Silicone-(meth)acrylate copolymers, and methods for their preparation and use in personal care compositions.

Abstract

Provided are silicone-(meth)acrylate copolymers and methods for preparing and using the copolymers. The copolymers are soluble in ethanol under ambient conditions. The copolymers or their homogeneous ethanol solutions can be used as film formers in personal care compositions such as foundations.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefit of U.S. Provisional Patent Application No. 63 / 106506, filed on 28 October 2020 under Section 119(e) of the U.S. Patent Act. U.S. Provisional Patent Application No. 63 / 106506 is incorporated herein by reference.

[0002] The present invention relates to silicone-(meth)acrylate copolymers (copolymers), and methods for preparing and using these copolymers. More specifically, copolymers can be prepared by free radical polymerization. Copolymers can be added to personal care compositions suitable for application to the skin. Copolymers may be useful as film-forming agents in personal care compositions.

[0003] Introduction Film-forming agents are important cosmetic raw material components and are more often widely used in personal care compositions, such as leave-on products applied to the skin, including skincare, sunscreens, and color cosmetics. DOWSIL® FA40xx series (where xx = 01-04 and 12), supplied by Dow Silicones Corporation (Midland, Michigan, USA), are used as film-forming agents in such products. However, the cosmetics industry continues to require sustainable and / or naturally derived ingredients that possess one or more of the following properties: water resistance, sebum resistance, abrasion resistance, and desirable sensory properties. [Overview of the Initiative]

[0004] Silicone-(meth)acrylate copolymers, and methods for their preparation and use in personal care compositions are provided. The copolymer can be obtained by copolymerizing a mixture of monomers comprising i) an acrylate monomer, ii) a (meth)acrylate monomer, and iii) an organosiloxane-(meth)acrylate macromonomer. The copolymer can be used in personal care compositions.

Mode for Carrying Out the Invention

[0005] The copolymer can be obtained by a method comprising copolymerizing the above mixture of monomers. More specifically, the mixture of monomers is Based on the total weight of the monomers, 15% to 45% by weight of i) a compound of the formula

[0006]

Chemical formula

[0007]

Chemical formula

[0008] <e000098>i) acrylate monomer The starting material i) is of the formula:

[0009]

Chemical formula

[41] ] 2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms. R 2Suitable alkyl groups include methyl, ethyl, propyl (including isopropyl and n-propyl), and butyl (including n-butyl, t-butyl, isobutyl, and sec-butyl). Alternatively, R 2 This can be an alkyl group with two or three carbon atoms.

[0010] Examples of suitable i) acrylate monomers are known and commercially available in the art. For example, i) acrylate monomers may be selected from the group consisting of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and combinations of two or more of these. Alternatively, i) acrylate monomers may include ethyl acrylate. Acrylate monomers are commercially available from various suppliers such as Sigma-Aldrich, Inc. (St. Louis, Missouri, USA) (Sigma) and The Dow Chemical Company (Midland, Michigan, USA) (Dow).

[0011] i) The acrylate monomer is used in amounts of 15% to 45% by weight, based on the total weight of the monomers, i.e., the total weight of all monomers used in the monomer mixture. Alternatively, i) the acrylate monomer may be used in amounts of at least 15%, alternatively at least 18%, alternatively at least 20%, alternatively at least 25%, and alternatively at least 27% of the monomer mixture. At the same time, i) the acrylate monomer may be used in amounts of up to 40%, alternatively up to 33%, alternatively up to 32%, alternatively up to 30%, and alternatively up to 27% of the monomer mixture.

[0012] ii) (Meth)acrylate monomer Starting material ii) is,

[0013] [ka] It is a (meth)acrylate monomer, in the formula R 1 R is selected from the group consisting of hydrogen and methyl. 3 R is a monovalent hydrocarbon group with 8 to 13 carbon atoms. Alternatively, 1 It can be methyl. 3 Suitable monovalent hydrocarbon groups include alkyl groups that may be linear, branched, cyclic, or combinations thereof. 3 Examples of alkyl groups include octyl, nonyl, decyl, undecyl, dodecyl (lauryl), tridecyl, and / or their branched isomers. Alternatively, alkyl groups may include cyclic moieties such as isobornyl groups. Alternatively, R 3 The (meth)acrylate monomer may be an alkyl group with 10 to 12 carbon atoms or a cycloalkyl group with 10 to 12 carbon atoms. Alternatively, ii) the (meth)acrylate monomer may be selected from the group consisting of tridecyl acrylate, tridecyl methacrylate, lauryl acrylate, lauryl methacrylate, isobornyl acrylate, isobornyl methacrylate, and combinations thereof. Alternatively, ii) the (meth)acrylate monomer may be selected from the group consisting of lauryl acrylate, lauryl methacrylate, isobornyl acrylate, isobornyl methacrylate, and combinations thereof. Alternatively, ii) the (meth)acrylate monomer may be selected from the group consisting of lauryl methacrylate, isobornyl methacrylate, and combinations thereof. The above (meth)acrylate monomers are commercially available from various suppliers such as Fujifilm WAKO Chemicals, Sigma, and Dow.

