Aminosiloxane ester copolymers and methods for preparing and using the copolymers - Patents.com

Abstract

Aminosiloxane ester copolymers, emulsions containing the copolymers, and processes for making the copolymers and emulsions are provided. The copolymers and emulsions may be formulated into hair care compositions, such as conditioners and styling products.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 63 / 215533, filed June 28, 2021. U.S. Provisional Patent Application No. 63 / 215533 is incorporated herein by reference.

[0002] FIELD OF THEINVENTION The present invention relates to aminosiloxane ester copolymers useful in hair care applications. The present invention further relates to processes for making the copolymers, emulsions containing the copolymers, and methods of using the copolymers and emulsions. [Background technology]

[0003] Introduction Aminofunctional polyorganosiloxanes, such as amine-terminated polydiorganosiloxanes, are useful for hair care applications, such as hair conditioning applications. Amine-terminated polydiorganosiloxanes made by condensation may suffer from instability, as indicated by viscosity change after aging and / or the development of ammonia odor, which is undesirable for hair care applications. Traditionally, primary amine-terminated polyorganosiloxanes are expensive to make by equilibration, as they require expensive starting materials and catalysts and require multiple process steps to complete.

[0004] Another method of making amine-terminated polyorganosiloxanes uses allylamines or derivatives that hydrolyze to allylamines, which are used to perform hydrosilylation chemistry with SiH-terminated polymers to form amine-terminated polyorganosiloxanes, however, this method suffers from the drawback that the amine-terminated polyorganosiloxane product may contain at least trace amounts of either SiH or allylamine, either of which must be removed before the product can be used in any hair care application.

[0005] Another method of making amine-terminated polyorganosiloxanes is by ammonolysis of chloropropyl-terminated siloxanes. This expensive multi-step method can suffer from the drawback of leaving residual salts (i.e., ammonium chloride) in the amine-terminated polyorganosiloxane product that may require extensive washing to remove, which is less cost-effective and less sustainable. Also, any residual ammonium chloride may produce a foul odor, which is undesirable for hair care applications.

[0006] Acrylic functional silicone compounds and methods for preparing them are disclosed in U.S. Patent No. 4,697,026 to Lee et al. Lee discloses that acrylic functional silicon compounds can be prepared by intimately mixing an amino functional silicon compound having at least one primary or secondary amine group with an acrylic functional compound having at least two acrylate, methacrylate, acrylamide, or methacrylamide groups per molecule. When the amine compound and the acrylic compound are mixed, there is a reaction that produces the acrylic functional silicon compound. This reaction is known as Michael-type addition. Without wishing to be bound by theory, the compounds described by Lee et al. are believed to be unsuitable for use in hair care applications because the acrylate functional groups of their compounds can be skin sensitizers and irritants, making them unsuitable for hair care applications where contact with the consumer's skin and potential accidental contact with the eyes can occur. Summary of the Invention

[0007] The aminosiloxane ester copolymer has the formula:

[0008] [ka] (In the formula, Each R 1 is an independently selected monovalent hydrocarbon radical of 1 to 12 carbon atoms; Each R Eindependently selected from the group consisting of hydroxyl and amino functional groups of the formula H2N-R A - and each R is independently a divalent hydrocarbon group having 1 to 12 carbon atoms, A each R is independently selected from the group consisting of H and methyl, 2 each R is an independently selected divalent hydrocarbon group having 2 to 20 carbon atoms, D each subscript a independently has a value such that 0 < a ≦ 220, and subscript b has a value such that 1 ≦ b ≦ 100), including .

[0009] The process for preparing the copolymer comprises 1) (A) a terminal primary amino-functional polyorganosiloxane of the formula

[0010]

Chemical formula

[0011]

Chemical formula

[0012] [ka] bis-silanol-terminated polydiorganosiloxanes of the formula: 1 and subscript a is as defined above, a bis-silanol-terminated polydiorganosiloxane, and (G) formula

[0013] [ka] where subscript c is 0 or 1, and each R 8 is an independently selected monovalent hydrocarbon radical of 1 to 18 carbon atoms, and each R 9 may further comprise preparing the compound by combining starting materials comprising a cyclic siloxazane, independently selected from the group consisting of hydrogen and an alkyl group having 1 to 15 carbon atoms.

