Bio-based resin for cosmetic compositions and method for producing the same

Abstract

The present invention relates to a bio-based polyester resin comprising a mixture of a diol and a polyacid, a method for preparing the same, and a film-forming composition and nail polish comprising the resin. The polyester resin may be particularly useful as a binder in nail polish.

Description

Technical Field

[0001] The present invention relates to a bio-based polyester resin containing a mixture of a diol and a polyacid, a method for preparing the same, a film-forming composition, and a nail polish containing the resin. The polyester resin can be particularly useful as a binder in nail polish.

Background Art

[0002] Today, major cosmetic groups and consumers desire nail polishes that are completely bio-based. However, currently, there are few bio-based resins that can serve as binders for nail polishes.

[0003] Copolymer polyesters of 1,2-propanediol, citric acid, succinic acid, and lauric acid are known and are sold, for example, under the name Natipol® 1303 by Maeder.

[0004] However, this resin does not function as well as petroleum-based resins, particularly in terms of gloss, adhesion, stability, hardness, and drying time.

[0005] Therefore, there is a need for bio-based resins as an alternative to petroleum-based resins in order to obtain nail polishes with suitable performance levels and that are more environmentally friendly.

Summary of the Invention

[0006] Accordingly, an object of the present invention is a polyester resin obtained by the polymerization of a mixture of a diol containing isosorbide and a branched C3-C6 diol and a mixture of polyacids containing succinic acid and sebacic acid.

[0007] Another object of the present invention is a method for preparing a polyester resin, comprising the following steps: namely, i) reacting isosorbide with a polyacid selected from succinic acid or sebacic acid; ii) reacting the mixture obtained in step i) with a polyacid selected from a branched C3-C6 diol and succinic acid or sebacic acid; comprising wherein the polyacid used in step i) is different from the polyacid used in step ii).

[0008] Another object of the present invention is a film-forming composition comprising a polyester resin according to the present invention, a film-forming cellulose polymer, and an organic solvent.

[0009] The present invention also relates to a manicure of a polyester resin according to the present invention, a film-forming cellulose polymer, an organic solvent, and a compound selected from a plasticizer, a second resin, a rheology agent, a coloring material, an additive, and mixtures thereof.

[0010] Another object of the present invention is the use of a polyester resin according to the present invention as a binder in a manicure.

Mode for Carrying Out the Invention

[0011] Polyester Resin The present invention relates to a polyester resin.

[0012] For the purposes of the present invention, "polyester resin" means a polymer containing ester functional groups obtained by the polymerization of a diol and a polyacid.

[0013] For the purposes of the present invention, "diol" means a compound having two hydroxyl functional groups.

[0014] For the purposes of the present invention, "polyacid" means a compound having at least two carboxylic acid functional groups.

[0015] When the term "organic solvent" is used in the singular in this application, it refers to both a single organic solvent and a mixture of organic solvents unless otherwise stated.

[0016] The polyester resin of the present invention is obtained by the polymerization of a mixture of at least two diols and a mixture of at least two polyacids.

[0017] The mixture of diols includes isosorbide and a branched C3-C6 diol.

[0018] According to a specific embodiment, the branched C3-C6 diol is selected from 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, and mixtures thereof. Preferably, the branched C3-C6 diol is 1,2-propanediol.

[0019] When using a branched C3-C6 diol, it is advantageously possible to obtain a resin having a Tg above -30°C and good solubility in solvents used in nail polish.

[0020] The mixture of diols can further include additional diols different from isosorbide and the branched C3-C6 diol. According to a specific embodiment, the mixture of diols further includes 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and mixtures thereof.

[0021] According to a specific embodiment, the mixture of diols consists of isosorbide and a branched C3-C6 diol.

[0022] According to a specific embodiment, the polyester resin does not contain units obtained by the polymerization of triols. Thus, the diol is the only hydroxylated monomer used in the polymerization reaction with the polyacid.

[0023] A mixture of diols (isosorbide, branched C3-C6 diols, and optionally additional diols) can, in particular, account for 30 to 65%, preferably 35 to 60%, more preferably 40 to 55% in moles of the monomers incorporated into the polyester resin.

[0024] Isosorbide can, in particular, account for 15 to 40%, preferably 20 to 35%, more preferably 25 to 30% in moles of the monomers incorporated into the polyester resin.

