WO2020010169A1

WO2020010169A1 - Blue light curable formulations

Info

Publication number: WO2020010169A1
Application number: PCT/US2019/040446
Authority: WO
Inventors: Joseph TEGLASI
Original assignee: Teglasi Joseph
Priority date: 2018-07-06
Filing date: 2019-07-03
Publication date: 2020-01-09

Abstract

In order to provide curing capability for formulations to be applied to one's fingernails or toenails, compositions and methods are provided. The compositions contain a perylene diimide compound or a derivative that makes the formulations curable under blue light.

Description

Blue Light Curable Formulations

[0001 ] Cross-reference to related application

[0002] This application claims priority to U.S. provisional patent application serial number 62/694,789, filed on July 6, 2018. The entire disclosure of the aforementioned patent application is hereby incorporated by reference into the present disclosure.

[0003] Field of the Invention

[0004] The present invention relates to the field of cosmetics.

[0005] Background of the Invention

[0006] Many people enjoy having a manicure and a pedicure and going to a salon to have them done. During the manicure and pedicure processes, one or more liquid chemical compositions are applied to the consumer’s fingernails and toenails. Because each composition is stored and applied as a liquid, one can use a brush or other applicator to transfer the formulation from the storage container, e.g., a nail polish bottle to the consumer’s nails.

[0007] Between the time that a nail polish or other coating is applied and when the consumer leaves the store, the liquid must become a solid. In conventional nail polish, the liquid dries as solvent evaporates, leaving a brittle lacquer on the nails that lasts only a few days to a week before chipping. Gel nail polishes are a viable alternative for more durable, chip-resistant manicures. In most applications of gel nail polish, the transition from liquid to solid is not simply a phase change and in general does not involve merely the drying of the liquid materials. Instead, the nail polish or other coating must be cured. Accordingly, after one selects a desired nail polish color and the product is applied, the customer typically sits with her or his nails under ultra violet (UV) light. [0008] The exposure to UV light has a distinct purpose. It allows for the forming of chemical bonds among certain components of a formulation. However, exposure to UV light can have deleterious side-effects.

[0009] Currently, there is a need for nail polish formulations that can be effectively and efficiently cured under light that is not ultra-violet, while still providing customers with the desired results. The present invention is directed to this need.

[0010] Summary of the Invention

[0011] The present invention provides formulations that are curable under blue light, as well as methods for making these formulations and methods for using these formulations. These formulations may, for example, be applied to a subject’s fingernails, toenails, or both.

[0012] According to a first embodiment, the present invention provides a mixture comprising a perylene diimide compound or a derivative thereof; an electron donor substance; and an acrylate substance, wherein the acrylate substance is capable of polymerizing in the presence of the perylene diimide compound or derivative thereof and the electron donor substance when the mixture is subjected to blue light. Each of the components is present in an effective amount and proportion so as to allow for effective and efficient curing when exposed to blue light.

[0013] According to a second embodiment, the present invention provides a method for curing nail polish comprising: creating the mixture of any of the embodiments described herein; applying the mixture to a surface; and exposing the surface to blue light.

[0014] According to a third embodiment, the present invention provides a cosmetic formulation, wherein the formulation comprises a mixture of: (1) a perylene diimide compound or a derivative thereof; and (2) an acrylate substance, wherein the acrylate substance has an electron donating moiety, and wherein the acrylate substance is capable of polymerizing in the presence of the perylene diimide compound or derivative thereof when the mixture is exposed to blue light. [0015] Different compositions and formulations of the present invention may be used as blue-light curable base-coats, blue-light curable top coats, or blue-light curable nail polishes, as well as 2-in-l or 3-in-l complete formulations. Thus, in some embodiments, the formulations may contain or have an omission of pigments (other than a catalytic amount of the perylene diimide compound) and other substances that cause the formulations to have color when stored, applied or cured. By using the various embodiments of the present invention, one can effectively and efficiently prepare compositions for application to one’s nails, apply them, and cure them under blue light, thereby avoiding unnecessary exposure to hazardous UV radiation.

[0016] Brief Description of the Figure

[0017] The figure is a representation of a polymerization scheme of the present invention.

[0018] Detailed Description of the Invention

[0019] Reference will now be made in detail to various embodiments of the present invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, unless otherwise indicated or implicit from context, the details are intended to be examples and should not be deemed to limit the scope of the invention in any way.

[0020] Additionally, unless otherwise indicated, any of the features of the various embodiments described herein can be used in conjunction with features described in connection with any other embodiments disclosed herein. Thus, features described in connection with the various or specific embodiments are not to be construed as not suitable in connection with other embodiments disclosed herein unless such exclusivity is explicitly stated or implicit from context.

[0021] Additionally, although this specification enumerates specific advantages of some embodiments, various embodiments may include some, none, or all of the enumerated advantages. Furthermore, headings are provided for the convenience of the reader and are not intended to be and should not be construed as limiting any of the embodiments described herein.

[0022] Formulations

[0023] The formulations of the present invention comprise a perylene diimide compound and/or a derivative thereof; an electron donor substance; and an acrylate substance. Each of these components is present in an effective amount.

[0024] By way of non-limiting examples, the components may be present in the following weight percentages (also referred to as % weight): l0%-99% or 20%-80% or 30%-50% or l0%-20% or 60%-99% or 70%-99% or 80%-99% or 60%-80% or 70%-85% polymerizable monomers or copolymerizable monomers or combinations thereof that are acrylate substances; 0.000l%-20% or 0.0l%-20% or 0.l%-20% or 1%-10% or \%-5% or 0.000l%-0.0l% or 0.000l%-0.l% or 0.000l%-2% PDI catalyst (or a combination of multiple PDI catalysts); 0.0l%-99% or 0.l%-99% or l%-90% or l%-50% or l0%-40% or 20%-30% or 5%-l0% or l0%-20% or 60-99% electron donor substance (which may be separate from or the same as the acrylate substance); and 0%-90% other ingredients (plasticizers, pigments, UV absorbers,“pearls’Vglitter, film formers, resins, etc.). These percent-weights are of the dried compound immediately prior to light-curing and exclude the mass of any solvent. The amount of solvent initially added when making the mixture, if any solvent is added, should be sufficient to create a gel or thick liquid containing the ingredients.