[0014] Alternatively, the process for preparing the copolymer may further comprise 1) combining starting materials including (F) the bis-silanol-terminated polydiorganosiloxane described above, (B) the bis-acryloyloxy-alkane described above, and (G) the cyclic siloxazane described above.

[0015] The emulsion comprises (I) a liquid continuous phase comprising water and (II) a discontinuous phase dispersed in the liquid continuous phase, the discontinuous phase comprising the aminosiloxane ester copolymer described above. The copolymer and / or emulsion described above are useful in hair care compositions. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The aminosiloxane ester copolymer (copolymer) has the formula:

[0017] [ka] (In the formula, each R 1 is an independently selected monovalent hydrocarbon radical of 1 to 12 carbon atoms, and each R E are independently hydroxyl and of the formula HN-R A -, each R A is a divalent hydrocarbon radical of 1 to 12 independently selected carbon atoms, and each R 2 is independently selected from the group consisting of hydrogen and methyl; D are independently a divalent hydrocarbon radical of 2 to 20 carbon atoms, each subscript a independently having a value such that 0≦a<220 and each subscript b independently having a value such that 1≦b≦100; Includes.

[0018] R 1 Suitable monovalent hydrocarbon groups for include alkyl, alkenyl, aryl, and combinations thereof (e.g., aralkyl and aralkenyl). For example, suitable alkyl groups include methyl, ethyl, propyl (including iso-propyl and n-propyl), butyl (including iso-butyl, n-butyl, sec-butyl, and tert-butyl), pentyl (including straight-chained pentyl and / or cyclopentyl) and branched alkyl groups having 5 carbon atoms, hexyl (including straight-chained hexyl and / or cyclohexyl) and branched alkyl groups having 6 carbon atoms, octyl (including straight-chained octyl and / or cyclooctyl), branched alkyl groups having 8 carbon atoms, decyl (including straight-chained decyl and / or cyclodecyl) and branched alkyl groups having 10 carbon atoms, and dodecyl (including straight-chained dodecyl and / or cyclododecyl) and branched alkyl groups having 12 carbon atoms. Alternatively, R 1 The alkyl group of R may be selected from the group consisting of methyl and ethyl, or may be methyl. 1Suitable alkenyl groups for R include vinyl, allyl and hexenyl, alternatively vinyl or hexenyl, alternatively vinyl. 1 Suitable aryl groups for R may include cyclopentadienyl, phenyl, naphthyl, and anthracenyl. 1 Suitable aralkyl groups for R include tolyl, xylyl, benzyl, 1-phenylethyl, and 2-phenylethyl. 1 The aryl group in R may be phenyl. Aralkyl groups, such as benzyl, 1-phenylethyl and 2-phenylethyl groups, and aralkenyl groups, such as styryl groups, are also included in R. 1 Alternatively, each R 1 may be selected from the group consisting of methyl and phenyl. Alternatively, each R 1 may be methyl.

[0019] Each R E are independently a hydroxyl group and a group of the formula HN-R A -amino functional groups of the formula R A is a divalent hydrocarbon group. Alternatively, each R E Alternatively, each R E is the formula H2N-R A Each R A R is an independently selected divalent hydrocarbon radical of 1 to 12 carbon atoms, alternatively 2 to 12 carbon atoms, alternatively 2 to 5 carbon atoms, alternatively 2 to 3 carbon atoms. A The divalent hydrocarbon group of R may be linear, branched, or cyclic, or a combination thereof. A Suitable divalent hydrocarbon groups for include alkylene groups, arylene groups, and combinations thereof (e.g., dialkylarylene groups). Alkylene groups are exemplified by ethylene, propylene, butylene. A The arylene group of R may be an arylene group such as phenylene. A is a dialkylarylene group, for example:

[0020] [ka] or

[0021] [ka] (wherein each subscript u is independently 1 to 6, alternatively 1 to 2). Alternatively, each R A may be an alkylene group such as ethylene, propylene or butylene, or it may be ethylene.

[0022] Each R 2 is independently selected from the group consisting of hydrogen and methyl. 2 may be hydrogen.