[0025] Branched C3-C6 diols can, in particular, account for 10 to 35%, preferably 15 to 30%, more preferably 20 to 25% in moles of the monomers incorporated into the polyester resin.

[0026] The molar ratio between isosorbide and branched C3-C6 diols incorporated into the polyester resin can be, in particular, 1 or more, specifically 1 to 2, more specifically 1 to 1.5.

[0027] The mixture of polyacids includes succinic acid and sebacic acid.

[0028] The mixture of polyacids can further include one or more additional polyacids different from succinic acid and sebacic acid. According to certain embodiments, the additional polyacid(s) include 2 or 3 carboxylic acid functional groups. More specifically, the mixture of polyacids further includes adipic acid, azelaic acid, citric acid, terephthalic acid, 2,5-furandicarboxylic acid, fumaric acid, itaconic acid, muconic acid, and mixtures thereof. Preferably, the mixture of polyacids further includes 2,5-furandicarboxylic acid, citric acid, and mixtures thereof.

[0029] The mixture of polyacids (succinic acid, sebacic acid, and optionally additional polyacids) can, in particular, account for 35 to 70%, preferably 40 to 65%, more preferably 45 to 60% in moles of the monomers contained in the polyester resin.

[0030] Succinic acid can particularly account for 5 to 50%, preferably 10 to 45%, more preferably 15 to 40% in terms of moles of the monomers incorporated into the polyester resin.

[0031] Sebacic acid can particularly account for 2 to 25%, preferably 5 to 20%, more preferably 10 to 15% in terms of moles of the monomers incorporated into the polyester resin.

[0032] The molar ratio between succinic acid and sebacic acid incorporated into the polyester resin can particularly be 1 or more, specifically 1 to 6, more specifically 1 to 4.

[0033] The additional polyacid(s) can particularly account for 0 to 30%, preferably 2 to 25%, more preferably 5 to 20% in terms of moles of the monomers incorporated into the polyester resin.

[0034] According to certain embodiments, the molar ratio between the diol (isosorbide and branched C3-C6 diol) and the polyacid (succinic acid, sebacic acid and optionally additional polyacid) is 1.1 or less, specifically 0.4 to 1, more specifically 0.6 to 1, even more specifically 0.8 to 1.

[0035] The amount of each monomer is adjusted to obtain a resin having a number average molecular weight and an appropriate glass transition temperature for the intended use.

[0036] The polyester resin according to the present invention particularly has a number average molecular weight (Mn) of 1000 to 3500 g / mol -1 , preferably 1100 to 3000 g / mol -1 , more preferably 1200 to 2500 g / mol -1 The polyester resin according to the present invention particularly has a number average molecular weight (Mn) of 1000 to 8000 g / mol -1 , preferably 1500 to 7000 g / mol -1 , more preferably 2500 to 6000 g / mol -1may have a weight average molecular weight (Mw). Mn and Mw can be measured according to the methods disclosed below.

[0037] The polyester resin according to the present invention may particularly have a glass transition temperature (Tg) of -30°C to 35°C, preferably -20°C to 25°C, and more preferably -10°C to 10°C. Tg can be measured according to the methods disclosed below.

[0038] The polyester resin according to the present invention may particularly have an acid value of 40 to 150 mg KOH / g, preferably 45 to 125 mg KOH / g, and more preferably 50 to 100 mg KOH / g. The acid value can be measured according to the process disclosed below. The acid value of the resin can be checked based on the progress of the polymerization reaction. Preferably, the polymerization is stopped before the esterification reaction is completed in order to retain free carboxylic acid groups in the resin. Without wishing to be bound by any theory, the presence of free carboxylic acid groups in the resin improves the interaction between the resin and the nail.

[0039] The resin can be obtained according to the preparation method disclosed below.

[0040] Preparation method of polyester resin The method for preparing the polyester resin according to the present invention includes a series of esterification steps that enable obtaining a soluble resin incorporating a large amount of isosorbide.

[0041] In step i), isosorbide reacts with a polyacid selected from succinic acid or sebacic acid.

[0042] In step ii), the mixture obtained in step i) reacts with a polyacid selected from a branched C3-C6 diol and succinic acid or sebacic acid.

[0043] The polyacid used in step i) is different from the polyacid used in step ii). Thus, when isosorbide reacts with succinic acid in step i), the mixture obtained in step i) reacts with a branched C3-C6 diol and sebacic acid. Alternatively, when isosorbide reacts with sebacic acid in step i), the mixture obtained in step i) reacts with a branched C3-C6 diol and succinic acid.