[0014] ii) (meth)acrylate monomers are used in amounts of 15% to 40% by weight, based on the total weight of monomers. Alternatively, ii) acrylate monomers may be used in amounts of at least 15%, alternatively at least 18%, alternatively at least 20%, and alternatively at least 28%, based on the total weight of monomers. At the same time, (meth)acrylate monomers may be used in amounts of up to 40%, alternatively up to 35%, alternatively up to 30%, and alternatively up to 28%, based on the same criteria.

[0015] iii) Organosiloxane-(meth)acrylate macromonomer Starting materials iii) are given by formula XSi(R 4 )3 organosiloxane-(meth)acrylate macromonomer (macromonomer), where X is a (meth)acryloxyalkyl group and each R 4 -OSi(R 5 ) Selected from 3 and R, however R 4 At least two of them are -OSi(R 5 )3, and each R is a monovalent hydrocarbon group, and each R 5 R, -DSi(R 6 )3, and -[OSiR2] m Selected from OSiR3, each R 6 R, -DSi(R 7 )3, and -[OSiR2] m Selected from OSiR3, each R 7 R, -DSi(R 8 )3, and -[OSiR2] m Selected from OSiR3, each R 8 R, and -[OSiR2] m Selected from OSiR3, each D is selected from oxygen and a divalent hydrocarbon group, with 0 ≤ m ≤ 100. Examples of (meth)acryloxyalkyl groups of X include acryloxymethyl, 3-acryloxypropyl, methacrylateoxymethyl, and 3-methacrylateoxypropyl. Alternatively, X may be 3-methacrylateoxypropyl. Each R is independently R 2R can be an alkyl group as described above and illustrated above. Alternatively, each R can be methyl. Each D is independently selected from an oxygen atom or a divalent hydrocarbon group. The divalent hydrocarbon group of D can be an alkylene group with 2 to 10 carbon atoms. Examples include linear alkylene groups such as ethylene, propylene, butylene, and hexylene, and branched alkylene groups such as methylmethylene, methylethylene, 1-methylphenyl, and 1,4-dimethylbutylene. Alternatively, the divalent hydrocarbon group can be ethylene. Alternatively, iii) the macromonomer may have 4 to 16 silicon atoms per molecule.

[0016] Alternatively, iii) macromonomers are given by formula:

[0017] [ka] It may have, in the formula, R 1 , R 4 , R 5 , R 6 , and D are as described above. Alternatively, macromonomers are, The following can be selected: 3-(5-((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxane-5-yl)propyl methacrylate, 3-(1,5-bis(2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)ethyl)-3-(((2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)ethyl)dimethylsilyl)oxy)-1,1,5,5-tetramethyltrisiloxane-3-yl)propyl methacrylate, and combinations thereof. Suitable macromonomers are known in the art and can be prepared by known methods, such as those disclosed in Japanese Patent Application Publication No. 11001530A by Furukawa et al., U.S. Patent No. 6,420,504 by Yoshitake et al., and PCT Publication No. 2020 / 142388 by Liu et al.

[0018] iii) Macromonomers are used in amounts of 20% to 60% by weight, based on the total weight of monomers. Alternatively, iii) the amount of macromonomers may be at least 20%, alternatively at least 25%, alternatively at least 30%, and alternatively at least 35%, based on the total weight of monomers. At the same time, iii) the amount of macromonomers may be up to 60%, alternatively up to 50%, alternatively up to 45%, alternatively up to 42%, alternatively up to 40%, and alternatively up to 35%, based on the same criteria.