[0023] Each R D R is an independently selected divalent hydrocarbon radical of 2 to 20 carbon atoms, alternatively 2 to 12 carbon atoms, alternatively 3 to 12 carbon atoms, alternatively 4 to 12 carbon atoms, alternatively 4 to 10 carbon atoms. D The divalent hydrocarbon group of R may be linear, branched, cyclic, or a combination thereof. D Suitable divalent hydrocarbon groups for each R include alkylene groups, arylene groups, and combinations thereof. D may be an alkylene group such as propylene, butylene, hexylene, octylene, decylene, or dodecylene, or each R D may be butylene, hexylene, or decylene. D R may be a branched alkylene group. D The arylene group of R may be an arylene group such as phenylene. D teeth,

[0024] [ka] or

[0025] [ka] and the like, where each subscript u is independently 1 to 6, alternatively 1 to 2.

[0026] The subscript a has a value such that 0≦a<220. Alternatively, the subscript a may have a value from 2 to 200, alternatively from 16 to 84, alternatively from 16 to 44, alternatively from 44 to 84.

[0027] The subscript b has a value such that 2≦b≦100. Alternatively, the subscript b may have a value from 2 to 20, or from 2 to 10.

[0028] The copolymers described above may have a number average molecular weight (Mn) of >1,000 g / mol to 250,000 g / mol as measured by GPC according to the test method described below. Alternatively, the copolymers may have a Mn of 4,000 g / mol to 250,000 g / mol, or 4,000 g / mol to 100,000 g / mol as measured by GPC.

[0029] Alternatively, the above copolymers may have a weight average molecular weight (Mw) of from 2,000 g / mole to 400,000 g / mole. Alternatively, Mw may be from 10,000 g / mol to 390,000 g / mol, alternatively from 12,000 g / mol to 200,000 g / mol, alternatively from 15,000 g / mol to 185,000 g / mol, alternatively from 19,000 g / mol to 175,000 g / mol, alternatively from 20,000 g / mol to 100,000 g / mol, alternatively from 21,000 g / mol to 80,000 g / mol, alternatively from 22,000 g / mol to 75,000 g / mol, alternatively from 25,000 g / mol to 65,000 g / mol, alternatively from 30,000 g / mol to 60,000 g / mol, alternatively from 35,000 g / mol to 55,000 g / mol, or alternatively from 40,000 g / mol to 50,000 g / mol.

[0030] Copolymer manufacturing process The copolymers described above are 1) Formula (A)

[0031] [ka] A terminal primary amino-functional polyorganosiloxane of the formula R 1 , R A and subscript a is as defined above, Formula (B)

[0032] [ka] Bis-acryloyloxy-alkanes of the formula R D may be prepared by a process comprising combining starting materials including a bis-acryloyloxy-alkane of the formula as described above, where starting materials (A) and (B) are present in amounts such that the molar ratio of (A):(B) ranges from 2:1 to 1:1.1, alternatively from 2:1 to 1:1.05, alternatively from 2:1 to 1:1. Alternatively, the molar ratio of (A):(B) may be at least 1:1, alternatively at least 1.1:1, alternatively at least 1.3:1, while the ratio may be up to 2:1, alternatively up to 1.8:1, alternatively up to 1.5:1. The copolymers produced by this process have amino functional ends, i.e., in the formula of the copolymer above, each R E is expressed as above by the formula H2N-R A - an amino functional group.

[0033] The above process may optionally further comprise, during step 1), the step of adding additional starting materials selected from the group consisting of (C) a catalyst, (D) a solvent, (E) an acrylate polymerization inhibitor, and combinations of two or more of (C), (D), and (E).

[0034] Step 1) involves mixing the starting materials, optionally with heating. The mixing in step 1) may be carried out for 1 to 48 hours, alternatively 4 to 24 hours, alternatively 6 to 15 hours. The temperature during step 1) may be 0°C to 180°C, alternatively 20°C to 160°C, alternatively 60°C to 150°C, alternatively 80°C to 120°C. The mixing (and heating) may be carried out by any convenient means, such as charging the starting materials into a vessel such as a stirred jacketed batch reactor or a reactive distillation apparatus having a jacketed reboiler, the jacket being capable of being heated and cooled by passing steam / water or a heat transfer fluid through the jacket. Step 1) may be carried out under inert conditions, such as less than 3% oxygen, by purging the reactor with an inert gas such as nitrogen. For example, step 1) may be carried out under an atmosphere containing less than 3% oxygen when operated above 60°C. Alternatively, prior to heating in step 1), the process may optionally further include mixing the starting materials at room temperature for up to 60 minutes, alternatively between 5 and 30 minutes, alternatively between 15 and 30 minutes. Without wishing to be bound by theory, it is believed that mixing at room temperature may promote the coalescence of the starting materials into one phase and initiate the reaction of (A) the terminal primary amino-functional polyorganosiloxane with (B) the bis-acryloyloxy-alkane. Furthermore, it is believed that this additional mixing step may prevent or minimize polymerization of the acrylate groups.