[0044] Additional polyacid(s) can be added in step i) or ii). Specifically, the additional polyacid(s) is added in step i).

[0045] The amounts of isosorbide, branched C3-C6 diol, sebacic acid, succinic acid, and additional polyacid introduced in steps i) and ii) are as previously defined for the resin. Indeed, the process according to the invention allows for the almost total incorporation of the monomers in the polyester resin.

[0046] The final molar ratio between the diols (isosorbide and branched C3-C6 diol) incorporated in the polyester resin and the polyacids (succinic acid, sebacic acid, optionally additional polyacid) is advantageously 1.1 or less, specifically 0.4 - 1, more specifically 0.6 - 1, even more specifically 0.8 - 1.

[0047] According to a particular embodiment, the molar ratio between the isosorbide introduced in step i) and the polyacid (succinic acid or sebacic acid, optionally additional polyacid) is 0.2 - 1.1, more specifically 0.3 - 1, even more specifically 0.4 - 1.

[0048] According to a particular embodiment, the molar ratio between the branched C3-C6 diol introduced in step ii) and the polyacid (succinic acid or sebacic acid, optionally additional polyacid) is 0.2 - 3, more specifically 0.4 - 2.5, even more specifically 0.6 - 2.

[0049] According to certain embodiments, steps i) and ii) of the method are carried out in the absence of an organic solvent.

[0050] According to certain embodiments, steps i) and ii) of the method are carried out in the absence of a catalyst.

[0051] Steps i) and ii) can in particular be carried out under an inert atmosphere. Carrying out step i) under an inert atmosphere is particularly important in order to avoid the thermal oxidation of isosorbide.

[0052] The esterification reaction can be accelerated by heating the reaction medium. Steps i) and ii) can in particular be carried out at a temperature of 120 °C to 200 °C.

[0053] The reaction can in particular be monitored by checking the acid value at each step. After reaching the target acid value, the temperature of the reaction medium can be lowered.

[0054] The method of the present invention can include step iii) of diluting the resin obtained by adding an organic solvent. This step in particular makes it possible to dissolve the resin and facilitates the subsequent use of the resin.

[0055] The organic solvent can be of the type disclosed below in the film-forming composition.

[0056] The organic solvent can be added to the resin in an amount sufficient to obtain a composition having a solid extract of 60 to 80% by weight, specifically 65 to 75% by weight, more specifically about 70% by weight.

[0057] The resin obtained after dilution with the solvent can be mixed with a film-forming cellulose polymer to form a film-forming composition as disclosed below.

[0058] Film-forming composition The film-forming composition according to the present invention contains the polyester resin, film-forming cellulose polymer, and organic solvent of the present invention.

[0059] "Film-forming composition" means a composition that can form a film after being applied to a surface, specifically, to the skin or a keratin material, for example, nails.

[0060] According to a specific embodiment, the film-forming composition contains 1 to 25% by weight, preferably 4 to 15% by weight, more preferably 5 to 10% by weight of the polyester resin based on the weight of the composition.

[0061] The film-forming cellulose polymer can be particularly selected from nitrocellulose, cellulose acetate butyrate, ethyl cellulose, hydroxypropyl cellulose, and mixtures thereof. Preferably, the film-forming cellulose polymer is nitrocellulose.

[0062] According to a specific embodiment, the film-forming composition contains 1 to 25% by weight, preferably 6 to 20% by weight, more preferably 10 to 15% by weight of the film-forming cellulose polymer based on the weight of the composition.

[0063] The organic solvent is preferably cosmetically acceptable, that is, it does not cause discomfort (redness, stinging) when applied to the skin and keratin materials. The organic solvent can be particularly selected from aliphatic compounds, for example, acetates, ketones, alcohols, alkanes, or mixtures thereof. Specifically, the solvent is selected from ethyl acetate, butyl acetate, propyl acetate, isobutyl acetate, ethanol, propanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, heptane, hexane, and mixtures thereof. More specifically, the organic solvent is selected from ethyl acetate, butyl acetate, and mixtures thereof. Even more specifically, the organic solvent is a mixture of ethyl acetate and butyl acetate.

[0064] According to a preferred embodiment, the film-forming composition is anhydrous, i.e., it contains no water at all.