[0025] By way of further non-limiting examples, in some embodiments:

1 The PDI is /V,/V’-bis(2,6-diisopropylphenyl)perylene-3,4,9,l0- bis(dicarboximide) in an amount of 0.0001-2% weight, the sacrificial (electron) donor is triethylamine in an amount of 2-5% weight, and the acrylate monomer is any single one of the acrylate monomers named in this document in an amount of 80-98%, containing a total of 0-18% of additional ingredients outlined below. The PDI is /V,/V’-bis(2,6-diisopropylphenyl)perylene-3,4,9,l0- bis(dicarboximide) in an amount of 0.0001-2% weight, the sacrificial (electron) donor/s is/are polyurethane acrylate oligomer/s and the acrylate monomers are polyurethane acrylate oligomer/s in an amount of 25-50% weight and HEMA and/or methyl methacrylate in an amount of 40%-60% weight, containing a total of 0-15% weight of additional ingredients outlined below.

The PDI is perylene-3,4,9,l0-bis(dicarboximide) in an amount of 0.0001- 2% weight, the sacrificial (electron) donor/s is/are polyurethane acrylate oligomer/s and the acrylate monomers are polyurethane acrylate oligomer/s in an amount of 25-50% and HEMA in an amount of 40%- 60%, containing a total of 0-15% of additional ingredients outlined below. The PDI is /V,/V’-bis(2,6-diisopropylphenyl)perylene-3,4,9,l0- bis(dicarboximide) in an amount of 0.0001-2% weight, the sacrificial (electron) donor/s is/are polyurethane acrylate oligomer/s and the acrylate monomers are polyurethane acrylate oligomer/s in an amount of 50-80%, HEMA in 0-10%, hydroxypropyl methacrylate in an amount of 0-10%, trimethylolpropane trimethacrylate in an amount of 25-50%, PEG-15 trimethylolpropane triacrylate in an amount of 0-0-25%, and PEG-4 dimethacrylate in an amount of 0-10%, containing a total of 0-10% of additional ingredients outlined below.

The PDI is perylene-3,4,9,l0-bis(dicarboximide) in an amount of 0.0001- 2% weight, the sacrificial (electron) donor/s is/are polyurethane acrylate oligomer/s and the acrylate monomers are polyurethane acrylate oligomer/s in an amount of 50-80%, HEMA in an amount of 0-10%, hydroxypropyl methacrylate in an amount of 0-10%, trimethylolpropane trimethacrylate in an amount of 25-50%, PEG- 15 trimethylolpropane triacrylate in an amount of 0-25%, and PEG-4 dimethacrylate in an amount of 0-10%, containing a total of 0-10% of additional ingredients outlined below. The PDI is Pigment Red 178 (C48H26N6O4 ) in an amount of 0.0001-2% weight, the sacrificial (electron) donor/s is/are polyurethane acrylate oligomer/s and the acrylate monomers are polyurethane acrylate oligomer/s in an amount of 50-80%, HEMA in an amount of 0-10%, hydroxypropyl methacrylate in an amount of 0-10%, trimethylolpropane trimethacrylate in an amount of 25-50%, PEG- 15 trimethylolpropane triacrylate in an amount of 0-0-25%, and PEG-4 dimethacrylate in an amount of 0-10%, containing a total of 0-10% of additional ingredients outlined below.

The PDI is /V,/V’-bis(3,5-dimethylphenyl)perylene-3,4,9,l0- bis(dicarboximide) in an amount of 0.0001-2% weight, the sacrificial (electron) donor/s is/are polyurethane acrylate oligomer/s and the acrylate monomers are polyurethane acrylate oligomer/s in an amount of 50-80%, HEMA in an amount of 0-10%, hydroxypropyl methacrylate in an amount of 0-10%, trimethylolpropane trimethacrylate in an amount of 25-50%, PEG- 15 trimethylolpropane triacrylate in an amount of 0-0-25%, and PEG-4 dimethacrylate in an amount of 0-10%, containing a total of 0-10% of additional ingredients outlined below.

The PDI is /V,/V’-bis(3,5-dimethylphenyl)perylene-3,4,9,l0- bis(dicarboximide) in an amount of 0.0001-2% weight, the sacrificial (electron) donor/s is/are polyurethane acrylate oligomer/s and N,N- dimethylacrylamide and the acrylate monomers are polyurethane acrylate oligomer/s in an amount of 20-40%, N,N-dimethylacrylamide in an amount of 2-10%, butyl methacrylate in an amount of 0-10%,

hydroxypropyl methacrylate in an amount of 0-10%, and dipentaerythritol hexaacrylate in an amount of 25-50%, containing a total of 0-10% of additional ingredients outlined below.

The PDI is /V,/V’-bis(2,6-diisopropylphenyl)perylene-3,4,9,l0- bis(dicarboximide) in an amount of 0.0001-2% weight, the sacrificial (electron) donor/s is/are polyurethane acrylate oligomer/s and N,N- dimethylacrylamide and the acrylate monomers are polyurethane acrylate oligomer/s in an amount of 50-80%, N,N-dimethylacrylamide in 2-10%, butyl methacrylate in 0-10% and hydroxypropyl methacrylate in an amount of 0-10%, and dipentaerythritol hexaacrylate in an amount of 25- 50%, containing a total of 0-10% of additional ingredients outlined below.

10 The PDI is /V,/V’-bis(3,5-dimethylphenyl)perylene-3,4,9,l0- bis(dicarboximide) in an amount of 0.0001-2% weight, the sacrificial (electron) donor/s is/are polyurethane acrylate oligomer/s and the acrylate monomers are polyurethane acrylate oligomer/s in an amount of 50-80%, HEM A in an amount of 0-10%, hydroxypropyl methacrylate in an amount of 0-10%, trimethylolpropane trimethacrylate an amount of in 25-50%, PEG- 15 trimethylolpropane triacrylate in an amount of 0-0-25%, and PEG-4 dimethacrylate in an amount of 0-10% and 0-10% isobornyl acrylate, containing a total of 0-10% of additional ingredients outlined below.

[0026] Perylene Diimide Compounds and Derivatives

[0027] Perylene (C20H12) refers to the following compound:

(Formula I).

