US20040176507A1 - Covalently bonding nail primer - Google Patents
Covalently bonding nail primer Download PDFInfo
- Publication number
- US20040176507A1 US20040176507A1 US10/383,826 US38382603A US2004176507A1 US 20040176507 A1 US20040176507 A1 US 20040176507A1 US 38382603 A US38382603 A US 38382603A US 2004176507 A1 US2004176507 A1 US 2004176507A1
- Authority
- US
- United States
- Prior art keywords
- primer
- nail
- amine
- solvent
- polyethyleneglycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 150000002576 ketones Chemical class 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims description 31
- 150000001412 amines Chemical class 0.000 claims description 27
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical group CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 claims description 6
- 238000004383 yellowing Methods 0.000 claims description 6
- 238000002845 discoloration Methods 0.000 abstract description 8
- 239000002318 adhesion promoter Substances 0.000 abstract description 5
- 230000006378 damage Effects 0.000 abstract description 5
- 208000027418 Wounds and injury Diseases 0.000 abstract description 4
- 208000014674 injury Diseases 0.000 abstract description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 abstract description 4
- 208000009043 Chemical Burns Diseases 0.000 abstract description 3
- 208000018380 Chemical injury Diseases 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000002798 polar solvent Substances 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 102000011782 Keratins Human genes 0.000 description 15
- 108010076876 Keratins Proteins 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- -1 acetoacetoxy group Chemical group 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 150000003141 primary amines Chemical class 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 210000000003 hoof Anatomy 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 0 */N=C(\C)CC(=O)OCCOC(=O)C(=C)C.*N.C=C(C)C(=O)OCCOC(=O)CC(C)=O.O Chemical compound */N=C(\C)CC(=O)OCCOC(=O)C(=C)C.*N.C=C(C)C(=O)OCCOC(=O)CC(C)=O.O 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 230000009972 noncorrosive effect Effects 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002262 Schiff base Substances 0.000 description 3
- 150000004753 Schiff bases Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- GEHJBWKLJVFKPS-UHFFFAOYSA-N bromochloroacetic acid Chemical compound OC(=O)C(Cl)Br GEHJBWKLJVFKPS-UHFFFAOYSA-N 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000010640 amide synthesis reaction Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 238000012863 analytical testing Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000018417 cysteine Nutrition 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920001184 polypeptide Polymers 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- BFHYUNGMDZAKAQ-UHFFFAOYSA-N 2-methylprop-2-enoyl 3-oxobutaneperoxoate Chemical compound CC(=O)CC(=O)OOC(=O)C(C)=C BFHYUNGMDZAKAQ-UHFFFAOYSA-N 0.000 description 1
- QUDQVUUWDONIJR-UHFFFAOYSA-N C=C(C)C(=O)OCCCN.C=C(CCC)C(=O)OCCCNC(C)=O.CC.CC(=O)O.O Chemical compound C=C(C)C(=O)OCCCN.C=C(CCC)C(=O)OCCCNC(C)=O.CC.CC(=O)O.O QUDQVUUWDONIJR-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 208000034874 Product colour issue Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 150000001945 cysteines Chemical group 0.000 description 1
- 210000001047 desmosome Anatomy 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical group CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 102000034240 fibrous proteins Human genes 0.000 description 1
- 108091005899 fibrous proteins Proteins 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q3/00—Manicure or pedicure preparations
- A61Q3/02—Nail coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
Definitions
- the present invention relates generally to the field of primers and adhesion promoters. More specifically, the primer of the present invention is comprised of one or more multi-carbonylated methacrylates. In a preferred embodiment, a non-ketone polar solvent is also employed.
- the disclosed primer has particular utility as a primer for nails and other proteinaceous substrates.
- nail technicians have searched for acceptable substitutes for extremely corrosive primers that cause yellowing of nail enhancements.
- These (meth)acrylic acid-based primers (and all other current nail primers) rely on relatively weak hydrogen bonding to achieve interfacial bonding.
- the present invention is a significant advance in the art—a non-corrosive, non-yellowing primer that covalently bonds to the nail plate.
