Functionalized polymers

Abstract

The present invention relates to functionalized polymers, methods for making functionalized polymers, and uses of functionalized polymers, particularly in the field of personal care.

Description

[Technical Field]

[0001] Technical field to which the invention belongs This invention relates to functionalized polymers, methods for producing functionalized polymers, and uses of functionalized polymers, particularly the use of functionalized polymers in the field of personal care.

[0002] Conventional technology U.S. Patent Application Publication No. 2016250137 discloses a personal care composition comprising an oil-in-water emulsion, at least one C12-C22 side-chain crystalline polymer (the side-chain crystalline polymer having a crystalline melting point of 35-70°C); and at least one active compound that interacts with the skin (the active compound is incorporated into the crystalline matrix of the side-chain crystalline polymer, and the active ingredient is released from the crystalline matrix at body temperature), but without a sunscreen active substance.

[0003] The object of the present invention is to provide a functionalized polymer that has extremely excellent properties for personal care applications.

[0004] Description of the Invention Surprisingly, the polymer described in claim 1 was found to have extremely excellent properties for personal care applications.

[0005] Therefore, the present invention provides a special polymer characterized by having a polydispersity index (PDI) greater than 4.5.

[0006] The present invention further provides a method for producing polymers, as well as personal care formulations containing specific polymers.

[0007] An advantage of the present invention is that the polymer results in a more concentrated formulation.

[0008] A further advantage of the present invention is that the polymer offers excellent compatibility with organic UV filters.

[0009] Another advantage of the present invention is that the polymer provides an improved, dry skin feel.

[0010] A further advantage of the present invention is that these polymers produce a protective film against unpleasant odors.

[0011] The polymers of the present invention, the methods of the present invention, the preparations obtained using them, and their uses are described herein by example, but the present invention is not intended to be limited to these exemplary embodiments. Where a range, general formula, or classification of compounds is described below herein, these shall encompass not only the corresponding range or group of compounds explicitly mentioned, but also all subranges and subgroups of compounds obtained by removing individual values ​​(ranges) or compounds. Where references to literature are cited in the context of this specification, their contents shall constitute a complete part of the disclosure of the present invention.

[0012] The term "natural number" as used in this invention does not include 0 (zero).

[0013] Unless otherwise specified, all percentages (%) are expressed as weight percentages.

[0014] Unless otherwise specified, all ppm values ​​are expressed in ppm by weight.

[0015] In the context of this invention, viscosity values ​​described herein should be understood to mean dynamic viscosity, which can be determined using methods well known to those skilled in the art, unless otherwise specified. The measurements described herein below were taken at a pressure of 101325 Pa and a temperature of 23°C, unless otherwise specified.

[0016] General formula (I) [ka] [In the formula, R 1= independently selected from the group consisting of alkyl and alkenyl groups, both of which may be branched or linear, unsubstituted or substituted, and have 6 to 30 carbon atoms, preferably 10 to 26 carbon atoms, more preferably 12 to 24 carbon atoms, R 2 = independently selected from the group consisting of H and methyl, preferably H] and contains monomer units of The polymer of general formula (I) is a polymer that constitutes at least 90% by weight, preferably 95% by weight of the total weight of the polymer, It is claimed that the polymer has a polydispersity index PDI of 4.5 to 20, preferably 4.6 to 15, more preferably 4.8 to 13.

[0017] The polymer according to the present invention is a copolymer including homopolymers and / or random copolymers, graft copolymers and block copolymers, preferably a homopolymer.

[0018] Preferably, the polymer according to the present invention consists of monomer units of general formula (I).

[0019] All R 1 At least 90% by weight may of course be a mixture, and at least 90% by weight of all R 1 Preferably contains a mixture of 0% to 5% cetyl, 40% to 55% stearyl, 1% to 15% arachidyl, 35% to 45% behenyl and 0% to 5% lignoceryl, where the weight percentage is based on the total of all R 1 present in the polymer.

[0020] Alternatively, at least 90% by weight of all R 1 Preferably contains a mixture of 0% to 3% myristyl, 40% to 50% cetyl, 40% to 50% stearyl and 0% to 1% arachidyl, where the weight percentage is based on the total of all R 1is based on the total.

[0021] All R 1 At least 90% by weight of which is preferably selected from the group of linear alkyls and alkenyls and is preferably an alkyl group having 12 to 22 carbon atoms, where stearyl and behenyl are particularly preferred.

[0022] Preferably, the polymer according to the invention is characterized in that the polymer has a melting point in the range of 31°C to 75°C, preferably 35°C to 72°C, more preferably 40°C to 69°C.

[0023] Preferably, the polymer according to the invention is characterized in that the polymer has a number average molecular weight M in the range of 3,000 to 300,000, preferably 4,000 to 200,000, more preferably 5,000 to 100,000 g / mol. n

[0024] Preferably, the polymer according to the invention is characterized in that the polymer has a weight average molecular weight M in the range of 13,500 to 6,000,000, preferably 18,000 to 3,000,000, more preferably 24,000 to 1,300,000 g / mol. w

[0025] Preferably, the polymer according to the invention R 1 = are independently selected from the group consisting of stearyl and / or behenyl R 2 = H

[0026] The polymers of the present invention can be obtained in various ways. The polymers of the present invention are preferably obtained by the method of the present invention described below in this specification.

