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    • 专利摘要:
    The subject of the present invention is a photopolymerizable liquid composition comprising at least one epoxidized polybutadiene prepolymer, at least one cationic photoinitiator, and at least one thioxanthone-derived photosensitizer, which may, for example, be in the form of a liquid bandage. The invention also relates to a process for obtaining a polymerized film from said photopolymerizable liquid composition, characterized in that said composition is applied to tissues such as skin, superficial body growths or mucous membranes so as to form a uniform film liquid, and the film thus obtained is subjected to ultraviolet radiation, preferably ultraviolet-visible wavelength between 380 and 405 nm, preferably between 385 and 395 nm.
    公开号:FR3014883A1
    申请号:FR1362568
    申请日:2013-12-13
    公开日:2015-06-19
    发明作者:Xavier Coqueret；Sadananda Das；Stephane Auguste
    申请人:Centre National de la Recherche Scientifique CNRS；Laboratoires Urgo SAS；Universite de Reims Champagne Ardenne URCA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a photopolymerizable liquid composition comprising at least one epoxidized polybutadiene prepolymer, at least one cationic photoinitiator, and at least one photosensitizer derived from thioxanthone, phenothiazine, fluoflavin, anthracene, curcumin, dithienothiophene, xanthene or fluorone dyes, preferably a thioxanthone derivative. The invention also relates to a process for obtaining a polymerized film from said photopolymerizable liquid composition. The film-forming compositions are intended to be applied, with or without an applicator, to tissues such as the skin, the integuments (the nails or the hair), the mucous membranes. They can also be used as a liquid dressing, and are then applied to wounds, lesions, scars, burnt tissue and / or skin conditions. They are generally liquid upon application and typically contain a film-forming polymer dissolved in a volatile solvent, typically water or an alcohol. Evaporation of the solvent then allows the formation of a protective solid film. However, water-based film-forming compositions have the disadvantage of having a fairly long drying time, and the longer the thickness of the desired film is important. Film-forming compositions based on alcohol or other organic solvents can provide significantly reduced drying times, but can be painful when applied to wounds or lesions, and are thus unsuitable for use of dressing type.
    [0002] In addition, the solidified films formed using these compositions based on film-forming polymers most often have limited mechanical properties, especially in terms of elasticity and resistance to fracture.
    [0003] There is therefore a need for novel non-cytotoxic film-forming compositions capable of forming in situ and rapidly solid films resistant to rupture, having good adhesion properties on tissues such as the skin, superficial body growths or mucous membranes, and good elasticity properties. The Applicant has found, surprisingly, that it is possible to form such films on tissues such as the skin, superficial body growths or mucous membranes, having excellent properties of resistance to fracture, adhesion, and elasticity, by means of a particular photopolymerizable liquid composition. The invention thus has, according to a first aspect, a photopolymerizable liquid composition comprising at least one epoxidized polybutadiene prepolymer, at least one cationic photoinitiator, and at least one photosensitizer derived from thioxanthone, phenothiazine , fluoflavin, anthracene, curcumin, dithienothiophene, xanthene or fluorone dyes, preferably a thioxanthone derivative.
    [0004] According to a second aspect, the invention also relates to a process for obtaining a polymerized film on the tissues such as skin, superficial body growths or mucous membranes from said photopolymerizable liquid composition. A more detailed description of some preferred embodiments of the invention is given below.
    [0005] DETAILED DESCRIPTION OF THE INVENTION According to a first aspect, the present invention relates to a photopolymerizable liquid composition comprising: at least one epoxidized polybutadiene prepolymer, at least one cationic photoinitiator, and at least one derived photosensitizer thioxanthone, phenothiazine, fluoflavin, anthracene, curcumin, dithienothiophene, preferably a thioxanthone derivative. The invention also relates to a process for obtaining a polymerized film from the photopolymerizable liquid composition described above, characterized in that: i. applying said composition to tissues such as skin, superficial body growths or mucous membranes, so as to form a uniform film, ii. the film obtained in step i is subjected. ultraviolet (UV) radiation, preferably visible UV-20 radiation of wavelength between 380 and 405 nm, preferably between 385 and 395 nm. In particular, the photopolymerizable liquid composition according to the invention is physiologically acceptable, ie non-toxic and capable of being applied to tissues such as the skin, superficial body growths or mucous membranes of human beings or animals. and allows formation of a biocompatible polymerized film. Epoxidized polybutadiene prepolymer The photopolymerizable liquid composition according to the invention comprises at least one epoxidized polybutadiene prepolymer. The epoxidized polybutadiene prepolymer is a low molecular weight liquid polybutadiene functionalized with at least one cationically polymerizable epoxide group. Indeed, the Applicant has demonstrated that by using a polybutadiene prepolymer epoxidized epoxies rather than low molecular weight monomers, the photopolymerizable liquid composition according to the invention could be used on open wounds without generating sensation. painful undesirable (burning, tingling ...) during its application. The use of this prepolymer also makes it possible to prevent the diffusion of monomers into the wounds during the application of the composition to lesions, burnt tissues and / or cutaneous affections. According to a particular embodiment, the epoxidized polybutadiene prepolymer has at least one of the following properties: a molecular mass of between 500 and 10,000 g / mol, preferably between 1000 and 5000 g / mol, and more preferentially between 1200 and 2500 g / mol, a dynamic viscosity at 25 ° C. (298 K) of between 0.1 and 100 Pa.s, preferably between 2.5 and 50 Pa.s, and more preferably between 5 and 25 Pa. .s, and an epoxide number of between 0.05 and 1 mol / 100 g, preferably between 0.1 and 0.5 mol / 100 g, and more preferentially between 0.15 and 0.45 mol / 100 g. . The epoxide number is the number of moles of epoxy groups per 100 grams of prepolymer. The epoxide index may in particular be measured according to standard NF EN ISO 3001 (May 1999, Plastics - Epoxy compositions - Determination of the epoxy equivalent). Epoxidized polybutadiene prepolymers that may be suitable in the context of the present application include the products marketed by Cray Valley under the name Poly BD605E and Poly BD600E. According to a particular embodiment, the epoxidized polybutadiene prepolymer is present in a content of between 5 and 99.8% by weight, preferably between 10 and 90% by weight, even more preferably between 15 and 80% by weight, relative to the total weight of the photopolymerizable liquid composition.