- the disclosed primer will not corrode or irritate the surrounding tissue or nail plate, nor will it discolor the artificial nail enhancement, while simultaneously bonding the enhancement to the keratin substrate far more strongly than currently available products.
- the nail plate (i.e., the natural nail) is primarily composed of keratin, a water-insoluble, fibrous protein that is a major structural component of skin, hair, wool, silk, feathers, scales, nails and hooves. While keratins can obviously differ greatly in their amino acid makeup, hard keratins may all be generally characterized as cross-linked polypeptides. Alpha-keratins such as nails and hooves may be further characterized by their relatively higher percentages of the amino acid cysteine. Typically, the alpha-helix coils of the polypeptides are cross-linked with disulphide bonds between adjacent cysteines. The resulting plate-like cells are cemented to each other with a sticky substance and held together by rivet-like structures called desmosomes. Many cell layers adhere to each other to form the nail plate—a structure that resembles a brick and mortar wall.
- Primers are adhesion promoters that improve adhesion by increasing interfacial compatibility between surfaces, e.g., the nail plate and an applied coating. For example, a coating of nail polish will resist chipping and peeling if a good base coat is used. Base coats are more compatible with the nail plate than the nail polish. Base coats act as the “go-between” or “anchor”, to improve adhesion.
- nail plate primers can be thought of as double-sided sticky tape, joining the nail plate to the nail enhancement.
- the nail plate surface is made up of chemical groups possessing specific structures. Primer molecules must match the chemical and structural characteristics of the nail plate. More particularly, one end of the primer is reactive with the methacrylate monomers. With these types of primers, physical abrasion of the nail plate is required to achieve proper levels of adhesion to the keratin substrate. Moreover, these acids are corrosive, and if used improperly they can cause damage to the nail plate and surrounding tissue.
- Hydrogen bonding on organic substrates such as keratin typically depends on the interaction between an oxygen or nitrogen atom that is covalently bonded to the upper surface of the nail plate and a hydrogen atom, covalently bonded to methacrylic acid, which is covalently linked to the polymer.
- a special type of interaction called a hydrogen bond exists between the interfaces of these dissimilar surfaces.
- Hydrogen bonds are types of attractive, intermolecular bonds that are characteristic of atoms with high electonegativity, i.e. fluorine, oxygen, sulfur, and nitrogen.
- methacrylic primers and acrylic acid adhesion promoters there are three fundamental problems with currently available methacrylic primers and acrylic acid adhesion promoters.
- First is the corrosive nature of their primary component, methacrylic acid.
- acid-based primers are a primary cause of nail enhancement discoloration.
- acid-based primers can result in chemical burn injuries.
- the present invention solves the discoloration and corrosiveness problems associated with currently available primers by providing the first truly non-corrosive, non-yellowing covalently bonding primer.
- nail primers and adhesion promoters have been corrosive due to their use of methacrylic or acrylic acid as the primary component.
- the present invention does not rely on these problematic components.
- Previous nail primers relied on relatively weak hydrogen bonding between nail and primer.
- the present invention employs components that are capable of creating continuous covalent bonds from the nail plate to the artificial nail enhancement, providing much improved adhesion. Additionally, previous nail primers were a prevalent cause of yellowing during “fills” when the primer came into direct contact with existing nail enhancement product on the natural nail.
- AAEMA acetoacetoxy ethyl methacrylate
- polyoxypropylenetriamine ethyl methacrylate
- Schiff base ethyl methacrylate
- triethyleneglycoldiamine or other primary amines can be used instead of triethyleneglycoldiamine to achieve similar results.
- an amine group of the polyoxypropylenetriamine may also react with a carbonyl ester group of AAEMA to form an amide.
- the Schiff base undergoes a further electron rearrangement reaction in which an electron shifts to the beta carbon of the acetoacetoxy group (as shown below).
- the resulting composition does not exhibit undesirable corrosive properties and is not based on (meth)acrylic acid and, in fact, contains no acidic functionality.
- the disclosed primer provides stronger adhesion than any commercially available nail primer because it allows certain amino acid functional groups on the surface of the nail plate to covalently bond with carbonyl groups in the primer, creating much stronger linkages than can be achieved with hydrogen bonding of traditional primers.
