solvent resistant pigments for cosmetic applications
IT202300003123A1 (en) * 2023-02-23 2024-08-23 Chromavis Spa USE OF A BROMOACID DYE AS AN ANTI-DYSCOLOURING AGENT OF NAIL IN NAIL POLISH COMPOSITIONS AND ANHYDROUS NAIL POLISH COMPOSITIONS COMPRISING SAID BROMOACID DYE

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US5324506A (en) * 1988-11-23 1994-06-28 Estee Lauder, Inc. Colored cosmetic compositions
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DE2055448A1 (en) * 1970-11-11 1972-05-18 Hoechst Ag Daylight fluorescent pigments - on a cross-linked polyester support
US3812054A (en) * 1971-02-02 1974-05-21 Hoechst Ag Daylight fluorescent pigments and process for preparing them
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014135915A1 (en) 2013-03-08 2014-09-12 Chanel Parfums Beaute Non bleeding and solvent resistant pigments for cosmetic applications
IT202300003123A1 (en) * 2023-02-23 2024-08-23 Chromavis Spa USE OF A BROMOACID DYE AS AN ANTI-DYSCOLOURING AGENT OF NAIL IN NAIL POLISH COMPOSITIONS AND ANHYDROUS NAIL POLISH COMPOSITIONS COMPRISING SAID BROMOACID DYE
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