    [0006] Cationic photoinitiator The photopolymerizable liquid composition according to the invention also comprises at least one cationic photoinitiator. According to a preferred embodiment, the cationic photoinitiator is an opium salt sensitive to UV or UV-visible radiation and makes it possible to initiate the photopolymerization reaction. It may especially be chosen from the group comprising diazonium and halonium salts and in particular iodonium, sulphonium, sulphoxonium and selenonium salts. Cationic photoinitiators which may be suitable in the context of the present application include aryldiazonium salts, aryliodonium salts, diaryliodonium salts, alkylaryliodonium salts, arylsulfonium salts, triarylsulfonium salts, and the like. , diarylbromonium salts, triarylselenonium salts, thioxanthonium salts, triarylsulfoxonium salts, aryloxysulfoxonium salts, dialkylacylsulfoxonium salts, dialkylphenacylsulfonium salts and dialkyl-4-hydroxyphenylsulfonium salts. According to one particular embodiment, the cationic photoinitiator is chosen from bis (4-tert-butylphenyl) iodonium perfluoro-1-butanesulphonate, bis (4-tert-butylphenyl) iodonium p-toluenesulphonate, bis (4-tert-butylphenyl) iodonium, -tert-butylphenyl) iodonium triflate, boc-methoxyphenyldiphenylsulfonium triflate, (4-bromophenyl) diphenylsulfonium triflate, (tert-butoxycarbonylmethoxynaphthyl) -diphenylsulfonium triflate, (4-tert-butylphenyl) diphenylsulfonium triflate, diphenyliodonium 9,10- dimethoxyanthracene-2-sulfonate, (pisopropylphenyl) (m-methylphenyl) iodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium nitrate, diphenyliodonium perfluoro-1-butanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium triflate, 4-fluorophenyl) diphenylsulfonium triflate, N-hydroxynaphthalimide triflate, N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate, (4-iodophenyl) l) diphenylsulfonium, (4-methoxyphenyl) diphenylsulfonium triflate, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazin, (4-methylphenyl) diphenylsulfonium, methylphenylsulfonium triflate, 1-naphthyl diphenylsulfonium triflate, (4-phenoxyphenyl) diphenylsulfonium triflate, (4-phenylthiophenyl) diphenylsulfonium triflate, triarylsulfonium hexafluoroantimonate salts, triarylsulfonium hexafluorophosphate salts, triphenylsulfonium perfluoro-1 -butanesufonate, triphenylsulfonium triflate, tris (4-tert-butylphenyl) sulfonium perfluoro-1-butanesulfonate, tris (4-tert-butylphenyl) sulfonium triflate, 4- (1-methylethyl) phenyl 4-methylphenyliodonium tetrakis (pentafluorophenyl) ) borate (or diaryl iodonium tetrafluoroborate), hexafluoroarsenates and mixtures thereof.
    [0007] According to a preferred embodiment, the cationic photoinitiator is chosen from diaryliodonium salts, and is preferably 4- (1-methylethyl) phenyl 4-methylphenyliodonium tetrakis (pentafluorophenyl) borate (or diaryl iodonium tetrafluoroborate).