- the present invention is a dramatically improved primer that is particularly appropriate for use with nails.
- nail refers to not only human nails, but also nails and hooves of animals, and any other hard surface proteinaceous materials.
- the nail primer of the present invention is principally comprised of multi-carbonylated methacrylates dissolved in a suitable solvent or other delivery system.
- the aforementioned components may be diluted in polar non-ketone solvents, however, non-polar solvents will work as well.
- One preferred embodiment comprises a polyether amine having a hydrophilic backbone, an acetoacetoxy methacrylate, and a polar non-ketone solvent.
- a polyether amine having a hydrophilic backbone, an acetoacetoxy methacrylate, and a polar non-ketone solvent.
- other components can be substituted as described below.
- One preferred polyether amine is triethyleneglycoldiamine.
- other similar components such as polyoxypropylenetriamine
- the preferred amines contain two or three primary amine functional groups, respectively.
- the primary amine functional groups are located on secondary carbon atoms at the ends of aliphatic polyether chains.
- Other primary amines including monofunctional, difunctional and trifunctional amines, may be used in the present invention to achieve the desired results.
- Such primary amines include all polyetheramines, including but not limited to polyethyleneglycolamine, polyoxypropyleneamine, polyethyleneglycol-polyoxypropyleneamine, polyoxypropylenediamine, polyethyleneglycol-polyoxypropylenediamine, polyethyleneglycoltriamine, polyethyleneglycol-polyoxypropylenetriamine.
- Some examples of the above-mentioned components include, but are not limited to melamine, N,N-dimethylformamide, 1,5-diaminopentane and dibutylamine.
- AAEMA acetoacetoxy ethyl methacrylate
- the preferred solvent of the present invention is a non-ketone solvent. This ensures that the solvent will not react with the carbonyl group in the methacrylate, nor compete with the AAEMA carbonyl reaction. In nail applications, this helps prevent yellowing of the nail enhancement. However, in alternative embodiments of the invention where perhaps a slight coloration to the solvent blend would not be objectionable, a ketone solvent can be utilized if appropriate conditions are used during the bulk chemical reaction.
- the solvent utilized in the present invention is also preferably a polar solvent to minimize the amount of discoloration which is observed when a non-polar solvent is utilized.
- a non-polar solvent can be utilized without compromising the integrity of the primer, which retains its adhesive and non-corrosive properties.
- Particularly preferred polar non-ketone solvents include ethanol and isopropanol.
- Other useful solvents include, but are not limited to, ethers, esters, glycol ethers, chlorinated solvents, siloxanes, tetrahydrofuran, methanol and other higher molecular weight alcohols, and suitable combinations thereof.
- the weight percentages of the epoxy amine component in the tested formulas ranged from 0.75 to 2.5 percent, while the molar ratios of AAEMA to amine ranged from 1 to 5.
- the carbonyl group of the acetoacetoxy group of AAEMA reacts with the primary amine group to form an imine, or Schiff base.
- the primary amine is triethyleneglycoldiamine. This reaction proceeds as follows:
- R represents the remainder of the amine.
- Other amine groups may also react with AAEMA. This reaction is followed by electron re-arrangement favoring the beta carbon of the acetoacetoxy group:
- amine groups can also react with AAEMA ester groups to form an amide:
- Comparative testing on the adhesion promoting activity of the improved primer of the present invention was performed both in a laboratory (with an instrument that tests adhesion) and in the field by professional nail technicians. Laboratory testing showed that the primer functioned better than its ingredients (amine, AAEMA, and ethanol) individually. More importantly, the nail primer of this invention worked better than all other commercially available nail primers tested.