It is a known photoinitiator. However, photoinitiation in the presence of this compound may occur under white light. Therefore, it is undesirable for use in connection with cosmetic applications, because when using it, undesirable curing might occur ( e.g ., prematurely during the manufacturing process or preparation), warranting additional precautions.

[0028] Perylene diimide, perylene-3,4,9,l0-bis(dicarboximide), refers to the following compound (a.k.a. Pigment Violet 29):

.

Collectively perylene diimide and its derivatives are referred to as PDIs, and within the scope of these compounds are their salts, though in some embodiments there is an absence of salts of PDIs. Each of Ri and R₂ may be an alkyl (linear, branched, cyclic, or a combination thereof) or aryl or a combination thereof, e.g., an aryl group in

combination with one or more linear and or branched alkyl groups. Further, each alkyl group may be saturated or unsaturated. Still further, each alkyl group may be exclusively a hydrocarbon group or contain one or more functionalized groups. The functionalized groups may, for example, be organic acid groups, keto groups, hydroxyl groups, amide or amine groups or sulfur containing groups.

[0030] In some embodiments of formula III, each of Ri and R₂ is a substituted aryl group that is substituted with an electron withdrawing group or an electron donor group at one or more or all of the positions as shown and described below. An electron withdrawing group refers to moieties from the following groups: halides, halo-saturated short-chain alkyl (C1-C6), nitro, triflyl, or cyano groups, sulfonates or sulfonic esters, ammonium (positively charged nitrogen, alkyl- or H-substituted), aldehydes or ketones, carboxylic acids or esters (C-bonded), acyl chlorides, amides (C-bonded), etc. An electron donor group refers to moieties from the following groups: phenoxides, amines, ethers, phenols, anilines, esters (O-bonded), amides (N-bonded), alkyl, phenyl, or vinyl groups.

[0031] In some embodiments, one or both of Ri and R₂ are aryl moieties that are optionally substituted. Thus, they may, for example, be of the formula:

or

ua ; or

(Formula X)

[0032] Each of R₃, R_4, Rs, R6, R7, Rs, R9, Rio, R11, R12, R13, R14, Ris, R½, Rn, Ris, R19, R20, R21, R22, R23, R24, R25, R26, R27, and R28 may independently be H, an electron withdrawing group or an electron donor group, e.g., a hydrogen, an alkyl, (linear, branched or a combination thereof) and optionally may be or comprise an aryl group alone or in combination with one or more linear and or branched alkyl groups. Further, each alkyl group may be saturated or unsaturated. Still further, each R₃, R_4, Rs, R₆, R₇, Rs_, R₉, Rio_, Rn, R12, R13, R14, RIS, Ri6, R17, RIS, R19, R20, R21, R22, R23, R24, R25, R26, R27, and R28 group that is present may be exclusively a hydrocarbon group or contain one or more functionalized groups. The functionalized groups may, for example, be organic acid groups, keto groups, hydroxyl groups, amide or amine groups or sulfur containing groups. In some embodiments, each R3, R4, Rs, R6, R7, Rs, R9, Rio, R11, R12, R13, R14, Ris, Ri6, R17, RIS, R19, R20, R21, R22, R23, R24, R25, R26, R27, and R28 group that is present is saturated, unsubstituted and has six or fewer carbons, for example, 1-6 carbons, 2-5 carbons, or 3-4 carbons.

[0033] In some embodiments of formula III, the molecule is /V,/V’-bis(dialkyl)perylene- 3,4,9, lO-bis(dicarboximide), wherein each of Ri and R₂ is a C1-C30 hydrocarbon that is saturated or unsaturated. In some of these embodiments, one or more or all of the Cl- C30 groups contains additional polar moieties that improve solubility in polar solvents.

Such polar moieties include but are not limited to aforementioned electron withdrawing groups and electron donating groups as described above, as well as ionic moieties such as metal carboxylate salts (a.k.a.“soaps”), including but not limited to lithium, sodium, potassium, calcium, and magnesium carboxylates, as well as ammonium salts, including but not limited to ammonium halides and ammonium carboxylates.

[0034] As the compounds of formulas III-X show, in some embodiments there is identity between Ri and R₂; however, within the scope of the present invention are when Ri and R₂ differ. The formulas also allow for identity and difference among any of R₃, R_4, Rs,

R₆, R7, Rs, R9, Rio, R11, RI_2, R , R14, RIS, R½, R17, Ris, R19, R20, R₂I, R₂₂, R₂3, R_24, R₂s, R%, R₂₇, and R₂₈ groups that are present.

[0035] By way of a non-limiting example, within formula IV is the perylene diimide derivative /V,/V’-bis(2,6-dialkylphenyl)perylene-3,4,9,l0-bis(dicarboximide), wherein the alkyl group is any Cl -C6 compound, including any and all isomers, or the alkyl groups are replaced with hydrogen moieties. Within formula V is the perylene diimide derivative /V,/V’-bis(4-alkylphenyl)perylene-3,4,9,l0-bis(dicarboximide), wherein the alkyl group is any Cl -C6 compound, including any and all isomers, or the alkyl groups are replaced with hydrogen moieties. Within formula VI is the perylene diimide derivative NN’- bis(3,5-dialkylphenyl)perylene-3,4,9,l0-bis(dicarboximide), wherein the alkyl group is any Cl -C6 compound, including any and all isomers, or the alkyl groups are replaced with hydrogen moieties.

[0036] In one embodiment the PDI is /V, AF-bi s(2, 6-di isopropyl phenyl )pcrylcnc-3, 4, 9, 10- bis(dicarboximide):

(Formula XI). [0037] In other embodiments, the PDI is perylene-3,4,9,l0-bis(dicarboximide)

(Formula XII).