[0027] Therefore A) General formula (II) [Chemical formula] [In the formula, R 1A =Selected independently from the group consisting of alkyl groups and alkenyl groups, both of which may be branched or linear, unsubstituted or substituted, and preferred hydrocarbons are alkyl groups having 6 to 30 carbon atoms, preferably 10 to 26, more preferably 12 to 24 carbon atoms. R 2A = A step of preparing 1 part by weight of a monomer selected independently from the group consisting of H and methyl, preferably H. B) A step of adding at least one initiator to polymerize the monomer and carrying out radical polymerization. C) A further step of adding 1 to 15 parts by weight, preferably 2 to 10 parts by weight, more preferably 3 to 8 parts by weight, of the monomer of general formula (II). D) A step of adding at least one initiator to polymerize a monomer and optionally carrying out radical polymerization. E) A step to remove excess monomers, and optionally F) Purification of the obtained polymer A method for producing a polymer, preferably the polymer of the present invention, is claimed.

[0028] R 1A Preferably, these are alkyl groups that are independently selected from the group consisting of unsubstituted alkyl and alkenyl groups, and more preferably have 6 to 30 carbon atoms, preferably 10 to 26, and more preferably 12 to 24 carbon atoms.

[0029] R 1A More preferably, these are selected independently from the group consisting of linear alkyls and alkenyls, and are preferably alkyl groups having 12 to 22 carbon atoms, with stearyls and behenyls being particularly preferred.

[0030] The method according to the present invention is a method for producing a polymer having a polydispersity index (PDI) greater than 4.5.

[0031] The initiator added in steps B) and D) of the present invention may be a solid, a liquid, or a solvent-soluble initiator.

[0032] The same or different initiators may be added in steps B) and D) according to the present invention.

[0033] A mixture of initiators may be added in step B) and / or D) according to the present invention without limiting the scope of the present invention.

[0034] The initiators added in steps B) and D) according to the present invention are preferably 2,2'-azobis(2-methylpropionitrile), 2,2'-azoddi(2-methylbutyronitrile), 1,1'-azoddi(hexahydrobenzonitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2-cyclobutylpropionitrile), 2,2'-azobis(2-cyclobutylpropio Nitriles), 2,2'-Azo-bis(2,4-dimethylvaleronitrile), 1,1'-Azo-bis(1-cycloheptanenitrile), 2,2'-Azo-bis(methylheptylnitrile), 2,2'-Azo-bis(2-cyclohexylpropionitrile), azo-bis-isobutylamidine 2HCl, phenyl-azo-triphenylmethane, 4-hydroxyphenyl-azo-triphenylmethane, peroxides and peroxy compounds, e.g., benzoyl peroxide, tert-butylperoxypivalate, tert-amylperoxy Pivalate, acetyl peroxide, propionyl peroxide, 2-isopropionyl peroxide, butyryl peroxide, diisobutyryl peroxide, dilauroyl peroxide, didecanoyl peroxide, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, tert-butyl peroxydiethyl acetate, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, 2-methoxybenzoyl peroxide, cu Milperoxyneoheptanoate, tert-amylperoxyneodecanoate, tert-butylperoxyneodecanoate, tert-butylperoxyneoheptanoate, tert-amylperoxyacetate, 4-benzylidenebutyrylperoxide, methylphthaloylperoxide, 1,1-di(tert-amylperoxy)cyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, hydroperoxide, e.g., isopropylcumylhydroperoxide, 1,1,3,3-Tetramethylbutylhydroperoxide, Cumylhydroperoxide, tert-butylhydroperoxide, tert-amylhydroperoxide, carbonates, e.g., diethylperoxydicarbonate, tert-butylperoxyisopropylcarbonate, tert-butylperoxy2-ethylhexylcarbonate, di-sec-butylperoxydicarbonate, diisopropylperoxydicarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate, di(2-ethylhexyl)peroxy Selected from the group consisting of sidic carbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, tert-amyl peroxy 2-ethylhexyl carbonate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy 2-ethylhexyl carbonate, ethyl tert-butyl peroxalate; benzyl (tert-butyl peroxy) oxalate; tert-butyl-N-(3-tolyl peroxy) carbamate and persodium compounds, such as potassium persulfate and mixtures thereof, Here, 2,2'-azo-bis(2-methylpropionitrile), 2,2'-azodi(2-methylbutyronitrile), dilauroyl peroxide, cumylperoxyneodecanoate, and tert-amylperoxy-2-ethylhexanoate are particularly preferred.

[0035] In the method according to the present invention, step B) and / or step D) preferably involves the addition of at least one initiator in an amount of 50 to 100,000 ppm, preferably 500 to 50,000 ppm, and more preferably 2,000 to 25,000 ppm, for each step B) and / or D), where ppm is based on the total weight of all monomers supplied in step A) (when the initiator is added in step B) and / or step C) (when the initiator is added in step D).

[0036] In the method according to the present invention, step B) and / or D), preferably B) only, is characterized in that at least one initiator for polymerization of monomers is added at least twice, and radical polymerization is carried out after each addition of the initiator.