- Table 1 illustrates the results of the laboratory tests: TABLE 1 Adhesion Standard Strength Deviation N N Main Ingredients Company Advanced 300 65 Methacrylic acid, Pinnacle Formula Isobutyl Methacry- Primer late X- 340 60 Methacrylic acid, Star Nail Strength Isobutyl Methacry- Primer late Original 400 65 Methacrylic acid, International Non- Isobutyl Methacry- Nail Lifting late Manufacturers No Lift 490 105 100% Methacrylic No Lift Nails Primer acid Bondex 500 80 Methacryloyloxy- O.P.I ethyl maleate, ethyl acetate Coval- 570 140 Polyoxypropylene- Creative Nail ently triamine, AAEMA, Design Bonding Ethanol Primer
- the improved nail primer of the present invention shows average adhesion strength of 570 N.
- the strongest commercially available primer had adhesion strength of only 500 N.
- the significant increase in strength achieved by the disclosed primer can be largely attributed to its ability to covalently bond to the nail plate.
- presently available primers including those identified in Table 1 (other than the present invention) are bonded to the nail plate via hydrogen bonding.
- applicant's primer takes advantage of the greatly increased bond strengths attained through covalent bonding.
- R′ is the rest of the primer.
Abstract
Description
- The present invention relates generally to the field of primers and adhesion promoters. More specifically, the primer of the present invention is comprised of one or more multi-carbonylated methacrylates. In a preferred embodiment, a non-ketone polar solvent is also employed.
- The disclosed primer has particular utility as a primer for nails and other proteinaceous substrates. For a number of years, nail technicians have searched for acceptable substitutes for extremely corrosive primers that cause yellowing of nail enhancements. These (meth)acrylic acid-based primers (and all other current nail primers) rely on relatively weak hydrogen bonding to achieve interfacial bonding. In contrast, the present invention is a significant advance in the art—a non-corrosive, non-yellowing primer that covalently bonds to the nail plate. In other words, the disclosed primer will not corrode or irritate the surrounding tissue or nail plate, nor will it discolor the artificial nail enhancement, while simultaneously bonding the enhancement to the keratin substrate far more strongly than currently available products.
- The nail plate (i.e., the natural nail) is primarily composed of keratin, a water-insoluble, fibrous protein that is a major structural component of skin, hair, wool, silk, feathers, scales, nails and hooves. While keratins can obviously differ greatly in their amino acid makeup, hard keratins may all be generally characterized as cross-linked polypeptides. Alpha-keratins such as nails and hooves may be further characterized by their relatively higher percentages of the amino acid cysteine. Typically, the alpha-helix coils of the polypeptides are cross-linked with disulphide bonds between adjacent cysteines. The resulting plate-like cells are cemented to each other with a sticky substance and held together by rivet-like structures called desmosomes. Many cell layers adhere to each other to form the nail plate—a structure that resembles a brick and mortar wall.
- Primers are adhesion promoters that improve adhesion by increasing interfacial compatibility between surfaces, e.g., the nail plate and an applied coating. For example, a coating of nail polish will resist chipping and peeling if a good base coat is used. Base coats are more compatible with the nail plate than the nail polish. Base coats act as the “go-between” or “anchor”, to improve adhesion.
- Primers are also frequently used with artificial nail enhancements since acrylic nail products normally have poor adhesion to nail plates. In general, nail plate primers can be thought of as double-sided sticky tape, joining the nail plate to the nail enhancement. The nail plate surface is made up of chemical groups possessing specific structures. Primer molecules must match the chemical and structural characteristics of the nail plate. More particularly, one end of the primer is reactive with the methacrylate monomers. With these types of primers, physical abrasion of the nail plate is required to achieve proper levels of adhesion to the keratin substrate. Moreover, these acids are corrosive, and if used improperly they can cause damage to the nail plate and surrounding tissue. These acids can also cause discoloration of the nail enhancement and are a leading cause of nail product discoloration. This invention eliminates a large percentage of discoloration problems for professional nail technicians. But even more importantly, in response to a number of chemical burn injuries, primarily to children, the Consumer Product Safety Commission recently issued a regulation requiring child-resistant packaging for all household products containing more than 5% methacrylic acid. However, child-resistant caps increase the risk of spills in the salon as Nail Professionals struggle to remove the cap. This invention solves both the burn injury and child-resistant cap issues because it utilizes a non-corrosive solvent, while still providing the desired adhesion properties.