[0038] In other embodiments, the PDI is a N,N'-bis(alkyl)perylene-3,4,9,l0- bis(dicarboximide), where the alkyl is a C1-C20 hydrocarbon attached at any carbon and in any isomeric configuration, such as:

1. N,N'-bis(methyl)perylene-3,4,9, lO-bis(dicarboximide)

2. N,N'-bis(ethyl)perylene-3,4,9,l0-bis(dicarboximide)

3. N,N'-bis(propyl)perylene-3,4,9,l0-bis(dicarboximide)

4. N,N'-bis(isopropyl)perylene-3,4,9,l0-bis(dicarboximide)

5. N,N'-bis(butyl)perylene-3,4,9,l0-bis(dicarboximide)

6. N,N'-bis(isobutyl)perylene-3,4,9,l0-bis(dicarboximide)

7. N,N'-bis(tertbutyl)perylene-3,4,9,l0-bis(dicarboximide)

8. N,N'-bis(secbutyl)perylene-3,4,9,l0-bis(dicarboximide)

9. N,N'-bis(pentyl)perylene-3,4,9,l0-bis(dicarboximide)

10. N,N'-bis(isopentyl)perylene-3,4,9,l0-bis(dicarboximide)

11. N,N'-bis(secpentyl)perylene-3,4,9,l0-bis(dicarboximide)

12. N,N'-bis(3-pentyl)perylene-3,4,9,l0-bis(dicarboximide)

13. N,N'-bis(neopentyl)perylene-3,4,9,l0-bis(dicarboximide)

[0039] In other embodiments, the PDI is a N,N'-bis(aryl)perylene-3,4,9,l0- bis(dicarboximide), such as N,N'-bis(phenyl)perylene-3,4,9,l0-bis(dicarboximide)

[0040] Other compounds within the scope of the PDIs of the present invention are 2- substituted phenyl derivatives, such as N,N'-bis(2-alkylphenyl)perylene-3,4,9,lO- bis(dicarboximide), wherein the alkyl is a C1-C4 hydrocarbon, e.g.,

1. N,N'-bis(2-methylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

2. N,N'-bis(2-ethylphenyl)perylene-3,4,9, lO-bis(dicarboximide)

3. N,N'-bis(2-propylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

4. N,N'-bis(2-isopropylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

5. N,N'-bis(2-butylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

6. N,N'-bis(2-isobutylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

7. N,N'-bis(2-secbutylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

8. N,N'-bis(2-tertbutylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

[0041] Other 2-substituted phenyl derivatives within the scope of PDIs of the present invention are N,N'-bis(2-halophenyl)perylene-3,4,9,lO-bis(dicarboximide) compounds, e-g·,

1. N,N'-bis(2-fluorophenyl)perylene-3,4,9, lO-bis(dicarboximide)

2. N,N'-bis(2-chlorophenyl)perylene-3,4,9,lO-bis(dicarboximide)

3. N,N'-bis(2-bromophenyl)perylene-3,4,9,lO-bis(dicarboximide)

4. N,N'-bis(2-iodophenyl)perylene-3,4,9,lO-bis(dicarboximide)

[0042] Other 2-substituted phenyl derivatives within the scope of PDIs of the present invention are N,N'-bis(2-(EWG)phenyl)perylene-3,4,9,lO-bis(dicarboximide) compounds, e.g., 1. N,N'-bis(2-(trifluoromethyl)phenyl)perylene-3,4,9,lO-bis(dicarboximide)

2. N,N'-bis(2-nitrophenyl)perylene-3,4,9, lO-bis(dicarboximide)

[0043] Other 2-substituted phenyl derivatives within the scope of PDIs of the present invention are N,N'-bis(2-(EDG)phenyl)perylene-3,4,9,lO-bis(dicarboximide) compounds, e-g·,

1. N,N'-bis(2-hydroxyphenyl)perylene-3 ,4,9, lO-bis(dicarboximide)

2. N,N'-bis(2-methoxyphenyl)perylene-3,4,9,lO-bis(dicarboximide)

3. N,N'-bis(2-ethoxyphenyl)perylene-3,4,9,lO-bis(dicarboximide)

4. N,N'-bis(2-aminophenyl)perylene-3,4,9, lO-bis(dicarboximide)

5. N,N'-bis(2-dimethylaminophenyl)perylene-3,4,9,lO-bis(dicarboximide)

6. N,N'-bis(2-diethylaminophenyl)perylene-3,4,9,lO-bis(dicarboximide)

[0044] Other compounds within the scope of the PDIs of the present invention are 3- substituted phenyl derivatives, such as N,N'-bis(3-alkylphenyl)perylene-3,4,9,l0- bis(dicarboximide), wherein the alkyl is a C1-C4 hydrocarbon, e.g.,

1. N,N'-bis(3-methylphenyl)perylene-3,4,9, lO-bis(dicarboximide)

2. N,N'-bis(3-ethylphenyl)perylene-3,4,9, lO-bis(dicarboximide)

3. N,N'-bis(3-propylphenyl)perylene-3,4,9,l0-bis(dicarboximide)

4. N,N'-bis(3-isopropylphenyl)perylene-3,4,9,l0-bis(dicarboximide)

5. N,N'-bis(3-butylphenyl)perylene-3,4,9,l0-bis(dicarboximide)

6. N,N'-bis(3-isobutylphenyl)perylene-3,4,9,l0-bis(dicarboximide)

7. N,N'-bis(3-secbutylphenyl)perylene-3,4,9,l0-bis(dicarboximide)

8. N,N'-bis(3-tertbutylphenyl)perylene-3,4,9, lO-bis(dicarboximide)

[0045] Other 3-substituted phenyl derivatives within the scope of PDIs of the present invention are N,N'-bis(3-halophenyl)perylene-3,4,9,l0-bis(dicarboximide) compounds, e-g·, 1. N,N'-bis(3-fluorophenyl)perylene-3,4,9, lO-bis(dicarboximide)

2. N,N'-bis(3-chlorophenyl)perylene-3,4,9,l0-bis(dicarboximide)

3. N,N'-bis(3-bromophenyl)perylene-3,4,9,l0-bis(dicarboximide)

4. N,N'-bis(3-iodophenyl)perylene-3,4,9,l0-bis(dicarboximide)

[0046] Other 3-substituted phenyl derivatives within the scope of PDIs of the present invention are N,N'-bis(3-(EWG)phenyl)perylene-3,4,9,l0-bis(dicarboximide)

compounds, e.g.,

1. N,N'-bis(3-(trifluoromethyl)phenyl)perylene-3,4,9, lO-bis(dicarboximide)

2. N,N'-bis(3-nitrophenyl)perylene-3,4,9, lO-bis(dicarboximide)

[0047] Other 3-substituted phenyl derivatives within the scope of PDIs of the present invention are N,N'-bis(3-(EDG)phenyl)perylene-3,4,9,l0-bis(dicarboximide) compounds, e.g.,