[0019] iv) Itaconic acid ester monomer Starting material iv) is an itaconic acid ester monomer that can be optionally added to a mixture of monomers used to prepare the copolymer. iv) The itaconic acid ester monomer is of formula

[0020] [ka] It has, in the formula, each R9 R is an independently selected alkyl group of 1 to 8 carbon atoms. Alkyl groups are exemplified by methyl, ethyl, propyl (including isopropyl and n-propyl), butyl (including n-butyl, t-butyl, isobutyl, and sec-butyl), and linear pentyl, hexyl, heptyl, and octyl groups (as well as branched alkyl groups of 5 to 8 carbon atoms), and linear, branched, and / or cyclic alkyl groups such as cyclopentyl, cyclohexyl, and / or cyclooctyl. Alternatively, each R 9 This can be methyl, ethyl, propyl, or butyl. Alternatively, each R 9 Itaconate may be methyl or butyl. Suitable examples of itaconic acid ester monomers include dimethylitaconate and dibutylitaconate. Itaconic acid ester monomers are known in the art and are commercially available, for example, from Sigma.

[0021] iv) Itaconic acid monomers may be used in amounts up to 20% by weight, and alternatively >0–20% by weight, based on the total weight of the monomers. If present, iv) itaconic acid monomers may be present in amounts up to 0%, alternatively at least 5%, alternatively at least 7%, and alternatively at least 10%, based on the total weight of the monomers. Simultaneously, iv) itaconic acid monomers may be present in amounts up to 20%, alternatively up to 17%, and alternatively up to 15%, based on the same criteria.

[0022] v) Small methacrylate monomers Starting material v) is an additional methacrylate monomer different from i) and ii) above, which can be optionally added to the mixture of monomers used to prepare the copolymer above. v) The additional methacrylate monomer is of formula

[0023] [ka] It has, in the formula, R 2The above is true. Suitable v) Examples of additional methacrylate monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, or a combination of two or more of these. v) Small methacrylate monomers are commercially available from various suppliers such as Sigma and Dow.

[0024] If present, v) additional methacrylate monomers may be present in amounts >0%, alternatively at least 1%, alternatively at least 2%, alternatively at least 3%, alternatively at least 4%, and alternatively at least 5%, based on the total weight of monomers. At the same time, v) additional methacrylate monomers may be present in amounts up to 10%, alternatively up to 9%, alternatively up to 8%, alternatively up to 7%, and alternatively up to 6%, based on the same criteria. If v) additional methacrylate monomers are present, i) the amount of acrylate monomers may be, for example, 15% to <30%, toward the lower end of the above range.

[0025] Method for preparing copolymers Copolymers can be prepared by a method comprising: 1) copolymerizing a mixture of monomers in the presence of a radical initiator and optionally a solvent to form a reaction mixture; and 2) quenching the reaction mixture. This method may further optionally include 3) purifying the copolymer and / or 4) dissolving the copolymer in a simple alcohol such as ethanol.

[0026] In step 1), the monomer mixture may be copolymerized by mixing and heating to form a reaction mixture. Copolymerization may be carried out by radical polymerization, and a radical initiator may be combined with the monomer mixture in step 1).

[0027] Radical initiators may include, for example, azobis compounds, organic peroxides, and combinations thereof. Radical initiators may include azobis compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methyl)butyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), and two or more combinations thereof. Alternatively, radical initiators may include organic peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxypivalate, cyclohexanone peroxide, isopropylcumyl hydroperoxide, di-tert-butyl peroxide, diisopropyl percarbonate, tert-butyl perbenzoate, tert-butyl peroctanoate, bis(3,5,5-trimethyl)hexanoyl peroxide, tert-butyl peroxypivalate, and combinations of two or more of these. Radical initiators are known in the art and commercially available. For example, organic peroxides such as peroxydicarbonate, diacyl peroxide, dialkyl peroxide, and peroxyether are available from Arkema Inc. (King of Prussia, Pennsylvania, USA) under the trade name LUPEROX®. The amount of radical initiator may be 0.1 to 5 parts by weight per 100 parts by weight of the monomer mixture used in step 1).

[0028] Copolymerization may be solution polymerization, and a solvent may be added in step 1). One or more of the starting materials (e.g., radical initiators and / or iii) macromonomers) may be supplied in the solvent. For example, radical initiators may be supplied in mineral spirits. The solvent for solution polymerization may be added to or instead of the solvent for supplying the starting materials. The solvent in step 1) is of formula R 2 It may contain simple alcohols of OH, where R 2As stated above, simple alcohols are exemplified by ethanol, n-propanol, isopropanol, n-butanol, t-butanol, or combinations thereof. Simple alcohols may include ethanol. Alternatively, simple alcohols may be selected from ethanol, isopropanol, or combinations thereof.