- Commercially available nail primers rely solely on hydrogen bonding. Hydrogen bonding on organic substrates such as keratin typically depends on the interaction between an oxygen or nitrogen atom that is covalently bonded to the upper surface of the nail plate and a hydrogen atom, covalently bonded to methacrylic acid, which is covalently linked to the polymer. A special type of interaction called a hydrogen bond exists between the interfaces of these dissimilar surfaces. Hydrogen bonds are types of attractive, intermolecular bonds that are characteristic of atoms with high electonegativity, i.e. fluorine, oxygen, sulfur, and nitrogen. They are many times weaker than the weakest covalent bond, which is found between a carbon and acidic hydrogens such as C—H as found in chloroform and acetylene. This weakness accounts for the attraction between the acidic hydrogen and a nearby organic, acidic hydroxyl group of acrylic or methacrylic acid primer, as well as the inherent relative weakness of hydrogen bonds. The overall strength of the hydrogen bond is determined by the strength of this relatively weak carbon/hydrogen bond. It is a controlling factor in hydrogen bond strength. Therefore, when acidic primers are used, the weakest adhesive link will exist between an oxygen molecule on the keratin surface and the acidic hydrogen of (meth)acrylic acid. Since covalent bonds are many times stronger than hydrogen bonding, improvements in adhesive bond strength can be achieved by eliminating the hydrogen bond and replacing it with a stronger, more permanent, organic covalent bond.
- It is clear from the foregoing that there are three fundamental problems with currently available methacrylic primers and acrylic acid adhesion promoters. First is the corrosive nature of their primary component, methacrylic acid. Second, they create temporary hydrogen bonds that are inherently weaker than covalent bonds, leading to a weaker interfacial adhesive bond between the natural nail plate and the primer molecule, with a stronger adhesive bond between the primer molecule and the polymer chain of the nail enhancement. Third, acid-based primers are a primary cause of nail enhancement discoloration. Fourth, acid-based primers can result in chemical burn injuries.
- The present invention solves the discoloration and corrosiveness problems associated with currently available primers by providing the first truly non-corrosive, non-yellowing covalently bonding primer. To date, nail primers and adhesion promoters have been corrosive due to their use of methacrylic or acrylic acid as the primary component. The present invention does not rely on these problematic components. Previous nail primers relied on relatively weak hydrogen bonding between nail and primer. The present invention employs components that are capable of creating continuous covalent bonds from the nail plate to the artificial nail enhancement, providing much improved adhesion. Additionally, previous nail primers were a prevalent cause of yellowing during “fills” when the primer came into direct contact with existing nail enhancement product on the natural nail. When using traditional primers, Nail Professionals must take great care to avoid the acid-based primer coming into contact with the artificial nail. Every two weeks when the artificial nail is “filled in” in the areas of new growth, dark yellow bands appear across the width of the nail enhancement when the (meth)acrylic acid primer comes into contact with the existing enhancement polymer.
- These and other advantages are accomplished by the present invention, which relates to a primer comprised of one or more multi-carbonylated methacrylates. In a preferred embodiment, acetoacetoxy ethyl methacrylate (“AAEMA”) is reacted with polyoxypropylenetriamine to produce an imine, or Schiff base, in an equilibrium reaction. In alternative embodiments, triethyleneglycoldiamine or other primary amines can be used instead of triethyleneglycoldiamine to achieve similar results. Simultaneous with this imine reaction, an amine group of the polyoxypropylenetriamine may also react with a carbonyl ester group of AAEMA to form an amide. Finally, the Schiff base undergoes a further electron rearrangement reaction in which an electron shifts to the beta carbon of the acetoacetoxy group (as shown below).
- The resulting composition does not exhibit undesirable corrosive properties and is not based on (meth)acrylic acid and, in fact, contains no acidic functionality. Moreover, the disclosed primer provides stronger adhesion than any commercially available nail primer because it allows certain amino acid functional groups on the surface of the nail plate to covalently bond with carbonyl groups in the primer, creating much stronger linkages than can be achieved with hydrogen bonding of traditional primers.