1. N,N'-bis(3-hydroxyphenyl)perylene-3,4,9,l0-bis(dicarboximide)

2. N,N'-bis(3-methoxyphenyl)perylene-3,4,9,l0-bis(dicarboximide)

3. N,N'-bis(3-ethoxyphenyl)perylene-3,4,9,l0-bis(dicarboximide)

4. N,N'-bis(3-aminophenyl)perylene-3,4,9,l0-bis(dicarboximide)

5. N,N'-bis(3-dimethylaminophenyl)perylene-3,4,9,l0-bis(dicarboximide)

6. N,N'-bis(3-diethylaminophenyl)perylene-3,4,9,l0-bis(dicarboximide)

[0048] Other compounds within the scope of the PDIs of the present invention are 4- substituted phenyl derivatives, such as N,N'-bis(3-alkylphenyl)perylene-3,4,9,l0- bis(dicarboximide) compounds, wherein the alkyl is a C1-C4 hydrocarbon, e.g.,

1. N,N'-bis(4-methylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

2. N,N'-bis(4-ethylphenyl)perylene-3,4,9, lO-bis(dicarboximide)

3. N,N'-bis(4-propylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

4. N,N'-bis(4-isopropylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

5. N,N'-bis(4-butylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

6. N,N'-bis(4-isobutylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

7. N,N'-bis(4-secbutylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

8. N,N'-bis(4-tertbutylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

[0049] Other 4-substituted phenyl derivatives within the scope of PDIs of the present invention are N,N'-bis(4-(EDG)phenyl)perylene-3,4,9,lO-bis(dicarboximide) compounds, e-g·,

1. N,N'-bis(4-aminophenyl)perylene-3,4,9, lO-bis(dicarboximide)

2. N,N'-bis(4-dimethylaminophenyl)perylene-3,4,9,lO-bis(dicarboximide)

3. N,N'-bis(4-diethylaminophenyl)perylene-3,4,9,lO-bis(dicarboximide)

4. N,N'-bis(4-dipropylaminophenyl)perylene-3,4,9,lO-bis(dicarboximide)

5. N,N'-bis(4-diisopropylaminophenyl)perylene-3,4,9,lO-bis(dicarboximide)

6. N,N'-bis(4-hydroxyphenyl)perylene-3,4,9,lO-bis(dicarboximide)

7. N,N'-bis(4-methoxyphenyl)perylene-3,4,9,lO-bis(dicarboximide)

8. N,N'-bis(4-ethoxyphenyl)perylene-3,4,9,lO-bis(dicarboximide)

9. N,N'-bis(4-acetoxyphenyl)perylene-3,4,9,lO-bis(dicarboximide)

[0050] Other 4-substituted phenyl derivatives within the scope of PDIs of the present invention are N,N'-bis(4-(EWG)phenyl)perylene-3,4,9,lO-bis(dicarboximide) compounds, e.g.,

1. N,N'-bis(4-trifluoromethylphenyl)perylene-3,4,9, lO-bis(dicarboximide)

2. N,N'-bis(4-nitrophenyl)perylene-3,4,9, lO-bis(dicarboximide)

3. N,N'-bis(4-fluorophenyl)perylene-3,4,9,lO-bis(dicarboximide)

4. N,N'-bis(4-chlorophenyl)perylene-3,4,9,lO-bis(dicarboximide)

5. N,N'-bis(4-bromophenyl)perylene-3,4,9,lO-bis(dicarboximide)

6. N,N'-bis(4-iodophenyl)perylene-3,4,9,lO-bis(dicarboximide)

7. N,N'-bis(4-acetylphenyl)perylene-3,4,9, lO-bis(dicarboximide)

[0051] Other compounds within the scope of the PDIs of the present invention are 2,6 phenyl derivatives, which include but are not limited to N,N'-bis(2,6- dialkylphenyl)perylene-3,4,9,l0-bis(dicarboximide), wherein the alkyl is a C1-C4 hydrocarbon, e.g.,

1. N,N'-bis(2,6-dimethylphenyl)perylene-3,4,9, lO-bis(dicarboximide)

2. N,N'-bis(2,6-diethylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

3. N,N'-bis(2,6-dipropylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

4. N,N'-bis(2,6-diisopropylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

5. N,N'-bis(2,6-dibutylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

6. N,N'-bis(2,6-diisobutylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

7. N,N'-bis(2,6-disecbutylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

8. N,N'-bis(2,6-ditertbutylphenyl)perylene-3,4,9,lO-bis(dicarboximide)

[0052] Other 2, 6 phenyl derivatives within the scope of the PD Is of the present invention are N,N'-bis(2,6-dihalophenyl)perylene-3,4,9,lO-bis(dicarboximide) such as:

1. N,N'-bis(2,6-difluorophenyl)perylene-3 ,4,9, lO-bis(dicarboximide)

2. N,N'-bis(2,6-dichlorophenyl)perylene-3,4,9,lO-bis(dicarboximide)

3. N,N'-bis(2,6-dibromophenyl)perylene-3,4,9,lO-bis(dicarboximide)

4. N,N'-bis(2,6-diiodophenyl)perylene-3,4,9,lO-bis(dicarboximide)

[0053] Still other 2, 6 phenyl derivatives within the scope of the PDIs of the present invention are N,N'-bis(2,6-di(EWG)phenyl)perylene-3,4,9,lO-bis(dicarboximide), e.g.