    [0008] According to one particular embodiment, the cationic photoinitiator is present in a content of between 0.1 and 10% by weight, preferably between 0.25 and 5% by weight, even more preferably between 0.5 and 1.5% by weight. % by weight, based on the total weight of the photopolymerizable liquid composition. Photo-sensitizer derived from thioxanthone, phenothiazine, fluoflavine, anthracene, curcumin, dithienothiophene, xanthene or fluorone dyes. The photopolymerizable liquid composition according to the invention also comprises at least one photosensitizer derived from thioxanthone, phenothiazine, fluoflavine, anthracene, curcumin, dithienothiophene, xanthene dyes or fluorone. For the purposes of the present application, the term "photosensitizer" is intended to mean a compound which passes into the excited state by exposure to UV, visible or UV-visible radiation, preferably UV-visible or visible radiation, and interacts directly with the cationic photoinitiator by transfer of energy or electron, or indirectly by generating in situ radical entities leading to a reduction of the cationic photoinitiator, all of these processes releasing cationic entities or protons responsible for initiating the cationic polymerization of epoxides. When introduced into the photopolymerizable liquid compositions according to the invention, the photosensitizer derived from thioxanthone, phenothiazine, fluoflavine, anthracene, curcumin, dithienothiophene, dye-based dyes, xanthene or fluorone gives the composition a photobleaching property, that is to say that it allows UV, visible or UV-visible radiation to penetrate the entire thickness of the liquid composition to be polymerized, thus promoting the rapid initiation of the photopolymerization in depth of the composition according to the invention. The film obtained is thus uniformly polymerized throughout its thickness, which gives it excellent properties of resistance to fracture, adhesion, and elasticity. According to a particularly preferred embodiment, the photosensitizer derived from thioxanthone, phenothiazine, fluoflavine, anthracene, curcumin, dithienothiophene, xanthene dyes or fluorone is sensitive to UV-visible radiation whose wavelength is between 200 and 500 nm, preferably between 300 and 450 nm, and even more preferably between 380 and 405 nm.
    [0009] This preferred range of wavelengths advantageously makes it possible not to damage the tissues such as the skin, the superficial body growths or the mucous membranes on which the photopolymerizable liquid composition is applied, during the photopolymerization.
    [0010] According to a particular embodiment, the photosensitizer derived from thioxanthone, phenothiazine, fluoflavine, anthracene, curcumin, dithienothiophene, xanthene or fluorone-based dyes is present in a certain amount. between 0.1 and 10% by weight, preferably between 0.25 and 5% by weight, more preferably between 0.5 and 1.5% by weight, relative to the total weight of the photopolymerizable liquid composition. According to another particular embodiment, the ratio between the photosensitizer content derived from thioxanthone, phenothiazine, fluoflavine, anthracene, curcumin, dithienothiophene, xanthene dyes or fluorone and the content of cationic photoinitiator in the photopolymerizable liquid composition of the invention is between 0.1 and 1, preferably between 0.5 and 0.75, more preferably between 0.6 and 0.7. A wide range of xanthene or fluorone dyes can be used in the present invention. Some examples include methylene blue, rhodamine B, Rose Bengal, 3-hydroxy-2, 4,5,7-tetraiodo-6-fluorone, 5,7-diiodo-3-butoxy-6-fluorone, l erythrosin B, eosin B, ethyl erythrosine, acridine orange, 6'-acetyl-4,5,6,710 tetrachloro-2 ', 4', 5 ', 6', 7'-tetraiodofluorescein ( RBAX). The photosensitizer is preferably a derivative of thioxanthone. The thioxanthone-derived photosensitizer is a compound of formula (I): wherein R 1 and R 2 are, independently of one another, selected from the group consisting of hydrogen, halogen, and a linear or branched carbon chain, substituted or unsubstituted, comprising from two to twenty-two carbon atoms, which may be interrupted by one or more oxygen atoms, and may include saturated or unsaturated carbon bonds. The groups R 1 and R 2 may include, for example, alkyl, alkenyl, alkynyl, alkoxy, alkenoxy, alkynoxy and similar linear or branched groups which may be functionalized with heteroatomic groups or hydrocarbon radicals carrying heteroatomic functions including hydroxy, nitro, thioether or other pharmaceutically or cosmetically acceptable functional groups.
    [0011] According to a particular embodiment, the photosensitizer derived from thioxanthone is chosen from 1-chloro-4-propoxythioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, thioxanthone, and mixtures thereof. According to a preferred embodiment, the photosensitizer derived from thioxanthone is isopropylthioxanthone.
    [0012] Second Pre-Polymer Other than Epoxidized Polybutadiene The photopolymerizable liquid composition according to the invention may also comprise a second prepolymer, different from the epoxidized polybutadiene. The addition of a second pre-polymer makes it possible in particular to adjust the viscosity of the epoxidized polybutadiene-based composition and / or the physico-chemical properties of the film once polymerized, for example its elasticity properties and adhesion to tissues such as skin, integuments or mucous membranes. The second prepolymer is preferably a natural plant oil functionalized with at least one cationically polymerizable epoxide group. According to a particular embodiment, the second prepolymer is chosen from epoxidized almond oil, epoxidized peanut oil, epoxidized argan oil, epoxidized rapeseed oil, coconut, epoxidized, epoxidized linseed oil, epoxidized corn oil, epoxidized mustard oil, epoxidized olive oil, epoxidized palm oil, epoxidized grape seed oil, epoxidized castor oil, epoxidized sesame oil, epoxidized soybean oil, epoxidized sunflower oil and mixtures thereof. According to a preferred embodiment, the second prepolymer is epoxidized soybean oil.