- Other objects, features, and characteristics of the present invention, as well as the methods of operation and functions of the related elements of the structure, and the combination of parts and economies of manufacture, will become more apparent upon consideration of the following detailed description, which forms part of this specification.
- As required, a detailed illustrative embodiment of the present invention is disclosed herein. However, techniques, systems, and operating structures in accordance with the present invention may be embodied in a wide variety of forms and modes, some of which may be quite different from those in the disclosed embodiment. Consequently, the specific structural and functional details disclosed herein are merely representative, yet in that regard, they are deemed to afford the best embodiment for purposes of disclosure and to provide a basis for the claims herein, which define the scope of the present invention. The following presents a detailed description of a preferred embodiment (as well as some alternative embodiments) of the present invention.
- The present invention is a dramatically improved primer that is particularly appropriate for use with nails. Herein, “nail” refers to not only human nails, but also nails and hooves of animals, and any other hard surface proteinaceous materials. The nail primer of the present invention is principally comprised of multi-carbonylated methacrylates dissolved in a suitable solvent or other delivery system. In a preferred embodiment of the present invention, the aforementioned components may be diluted in polar non-ketone solvents, however, non-polar solvents will work as well.
- Various formulas have been tested by the applicant. One preferred embodiment comprises a polyether amine having a hydrophilic backbone, an acetoacetoxy methacrylate, and a polar non-ketone solvent. Of course, other components can be substituted as described below. One preferred polyether amine is triethyleneglycoldiamine. Again, other similar components (such as polyoxypropylenetriamine) can be utilized to achieve the results of this invention.
- The preferred amines contain two or three primary amine functional groups, respectively. The primary amine functional groups are located on secondary carbon atoms at the ends of aliphatic polyether chains. Other primary amines, including monofunctional, difunctional and trifunctional amines, may be used in the present invention to achieve the desired results. Such primary amines include all polyetheramines, including but not limited to polyethyleneglycolamine, polyoxypropyleneamine, polyethyleneglycol-polyoxypropyleneamine, polyoxypropylenediamine, polyethyleneglycol-polyoxypropylenediamine, polyethyleneglycoltriamine, polyethyleneglycol-polyoxypropylenetriamine. Some examples of the above-mentioned components include, but are not limited to melamine, N,N-dimethylformamide, 1,5-diaminopentane and dibutylamine.
- One particularly preferred multi-carbonylated methacrylate is acetoacetoxy ethyl methacrylate (referred to herein as “AAEMA”).
- The preferred solvent of the present invention is a non-ketone solvent. This ensures that the solvent will not react with the carbonyl group in the methacrylate, nor compete with the AAEMA carbonyl reaction. In nail applications, this helps prevent yellowing of the nail enhancement. However, in alternative embodiments of the invention where perhaps a slight coloration to the solvent blend would not be objectionable, a ketone solvent can be utilized if appropriate conditions are used during the bulk chemical reaction.
- The solvent utilized in the present invention is also preferably a polar solvent to minimize the amount of discoloration which is observed when a non-polar solvent is utilized. However, in alternative embodiments of the present invention, a non-polar solvent can be utilized without compromising the integrity of the primer, which retains its adhesive and non-corrosive properties. Particularly preferred polar non-ketone solvents include ethanol and isopropanol. Other useful solvents include, but are not limited to, ethers, esters, glycol ethers, chlorinated solvents, siloxanes, tetrahydrofuran, methanol and other higher molecular weight alcohols, and suitable combinations thereof.
- The weight percentages of the epoxy amine component in the tested formulas ranged from 0.75 to 2.5 percent, while the molar ratios of AAEMA to amine ranged from 1 to 5. Upon mixing, the carbonyl group of the acetoacetoxy group of AAEMA reacts with the primary amine group to form an imine, or Schiff base. In a preferred embodiment, the primary amine is triethyleneglycoldiamine. This reaction proceeds as follows:
-
-
- Analytical testing using a Liquid Chromatography Mass Spectrometer (LC-MS) demonstrates that the imine formation reaction takes place more readily than the amide formation reaction. Further analytical testing using a Gas Chromatograph Mass Spectrometer (GC-MS) indicates that less than 10 percent of the AAEMA reacted in the amide formation reaction. Additional testing confirms that increasing the molar ratio of AAEMA to amine increases the number of amine functional groups that react with AAEMA.