[0037] Steps B) and / or D) in the method according to the present invention are carried out neat or in a solvent, preferably neat. The amount of solvent may vary from 1% to 95% by weight, preferably from 2% to 50% by weight, and more preferably from 3% to 40% by weight, where the weight percentage is based on the total weight of all monomers supplied in step A).

[0038] Possible solvents include, but are not limited to, the following: alcohols, e.g., methanol, ethanol, isopropanol, butanol, hexanol, tert-butanol, isoamyl alcohol; glycols, hexylene glycol, propylene glycol, butyl glycol, butyl diglycol, glycerin; ketones, e.g., ethyl methyl ketone, methyl butyl ketone; acetone; esters, e.g., methyl acetate, ethyl acetate, isopropyl acetate, propyl acetate, butyl acetate, hexyl acetate, isooctyl acetate, methoxy Propyl acetate, acids, e.g., formic acid, acetic acid, propionic acid, ethers, e.g., diethyl ether, dibutyl ether, tert-butyl methyl ether, petroleum ether, tetrahydrofuran, dioxane, polyethers, carbonates, e.g., ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, nitriles, e.g., benzonitrile, acetonitrile, toluene, xylene, ionic liquids, water, organic oils, e.g., TEGOSOFT® type and mixtures thereof.

[0039] In step A) and / or C), preferably A) and C), the method according to the present invention may add at least one chain transfer agent in an amount such that the weight ratio of the initiator added in step B) and / or D) to the chain transfer agent added in step A) (when the initiator is added in step B)) and / or C) (when the initiator is added in step D)) is in the range of 1:5 to 1:0.01, preferably 1:1 to 1:0.02, more preferably 1:0.5 to 1:0.05.

[0040] In the method according to the present invention, the chain transfer agent added preferably in step A) and / or C) is tetrachloromethane, bromotrichloromethane, isooctyl 3-mercaptopropionate, 4-methylbenzenethiol, tert-nonyl mercaptan, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 4,4'-thiobisbenzenethiol, trimethylolpropanetris(3-mercaptopropionate) At least one of the following is selected: (t) 1,8-dimercapto-3,6-dioxaoctane, n-dodecanethiol, ethyl mercaptan, mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptohexanol, mercaptooctanol, propanethol, dithiothreitol, cysteine, homocysteine, glutathione, tert-dodecanethiol, thioglycolic acid, dimercaptosuccinic acid, 2,3-dimercapto-1-propanesulfonic acid, acetylcysteine, and thiophenol.

[0041] In the alternative method according to the present invention, the chain transfer agent is not present during the process.

[0042] Steps B) and D) in the method according to the present invention are preferably carried out at a temperature of 10°C to 250°C, preferably 20°C to 200°C, and more preferably 60°C to 180°C.

[0043] Steps B) and D) in the method according to the present invention are preferably carried out at a pressure of 0.5 to 20 bar, more preferably 1 to 5 bar, and even more preferably at atmospheric pressure.

[0044] Steps B) and D) in the method according to the present invention are preferably carried out at a pH of 3 to 10, more preferably 4 to 9, and even more preferably 5 to 8.

[0045] Steps B) and D) in the method according to the present invention can preferably be carried out not only in sunlight but also in the absence of light, and are preferably carried out in the absence of light.

[0046] Step E) in the method according to the present invention serves the purpose of removing excess monomers.

[0047] If step E) of the method according to the present invention is a follow-up step, it is a preferred method according to the present invention. Therefore, it is preferable that step E) in the method according to the present invention includes adding a further initiator to remove excess monomer after the completion of step D). The further initiator is preferably applied at a concentration of 0.01% to 5% by weight, preferably 0.1% to 2.5% by weight, and more preferably 0.2% to 2% by weight, where the weight percentage is based on the total weight of all monomers supplied in steps A) and C). The addition of the further initiator in step E) of the method according to the present invention is preferably repeated up to four times, preferably twice, and more preferably once. The initiator added in step E) of the present invention is selected from the same initiators that can be used in steps B) and D) of the present invention, with the same level of priority. The reaction conditions in step E) of the present invention are also selected from the same conditions that can be applied in steps B) and D) of the present invention, with the same level of priority.

[0048] A further purification step F) of the method according to the present invention may be selected from extraction with water and / or organic solvents, distillation with or without vacuum, and / or recrystallization from water and / or organic solvents.

[0049] Step F) of the method according to the present invention preferably comprises steam distillation. Here, some water is added to the reaction mixture to remove excess monomer, undesirable by-products, decomposed initiator and / or solvent from the reaction. The amount of water added may vary from 0.1% to 20% by weight, preferably 0.5% to 10% by weight, and more preferably 1% to 5% by weight, where the weight percentage is based on the total weight of all monomers provided in steps A) and C).

[0050] It is preferable that step E), more preferably step E) and step F), are included in the method according to the present invention.

[0051] In the preferred method according to the present invention, the monomer of general formula (II) accounts for at least 90% by weight, preferably 95% by weight, of all polymerizable monomers present throughout the entire process.