1. N,N'-bis(2,6-di(trifluoromethyl)phenyl)perylene-3,4,9, 10- bis(dicarboximide)

2. N,N'-bis(2,6-dinitrophenyl)perylene-3,4,9,lO-bis(dicarboximide)

[0054] Other compounds within the scope of PDIs of the present invention are N,N'- bis(2,6-di(EDG)phenyl)perylene-3,4,9,lO-bis(dicarboximide) compounds, e.g.,

1. N,N'-bis(2,6-dihydroxyphenyl)perylene-3,4,9,lO-bis(dicarboximide)

2. N,N'-bis(2,6-dimethoxyphenyl)perylene-3,4,9,lO-bis(dicarboximide)

3. N,N'-bis(2,6-diaminophenyl)perylene-3 ,4,9, lO-bis(dicarboximide)

[0055] Other compounds within the scope of the PDIs of the present invention are:

1. N,N'-bis(benzyl)perylene-3,4,9,l0-bis(dicarboximide)

2. N,N'-bis(benzoyl)perylene-3,4,9,l0-bis(dicarboximide)

3. Pigment Red 178

[0056] Further, within the scope of the present invention are any derivatives of the above referenced compounds, or any derivative featuring further alkylation, halogenation, nitration, carboxylation, or any other type of substitutions anywhere on the structure, or substitutions on the bis-phenyl rings.

[0057] Electron Donor Substances

[0058] The electron donor substance is a molecule that may donate or sacrifice one or more electrons in order to activate the photoinitiator. Thus, the electron donor substance may also be referred to as a sacrificial donor molecule. This substance may be a molecule separate from the acrylate substances described below, or it may exist as a functionality within the monomer. Examples of moieties that render a molecule an electron donor substance are amines, amides, sulfides, disulfides, phosphines, and thiols.

[0059] In some embodiments, the electron donor substance comprises at least one molecule selected from the group consisting of an amine, an amide, or a molecule that contains one or more sulfur or phosphorous atoms that are not oxidized.

[0060] Examples of electron donor molecules include but are not limited to trialkyl amines, wherein the alkyl group is a C1-C30 hydrocarbon that is saturated or unsaturated; di-(R_x) R_y-amines, wherein the each of R_x and R_y is a C1-C30 hydrocarbon that is saturated or unsaturated; and polymers that consist of monomers that are amines, amides, sulfides, disulfides, phosphines, and/or thiols. [0061] By way of further non-limiting examples, the electron donor substance may be any of the following molecules: tetrathiafulvalene, triethanolamine, triethylamine, trimethylamine, trimethanolamine, tripropanolamine, triisopropylamine,

triisopropanolamine, tripropylamine, ethylenediamine, dimethylamylamine,

diethylamylamine, diisopropanolamine, a polyamide (nylon) polymer (which may be an oligomer), dimethyl formamide, diethylformamide, mercaptopropyltrimethoxysilane, and mercaptoethyltrimethoxysilane.

[0062] Acrylate Substances

[0063] Acrylate substances include acrylate monomers, derivatives thereof and polyurethane acrylate oligomers. These substances are well known to persons of ordinary skill in the art, as are their use in nail polish. By way of non-limiting examples, they may be acrylate esters or derivatives thereof, poly-(acrylate) esters or derivatives thereof, and anhydrides and derivatives thereof, as well as combinations of the aforementioned substances.

[0064] By way of further non-limiting examples, the acrylates and monomers in a formulation may be any one or more of the following substances: methyl acrylate (MA), ethyl acrylate (EA), methyl methacrylate (MM A), ethyl methacrylate (EM A), methyl 2- methylenebutanoate, ethyl 2-methylenebutanoate, 1- or 2-hydroxymethyl 2- methylenebutanoate, 1- or 2-hydroxyethyl 2-methylenebutanoate, 1- or 2-hydroxymethyl methacrylate (HMMA), 1- or 2-hydroxyethyl methacrylate (HEMA), 1- or 2- or 3- hydroxypropyl methacrylate, 1- or 2- or 3-hydroxypropyl 2-methylenebutanoate, isobornyl methacrylate, isobomyl 2-methylenebutanoate, methacryloyl

propyltrimethoxysilane, methacryloyl ethyltrimethoxysilane, triethylene glycol dimethacrylate, trimethylene glycol dimethacrylate, trimethylene glycol di-(2- methylenebutanoate), triethylene glycol di-(2-methylenebutanoate), di-hema

trimethylhexyl dicarbamate, polyurethane acrylate oligomer, hydroxypropyl

methacrylate, poly ethylene glycol-n dimethacrylate, where n is between 2 and 2000, tetrahydrofurfuryl dimethacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl (2- methylenebutanoate), tetrahydrofurfuryl di-(2-methylenebutanoate), adipic acid/ neopentyl glycol/ trimellitic anhydride copolymer, sucrose benzoate/sucrose acetate isobutyrate copolymer, glycidyl c8-l l acidate/trimethylol propane/phthalic anhydride copolymer and butyl acetate, trimethylolpropane trimethacrylate, sosorbide

dicaprylate/caprate, polyurethane-l l, ethylene/va copolymer, acrylates/dimethicone copolymer, cetyl peg/ppg-lO/l dimethicone, styrene/acrylates copolymer, polybutylene glycol/mdi copolymer, butyraldehyde, vinyl alcohol or acetaldehyde, vinyl acetate, tosylamide/epoxy resin, rhthalic anhydride/trimellitic anhydride/glycols copolymer, trimethyl pentanyl diisobutyrate, diisopropanolamine/methylhexahydrophthalic anhydride nonanoate copolymer, and any oligomeric polymer/s or copolymer/s from any combination of the above monomers, including (but not limited to) any dimers, trimers, and tetramers.

[0065] Additional Ingredients

[0066] The formulations may also optionally comprise one or more of the following additional ingredients.

[0067] In some embodiments, the formulations comprise solvents. Solvents are liquids used to mix the other ingredients and to yield a uniform product. Typically after one applies nail polish, solvents evaporate away. The amount and type of solvent can help to determine how thick a polish is and how long it takes to dry. Examples of common solvents include ethyl acetate, butyl acetate and alcohol. These may be used individually or in combination. Less common today, but historically used solvents were toluene, xylene and formalin or formaldehyde, the uses of which are within the scope of the present invention.

[0068] Examples of esters that may be used as solvents include but are not limited to (C1-C15) esters, e.g., ethyl acetate, methyl acetate, propyl or isopropyl acetate, butyl acetate (n-/iso-/tert-/sec-/etc.) and diisobutyl adipate.