[0029] Step 1) can be carried out in batch, semi-batch, or continuous mode over a period of 3 to 20 hours at a temperature of, for example, >30°C, or alternatively, 50°C to 150°C. In semi-batch mode, a fraction of the reagents may be supplied to the reactor (e.g., a radical initiator, a mixture of monomers, and / or a solvent to which the mixture of radical initiators and monomers is supplied), and the remaining reagents are metered and supplied to the reactor over a target supply time, typically 1 to 20 hours. In continuous mode, the reagents are metered and supplied to the reactor continuously, and the reaction mixture containing the copolymer is continuously removed from the reactor. The starting materials used in Step 1) may not contain acids.

[0030] In step 2), quenching can be carried out by quenching the reaction mixture to 25±5°C.

[0031] This method may optionally further include step 3) purification of the copolymer. Purification may be carried out by any convenient means. For example, if one or more unreacted monomers are present and / or if a solvent is used, these may be optionally removed by reduced pressure, for example, by heating. For example, the copolymer may be purified using stripping and / or distillation. Alternatively, unreacted monomers may be reduced by a chemical chase in which an additional radical initiator is added to consume the unreacted monomers and reduce their level to a sufficiently low level (e.g., <500 ppm) where the unreacted monomers do not need to be removed.

[0032] This method may optionally further include step 4) dilution of the copolymer with a simple alcohol containing ethanol. While we do not wish to be bound by theory, a homogeneous solution of the copolymer in ethanol may be desirable for ease of blending the copolymer into a personal care composition and / or for the stability of the resulting personal care composition. The homogeneous solution may contain 10% to 90% by weight of ethanol and 10% to 90% by weight of the copolymer (alternatively, 40% to 60% of the copolymer and the remainder being ethanol). For example, personal care compositions such as cosmetics suitable for application to the skin (e.g., foundation) may be formulated to include the copolymer described herein. While we do not wish to be bound by theory, oils (such as silicone oils) are not considered necessary for supplying the copolymer described herein. Furthermore, since a homogeneous solution of the copolymer dissolved in ethanol can be provided that is stable (without phase separation) for at least 6 months at room temperature (25±5℃), the copolymers described herein are considered to offer improved stability compared to previously proposed silicone-(meth)acrylate copolymers.

[0033] Alternatively, the method may further include a solvent exchange step 5) after step 3) or after step 4). If a different support for the copolymer is desired, the above simple alcohol may be removed and replaced with a different support. Any desired support having a solubility parameter of 14.0 to 28.0 MPa¹ / ² may be used, as the solubility parameters are described in Brandrup, J.; Immergut, EH; Grulke, EA “Polymer Handbook”, 4th edition, page VII / 675-714, John Wiley & Sons Inc, 1999. ISBN: 0-471-16628-6. Alternatively, the carrier may be a monohydric alcohol such as isopropyl alcohol, n-propanol, tert-butanol, and sec-butanol; a dihydric alcohol such as 1,3-propanediol, 1,3-butylene glycol, 1,2-butylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, dibutylene glycol, pentyl glycol, hexylene glycol, and octylene glycol; a trihydric alcohol such as trimethylolpropane and 1,2,6-hexanetriol; a polyhydric alcohol including tetrahydric or higher alcohols such as pentaerythritol and xylitol; or a sugar alcohol including sorbitol. The following may be selected from the group consisting of: ketones including acetone and methyl ethyl ketone; aliphatic esters including isopropyl myristate and isopropyl palmitate; natural oils including sunflower seed oil, caprylic / capric triglycerides, coconut oil, castor oil, argan oil, and jojoba oil; hydrocarbon oils including isododecane, isohexadecane, paraffin, isoparaffin, squalane, and squalene, and alkanes with 9 to 11 carbon atoms; siloxane or silicone oils such as decamethylcyclopentasiloxane (D5); and linear low-viscosity polydimethylsiloxane (PDMS) such as polydimethylsiloxane having a viscosity at 25°C as 1.5 cSt (mm² / sec) to 6.0 cSt (mm² / sec); glycerin; or two or more combinations thereof.