[0052] A further subject of the present invention is the polymer obtained by the method of the present invention. The polymer obtained by this method is preferably characterized by having a polydispersity index PDI greater than 4.5.

[0053] A further subject of the present invention is a personal care formulation containing at least one polymer of the present invention or at least one polymer obtained by the method of the present invention.

[0054] Furthermore, the formulation according to the present invention is Skin softener, emulsifier, Thickeners / viscosity modifiers / stabilizers, UV light protection filter, Antioxidants, Hydrotrope (or polyol), Solids and fillers, Film-forming agent, Pearlescent luster additive, Deodorant and antiperspirant active ingredients, Insect repellent, Self-tanning products, Preservatives, conditioner, fragrance, dye, Odor absorber, Cosmetic active ingredients, Care additives, Degreasing agent, solid particles, solvent It may include at least one additional component selected from the group, Fragrances, solid particles, and / or UV light protection filters, particularly organic filters, are preferably included.

[0055] Preferably, the solid particles included are characterized by having an average particle size d50 of 0.1 to 1000 μm.

[0056] The average particle size d50 is preferably measured by light scattering in a laser beam using a Malvern Mastersizer 2000. This measurement is performed using a dry measurement method. 20-40 g of powder is supplied each time using a Scirocco dry powder feeder. The particle flow is controlled by operating a vibrating tray at 70% of the supply rate. The dispersion air pressure is adjusted to 3 bar. Each measurement is accompanied by a background measurement (single measurement at 10 seconds / 10,000). The sample measurement time is 5 seconds (single measurement at 5,000). The refractive index and blue light value are fixed at 1.52. The evaluation is performed using Mie theory.

[0057] Substances that can be used as exemplary representatives of the individual groups contained in the formulations according to the present invention are known to those skilled in the art and can be found, for example, in the German Patent Application Publication No. 102008001788 of a German patent application. This application is incorporated herein by reference and thereby forms part of this disclosure.

[0058] For further optional ingredients and the amounts of these ingredients used, relevant handbooks known to those skilled in the art are explicitly referenced, e.g., K. Schrader, “Grundlagen und Rezepturen der Kosmetika [Fundamentals and Formulations of Cosmetics]”, 2nd edition, pp. 329-341, Huethig Buch Verlag Heidelberg.

[0059] The amount of each additive is determined according to its intended use.

[0060] Typical guideline formulations for each application are known from the prior art and are shown, for example, in the brochures of the manufacturers of the respective base materials and active ingredients. These existing formulations can generally be adopted without modification. However, where necessary, desirable modifications can be made through simple experiments aimed at adapting and optimizing without complexity.

[0061] The use of at least one polymer of the present invention or at least one polymer obtained by the method of the present invention for forming a film on a surface, particularly skin and / or hair, is also claimed.

[0062] The use of at least one polymer of the present invention or at least one polymer obtained by the method of the present invention for retaining fragrance on a surface, particularly on the skin and / or hair, is also claimed.

[0063] The use of at least one polymer of the present invention or at least one polymer obtained by the method of the present invention for imparting a dry skin feel to formulations, particularly emulsions, is also claimed.

[0064] The use of at least one polymer of the present invention or at least one polymer obtained by the method of the present invention for dispersing a solid pigment is also claimed. The solid pigment is preferably included in the formulation according to the present invention.

[0065] Two or more polymers according to the present invention may be used together.

[0066] The following examples illustrate the present invention, and there is no intention to limit the scope of application of the present invention, which is clear from the entirety of this specification and claims, to the embodiments described in the examples. [Brief explanation of the drawing]

[0067] [Figure 1] This figure shows a grayscale image analyzing the transparency of an oil gel. [Figure 2] This figure shows the bubble-corrected image of Figure 1 used for quantification.

[0068] Examples: Measurement of molecular weight by gel permeation chromatography (GPC): GPC measurements were performed under the following conditions to determine polydisperse PDI, which is the quotient of weight-average molecular weight Mw and number-average molecular weight Mn: Samples were prepared by creating a 10 mg / mL solution using tetrahydrofuran as a diluent. The sample preparation was placed in a 54°C oven for 10 minutes, followed by 60 minutes in a list-action shaker to aid dissolution. Visual inspection revealed that the samples appeared to be completely dissolved in the diluent. The prepared samples were analyzed using two 300 × 7.5 mm polypore columns (Agilent Technologies), a Waters 2695 chromatography system, tetrahydrofuran mobile phase, and refractive index detection. The samples were filtered through a 0.45 μm nylon filter before injection into a liquid chromatograph.

[0069] The calibration standards used were Agilent Technologies' EasiVial narrow polystyrene (PS) standards. Narrow polystyrene standards in the range of 2,520,000 to 162 Daltons were used for calibration. This system uses a PSS SECcurity 1260 RI detector. The molecular weight average was determined using a PS calibration curve. Figure recording and various molecular weight measurements were performed using Win GPC Unichrom 8.1 software.

[0070] Melting point measurement by DSC: This method describes a general procedure for determining the melting temperature of a polymer by differential scanning calorimetry (DSC). This method is based on ASTM E7941 and ASTM D 34182. The DSC is calibrated according to ASTM E 9672.