- While the preferred embodiment of the present invention has been illustrated with the reaction of an AAEMA and a polyether amine (such as polyoxypropylenetriamine), other multi-carbonyl methacrylate chemicals, and other amines may also be used. By using chemicals with slightly different properties, the resulting primer can effectively adhere to a wide variety of surfaces, such as glass, metal, sheetrock, etc., to act as a primer for other applications.
- Comparative testing on the adhesion promoting activity of the improved primer of the present invention was performed both in a laboratory (with an instrument that tests adhesion) and in the field by professional nail technicians. Laboratory testing showed that the primer functioned better than its ingredients (amine, AAEMA, and ethanol) individually. More importantly, the nail primer of this invention worked better than all other commercially available nail primers tested.
- The following procedure was used in the laboratory testing. First, a clean keratin substrate (hoof) was coated with the tested primer. A system utilizing ethyl methacrylate monomer liquid and a methacrylate copolymer powder was applied to the top of the primed hoofs. After the monomer and copolymer completely polymerized, adhesion testing apparatus utilizing a computer controlled assembly, including a sharp blade held at a precise angle to the surface of the hoof, was used to peel or delaminate the methacrylate polymer from the coated keratin substrate at a predetermined speed. The force needed to delaminate the polymer was detected and recorded by the computerized control system. The greater the force needed to peel or delaminate the polymer from the keratin substrate, the stronger the adhesive bond was to the keratin substrate. Table 1 illustrates the results of the laboratory tests:
TABLE 1 Adhesion Standard Strength Deviation N N Main Ingredients Company Advanced 300 65 Methacrylic acid, Pinnacle Formula Isobutyl Methacry- Primer late X- 340 60 Methacrylic acid, Star Nail Strength Isobutyl Methacry- Primer late Original 400 65 Methacrylic acid, International Non- Isobutyl Methacry- Nail Lifting late Manufacturers No Lift 490 105 100% Methacrylic No Lift Nails Primer acid Bondex 500 80 Methacryloyloxy- O.P.I ethyl maleate, ethyl acetate Coval- 570 140 Polyoxypropylene- Creative Nail ently triamine, AAEMA, Design Bonding Ethanol Primer - The improved nail primer of the present invention shows average adhesion strength of 570 N. The strongest commercially available primer had adhesion strength of only 500 N.
- The significant increase in strength achieved by the disclosed primer can be largely attributed to its ability to covalently bond to the nail plate. As was previously discussed, presently available primers, including those identified in Table 1 (other than the present invention) are bonded to the nail plate via hydrogen bonding. In contrast, applicant's primer takes advantage of the greatly increased bond strengths attained through covalent bonding.
- Obviously, with individual differences in both keratins and nail surfaces, a number of covalent reaction mechanisms are possible. It is anticipated, however, that two reactions will dominate. Because of the surprisingly high level of adhesion, we believe our data shows that the dominant reaction involves a direct, continuous series of covalent bonds between the keratin and the enhancement polymer. In the first, ester groups in the primer react with amines in keratin:
-
- where R′ is the rest of the primer.
- In any given case, one reaction might dominate over the other, or both reactions may proceed simultaneously. Those of skill in the art will appreciate that it is not the precise reaction mechanism that is important, but rather the fact that covalent bonding, via one or more mechanisms, is occurring. This is the advance that arguably will make all previous nail primers obsolete.
- Confirmatory data was also collected in field tests. In a two month study, 18 nail technicians performed tests on a total of 429 clients. The tests showed that the client's nail enhancements were less likely to lift when using the primer of the present invention. Moreover, while discoloration of nail enhancements is inevitable when using a primer that contains methacrylic acid, use of the primer of the present invention eliminated such discoloration. To date, the improved primer of the present invention has been field tested on 4,582 people yielding equally successful results.