[0069] Examples of alcohols that may be used as solvents include but are not limited to (C1-C10) alcohols, e.g., methanol, ethanol, propanol or isopropanol, butanol (n-/iso-/tert- / ee-/ el c.) and pentanol. [0070] Examples of ketones and aldehydes that may be used as solvents include but are not limited to (C1-C10), e.g., formaldehyde, acetaldehyde, acetone, diethyl ketone, and methyl ethyl ketone.

[0071] Examples of hydrocarbons that may be used as solvents include but are not limited to (C1-C10), e.g., butanes, pentanes, hexanes, heptanes, octanes, nonanes, and decanes.

[0072] By way of non-limiting examples, prior to drying, solvents may comprise 0-10 wt.% of the formulation, 0-5 wt.% of the formulation, 5-10 wt.% of the formulation, 5-15 wt.% of the formulation, or 10-20 wt.% of the formulation.

[0073] In some embodiments, the formulations comprise film formers. Film formers are chemicals that form the smooth surface on a coat of nail polish. The most common film former is nitrocellulose. Examples of other film formers are synthetic wax, PEG-n di(trialkylsilane), wherein n is from 2 to 2000, alkyl is C1-C10, and benzoyl isopropanol.

[0074] By way of non-limiting examples, film formers may comprise 0-10 wt.% of the formulation, 0-5 wt.% of the formulation, or 0-2 wt.% of the formulation.

[0075] In some embodiments, the formulations comprise resins. Resins make the film adhere to the nail bed. Resins are ingredients that add depth, gloss and hardness to the film of a nail polish. Examples of a polymers used as a resin in nail polish are tosylamide-formaldehyde resin and shellac.

[0076] By way of non-limiting examples, resins may comprise 0-10 wt.% of the formulation, 0-5 wt.% of the formulation, 0-2 wt.% of the formulation, 5-10 wt.% of the formulation, 5-15 wt.% of the formulation, or 10-20 wt.% of the formulation.

[0077] In some embodiments, the formulations comprise plasticizers. While resins and film formers give polish strength and gloss, they produce a brittle lacquer. Plasticizers are chemicals that help keep polish flexible and reduce the chance that it will crack or chip. They do this by linking to polymer chains and increasing the distance between them. Examples of plasticizers include but are not limited to camphor, silicone/s or

polysilicone/s, glycerol, polyglicyrides, fatty acid/s or their corresponding esters, castor oil, amyl or butyl stearate, and acetic acids or acetate esters. [0078] By way of non-limiting examples, plasticizers may comprise 0-10 wt.% of the formulation, 0-5 wt.% of the formulation, 0-2 wt.% of the formulation, 5-10 wt.% of the formulation, 5-15 wt.% of the formulation, or 10-20 wt.% of the formulation.

[0079] In some embodiments, the formulations comprise pigments. Pigments are chemicals that add color to nail polish. An astonishing variety of chemicals may be used as pigments in nail polish. Common pigments include iron oxides and other colorants, such as one would find in paint or varnish. When the formulation is to be clear or used as a based or topcoat, there may be an absence of pigments.

[0080] By way of non-limiting examples, pigments may comprise 0-10 wt.% of the formulation, 0-5 wt.% of the formulation, 0-2 wt.% of the formulation, or 0-1 wt.% of the formulation.

[0081] In some embodiments, the formulations comprise pearls. Nail polish that has a shimmery or glittery effect may contain pearlescent minerals, such as titanium dioxide or ground mica. Some polishes may contain bits of plastic glitter or other additives that produce a special effect. Examples of pearls include but are not limited to Ti0_2, silica, mica, stearalkonium hectorite, synthetic fluorphlogopite, tin oxide, tin oxides, and isopropyl titanium triisostearate.

[0082] By way of non-limiting examples, pearls may comprise 0-10 wt.% of the formulation, 0-5 wt.% of the formulation, 0-2 wt.% of the formulation, or 0-1 wt.% of the formulation.

[0083] Formulations of the present invention may contain thickening agents, such as stearalkonium hectorite, to keep the other ingredients from separating and to make the polish easier to apply. Additionally, optionally, they may contain ultraviolet filters, such as benozophenone-l, which help prevent discoloration when the polish is exposed to sunlight or other forms of UV light, benzophenone-l, triphenylphosphine or

triphenylphosphine oxide, or combinations thereof.

[0084] By way of non-limiting examples, thickening agents, UV filters, and any other additional ingredients may comprise 0-10 wt.% of the formulation, 0-5 wt.% of the formulation, 0-2 wt.% of the formulation, or 0-1 wt.% of the formulation. [0085] Combination of Ingredients

[0086] When creating the nail polish formulations of the present invention, one may, for example, use mechanical mixing techniques e.g., stirring and/or agitation at or below room temperature. Preferably, one combines all ingredients under non-blue visible light, e.g., greater than 500nm or greater than 550 nm and less than ~800nm (the upper-bound of the visible light spectrum), and packs the ingredients into dark/opaque nail polish bottles.

[0087] Acrylate Polymerization

[0088] In some embodiments, the formulation is created in the presence of white light and then cured in the presence of blue light. In other applications, the formulation is created in the absence of blue light and then exposed to blue light only when one is ready to cure the formulation. The blue light may be in the form of a narrow or highly specific band of wavelengths or within a broader band of wavelengths (e.g., the blue light may come as a fraction of white light).

[0089] Following application of nail polish to the nail, one allows the polish to dry (solvent to evaporate) for 5 seconds - 5minutes. A heating lamp, hair dryer, fan, or other heating or air-blowing device may be used to facilitate the evaporation of solvent. Then one irradiates the polish on the nail with blue light.

[0090] The polish may be applied in one thick layer and then irradiated, or it may be applied in several thinner layers with drying and light-curing occurring between the application of each layer.

[0091] In some embodiments, polymerization occurs under blue light for a period 1 second to 1 hour, 1 minute to 30 minutes, or 5 minutes to 20 minutes. The blue light may for example be light with a wave length of approximately 456nm, +/- 75nm, +/- 50nm,

+/- 25nm, or +/- l5nm.