    [0013] The second pre-polymer may in particular be introduced in a content of between 20 and 80% by weight, preferably between 25 and 60% by weight, more preferably between 30 and 50% by weight, relative to the total weight of the prepolymer of epoxidized polybutadiene and the second prepolymer. Hydrogen donor compound The photopolymerizable liquid composition according to the invention may also comprise a hydrogen donor compound. Advantageously, the hydrogen donor compound may in particular make it possible to increase the kinetics of the photopolymerization reaction. The hydrogen donor compound may be a primary, secondary or tertiary alcohol, especially chosen from n-propanol, isopropanol, benzyl alcohol, t-butanol and mixtures thereof. The amount of the hydrogen donor compound may be between 1 and 10% by weight, preferably between 2 and 8% by weight, and more preferably between 3 and 5% by weight, relative to the total weight of the photopolymerizable liquid composition. . Additives The photopolymerizable liquid composition according to the invention may further comprise one or more additives, preferably non-basic. Indeed, the basic additives are capable of altering the photopolymerization of the composition according to the invention by interacting with the active centers ensuring the propagation of the cationic polymerization. The additives that may be introduced into the photopolymerizable liquid composition according to the invention may especially be chosen from perfumes, flavorings, dyes, pigments, mattifying agents, rheological agents, preservatives, vitamins, essential oils and active agents, especially chosen from antibacterial agents, antiseptics, anti-virals, antifungal agents, anti-pain agents, anti-inflammatory agents, agents promoting healing, moisturizing agents, depigmenting agents, keratolytic agents, restructuring assets, anesthetics and their mixtures. In particular, the active agents that may be introduced into the composition according to the invention may be chosen from: anti-bacterials such as polymyxin B, penicillins (amoxycillin), clavulanic acid, tetracyclines, minocycline, chlorotetracycline Aminoglycosides, Amikacin, Gentamicin, Neomycin, silver and its salts (silver sulfadiazine), probiotics; antiseptics such as sodium mercurothiolate, eosin, chlorhexidine, phenylmercury borate, hydrogen peroxide, Dakin liquor, triclosan, biguanide, hexamidine, thymol, Lugol, Povidone iodine, Merbromine, Benzalkonium and Benzethonium Chloride, ethanol, isopropanol; anti-virals such as [Gamma] Aciclovir, Famciclovir, Ritonavir; antifungals such as polyenes, Nystatin, Amphotericin B, Natamycin, imidazoles (Miconazole, Ketoconazole, Clotrimazole, Econazole, Bifonazole, Butoconazole, Fenticonazole, Isoconazole, Oxiconazole, Sertaconazole, Sulconazole, Thiabendazole, Tioconazole), triazoles (Fluconazole, Itraconazole, Ravuconazole, Posaconazole, Voriconazole), allylamines, Terbinafine, [Gamma] Amorolfme, Naftifme, Butenafine; Flucytosine (antimetabolite), Griseofulvin, Caspofungin, Micafungin; anti-pain agents such as Paracetamol, Codeine, Dextropropoxyphene, Tramadol, Morphine and its derivatives, Corticosteroids and derivatives; anti-inflammatories such as Glucocorticoids, Nonsteroidal Anti-inflammatories, Aspirin, Ibuprofen, Ketoprofen, Flurbiprofen, Diclofenac, Aceclofenac, Ketorolac, Meloxicam, Piroxicam, Tenoxicam, Naproxen , Indomethacin, Naproxcinod, Nimesulide, Celecoxib, Etoricoxib, Parecoxib, Rofecoxib, Valdecoxib, Phenylbutazone, Niflumic acid, Mefenamic acid; healing promoting agents such as retinol, vitamin A, vitamin E, N-acetylhydroxyproline, extracts of Centella Asiatica, papain, silicones, essential oils of thyme, niaouli, rosemary and sage, hyaluronic acid, synthetic polysulfated oligosaccharides having 1 to 4 unsaturated units such as the potassium salt of octasulfated sucrose, the silver salt of octasulfated sucrose or sucralfate, metformin, aspirin, Allantoin; moisturizing agents such as hyaluronic acid, urea, glycerol, fatty acids, modulators of aquaporins, vegetable oils, chitosan, certain sugars including sorbitol, butters and waxes; depigmenting agents such as kojic acid (Kojic Acid SL (R) - Quimasso (Sino Lion)), Arbutin (Olevatin (R) - Quimasso (Sino Lion)), palmitoylpropyl mixture of sodium and extract white water lily (Sepicalm (R) - Seppic), undecylenoyl phenylalanine (Sepiwhite (R) - Seppic), licorice extract obtained by fermentation of Aspergillus and ethoxydiglycol (Gatuline Whitening (R) Gattefossé), the acid octadecenedioic acid (ODA White (R) - Sederma), alphaarbutin (Alpha-arbutin (R), SACI-CFPA (Pentapharm)), aqueous leaf extract Arctophylos Uva, Ursi (Melfade-J (R) - SACI- CFPA (Pentapharm)), Gigawhite (R) Complex Plant Blend (SACI-CFPA (Alpaflor)), Diacetyl Boldine (Lumiskin (R) -Sederma), Mandarin Extract from Japan (Melaslow (R) - Sederma ), lemon extract mixture enriched in citric acid and cucumber extract (Uninontan (R) U-34 - Unipex), the mixture of Rumex occidentalis extract and vitamin C (Tyrostat (R) 11 - Unipex) igopeptides (Melanostatin 5 (R) - Unipex), kojic dipalmitate (KAD-15 (R) - Quimasso (Sino Lion)), LCW Vegewhite (R) natural complex, wheat germ extracts (Clariskin (R) II-Silab), ethyldiamine triacetate (EDTA); keratolytic agents such as salicylic acid, zinc salicylate, ascorbic acid, alpha hydroxylated acids (glycolic acid, lactic acid, malic acid, citric acid, tartaric acid), extracts of silver maple, Griottier, tamarind, urea, topical retinoid Keratin (R) (Sederma), proteases obtained by fermentation of Bacillus Subtilis, the product Linked-Papain (R) (SACI-CFPA), papain (proteolytic enzyme derived from papaya fruit); restructuring assets (for example rescutants of integuments) such as silica derivatives, vitamin E, chamomile, calcium, horsetail extract, silk lipester; anesthetics such as benzocaine, lidocaine, dibucaine, pramoxine hydrochloride, bupivacaine, mepivacaine, prilocaine, etidocaine.