[0034] Copolymer Copolymers prepared as described herein may have number-average molecular weights (Mn) of 2–100 kg / mol, alternatively 5–50 kg / mol, and alternatively 10.1–10.9 kg / mol. Copolymers may have weight-average molecular weights (Mw) of 5–1000 kg / mol, alternatively 20–200 kg / mol, and alternatively 23.0–29.0 kg / mol. Copolymers may have polydispersity of 2–10, alternatively 2–5, and alternatively 2.25–2.89. Mn and Mw may be measured by gel permeation chromatography using tetrahydrofuran containing 1% by weight formic acid as the mobile phase to a polystyrene standard, and polydispersity may be calculated from the Mn and Mw measured as described above.

[0035] Silicone-(meth)acrylate copolymers prepared as described herein may have a copolymer backbone composed of up to 60% carbon atoms. Alternatively, if the copolymer is supplied in solution, the solution may have a carbon content of up to 84% based on the weight of the solution. The carbon content of the copolymer and its solution are preferably derived from renewable resources other than fossil fuels or natural gas. When used in personal care compositions for application to the skin, the copolymers described herein may provide the benefits of good water resistance (as indicated by the water contact angle), good sebum resistance, and / or good abrasion resistance, as described in the following examples.

[0036] Personal care composition Copolymers prepared as described herein may be added to personal care compositions. For example, the copolymers may act as film-forming agents in personal care compositions. Personal care compositions are not particularly limited, but may be leave-on products suitable for application to the skin, such as skin care products, sunscreens, and color cosmetics (e.g., foundations). Copolymers or solutions of copolymers prepared as described above may be added to personal care compositions by any convenient means, such as mixing. Personal care compositions may contain the copolymers in any amount, based on the weight of all components of the personal care composition (excluding carriers for supplying the copolymers), for example, at least 1%, alternatively at least 2%, alternatively at least 5%, alternatively at least 10%, alternatively at least 20%, and alternatively at least 30%. Simultaneously, the personal care composition may contain the copolymer in amounts of up to 99%, alternatively up to 90%, alternatively up to 80%, alternatively up to 70%, alternatively up to 50%, alternatively up to 10%, alternatively up to 8%, and alternatively up to 6%, based on the weight of all components of the personal care composition (excluding the carrier for supplying the copolymer). The exact amount of copolymer used depends on various factors, such as the type of personal care composition being formulated. Alternatively, the personal care composition may contain the copolymer in amounts of 1% to 99% by weight, alternatively 5% to 95% by weight, alternatively 1% to 10% by weight, alternatively 2% to 8% by weight, and alternatively 4% to 6% by weight, based on the weight of all components of the personal care composition (excluding the carrier for supplying the copolymer). The copolymers prepared as described above may be used as substitutes for different copolymers in personal care compositions known in the art, such as those disclosed in U.S. Patent No. 6,280,748 by Morita et al., U.S. Patent No. 7,488,492 by Furukawa et al., U.S. Patent No. 9,670,301 by Furukawa et al., U.S. Patent No. 10,047,199 by Iimura et al., U.S. Patent No. 10,172,779 by Hori et al., and U.S. Patent Application Publication No. 2020 / 0222300 by Souda et al. [Examples]

[0037] The following examples are provided to illustrate the present invention to those skilled in the art and should not be construed as limiting the scope of the invention as defined in the claims. The starting materials used in these examples are listed in Table 1.

[0038] [Table 1]

[0039] In this Reference Example 1, copolymer samples were prepared according to the following general procedure. A 300 mL straight-walled glass resin reactor was equipped with a 4-pitch stainless steel propeller, water condenser, and thermocouple, and housed in a 4-well temperature control block (PolyBLOCK, Parallel Synthesis) designed by HEL Group (www.helgroup.com). The propeller was driven by an overhead mechanical stirrer, and the thermocouple was connected to a J-KEM temperature controller, providing input to the PolyBLOCK unit to obtain the desired temperature. The flask was first filled with 50.0 g of ethanol (SDA 3-C grade, a mixture of 200 proof ethanol and isopropanol in a volume ratio of 95.24:4.76), and the temperature was raised to 78°C. An N2 blanket was applied to remove entrained air, and the stirring speed was 300 rpm, allowing for sufficient stirring (indicated by a small vortex in the center). In separate 1L glass bottles, the monomers were mixed and a homogeneous mixture was formed with the help of magnetic stirring. The selection and amount of each monomer are shown in Table 2 below. The co-supply initiator was 1.71g of Trigonox 125-C75 (tert-amyl peroxypivalate, 75% active in mineral spirits) in 43.49g of SDA 3-C ethanol.