- While the present invention has been described with reference to one or more preferred embodiments, which embodiments have been set forth in considerable detail for the purposes of making a complete disclosure of the invention, such embodiments are merely exemplary and are not intended to be limiting or represent an exhaustive enumeration of all aspects of the invention. The scope of the invention, therefore, shall be defined solely by the following claims. Further, it will be apparent to those of skill in the art that numerous changes may be made in such details without departing from the spirit and the principles of the invention.
Claims (25)
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/383,826 US20040176507A1 (en) | 2003-03-07 | 2003-03-07 | Covalently bonding nail primer |
ES04717489.1T ES2688142T3 (en) | 2003-03-07 | 2004-03-04 | Primer for covalent bond nails |
DK04717489.1T DK1670431T3 (en) | 2003-03-07 | 2004-03-04 | COVALENT-BINDING NIGLE PRIMER |
EP04717489.1A EP1670431B1 (en) | 2003-03-07 | 2004-03-04 | Covalently bonding nail primer |
PCT/US2004/006874 WO2004080231A2 (en) | 2003-03-07 | 2004-03-04 | Covalently bonding nail primer |
PL04717489T PL1670431T3 (en) | 2003-03-07 | 2004-03-04 | Covalently bonding nail primer |
US12/127,769 US8481010B2 (en) | 2003-03-07 | 2008-05-27 | Covalently bonding nail primer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/383,826 US20040176507A1 (en) | 2003-03-07 | 2003-03-07 | Covalently bonding nail primer |
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US12/127,769 Continuation US8481010B2 (en) | 2003-03-07 | 2008-05-27 | Covalently bonding nail primer |
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Publication Number | Publication Date |
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US20040176507A1 true US20040176507A1 (en) | 2004-09-09 |
Family
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Family Applications (2)
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US10/383,826 Abandoned US20040176507A1 (en) | 2003-03-07 | 2003-03-07 | Covalently bonding nail primer |
US12/127,769 Expired - Lifetime US8481010B2 (en) | 2003-03-07 | 2008-05-27 | Covalently bonding nail primer |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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US12/127,769 Expired - Lifetime US8481010B2 (en) | 2003-03-07 | 2008-05-27 | Covalently bonding nail primer |
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US (2) | US20040176507A1 (en) |
EP (1) | EP1670431B1 (en) |
DK (1) | DK1670431T3 (en) |
ES (1) | ES2688142T3 (en) |
PL (1) | PL1670431T3 (en) |
WO (1) | WO2004080231A2 (en) |
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JP5756604B2 (en) | 2009-07-21 | 2015-07-29 | リー ヘイル ダニー | Compositions for removable gel applications for nails and methods for their use |
WO2019014195A1 (en) | 2017-07-10 | 2019-01-17 | Coty Inc. | Nail hardening composition and method of use |
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2003
- 2003-03-07 US US10/383,826 patent/US20040176507A1/en not_active Abandoned
-
2004
- 2004-03-04 ES ES04717489.1T patent/ES2688142T3/en not_active Expired - Lifetime
- 2004-03-04 DK DK04717489.1T patent/DK1670431T3/en active
- 2004-03-04 PL PL04717489T patent/PL1670431T3/en unknown
- 2004-03-04 WO PCT/US2004/006874 patent/WO2004080231A2/en active Application Filing
- 2004-03-04 EP EP04717489.1A patent/EP1670431B1/en not_active Expired - Lifetime
-
2008
- 2008-05-27 US US12/127,769 patent/US8481010B2/en not_active Expired - Lifetime
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US3417054A (en) * | 1964-01-28 | 1968-12-17 | Gaf Corp | Alkylated polymers of heterocyclic n-vinyl monomers and process of preparing the same |
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Also Published As
Publication number | Publication date |
---|---|
DK1670431T3 (en) | 2018-10-29 |
EP1670431A2 (en) | 2006-06-21 |
EP1670431B1 (en) | 2018-07-11 |
US8481010B2 (en) | 2013-07-09 |
WO2004080231A2 (en) | 2004-09-23 |
ES2688142T3 (en) | 2018-10-31 |
WO2004080231A3 (en) | 2005-04-07 |
US20080226573A1 (en) | 2008-09-18 |
PL1670431T3 (en) | 2019-09-30 |
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