[0065] According to a particular embodiment, the film-forming composition contains 50 to 98% by weight, preferably 65 to 90% by weight, more preferably 75 to 85% by weight of an organic solvent, based on the weight of the composition.

[0066] The film-forming composition according to the present invention can be introduced into a nail polish, as disclosed below.

[0067] Nail polish The nail polish according to the present invention a polyester resin, a film-forming cellulose polymer, and an organic solvent as defined above or prepared by the method disclosed above according to the present invention, and a compound selected from a plasticizer, a second resin, a rheology agent, a coloring material, an additive, and mixtures thereof, and comprises.

[0068] The contents of the film-forming cellulose polymer, the organic solvent, and the polyester resin according to the present invention are as defined above with respect to the film-forming composition.

[0069] The plasticizer can, in particular, make it possible to adjust the hardness of the formed film in order to obtain the desired physicochemical properties of the film. Examples of plasticizers are acetyl tributyl citrate, acetyl triethyl citrate, tributyl citrate, triethyl citrate, dibutyl phthalate, triphenyl phosphate, triacetin, trimethylpentanyl diisobutyrate, triethylhexanoin, sucrose benzoate, dibutyl adipate, diethyl phthalate, diisobutyl adipate, diisopropyl adipate, and di(propylene glycol) dibenzoate.

[0070] According to a particular embodiment, the plasticizer occupies 2 to 12% by weight, specifically 4 to 10% by weight, more specifically 5 to 8% by weight, based on the weight of the nail polish.

[0071] The second resin can, in particular, make it possible to improve the gloss and adhesion of the abrasive to the nail polish. The second resin is different from the polyester resin according to the present invention. Examples of the second resin are tosylamide / formaldehyde resins (Ketjenflex® MH or Ketjenflex® MS-80 sold by Akzo Nobel, or Sulfonex® M-80 sold by Estron), tosylamide / epoxy resins (Lustrabrite® S or Lustrabrite® S-70 or Nagellite® 3050 sold by Telechemische, or Polytex® E-100 or Polytex® NX-55 sold by Estron), adipic acid / neopentyl glycol / trimellitic anhydride copolymer (Uniplex® 670-P sold by Unitex), phthalic anhydride / glycerin / glycidyl decanoate copolymer, phthalic anhydride / trimellitic anhydride / glycol copolymer (Polynex® sold by Estron), glycerin / phthalic acid copolymer, styrene / acrylate / acrylonitrile copolymer, polyacrylate, acrylate copolymer, acrylate styrene copolymer, sucrose acetate isobutyrate (SAIB), polyvinyl butyral, and rosin resin (also called "rosin") obtained by distillation of rosin.

[0072] According to a particular embodiment, the second resin occupies from 0.1 to 15% by weight, specifically from 0.5 to 12% by weight, more specifically from 1 to 10% by weight, even more specifically from 1 to 7% by weight, based on the weight of the nail polish.

[0073] Rheology agents can, in particular, adjust the viscosity of the nail polish, keep the particles insoluble, and in particular make it possible to retain the coloring material suspended in the nail polish. Examples of rheology agents are clays, in particular hectorite or bentonite, and silica.

[0074] According to certain embodiments, the rheology agent occupies 0.1 to 3% by weight, specifically 0.2 to 2% by weight, more specifically 0.5 to 1% by weight, based on the weight of the manicure.

[0075] The coloring material can, in particular, provide color to the manicure. Examples of coloring materials are pigments, soluble dyes, nacre, flakes and metal particles.

[0076] According to certain embodiments, the coloring material occupies 0.1 to 20% by weight, specifically 0.5 to 12% by weight, more specifically 5 to 10% by weight, based on the weight of the manicure.

[0077] Additives make it possible to impart specific properties to the manicure. Thus, antioxidants that make it possible to protect the formulation, in particular the coloring material, from ultraviolet light, surfactants or even treatment agents for strengthening the nails, in particular keratin, vitamins, amino acids, and alpha-hydroxy acids can be mentioned.

[0078] According to certain embodiments, the additive occupies 0.01 to 5% by weight, specifically 0.2 to 2% by weight, more specifically 0.5 to 1% by weight, based on the weight of the manicure.

[0079] Use The polyester resin according to the invention is a bio-based resin and makes it possible to impart gloss and hardness to the manicure.

[0080] Accordingly, the present invention aims to protect the use of the polyester resin according to the invention as a binder in a manicure.