    [0014] According to a particular embodiment, the photopolymerizable liquid composition is in the form of a liquid dressing.
    [0015] Indeed, the composition according to the invention makes it possible to obtain a polymerized film presenting properties that are particularly advantageous for use as a liquid dressing, that is to say a film that adheres to the skin for several hours, that does not exhibit Superficial pantyhose that resists water, including several hand washes. According to another aspect, the subject of the invention is a process for obtaining a polymerized film from the photopolymerizable liquid composition described above, characterized in that: i. applying said composition to tissues such as skin, superficial body growths or mucous membranes so as to form a uniform liquid film, ii. the film obtained in step i is subjected. UV radiation, preferably UV-visible radiation of wavelength between 380 and 405 nm, preferably between 385 and 395 nm. According to a particular embodiment, the UV radiation is produced at a fixed wavelength of between 385 and 395 nm. Advantageously, the method according to which the value is the invention allows the easy and fast obtaining of a polymerized film having excellent properties of resistance to fracture, adhesion, and elasticity. In particular, the choice of an epoxidized polybutadiene prepolymer makes it possible to rapidly obtain a polymerized film since no inhibitory effect of the photopolymerization by oxygen is undergone.
    [0016] In addition, the range of wavelengths chosen advantageously not to damage the tissues such as skin, superficial body growths or mucous membranes on which the photopolymerizable liquid composition is applied, during the photopolymerization. According to a preferred embodiment, the uniform film formed in step i. has a thickness greater than 500 nm, preferably between 1 and 300 pm, more preferably between 2 and 200 pm.
    [0017] According to a particular embodiment, the film obtained in step i. is subjected to UV radiation, preferably UV-visible for a time sufficient to obtain a conversion of the epoxide groups of at least 50%, preferably at least 75%. In fact, the polymerized films obtained from the compositions according to the invention has the desired physicochemical properties when the conversion of the epoxide groups is at least 50% and preferably at least 75%. The conversion of the epoxide groups is established from the FTIR spectroscopy experiment. It is calculated by measuring the initial height (ho) and the height at each instant (ht) of the characteristic absorption peaks of the epoxide groups and by applying the formula below: conversion = 1- (ht / h0) The film obtained in step i. is thus subjected to UV radiation, preferably UV-visible for a period of between 5 seconds and 60 minutes, preferably between 5 seconds and 30 minutes, more preferably between 5 seconds and 10 minutes. These exposure time ranges advantageously make it possible not to damage the tissues such as the skin, the superficial body growths or the mucous membranes on which the photopolymerizable liquid composition is applied.
    [0018] According to a particular embodiment, the exposure to UV radiation, preferably UV-visible, is carried out continuously. According to a particular embodiment, exposure to UV radiation, preferably UV-visible, is carried out discontinuously. The present invention is further illustrated in the non-limiting examples described below. EXAMPLES Example 1 Preparation of a photopolymerizable liquid composition A photopolymerizable liquid composition was prepared comprising the compounds described in the table below: Compound (wt.%) Prepolymer Polybutadiene 97.5 Epoxidized (Poly BD605E) Diaryl iodonium 1 tetrakis (pentafluorophenyl) borate (Bluesil PI2074) Isopropylthioxanthone (ITX) 1.5 The epoxidized polybutadiene prepolymer (Poly BD605E) is commercially available from Sartomer. Diaryl iodonium borate (Bluesil PI2074) is 4- (1-methylethyl) phenyl 4-methylphenyliodonium tetrakis (pentafluorophenyl) borate marketed by BlueStar. The isopropylthioxanthone (ITX) used is marketed by Aldrich. All compounds were mixed until a homogeneous solution was obtained. The solution thus obtained was then stored at room temperature and was protected from light until used.
    [0019] Study of the conversion of the epoxy groups of the prepared photopolymerizable liquid composition The conversion of the epoxide groups of the photopolymerizable liquid composition is followed by IFTR spectroscopy (Vertex 70 Spectrometer, Bruker). Its evolution is followed continuously by controlling the disappearance of the absorption peak characteristic of the epoxide group of Poly-1 BD605E at 890 cm.