[0040] When the reactor temperature reached 78°C, 5.0 g of the monomer mixture was added to the reactor and heat was continued. The remaining monomer mixture and co-feed initiator were then metered and fed at rates of 0.63 g / min and 0.30 g / min, respectively, over 150 minutes. Moderate reflux was observed throughout polymerization. When the supply of monomer mixture was complete, 11.84 g of SDA 3-C ethanol was added to the monomer bottle and rinsed into the reactor. The batch was held at 78°C for 15 minutes. Then, two chemical chases of 2.54 g of Trigonox 125-C75 in 8.57 g of SDA 3-C ethanol were metered and fed at a rate of 0.37 g / min over 30 minutes, with a 15-minute hold in between. The batch was then held for another 15 minutes and quenched by air cooling. 66.35 g of SDA 3-C grade ethanol was added during cooling as the final dilution. Next, the resulting copolymer solution was analyzed as follows.

[0041] Turbidity measurement The turbidity of the copolymer solution was measured by following the ASTM D7315-17 method, "Standard Test Method for Determination of Turbidity Above 1 Turbidity Unit (TU) in Static Mode." Although ASTM D7315-17 applies to turbidity in water, the same principle applies, and this method was used without modification for these copolymer solutions in various organic solvents such as ethanol. The copolymer solution was filled into a 1-ounce clear glass vial at 23°C. Care was taken to minimize disturbance of the copolymer solution to avoid air entrainment. Turbidity was measured using an HF Scientific, Inc. Micro100 turbidimeter. The turbidimeter was newly calibrated using an HF Scientific, Inc. ProCal Calibration kit (containing three standards: 1000 NTU, 10 NTU, and 0.02 NTU). Turbidity was reported in nephelometric turbidity units (NTU).

[0042] Foundation ingredients Foundation formulation samples were prepared by combining the components in the amounts shown in Table 3, as follows: The components of Phase B were mixed together using an overhead mixer at a speed of <500 rpm. The components of Phase A were mixed together using a Flacktek apparatus. Phase A was added to B. The components of Phase C were mixed together. Phase C was slowly added (dropwise) to the mixture of Phase A and B using an overhead mixer at high mixing speed (over 1200 rpm). The pH and viscosity were checked and observed the following day.

[0043] Contact angle measurement of polymer films and foundation films Contact angle data was acquired from the surface of each film using both water and sebum with a Kruss DSA100 meter. Data was acquired as quickly as possible (0 seconds) and approximately 200 seconds later for the same droplet. Two types of films were available for contact angle measurement: neat polymer films (directly cast from copolymer solution in ethanol) or foundation films (cast onto film from a foundation formulation containing copolymer; data in Table 2 are from neat copolymer films, and data in Table 4 are from foundation films). Thin films of copolymer or foundation formulation were prepared either at an automated high-throughput coating station or manually on a LENTA P121-16 black plastic chart using a 6-mil doctor blade. The films were dried in an environmentally controlled room (22°C, 50% relative humidity) for at least 72 hours. Tables 2 and 4 list the contact angle measurements from these two types of films.

[0044] Sebum resistance The sebum contact angle was measured and used to evaluate the sebum resistance of neat polymers and foundation formulations. Contact angle data was acquired from the surface of each film using both water and sebum with a Kruss DSA100 meter. Data was acquired as quickly as possible (0 seconds) and approximately 200 seconds later for the same droplet. Higher numbers are associated with higher resistance, and vice versa.

[0045] glass transition temperature A small amount of copolymer solution was transferred to an aluminum pan and dried first at ambient temperature, then dried at 60°C under house vacuum for at least 24 hours until a certain mass was obtained. The mass of the dried copolymer was typically 3–10 mg. The aluminum pan was sealed and analyzed with a TA Instruments Q1000 differential scanning calorimeter. Two heating scans were applied at a rate of 20°C / min between -90°C and 150°C. Tg was defined as the midpoint during the process change of the heat flow, and measurements from the second heating scan for each sample are reported.