[0035] The starting material (A) used in the above process has the formula

[0036] [ka] wherein R 1 , R Aand subscript a are as described above. A suitable terminal primary amino functional polyorganosiloxane is exemplified by bis-3-aminopropyl terminated polydimethylsiloxane, which is commercially available, for example, from Milliken Chemical (Spartanburg, South Carolina, USA) under the trade name SiVance. Terminal primary amino functional polyorganosiloxanes may be made by known methods, such as those disclosed in U.S. Patent Application Publication No. 2004 / 0210074 to Hupfield et al., U.S. Patent No. 11,028,229 to Suthiwangcharoen et al., U.S. Patent No. 11,028,233 to Suthiwangcharoen et al., U.S. Patent No. 7,238,768 to Hupfield, and U.S. Patent No. 8,796,198 to Henning et al.

[0037] The starting material (B) used in the above process has the formula

[0038] [ka] where R D is as described above. Examples of suitable bis-acryloyloxy-alkanes include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate; 1,6-hexanediol diacrylate [also called 1,6-bis(acryloyloxy)hexane], 1,9-bis(acryloyloxy)nonane, 1,10-decanediol diacrylate, and combinations thereof. Suitable bis-acryloyloxy-alkanes are known in the art and are commercially available from a variety of sources, including, for example, Sigma-Aldrich, Inc., St. Louis, Missouri, USA.

[0039] Starting material (C) is a catalyst that may be optionally added during the above process. Without wishing to be bound by theory, it is believed that the catalyst may facilitate the synthesis of the copolymer. If used, the catalyst is present in an amount of >0 to <90% by weight based on the combined weight of starting materials (A) and (B). The exact amount of solvent depends on the type of catalyst selected. For example, if the catalyst is an alcohol, it may also be used as a solvent as described below, and the amount of catalyst may be greater than when a different catalyst is used. For example, alcohol may be used in an amount of up to 90% based on the above, while other catalysts described herein may be used in an amount of >0 to <5% by weight based on the combined weight of starting materials (A) and (B).

[0040] The catalyst may include an alcohol, a tertiary amine, pyridine, a pyridine derivative, or another aromatic heterocycle. Suitable alcohols include methanol, ethanol, isopropanol, butanol, n-propanol, and isophor-12 (2-butyl-octanol), isophor-20 (2-octyl-1-dodecanol, and INCI: octyldodecanol). Without wishing to be bound by theory, longer chain alcohols such as isophor-12 (2-butyl-octanol), isophor-20 (2-octyl-1-dodecanol, INCI: octyldodecanol) may act as co-solvents for the copolymers produced and may be incorporated into the personal care composition. These alcohols are commercially available from Sasol, Sandton, South Africa.

[0041] Suitable tertiary amines include trimethylamine, triethylamine, tributylamine, tetramethylethylenediamine, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (1,3,4,6,7,8-hexahydro-2H- Examples of suitable pyridine derivatives include pyrimido[1,2,-a]pyrimidine (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (mTBD), N-(2-hydroxyethyl)piperazine, tetramethylguanidine (TMG), 1,2,2,6,6-pentamethylpiperidine, N-methylmorpholine (NMP), 2,2,6,6-tetramethylpiperidine (TMP), and 1-azabicyclo[2.2.2]octane. Suitable pyridine derivatives include dimethylpyridines, such as 2,6-dimethylpyridine (also known as 2,6-lutidine), and trimethylpyridine. The above-mentioned catalysts are commercially available from various sources, including Sigma Aldrich, Inc. and Fisher Scientific (Hampton, New Hampshire, USA).

[0042] Starting material (D) is a solvent that may be added optionally during the above process. Suitable solvents include polydialkylsiloxanes, alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, ethers, or combinations thereof. Polydialkylsiloxanes with suitable vapor pressures may be used as solvents, including hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, dodecamethylcyclohexasiloxane, tetradecamethylcycloheptasiloxane, and other low molecular weight polyalkylsiloxanes, such as DOWSIL™ 200 Fluid and DOWSIL™ OS FLUID, available from DSC, with a molecular weight of 0.5-1.5 cSt.