    [0020] The conversion of the epoxide groups of the composition is calculated as previously described. The photopolymerizable liquid composition is prepared according to the following protocol. Deposition of said composition is made on a silicon wafer, attached to an aluminum support. The thickness of the deposited liquid film is 20 μm. The composition is then exposed, under air and at ambient temperature, to UV radiation, preferably UV-visible, with a wavelength of 385 nm emitted by an LED-LC3 (Hamamatsu Photonics KK) positioned at a distance of 7 5 cm of the composition and with a pfd density of 0.1603 W.cm-2. The exposure is carried out continuously for a period of 50 seconds. Figure 1 shows the evolution of the conversion of the epoxide groups of the composition (in%) as a function of the exposure time. Under the conditions of the experiment, after 50 seconds of exposure, the conversion of the epoxide groups is greater than 81%. The film thus obtained is elastic, adheres to the skin, has no superficial tack, is water-resistant, and has good breaking strength.
    [0021] Example 2 Study of the Addition of a Second Pre-Polymer to a Light-Curing Liquid Composition As in Example 1, a photopolymerizable liquid composition comprising the compounds described in the table below was prepared. Compound% Poly Poly BD605E 58.5 Epoxidized Soybean Oil (ESO) Bluesil PI2074 1 ITX 1.5 Epoxidized soybean oil (ESO) is a second pre-polymer marketed by Ackross. The conversion of the epoxide groups of this composition was studied according to a protocol equivalent to that described in Example 1. However, the disappearance of the absorption peak characteristic of the epoxy group of epoxidized soybean oil is monitored at 823 cm. -1. In addition, the exposure time is 600 seconds. Under the conditions of the experiment, after 600 seconds of exposure, the conversion of the epoxide groups is greater than 80%. It appears that the addition of epoxidized soybean oil makes it possible to obtain a film having properties of elasticity and adhesion to the skin that are still improved compared with those of the composition of Example 1. In addition, as for the film obtained with the composition of Example 1, the film obtained with the composition of Example 2 does not have superficial tack, is water-resistant, and has good breaking strength. Example 3 Study of the addition of a hydrogen donor compound to a photopolymerizable liquid composition. As in Example 1, a photopolymerizable liquid composition comprising the compounds described in the table below was prepared. Compound% by weight Poly BD605E 92.5 Bluesil PI2074 1 ITX 1.5 Benzyl alcohol 5 Benzyl alcohol is used here as a hydrogen-donating compound, it is marketed by Aldrich. Before use, it is stored on molecular sieves to reduce the moisture content.
    [0022] The conversion of the epoxide groups of this composition was studied according to a protocol identical to that described in Example 1. Under the conditions of the experiment, after 50 seconds of exposure, the conversion of the epoxide groups is greater than 84%. . The polymerization is accelerated by the addition of benzyl alcohol. In addition, as in Example 1, the film obtained with the water-based, elastic, superficial composition resists breakage. EXAMPLE 4 Study of the effect of the photo-sensitizer derived from thioxanthone on the phenomenon of photobleaching, at different thicknesses of photopolymerizable films.
    [0023] A photopolymerizable liquid composition identical to that of Example 1 was prepared. Photobleaching of isopropylthioxanthone was studied by continuous measurement of the absorbance at 385 nm of the composition prepared in a UV-Visible spectrophotometer. The protocol followed is as follows. Samples of different thicknesses (between 15 and 200 μm) of the prepared composition were first placed between two thin glasses (150 μm). They were then exposed to UV-visible radiation of 385 nm wavelength emitted by an LED-LC3 (Hamamatsu Photonics KK) positioned at a distance of 6 cm and with a pfd density of 0.1807 W · cm-2. The exposure is carried out continuously for a period of 20 seconds. Under the conditions of the experiment, and after the 20 seconds of exposure, the rate of progress of the photobleaching is between 0.95 and 1 for all the samples. The phenomenon of photobleaching allows deep priming of the photopolymerization. A photobleaching rate of between 0.95 and 1 obtained in the present conditions thus allows polymerization of the film uniformly throughout its thickness. Example 5 Application of the photopolymerizable liquid composition to the skin.
    [0024] On a clean, dry 3 cm 2 skin surface, the photopolymerizable liquid composition of Example 1 was applied with a brush in a single 150 μm layer.
    [0025] The coated skin surface is then continuously exposed, in air and at ambient temperature, to UV-visible radiation with a wavelength of 385 nm emitted by an LED-LC3 (Hamamatsu Photonics KK) positioned at a distance of 7.5 cm from the skin surface and with a pfd density of 0.1603 W.cm-2. After 10 minutes of exposure, the skin is covered with a polymerized film which is elastic, which adheres to the skin for several hours, has no superficial tights, is water-resistant, especially with several washes of hands and which has good breaking strength.
    权利要求:
    Claims (14)
    [0001]
    REVENDICATIONS1. A photopolymerizable liquid composition comprising: at least one epoxidized polybutadiene prepolymer, at least one cationic photoinitiator, and at least one photosensitizer derived from thioxanthone, phenothiazine, fluoflavin, anthracene, curcumin, dithienothiophene, xanthene or fluorone dyes, preferably a thioxanthone derivative.