[0046] [Table 2]

[0047] In the table above, NM means not measured. Comparative Examples 8, 9, and 10 each used the same selection and amount of starting materials, but used different solvents during polymerization, polymerization temperatures, feed times, and post-polymerization treatments (as summarized below). [Table 3]

[0048] Comparative Examples 1 and 2 do not contain monomers corresponding to i). Comparative Example 3 contains too low (<15%) amounts of i)EA and too high (>20%) amounts of iv)DBI. Comparative Example 4 contains too high (>40%) amounts of ii)LMA and IBOMA combination (5+42=47%). Comparative Example 5 contains too high (>40%) amounts of ii)LMA and IBOMA combination (10+44=54%). Comparative Example 6 is for comparison because SMA has too many carbon atoms. Comparative Examples 1-6 demonstrate that when the amounts of each monomer differ from those of this invention, the resulting copolymers are not sufficiently soluble in the simple alcohol (ethanol) of this application. Comparative Example 7 is a repeat of Comparative Example 3 of US2020 / 0222300 and does not contain i) acrylate monomers. * indicates that the monomer mixture of Comparative Example 7 did not react completely. It had a conversion rate of only 95%, resulting in unreacted silicone-(meth)acrylate macromonomers, the most expensive component of the copolymer.

[0049] Examples of the present invention demonstrate that when a mixture of monomers (selection and amount of each monomer) is used as described herein, the monomers react completely (high conversion rate of ≥99%). The resulting copolymers are soluble in ethanol and possess a glass transition temperature, water resistance, and / or sebum resistance suitable for personal care applications. These monomer combinations exhibited excellent reaction rates using free radical polymerization, as exemplified by solution polymerization with high conversion rates. Furthermore, polymerization can be carried out directly in ethanol, a commercially available carrier supplied from biomass. Solvent exchange to remove excess residual monomers is not required to meet the requirements of personal care applications, reducing production costs and streamlining the supply chain. Furthermore, the inventors have found that the copolymers of the present invention have the following advantages: 1. The internal performance of the foundation in the embodiment of the present invention demonstrated excellent water repellency. 2. The performance of the foundation in the embodiment of the present invention demonstrated durable sebum-repellent properties (demonstrated by a significantly higher CA sebum 250s value than the comparison).

[0050] [Table 4]

[0051] [Table 5]

[0052] The amount of each copolymer is expressed as the amount (weight %) of the added solution. The goal was to provide 5% copolymer (excluding the carrier) in the foundation formulation.

[0053] [Table 6]

[0054] Industrial applicability The silicone-(meth)acrylate copolymers described herein exhibit excellent solubility in ethanol, thus enabling direct free-radical polymerization in ethanol for copolymer preparation. While we do not wish to be bound by theory, the use of ethanol in methods for copolymer preparation is considered to reduce manufacturing costs and streamline the supply chain, as it eliminates the need for additional solvent exchange for the copolymer solution. Furthermore, given its ubiquitous presence in personal care applications, ethanol is considered a commercially important bio-based carrier that can improve the overall sustainability profile of the copolymer solution as a product.

[0055] In addition, i) (small) acrylate monomers are thought to mitigate steric hindrance and facilitate the quantitative conversion of other monomers, particularly iii) silicone-(meth)acrylate macromonomers. Copolymerization of acrylate and methacrylate is generally methacrylate-favored, which often means that methacrylate is consumed first. However, we have found that a method for producing copolymers via free radical polymerization reduces residual monomer to <500 ppm, or alternatively <100 ppm, which makes the resulting copolymer suitable for personal care applications in a method for preparing copolymers and / or homogeneous solutions thereof, without the need for extra stripping and / or solvent exchange steps.

[0056] The copolymers described herein exhibit excellent properties, including water repellency and sebum repellency, as neat films and in exemplary foundation formulations. Surprisingly, iii) the silicone-(meth)acrylate macromonomer content can be reduced to as low as 20%, or alternatively 20% to 30%, of the monomer mixture used to prepare the copolymer, while maintaining the excellent water repellency and sebum repellency of the resulting copolymer, as demonstrated by the above examples of the present invention. iii) Due to the relatively low amount of silicone-(meth)acrylate macromonomer, the formulation is less expensive compared to comparative compositions having a higher amount of silicone (meth)acrylate material. Furthermore, the formulation may contain more bio-derived monomers to improve the product's sustainability profile compared to comparative products containing a higher amount of silicone-containing material.