[0092] Under these methods, which are summarized in the figure, polymerization proceeds through three phases. Phase I is the initiation phase. As shown, a PDI and a sacrificial donor (SD) are exposed to blue light to generate a radical anionic PDI

(negatively charged), denoted by PDI and a radical SD that is positively charged, denoted by SD ⁺. Also within the first phase, the blue light activates the PDI to become an initiator of polymerization, denoted by PDI^* . The denotes a radical and the + or - denotes the charge.

[0093] Following the initiation phase, the process enters the propagation phase. There the PDI^* , which is capable of photoinitiation (and thus may be referred to as a photoinitiator) interacts with a monomer M in order to render it capable of interacting with other monomers. As a person of ordinary skill in the art will recognize, the first equation within the propagation phase shows that the monomer M begins with no charge. After initiation with the photoinitiator (PDI^* ), the monomer has a negative charge and the PDI loses its charge. The PDI is then cycled back to the initiation phase where in the presence of blue light and the SD, it can again become a photoinitiator.

[0094] The now charged monomer M is capable of interacting with a monomer that is a neutral molecule M to form a dimer M₂ . This dimer can grow by combining with other monomers, multiple times (as shown in the third equation of the propagation phase) to form a polymerized monomer of length n+l, wherein n is the number of cycles of combination of monomers. Thus, the resulting chain at any point during the propagation phase is M _n+i .

[0095] The termination phase caps the polymer with a terminal monomer M and renders the molecule neutral and thus cured. As shown in the third section of figure 1, the negatively charged monomer M _n combines with the positively charge SD ⁺, which has been oxidized.

Claims

Claims I claim:

1. A cosmetic formulation, wherein the formulation comprises:

a. a perylene diimide compound or a derivative thereof;

b. an electron donor substance; and

c. an acrylate substance, wherein the acrylate substance is capable of

polymerizing in the presence of the perylene diimide compound or derivative thereof, and the electron donor substance when the formulation is exposed to blue light.

2. The formulation of claim 1, wherein the perylene diimide compound or

derivative thereof is

(Formula III),

wherein Ri and R₂ are independently H, an alkyl, or aryl group or combination thereof that is substituted or unsubstituted and saturated or unsaturated, wherein each alkyl or aryl group comprises 1 to 30 carbons.

3. The formulation of claim 2, wherein the perylene diimide compound or

derivative thereof is selected from the group consisting of

;

, wherein, each R₃, R_4, Rs, R6, R7, Rs, R9, Rio, R11, R12, R13, R14, Ris, R½, R17, Ris, R19, R20, R21, R22, R23, R24, R25, R26, R27, and R28, may be a hydrogen, an alkyl, (linear, branched or a combination thereof) or an aryl group or a combination thereof and each of R₃, R_4, Rs, R₆, R7, Rs, R9, Rio, R11, R12, R , R14, RIS, R½, R17, RIS, R19, R20, R21, R22, R23, R24, R25, R26, R₂₇, and R₂₈ may be saturated or unsaturated and may be substituted or unsubstituted.

4. The formulation of claim 3, wherein the perylene diimide compound or a derivative thereof is /V,/V’-bis(2,6-diisopropylphenyl)perylene-3,4,9, lO-bis(dicarboximide).

5. The formulation of any of claims 1 to 4, wherein the electron donor substance

comprises at least one molecule selected from the group consisting of an amine, an amide or a molecule that contains one or more sulfur or phosphorous atoms that are not oxidized.

6. The formulation of claim 5, wherein the electron donor substance comprises

triethylamine, triethanolamine or tetrathiafulvalene or a derivative thereof.

7. The formulation of any of claims 1 to 4, wherein the acrylate substance comprises an acrylate monomer.

8. The formulation of claim 7, wherein the acrylate monomer is 2- (Hydroxyethyl)methacrylate.

9. The formulation of claim 7, wherein the acrylate monomer is di-2- (Hydroxyethyl)methacrylate trimethylhexyl dicarbamate

10. The formulation of claim 7, wherein the acrylate monomer is hydroxypropyl

methacrylate.

11. The formulation of claim 1, wherein the acrylate substance comprises a polyurethane acrylate oligomer.

12. The formulation of claim 1 further comprising a color pigment other than the

perylene diimide compound.

13. The formulation of claim 1, wherein there is an absence of any color pigment other than the perylene diimide compound.

14. A method for curing nail polish comprising:

(a) creating the formulation of any of claims 1 to 4 or 11 to 13; (b) applying the formulation to a surface; and

(c) exposing the surface to blue light.

15. The method of claims 14, wherein the surface is a fingernail or a toenail.

16. A cosmetic formulation, wherein the formulation comprises a formulation of:

a. a perylene diimide compound or a derivative thereof;

and

b. an acrylate substance, wherein the acrylate substance has an electron donating moiety, wherein the acrylate substance is capable of polymerizing in the presence of the perylene diimide compound or derivative thereof, when the formulation is exposed to blue light.

17. The formulation of claim 16, wherein the perylene diimide compound or derivative thereof is

(Formula III),

18. The formulation of claim 17, wherein the perylene diimide compound or

derivative thereof is selected from the group consisting of

;

19. The formulation of claim 18, wherein the perylene diimide compound or a derivative thereof is /V,/V’-bis(2,6-diisopropylphenyl)perylene-3,4,9, lO-bis(dicarboximide).

20. The formulation of any of claims 16 to 19, wherein the acrylate substance comprises an acrylate monomer.

21. The formulation of claim 20, wherein the acrylate monomer is 2- (Hydroxyethyl)methacrylate.

22. The formulation of claim 20, wherein the acrylate monomer is di-2- (Hydroxyethyl)methacrylate trimethylhexyl dicarbamate

23. The formulation of claim 20, wherein the acrylate monomer is hydroxypropyl

methacrylate.

24. The formulation of any of claims 16 to 19, wherein the acrylate substance comprises a polyurethane acrylate oligomer.

25. The formulation of any of claims 16 to 19 further comprising a color pigment other than the perylene diimide compound.

26. The formulation of any of claims 16 to 19, wherein there is an absence of any color pigment other than the perylene diimide compound.

27. A method for curing nail polish comprising:

(d) creating the formulation of any of claims 16 to 19;

(e) applying the formulation to a surface; and

(f) exposing the surface to blue light.

28. The method of claims 27, wherein the surface is a fingernail or a toenail.