[0071] Chemicals: Behenyl acrylate (abcr) Stearyl acrylate (abcr) 2-Mercaptoethanol (Aldrich) Isopropyl alcohol (Aldrich) tert-butylperoxy-3,5,5-trimethylhexanoate (Akzo Nobel) tert-amylperoxy-2-ethylhexanoate (Akzo Nobel)

[0072] Example 1: 4 g of isopropanol and 16 g of stearyl acrylate were added to a four-necked flask equipped with a KPG blade stirrer, internal thermometer, two dropping funnels, reflux condenser, and an extension for two additional necks. Oxygen was removed from the system by nitrogen purging for approximately 20 minutes, and the mixture was heated to 80°C and added while stirring. 0.27 g of tert-amylperoxy-2-ethylhexanoate, dissolved in 0.75 g of isopropanol, was added, and the mixture was stirred for a further 30 minutes. Subsequently, 64 g of stearyl acrylate and 1.1 g of tert-amylperoxy-2-ethylhexanoate, dissolved in 3 g of isopropanol, were added within 60 minutes, and the mixture was stirred at 80°C for a further 3 hours. The temperature was raised to 125°C, and the residual solvent was removed by distillation. Finally, 0.4 g of tert-butylperoxy-3,5,5-trimethylhexanoate was added within 15 minutes, and the mixture was stirred at 125°C for 60 minutes. This procedure was repeated once.

[0073] Mn=11000g / mol, Mw=76000g / mol, PDI=6.9 Tm = 49℃.

[0074] Example 2: 122 g of stearyl acrylate and 0.2 g of 2-mercaptoethanol were added to a four-necked flask equipped with a KPG blade stirrer, internal thermometer, two dropping funnels, reflux condenser, and an extension for two additional necks. The mixture was purged with nitrogen for approximately 20 minutes to remove oxygen from the system, heated to 100°C, and then added while stirring. 0.29 g of tert-amylperoxy-2-ethylhexanoate was added within 5 minutes, and the mixture was stirred at 125°C for a further 60 minutes. Subsequently, an additional 1.8 g of tert-amylperoxy-2-ethylhexanoate was added within 25 minutes, and the mixture was stirred for 5 minutes. Next, 487 g of stearyl acrylate, 0.8 g of 2-mercaptoethanol, and 8.6 g of tert-amylperoxy-2-ethylhexanoate were added within 90 minutes, and the mixture was stirred at 125°C for a further 30 minutes. Finally, 3 g of tert-butylperoxy-3,5,5-trimethylhexanoate was added within 15 minutes, and the mixture was stirred at 125°C for 60 minutes. This procedure was repeated twice.

[0075] Mn=9900g / mol, Mw=98000g / mol, PDI=9.9 Tm = 47.3℃.

[0076] Example 3: 143 g of behenyl acrylate and 0.2 g of 2-mercaptoethanol were added to a four-necked flask equipped with a KPG blade stirrer, internal thermometer, two dropping funnels, reflux condenser, and an extension for two additional necks. Oxygen was removed from the system by nitrogen purging for approximately 20 minutes, and the mixture was heated to 100°C and then added while stirring. 0.29 g of tert-amylperoxy-2-ethylhexanoate was added within 5 minutes, and the mixture was stirred at 125°C for a further 60 minutes. Subsequently, an additional 1.8 g of tert-amylperoxy-2-ethylhexanoate was added within 25 minutes, and the mixture was stirred for 5 minutes. Next, 487 g of stearyl acrylate, 0.8 g of 2-mercaptoethanol, and 8.6 g of tert-amylperoxy-2-ethylhexanoate were added within 90 minutes, and the mixture was stirred at 125°C for a further 30 minutes. Finally, 3 g of tert-butylperoxy-3,5,5-trimethylhexanoate was added within 15 minutes, and the mixture was stirred at 125°C for 60 minutes. This procedure was repeated twice.

[0077] Mn=9500g / mol, Mw=89000g / mol, PDI=9.4 Tm = 64℃.

[0078] Comparative example: 20 g of isopropanol was added to a four-necked flask equipped with a KPG blade stirrer, internal thermometer, two dropping funnels, reflux condenser, and an extension for two additional necks. Oxygen was removed from the system by nitrogen purging for approximately 20 minutes, and the mixture was heated to 80°C, then added while stirring. Within 90 minutes, 1.03 g of tert-amylperoxy-2-ethylhexanoate dissolved in 4.1 g of isopropanol, 60 g of stearyl acrylate, and 0.1 g of 2-mercaptoethanol were added, and the mixture was stirred for a further 3 hours. The temperature was raised to 125°C, and the residual solvent was removed by distillation under a vacuum of 50 mbar. Subsequently, 0.3 g of tert-butylperoxy-3,5,5-trimethylhexanoate was added, and the mixture was stirred at 125°C for 60 minutes. This procedure was repeated.

[0079] Mn=4200g / mol, Mw=11000g / mol, PDI=2.6 Tm = 49℃.