[0081] The present invention is illustrated in more detail in the non-limiting examples disclosed below.

Examples

[0082] Measurement method Molecular weight measurement SEC analysis was performed using THF as the eluent at a flow rate of 1 mL / min, a sample concentration of 10 - 15 mg / mL -1 at 40 °C on an Alliance® e2695 (Waters) chromatograph equipped with an Optilab® T-rEX refractometer (Wyatt Technology) and a set of HR1, HR2 and HR4 columns (Styragel). Finally, a molecular weight calibration curve was applied using monodisperse polystyrene standards.

[0083] Measurement of monomer conversion Monomer conversion was measured by determining the level of residual monomer in the final polymer. The latter was measured using a 430-GC chromatograph (Varian) equipped with a split / splitless injection port (50:1 ratio), a flame ionization detector, and a ZB-5ms column (Zebron). The oven was heated from 50 °C to 250 °C at a heating rate of 10 °C / min. Prior to injection, the polymer and internal standard (octanol) were silylated with N,O-bis(trimethylsilyl)trifluoroacetamide in the presence of 1% trimethylsilyl chloride.

[0084] The incorporation of the monomer was measured by 1H NMR. Spectra were recorded at ambient temperature on a Bruker Avance I 300 MHz spectrometer in CDCl3 or DMSO. All spectra were obtained by accumulating 16 scans.

[0085] Measurement of glass transition temperature (Tg) The thermal properties of the resin were measured by differential scanning calorimetry on a DSC Q20 device (TA instrument). Samples were first cooled to -90 °C for 10 minutes. Then, the first heating was carried out to 115 °C at a rate of 10 °C / min and the samples were left at this temperature for 5 minutes. Then, cooling was carried out to -90 °C at the same rate and the same second heating as the first heating was applied. Tg was measured during the second heating.

[0086] Measurement of acid value The acid value was measured by an assay according to standard ISO 2114:2000, using a potassium hydroxide solution in methanol of 0.5 mol.L -1 and using phenolphthalein as the color indicator. The sample was dissolved in a dimethyl sulfoxide / dichloromethane mixture and the solution was titrated until a persistent color change was obtained.

[0087] Gloss measurement A coating with a thickness of 100 μm was applied to a contrast card and oven-dried at 50 °C for 15 - 30 minutes. Then, the gloss was measured at 60° using a micro-TRI glossmeter (BYK-Gardner) according to ISO standard 2813:2014.

[0088] Hardness measurement A coating with a thickness of 100 μm was applied to a glass plate and dried at ambient temperature for 24 hours. Then, the hardness was measured using a Persoz pendulum (Brandt) according to ISO standard 1522:2006.

[0089] Adhesion measurement A coating with a thickness of 100 μm was applied to a glass plate and dried at ambient temperature for 24 hours. Then, the adhesion was measured using a cross-cut test according to ISO standard 2409:2013. In this test, the coating was cut into 25 squares using a cutter (Byk-Gardner). Then, a standard tape was applied to the coating and then removed. The cut surface was inspected to verify the proportion of the peeled coating. Then, a score of 0 - 5 was given to the adhesion of the coating, where 0 represents perfect adhesion with no peeled parts, and 5 represents the case where the entire coating has peeled off.

[0090] Drying time measurement A coating with a thickness of 100 μm was applied to a contrast card and dried at ambient temperature. The drying time was measured using a Rheolaser COATING (Formulaction). The dry-to-touch drying was selected as the characteristic drying time for easy identification on the curve.

[0091] Example 1: Preparation of the polyester resin according to the present invention Isosorbide (20.09 g, 137.5 mmol), sebacic acid (11.12 g, 55 mmol), and citric acid (15.86 g, 82.6 mmol) were introduced into a 100 mL reactor placed under an inert atmosphere. Subsequently, the reactor was heated to 120 °C using a heating mantle and stirred by mechanically stirring at 200 rpm. After the medium melted (at about 80 °C), 5 - 6 deoxygenation cycles (nitrogen - vacuum) were performed. Then, the temperature was gradually raised to 200 °C. The reaction was monitored by the acid value (AV). After reaching the target acid value (AV = 110 mg KOH / g), the temperature was lowered to 130 °C. 1,2 - Propanediol (8.30 g, 109.1 mmol) and succinic acid (19.40 g, 164.3 mmol) were added to the reactor. Then, the temperature was raised to 190 °C and the reaction was monitored by the acid value until an acid value of 50 - 100 mg KOH / g was reached. Then, the temperature was lowered to 120 °C and the resin was diluted with 30 wt% of a mixture of butyl acetate and ethyl acetate (23 g, 50 / 50 weight basis).