    [0002]
    2. The photopolymerizable liquid composition according to claim 1, characterized in that the epoxidized polybutadiene prepolymer has a molecular mass of between 500 and 10,000 g / mol, preferably between 1000 and 5000 g / mol, and more preferably between 1200 and 2500 g / mol and / or an epoxide index of between 0.05 and 1 mol / 100 g, preferably between 0.1 and 0.5 mol / 100 g, and more preferably between 0.15 and 0.45 mol / 100g.
    [0003]
    3. A photopolymerizable liquid composition according to any one of the preceding claims, characterized in that the epoxidized polybutadiene prepolymer is present in a content of between 5 and 99.8% by weight, relative to the total weight of the photopolymerizable liquid composition. .
    [0004]
    4. A photopolymerizable liquid composition according to any one of the preceding claims, characterized in that the cationic photoinitiator is an onium salt sensitive to UV or UV-visible radiation, especially chosen from bis (4-tert-butylphenyl) iodonium perfluoro-1-butanesulfonate, bfs (4-tert-butylphenyl) iodonium p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium triflate, bocethoxyphenyldiphenylsulfonium triflate, (4-bromophenyl) diphenylsulfonium triflate, (tert-butoxycarbonylmethoxynaphthyl) diphenylsulfonium triflate, (4-tert-butylphenyl) diphenylsulfonium triflate, diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate, (p-isopropylphenyl) (m-methylphenyl) iodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium nitrate, diphenyliodonium perfluoro-1-butanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium triflate, (4-fluorophenyl) diphenylsulfonium triflate, N-hydroxynaphthalimide triflate, N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate, (4-iodophenyl) diphenylsulfonium, (4-methoxyphenyl) diphenylsulfonium triflate, 2- (4- Methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazin, (4-methylphenyl) diphenylsulfonium, (4-methylthiophenyl) methylphenylsulfonium triflate, 1-naphthyl diphenylsulfonium triflate, phenoxythienyl) diphenylsulfonium triflate, (4-phenylthiophenyl) diphenylsulfonium triflate, triarylsulfonium hexafluoroantimonate salts, triarylsulfonium hexafluorophosphate salts, triphenylsulfonium perfluoro-1-butanesulfonate, triphenylsulfonium triflate, tris (4-tert-butylphenyl) sulfonium perfluoro-1-butanesulfonate, tris (4-tert-butylphenyl) sulfonium triflate, 4- (1-methylethyl) phenyl-4-methylphenyliodonium tetrakis (pentafluorophenyl) borate (or diaryl iodonium tetrafluoroborate), hexafluorides oarsenates and mixtures thereof, preferably the cationic photoinitiator is selected from diaryliodonium salts, and is preferably 4- (1-methylethyl) phenyl 4-methylphenyliodonium tetrakis (pentafluorophenyl) borate (or diaryl iodonium tetrafluoroborate).
    [0005]
    5. The photopolymerizable liquid composition according to any one of the preceding claims, characterized in that the cationic photoinitiator is present in a content of between 0.1 and 10% by weight, relative to the total weight of the photopolymerizable liquid composition.
    [0006]
    6. The photopolymerizable liquid composition according to any one of the preceding claims, characterized in that the photosensitizer is present in a content of between 0.1 and 10% by weight, relative to the total weight of the photopolymerizable liquid composition.
    [0007]
    7. The photopolymerizable liquid composition according to any one of the preceding claims, characterized in that the photosensitizer is a derivative of thioxanthone chosen from 1-chloro-4-propoxythioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone , isopropylthioxanthone, thioxanthone, and mixtures thereof, and preferably is isopropylthioxanthone.
    [0008]
    8. A photopolymerizable liquid composition according to any one of the preceding claims, characterized in that it comprises a second prepolymer, different from the epoxidized polybutadiene.
    [0009]
    9. photopolymerizable liquid composition according to the preceding claim, characterized in that the second prepolymer is selected from epoxidized almond oil, epoxidized peanut oil, epoxidized argan oil, oil epoxidized rapeseed oil, epoxidized coconut oil, epoxidized linseed oil, epoxidized corn oil, epoxidized mustard oil, epoxidized olive oil, epoxidized palm oil, epoxidized grape seed oil, epoxidized castor oil, epoxidized sesame oil, epoxidized soybean oil, epoxidized sunflower oil and mixtures thereof, preferably the second prepolymer is oil of epoxidized soy.
    [0010]
    10. A photopolymerizable liquid composition according to claim 8 or 9, characterized in that the second prepolymer is introduced in a content of between 20 and 80% by weight, relative to the total weight of the epoxidized polybutadiene prepolymer and the second pre-polymer.
    [0011]
    11. A process for obtaining a polymerized film from the photopolymerizable liquid composition according to any one of claims 1 to 10, characterized in that: i. applying said composition to tissues such as skin, superficial body growths or mucous membranes so as to form a uniform liquid film, ii. the film obtained in step i is subjected. UV radiation, preferably UV-visible radiation of wavelength between 380 and 405 nm, preferably between 385 and 395 nm.