[0080] Application Example 1: Higher concentration of the formulation The functionalized polymer according to the present invention was found to have advantages in terms of skin feel. To illustrate this effect, oil-in-water (O / W) sun care emulsions were prepared in 200g scales according to the table below. Formulations containing functionalized polymers other than those according to the present invention were prepared for reference. [Table 1]

[0081] One month after manufacturing, viscosity was measured at 10 rpm using a Brookfield RV-DV I apparatus with a 93 spindle. All formulations showed similar viscosities in the range of 24–32 Pa·s and exhibited a paste-like, soft texture.

[0082] The skin feel of the emulsions was evaluated using a sensory panel test. Thirteen trained panelists, without knowing the composition of each formulation, applied 20 μL of each formulation to approximately 10 cm of their palmar forearm. 2The formulation was applied to a specified test area. The formulation was distributed within the test area by using a finger to move in a circular motion until it was completely absorbed (or up to 60 times). Skin tactile parameters were evaluated while the formulation was being distributed to the skin.

[0083] In functional cosmetics, such as those for anti-aging purposes, the "richness" of the formulation is desirable, and a rich skin feel is associated with consumers' anti-aging activities. Richness is indicated not only by the viscosity of the formulation but also by the behavior of the formulation when applied to the skin and by the mechanical breakdown of the emulsion structure, which is best represented by skin feel parameters such as "spreadability" and "waxiness." The lower the spreadability and the higher the waxiness, the higher the perceived richness of the formulation.

[0084] Panelists were instructed to rate three formulations on a scale of 0 (very difficult to spread) to 10 (very easy to spread) for spreadability and on a scale of 0 (not waxy) to 10 (very waxy) for waxiness. The scores obtained from all panelists were averaged, and the average evaluation was subjected to factor analysis (one-factor principal component analysis, Varimax rotation). The relative "concentration" of the three formulations was extracted by normalizing the data on a scale from -1 to +1. In this way, a value of -1 corresponds to the lowest concentration (relatively light; high spreadability, low waxiness), and a value of +1 corresponds to the highest concentration (relatively low spreadability, high waxiness). [Table 2]

[0085] Surprisingly, the organic polymers according to the present invention (Examples 1 and 2) exhibited significantly greater "concentration" than organic polymers not according to the present invention (Comparative Example), making them ideally suited, particularly for anti-aging applications.

[0086] Application Example 2: Compatibility with Organic UV Filters (Oil Gel Viscosity and Transparency) The functionalized polymer according to the present invention was found to have advantages in terms of compatibility with UV filters. To illustrate this effect, oil gel systems with organic UV filters as shown in the table below were prepared in 50 g scales. An oil gel containing a functionalized polymer other than that according to the present invention was prepared for reference. [Table 3]

[0087] The oil gel was prepared by mixing the ingredients and heating to 60-70°C until a clear solution was obtained. After cooling with gentle stirring, when the initial turbidity was observed, it was homogenized using an UltraTurrax at 20,500 rpm for 30 seconds. This mixture was immediately filled into glass bottles and left to crystallize without further stirring.

[0088] The high compatibility between the oil / UV filter and the organic polymer is demonstrated by the high viscosity and high transparency of the resulting oil gel. A common assumption is that in such cases, the organic UV filter and softener are most effectively and uniformly embedded within the three-dimensional network formed by the organic polymer.

[0089] The viscosity of the oil gel was measured one week after preparation using a Brookfield RV-DV I instrument, spindle 96, 100 rpm.

[0090] Photographs of the oil gel in a glass bottle were taken under standardized conditions with a light source positioned behind the bottle.

[0091] The transparency of the oil gel was analyzed using image processing with ImageJ 1.51k by examining a grayscale image (see Figure 1). The higher the transparency of the oil gel, the more background light passes through, resulting in a brighter image. Therefore, the image was converted to a black and white image by thresholding, specifically by removing all pixels with grayscale values ​​between 0 and 209 (0 = converted to white) and converting all grayscale values ​​from 210 to 255 to black (=255). If bubbles, indicated by white circles, were present in the resulting binary image, these were manually corrected by filling them with surrounding (black) pixel information (compare Figure 2). In this way, the transparency of the oil gel can be quantified by the amount of black pixels, or more precisely, by the percentage of area covered by black pixels.

[0092] The results are summarized in the table below. [Table 4]

[0093] Surprisingly, it was found that the higher the polydispersity index of the organic polymer, the higher the viscosity and transparency of the resulting oil gel. This means that a higher PDI leads to better interaction in composite mixtures with cosmetic softeners (mixtures) and in various combinations of organic UV filters. This experiment demonstrates that the organic polymer according to the present invention is most compatible with organic UV filters, and is therefore ideally suited, in particular, for sun care applications.