[0092] Example 2: Preparation of the polyester resin according to the present invention Isosorbide (18.27 g, 125 mmol), sebacic acid (15.17 g, 75 mmol), 2,5-furandicarboxylic acid (FDCA) (3.90 g, 25 mmol) and citric acid (14.41 g, 75 mmol) were introduced into a 100 mL reactor. Then, the reactor was heated to 120 °C using a heating mantle. After the medium was almost melted (about 110 °C), 5 - 6 deoxygenation cycles (nitrogen - vacuum) were performed. Then, the temperature was gradually raised to 200 °C. The reaction was monitored by acid value. After reaching the target acid value (AV = 210 mg KOH / g), the temperature was lowered to 140 °C. 1,2 - Propanediol (9.50 g, 124.9 mmol) and succinic acid (8.84 g, 74.9 mmol) were added to the reactor. Then, the temperature was raised to 200 °C and the reaction was monitored by acid value until an acid value of 50 - 100 mg KOH / g was reached. Then, the temperature was lowered to 120 °C and the resin was diluted with 30 wt% of a mixture of butyl acetate and ethyl acetate (24 g, 50 / 50 weight basis).

[0093] Example 3: Preparation of the polyester resin according to the present invention Isosorbide (18.27 g, 125 mmol), sebacic acid (15.17 g, 75 mmol) and citric acid (14.41 g, 75 mmol) were introduced into a 100 mL reactor. Then, the reactor was heated to 120 °C using a heating mantle. After the medium was almost melted (about 80 - 90 °C), 5 - 6 deoxygenation cycles (nitrogen - vacuum) were performed. Then, the temperature was gradually raised to 200 °C. The reaction was monitored by acid value. After reaching the target acid value (AV = 160 mg KOH / g), the temperature was lowered to 140 °C. 1,2 - Propanediol (9.50 g, 124.9 mmol) and succinic acid (11.80 g, 99.9 mmol) were added to the reactor. Then, the temperature was raised to 190 °C and the reaction was monitored by acid value until an acid value of 50 - 100 mg KOH / g was reached. Then, the temperature was lowered to 120 °C and the resin was diluted with 30 wt% of a mixture of butyl acetate and ethyl acetate (23 g, 50 / 50 weight basis).

[0094] Example 4: Preparation of the polyester resin according to the present invention Isosorbide (24.13 g, 165.1 mmol) and succinic acid (25.98 g, 220 mmol) were introduced into a 100 mL reactor. Then, the reactor was heated to 120 °C using a heating mantle. After the medium was almost melted (about 90 °C), 5 - 6 deoxygenation cycles (nitrogen - vacuum) were performed. Then, the temperature was gradually raised to 200 °C. The reaction was monitored by acid value. After reaching the target acid value (AV = 140 mg KOH / g), the temperature was lowered to 140 °C. 1,2 - Propanediol (8.38 g, 110.1 mmol) and sebacic acid (11.12 g, 55 mmol) were added to the reactor. Then, the temperature was raised to 190 °C, and the reaction was monitored by acid value until an acid value of 50 - 100 mg KOH / g was reached. Then, the temperature was lowered to 120 °C, and the resin was diluted with 30 wt% of a mixture of butyl acetate and ethyl acetate (21 g, 50 / 50 weight basis).

[0095] Comparative Example 1: Preparation of a polyester resin not according to the present invention Isosorbide (30.90 g, 211.4 mmol), sebacic acid (11.41 g, 56.4 mmol), 2,5 - furandicarboxylic acid (FCDA) (3.67 g, 23.5 mmol), citric acid (16.25 g, 84.6 mmol) and 1,2 - propanediol (7.21 g, 94.8 mmol) were introduced into a 100 mL reactor. Then, the reactor was heated to 120 °C using a heating mantle. After the medium was almost melted (about 110 °C), 5 - 6 deoxygenation cycles (nitrogen - vacuum) were performed. Then, the temperature was gradually raised to 200 °C. The reaction was monitored by acid value. After reaching the target acid value (AV = 50 - 100 mg KOH / g), the temperature was lowered to 120 °C, and the resin was diluted with 30 wt% butyl acetate (23 g). However, the resin was not soluble in the solvent and precipitated at ambient temperature. This was due to poor incorporation of isosorbide (about 70 - 75%) and 2,5 - furandicarboxylic acid.