    [0012]
    12. The method of claim 11, characterized in that the thickness of the uniform liquid film is greater than 500 nm, preferably between 1 and 300 pm, more preferably between 2 and 200 pm.
    [0013]
    13. The method of claim 11 or 12, characterized in that film obtained in step i. is subjected to UV radiation, preferably UV-visible for a period of between 5 seconds and 60 minutes, preferably between 5 seconds and 30 minutes, more preferably between 5 seconds and 10 minutes.
    [0014]
    14. Use of the composition according to claims 1 to 10 for its application to tissues such as skin, superficial body growths and / or mucous membranes.
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    同族专利:
    公开号 | 公开日
    EP3079677A1|2016-10-19|
    EP3079677B1|2017-10-25|
    ES2651188T8|2018-02-12|
    CN105960233A|2016-09-21|
    ES2651188T3|2018-01-24|
    US20170014544A1|2017-01-19|
    WO2015087020A1|2015-06-18|
    FR3014883B1|2016-11-11|
    US10155065B2|2018-12-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS61231022A|1985-04-04|1986-10-15|Nippon Soda Co Ltd|Photocurable sealing composition|
    US5849460A|1994-07-27|1998-12-15|Hitachi, Ltd.|Photosensitive resin composition and method for using the same in manufacture of circuit boards|
    JP2001040068A|1999-07-27|2001-02-13|Asahi Denka Kogyo Kk|Photopolymerizable composition|
    JP2007126612A|2005-11-07|2007-05-24|Kawasaki Kasei Chem Ltd|Photosensitizer, photosensitive acid generator and photocurable composition|
    JPS61213217A|1985-03-19|1986-09-22|Nippon Soda Co Ltd|Photosetting resin composition for sealing|
    US4882201A|1988-03-21|1989-11-21|General Electric Company|Non-toxic aryl onium salts, UV curable coating compositions and food packaging use|
    US5992314A|1997-06-30|1999-11-30|Ncr Corporation|UV curable adhesive for stencil media|
    US6458865B2|1999-01-15|2002-10-01|Curators Of The University Of Missouri|Photopolymerizable vinyl ether based monomeric formulations and polymerizable compositions which may include certain novel spiroorthocarbonates|
    GB0204468D0|2002-02-26|2002-04-10|Coates Brothers Plc|Novel thioxanthone derivatives, and their use as cationic photoinitiators|
    WO2007134219A2|2006-05-11|2007-11-22|Living Proof, Inc.|In situ polymerization for skin treatment|
    FR2972928B1|2011-03-25|2013-11-29|Urgo Lab|COMPOSITION CONTAINING CELLULOSE, VEGETABLE OIL AND VOLATILE SOLVENT, ITS USES AS DRESSING|WO2017154983A1|2016-03-09|2017-09-14|株式会社トクヤマデンタル|Photopolymerization initiator and photocurable composition|
    CN107200820A|2017-06-27|2017-09-26|江门盈骅光电科技有限公司|Epoxidation vinyl benzene butadiene double-heptene block copolymer and its production and use|
    CN107474628A|2017-10-11|2017-12-15|至远彩色印刷工业（惠州）有限公司|Beautiful LED cured printing ink compositions of a kind of color and luster and preparation method thereof|
    WO2020215297A1|2019-04-26|2020-10-29|四川大学|Polyurethane-based jet-type precursor liquid of photocurable hydrogel dressing and preparation method therefor|
    法律状态:
    2015-12-30| PLFP| Fee payment|Year of fee payment: 3 |
    2016-12-20| PLFP| Fee payment|Year of fee payment: 4 |
    2017-05-26| TP| Transmission of property|Owner name: URGO RECHERCHE INNOVATION ET DEVELOPPEMENT, FR Effective date: 20170424 |
    2017-10-13| TQ| Partial transmission of property|Owner name: URGO RECHERCHE INNOVATION ET DEVELOPPEMENT, FR Effective date: 20170912 Owner name: INSTITUT DE SOUDURE ASSOCIATION, FR Effective date: 20170912 |
    2017-12-20| PLFP| Fee payment|Year of fee payment: 5 |
    2019-09-27| ST| Notification of lapse|Effective date: 20190906 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362568A|FR3014883B1|2013-12-13|2013-12-13|PHOTOPOLYMERIZABLE LIQUID COMPOSITION|FR1362568A| FR3014883B1|2013-12-13|2013-12-13|PHOTOPOLYMERIZABLE LIQUID COMPOSITION|
    PCT/FR2014/053318| WO2015087020A1|2013-12-13|2014-12-12|Photopolymerizable liquid composition|
    CN201480074441.4A| CN105960233A|2013-12-13|2014-12-12|Photopolymerizable liquid composition|
    US15/104,193| US10155065B2|2013-12-13|2014-12-12|Photopolymerizable liquid composition|
    EP14827507.6A| EP3079677B1|2013-12-13|2014-12-12|Photopolymerizable liquid composition|
    ES14827507.6T| ES2651188T3|2013-12-13|2014-12-12|Light-curing liquid composition.|
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