Claims

1. A copolymer obtained by copolymerizing a mixture of monomers, wherein the mixture of monomers is i) Based on the total weight of the monomers, 15% to 45% by weight of the formula 【Chemistry 1】 The acrylate monomer and ii) Based on the total weight of the monomers, 15% to 40% by weight of the formula 【Chemistry 2】 (Meth)acrylate monomer and iii) Based on the total weight of the monomers, 20% to 60% by weight of the formula XSi(R ４ ) ３ The formula comprises an organosiloxane-(meth)acrylate macromonomer, in which, R １ However, selected from the group consisting of hydrogen and methyl, R ２ However, it is a monovalent hydrocarbon group with 1 to 4 carbon atoms. R ３ However, it is a monovalent hydrocarbon group with 8 to 13 carbon atoms. Each X is a (meth)acryloxyalkyl group, Each R ４ is selected from -OSi(R ５ ) ３ and R, provided that at least two of the Rs[[ID=�]] ４ are -OSi(R ５ ) ３ Each R is a monovalent hydrocarbon group, and each R ５ is selected from R, -DSi(R ６ ) ３ , and -[OSiR ２ ｍ OSiR ３ Each R ６ is selected from R, -DSi(R ７ ) ３ , and -[OSiR ２ ｍ OSiR ３ Each R ７ is selected from R, -DSi(R ８ ) ３ , and -[OSiR ２ ｍ OSiR ３ Each R ８ is selected from R and -[OSiR ２ ｍ OSiR ３ Each D is selected from oxygen and a divalent hydrocarbon group, 0 ≤ m ≤ 100,​​​​ The monomer mixture is, iv) based on the total weight of the monomers, >0 to 20% by weight of the formula 【Transformation 3】 A copolymer comprising an itaconic acid ester monomer, wherein each R9 is an independently selected alkyl group of 1 to 8 carbon atoms.

2. The copolymer according to claim 1, wherein the monomer mixture comprises 5 to 20% by weight of the itaconic acid ester monomer based on the total weight of the monomers.

3. iv) The copolymer according to claim 2, wherein the itaconic acid ester monomer comprises dibutylitaconate.

4. i) In the formula for the acrylate monomer, R ２ The copolymer according to claim 1, wherein the alkyl group is a two- or three-carbon alkyl group.

5. i) The copolymer according to claim 4, wherein the acrylate monomer comprises ethyl acrylate.

6. ii) In the formula for the (meth)acrylate monomer, R １ However, it is methyl, and R ３ The copolymer according to claim 1, wherein the alkyl group is 10 to 12 carbon atoms or cycloalkyl group is 10 to 12 carbon atoms.

7. ii) The copolymer according to claim 6, wherein the (meth)acrylate monomer is selected from the group consisting of lauryl methacrylate, isobornyl methacrylate, and combinations thereof.

8. iii) The macromonomer is of formula: 【Chemistry 4】 It has, in the formula, R １ , R ４ , R ５ , R ６ The copolymer according to claim 1, wherein D is as described above.

9. iii) The macromonomer is, 3-(5-((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxane-5-yl)propyl methacrylate, 3-(1,5-bis(2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)ethyl)-3-(((2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)ethyl)dimethylsilyl)oxy)-1,1,5,5-tetramethyltrisiloxane-3-yl)propyl methacrylate, The copolymer according to claim 8, selected from the group consisting of and combinations thereof.

10. The monomer mixture is given by formula v) > 0 to 10% by weight. 【Transformation 5】 It further contains a small (meth)acrylate monomer, in the formula R ２ However, the copolymer according to claim 1 is as described above.

11. A composition comprising a copolymer according to any one of claims 1 to 10 and ethanol, wherein the copolymer is soluble in ethanol and the composition is a homogeneous solution.

12. A method for preparing the copolymer according to any one of claims 1 to 10, 1) Radical initiator and formula R ２ The mixture of monomers is copolymerized in the presence of a solvent containing a simple alcohol of OH, where R ２ However, it is a monovalent hydrocarbon group with 1 to 4 carbon atoms, and thereby forms a reaction reaction. 2) A method comprising quenching the reaction mixture.

13. The method according to claim 12, further comprising: 3) purifying the copolymer; optionally 4) dissolving the copolymer in ethanol; and / or optionally 5) performing solvent exchange, thereby dissolving the copolymer in a carrier selected from the group consisting of isopropyl alcohol, acetone, caprylic / capric triglycerides, isododecane, alkanes with 9 to 11 carbon atoms, cyclic polydiorganosiloxanes, linear polydiorganosiloxanes having a viscosity at 25°C as 1.5 cSt to 6.0 cSt, or two or more combinations thereof.

14. A method for preparing a personal care composition, comprising adding a copolymer according to any one of claims 1 to 10 to the personal care composition.

15. The method according to claim 14, wherein the composition is a foundation.

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