[0096] Example 5: Preparation of the polyester resin according to the present invention The resins obtained in Examples 1 to 4 were characterized by their molecular weights Mn and Mw, their acid values, and their Tg according to the measurement methods disclosed above. The resin according to the present invention is compared with other resins. Resins CEx 1 to CEx 4 are petroleum-based resins sold under the names of reference Coverpol 1311 (Maeder), Coverpol 1312 (Maeder), TSER (Polytex E 75 by Estron), and TSFR (Lustralite 44.444 by DIC), respectively. Resin CEx 5 is a bio-based resin sold under the name of Natipol1303 (Maeder). The results are shown in the following table.

[0097]

Table 1

[0098] The resin according to the present invention has a molecular weight Mn of 1200 to 2000 g / mol, -1 a molecular weight Mw of 2500 to 6000, an acid value of 50 to 100 mg KOH / g, and a Tg of -15 to 10°C.

[0099] Example 6: Film-forming composition The resin of Example 5 was introduced into a film-forming composition containing 7% resin, 14% nitrocellulose, and 79% ethyl acetate / butyl acetate mixture (50 / 50 by volume). The percentages are weight percentages based on the weight of the composition.

[0100] The hardness, adhesiveness, and gloss of the formed film were measured by the measurement methods disclosed above.

[0101]

Table 2

[0102] The composition containing the resin according to the present invention exhibits hardness, adhesiveness, and gloss equivalent to those of the comparative formulation. The drying times of the compositions of Examples 1 and 2 according to the present invention are shorter than those of the formulation containing the CEx 5 bio-based resin.

[0103] Industrial applications This technical solution can be specifically applied to the formulation of bio-based nail polish.

[0104] This disclosure is not limited to the examples of the polyester resin and the film-forming composition disclosed above, which are shown by way of example only, and encompasses all modifications that can be conceived by those skilled in the art in the context of the required protection.

Claims

1. A diol containing isosorbide and a branched C ３ -C ６ a mixture with a diol, and A mixture of polyacids containing succinic acid and sebacic acid, and obtained by polymerization of a polyester resin, wherein the branched C3-C6 diol occupies 15 to 30% in terms of moles of incorporated monomers.

2. Said branch C ３ -C ６ The polyester resin according to claim 1, wherein the diol is selected from 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, and mixtures thereof.

3. The polyester resin according to claim 1 or 2, characterized in that the mixture of polyacids further comprises one or more additional polyacids selected from adipic acid, azelaic acid, citric acid, terephthalic acid, 2,5-furandicarboxylic acid, fumaric acid, itaconic acid, muconic acid, and mixtures thereof.

4. The polyester resin according to any one of claims 1 to 3, characterized in that the mixture of polyacids occupies 40 to 65% in terms of moles of incorporated monomers in the polyester resin.

5. The polyester resin according to any one of claims 1 to 4, characterized in that the mixture of diols occupies 35 to 60% in terms of moles of incorporated monomers in the polyester resin.

6. The polyester resin according to any one of claims 1 to 5, characterized in that the polyester resin has an acid value of 50 to 100 mg KOH / g.

7. A method for preparing a polyester resin, comprising the following steps, namely, i) reacting isosorbide with a polyacid selected from succinic acid or sebacic acid, and ii) reacting the mixture obtained in step i) with a diol having a branched C ３ -C ６ and a polyacid selected from succinic acid or sebacic acid; comprising the polyacid used in step i) is different from the polyacid used in step ii), a method, wherein the branched C3-C6 diol occupies 15 to 30% in terms of moles of incorporated monomers.

8. A film-forming composition comprising a polyester resin defined in any one of claims 1 to 6 or prepared by the method according to claim 7, a film-forming cellulose polymer, and an organic solvent.

9. A polyester resin defined in any one of claims 1 to 6 or prepared by the method according to claim 7, a film-forming cellulose polymer, and an organic solvent, a compound selected from plasticizers, second resins, rheology agents, coloring materials, additives, and mixtures thereof, a nail polish.

10. Use of a polyester resin defined in any one of claims 1 to 6 or prepared by the method according to claim 7 as a binder in a nail polish.

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