[0094] Application Example 3: Compatibility with Organic UV Filters (In vitro UV APF / SPF of Sun Care formulations) The functionalized polymer according to the present invention was found to have advantages in terms of compatibility with UV filters. To illustrate this effect, oil-in-water (O / W) sun care emulsions were prepared in 200g scales as shown in the table below. For reference, formulations containing functionalized polymers other than those according to the present invention were also prepared. [Table 5]

[0095] 1 mg / cm³ 2 The emulsion was spread onto a roughened polymethyl methacrylate (PMMA) plate (7.0 × 3.5 cm, 2 μm roughness, Schoenberg GmbH & Co. KG) and dried at 30°C for 30 minutes. SPF testing was performed using a Labsphere UV-2000S ultraviolet transmission analyzer. UVAPF / SPF is the ratio between the in vitro UVA protection factor and the in vitro SPF, obtained experimentally. This value is an indicator of broadband UV protection, and since 2006, the European Commission has recommended that all sunscreen products have a UVAPF / SPF ≥ 0.33 (in vivo) for sufficient width. The absolute value of in vitro UVAPF / SPF does not necessarily correspond to the absolute value in vivo, but in vitro testing is usually used for screening purposes and to compare different film-forming agents before selecting candidates for time-consuming and costly in vivo SPF testing. Therefore, in vitro UVAPF / SPF should be optimized (as close to 0.33 as possible) and should not be adversely affected by film-forming agents.

[0096] The results of the in vitro SPF test are summarized in the table below. [Table 6]

[0097] Surprisingly, organic polymers with a higher polydispersity index were also found to yield higher UVAPF / SPF values ​​in in vitro SPF tests.

[0098] This experiment demonstrates that the organic polymer according to the present invention is most suitable for use in sun care formulations, as indicated by optimized UVAPF / SPF values.

[0099] Application Example 4: Improvement of sensation and dry skin feel The functionalized polymer according to the present invention was found to have advantages in terms of skin feel. To illustrate this effect, oil-in-water (O / W) sun care emulsions were prepared in 200g scales according to the table below. Formulations containing functionalized polymers other than those according to the present invention were prepared for reference. [Table 7]

[0100] The skin feel of the emulsions was evaluated using a sensory panel test. Fourteen trained panelists, without knowing the composition of each formulation, tested 20 μL of each formulation on approximately 10 cm of their palmar forearm. 2 The formulation was applied to a specified test area. The formulation was distributed within the test area by using a finger to move in a circular motion until completely absorbed (or up to 60 times). Skin feel parameters were evaluated while the formulation was being distributed to the skin. In particular, the "dry feel" of the formulation was evaluated by the oiliness, absorbency, and slipperiness of the skin feel parameters. A dry feel is desirable in functional formulations such as sun care emulsions, which tend to leave an oily and slippery residue when they contain organic UV filters. Therefore, in such systems, it is preferable that there is little oiliness or slipperiness remaining and that the formulation is absorbed quickly.

[0101] The panelists were instructed to rate the three sun care formulations from Example 1 on a scale from 0 (not significant attribute) to 10 (very significant attribute) based on their skin feel parameters.

[0102] The scores obtained from all panelists were averaged, the average evaluation was subjected to factor analysis (one-factor principal component analysis, varimax rotation), and the data was normalized on a scale from -1 to +1 to extract the relative "dryness" of the three formulations. In this way, a value of -1 corresponds to the lowest dryness (relatively oily, slippery, and less absorbent), and a value of +1 corresponds to the highest dryness (less oily, less slippery, and more absorbent). [Table 8]

[0103] Surprisingly, the organic polymer according to the present invention exhibits significantly better drying properties than organic polymers not according to the present invention, making it ideally suited for sun care applications in particular.

[0104] Application Example 5: Protective film against cigarette smoke The functionalized polymer according to the present invention has been found to have advantages in protecting the skin from the malodorous odor caused by cigarette smoke. To illustrate this effect, oil-in-water (O / W) body care emulsions were prepared in 200g scales as shown in the table below. Formulations containing functionalized polymers other than those according to the present invention were prepared for reference. [Table 9]

[0105] The protective effect of the emulsion was evaluated by a sensory panel test. Nine volunteers were recruited for the study. Each panelist applied one formulation to the palmar side of their forearm (Volunteer 1: Formulations 1 and 2, Volunteer 2: Formulations 3 and 1, Volunteer 3: Formulations 2 and 3, etc.), thus testing each formulation on six forearms. The forearms were prepared by washing with SLES solution (sodium laureth sulfate in 12% water) for 30 seconds and drying for 5 minutes. 200 mg of each formulation was applied to approximately 100 cm² of the palmar side of the forearm (entire arm). 2The sample was applied to the specified test area. A deep fryer (Tristar FR-6935) was filled with 2 liters of frying oil (Palmin) and adjusted to 170°C. 750g of French fries (McCain's 1-2-3-Frites Original, equilibrated at room temperature) were fried for 10 minutes. During the frying process, each volunteer held both palmar forearms at a specified distance of approximately 50 cm for 30 seconds, one at a time, in the steam evaporating from the fryer. Starting 5 minutes after the frying process, the volunteers were treated, followed by odor evaluation by three trained professional olfactors. Olfactory evaluation was performed 5 minutes after steam treatment, and the degree of rancid / fatty odor in the palmar forearms was rated on a scale from 0 (undetectable) to 5 (very noticeable). Perceptible differences between the right and left forearms were evaluated by the difference of at least one value on the rating scale. The average evaluation score determined by three experts for each formulation is summarized in the table below: [Table 10]

[0106] Surprisingly, the organic polymer according to the present invention exhibits the most remarkable protective properties against the adhesion of unpleasant odors to the skin, making it ideally suited for facial and body care applications where protection is particularly required.

[0107] Combination example The following formulation examples list "organic polymers" without providing further details. According to this embodiment, all of the following examples are formulated with organic polymer (Example 1), organic polymer (Example 2), and organic polymer (Example 3); thus, each formulation is produced in three different embodiments.

[0108] [Table 11]

[0109] [Table 12]

[0110] Table 13

[0111] Table 14

[0112] Table 15

[0113] Table 16

[0114] Table 17

[0115] Table 18

[0116] Table 19

[0117] Table 20

[0118] Table 21

[0119] Table 22

[0120] Table 23

[0121] Table 24

[0122] Table 25

[0123] Table 26

[0124] Table 27

[0125] Table 28

[0126] Table 29

[0127] Table 30

[0128] Table 31

[0129] Table 32

[0130] Table 33

[0131] Table 34

[0132] Table 35

[0133] Table 36

[0134] Table 37

[0135] Table 38

[0136] Table 39

[0137] Table 40

[0138] Table 41

[0139] Table 42

[0140] Table 43

[0141] Table 44

[0142] Table 45

[0143] Table 46

[0144] Table 47

[0145] Table 48

[0146] Table 49

[0147] Table 50

[0148] Table 51

[0149] Table 52

[0150] Table 53

[0151] Table 54

[0152] Table 55

[0153] Table 56

[0154] Table 57

[0155] Table 58

[0156] Table 59

[0157] Table 60

[0158] Table 61

[0159] Table 62

[0160] Table 63

[0161] Table 64

[0162] Table 65

[0163] Table 66

[0164] Table 67

[0165] Table 68

[0166] Table 69

[0167] Table 70

[0168] Table 71

[0169] Table 72

[0170] Table 73

[0171] Table 74

[0172] Table 75

[0173] Table 76

[0174] Table 77

[0175] Table 78

Claims

1. General formula (I) 【Chemistry 1】 [In the formula, R １ = Selected from the group consisting of alkyl groups having 10 to 30 carbon atoms independently of each other, and may be branched or linear, unsubstituted or substituted. R ２ It contains monomer units of =H, A polymer in which monomer units of general formula (I) constitute at least 90% by weight of the total weight of the polymer, 4. A polymer characterized by having a polydispersity index PDI of 8 to 20.

2. All R １ The polymer according to claim 1, wherein at least 90% by weight of the polymer is a linear alkyl group having 10 to 30 carbon atoms.

3. The polymer according to claim 1 or 2, characterized by having a melting point in the range of 31°C to 75°C.

4. Number average molecular weight M in the range of 3,000 to 300,000 g / mol ｎ The polymer according to claim 1 or 2, characterized by having the following properties.

5. Weight-average molecular weight M in the range of 13,500 to 6,000,000 g / mol ｗ The polymer according to claim 1 or 2, characterized by having the following properties.

6. A) General formula (II) 【Chemistry 2】 [In the formula, R １Ａ = Selected from the group consisting of alkyl groups having 10 to 30 carbon atoms independently of each other, and may be branched or linear, unsubstituted or substituted. R ２Ａ A step to prepare 1 part by weight of monomer [=H], B) A step of adding at least one initiator to polymerize a monomer and carrying out radical polymerization. C) A step of further adding 1 to 15 parts by weight of the monomer of general formula (II), D) A step of adding at least one initiator to polymerize a monomer and carrying out radical polymerization, optionally, E) A step to remove excess monomers, and optionally F) Purification of the obtained polymer including, A method for producing the polymer according to claim 1.

7. The initiators are 2,2'-azobis(2-methylpropionitrile), 2,2'-azoddi(2-methylbutyronitrile), 1,1'-azoddi(hexahydrobenzonitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2-cyclobutylpropionitrile), 1,1'-azobis(1-cycloheptanenitrile), 2,2'-azobis(methylheptylnitrile), 2,2' The method according to claim 6, characterized in that a selection is made from the group consisting of - azo-bis(2-cyclohexylpropionitrile), azo-bis-isobutylamidine 2HCl, phenyl-azo-triphenylmethane, 4-hydroxyphenyl-azo-triphenylmethane, peroxides and peroxy compounds, hydroperoxides, carbonates, ethyl tert-butylperoxalate; benzyl(tert-butylperoxy)oxalate; tert-butyl-N-(3-tolylperoxy)carbamate and perate compounds, and mixtures thereof.

8. The method according to claim 6 or 7, characterized in that in step B) and / or D), at least one initiator for polymerization of monomers is added at least twice, and radical polymerization is carried out after each addition of the initiator.

9. The method according to claim 6 or 7, characterized in that at least one chain transfer agent is added in step A) and / or C).

10. A personal care formulation containing the polymer described in claim 1.

11. Use of the polymer according to claim 1 or the formulation according to claim 10 for forming a film on the surface.

12. Use of the polymer according to claim 1 or the formulation according to claim 10 to give the formulation a dry skin feel.

13. Use of the polymer according to claim 1 or the formulation according to claim 10 for retaining fragrance on the surface.

14. Use of the polymer according to claim 1 or the formulation according to claim 10 for dispersing a solid pigment.

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