[0043] Alternatively, the starting material (D) may comprise an organic solvent. The organic solvent may be an alcohol such as methanol, ethanol, isopropanol, butanol, n-propanol, and isophor-12 (2-butyl-octanol), isophor-20 (2-octyl-1-dodecanol, and INCI: octyldodecanol; aromatic hydrocarbons such as benzene, toluene, or xylene; aliphatic hydrocarbons such as heptane, hexane, octane, or isododecane; or combinations thereof. Suitable organic solvents are commercially available from a variety of sources, including Sigma-Aldrich, Inc. (St. Louis, Missouri, USA).

[0044] A solvent is optional. If present, the amount of solvent depends on a variety of factors, including the type of solvent selected, as well as the amounts and types of other starting materials selected for use in the process. However, if used, the amount of solvent may be from 0% to 90% based on the total weight of all starting materials used in step (1). A solvent may be added, for example, to facilitate mixing and delivery of one or more starting materials. For example, a catalyst may be delivered in a solvent. All or a portion of the solvent may be optionally removed after step 1).

[0045] Starting material (E) is an acrylate polymerization inhibitor that may be optionally added during the above-described process. When present, starting material (E), the inhibitor may be used in an amount of >0 to <0.01% based on the combined weight of starting materials (A) and (B), alternatively >0 to <10,000 ppm on the same basis, alternatively 1 ppm to 2,000 ppm, alternatively 10 ppm to 500 ppm. Suitable inhibitors are commercially available and include, for example, nitrobenzene, butylated hydroxyltoluene (BHT), diphenylpicrylhydrazyl (DPPH), p-methoxyphenol, 4-methoxyphenol (MEHQ), 2,4-di-t-butylcatechol, phenothiazine, N,N-diethylhydroxylamine, salts of N-nitrosophenylhydroxylamine, (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO), and 4-hydroxy-(2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (4-hydroxyTEMPO), phenothiazine (PTZ).

[0046] Those skilled in the art will recognize that certain starting materials may have more than one function. For example, the alcohols mentioned above may function as both catalysts and solvents. Long chain alcohols such as isophor-12 (2-butyl-octanol), isophor-20 (2-octyl-1-dodecanol, and INCI: octyldodecanol) may function as both solvents and emollients when the copolymer is formulated into a personal care product.

[0047] Alternatively, the copolymer described above may be 1) (B) the bis-acryloyloxy-alkane described above, (F) formula

[0048] [ka] bis-silanol-terminated polydiorganosiloxanes of the formula: 1and subscript a is as defined above, a bis-silanol-terminated polydiorganosiloxane, and (G) formula

[0049] [ka] where subscript c is 0 or 1, and each R 8 is an independently selected monovalent hydrocarbon radical of 1 to 18 carbon atoms, and each R 9 are independently selected from the group consisting of hydrogen and alkyl groups of 1 to 15 carbon atoms;

[0050] The process may optionally further comprise adding during step 1) additional starting materials selected from the group consisting of (C) a catalyst, (D) a solvent, (E) an acrylate polymerization inhibitor, and combinations of two or more of (C), (D), and (E), each of which is described above.

[0051] Step 1) involves mixing the starting materials, optionally with heating. The mixing in step 1) may be carried out for 1 to 48 hours, alternatively 4 to 24 hours, alternatively 6 to 15 hours. The temperature during step 1) may be 0°C to 180°C, alternatively 20 to 160, alternatively 60°C to 180°C, alternatively 60°C to 150°C. The mixing (and heating) may be carried out by any convenient means, such as charging the starting materials into a vessel such as a stirred jacketed batch reactor or a reactive distillation apparatus having a jacketed reboiler, the jacket being capable of being heated and cooled by passing steam / water or a heat transfer fluid through the jacket. Step 1) may be carried out under inert conditions, such as less than 3% oxygen, by purging the reactor with an inert gas such as nitrogen. For example, step 1) may be carried out under an atmosphere containing less than 3% oxygen when operated above 60°C.

[0052] The copolymers produced by this process are represented by the formula R E The choice of end group depends on the amount of starting materials used in the process. For example, if the molar equivalents of (B) bis-acryloyloxy-alkane, (F) bis-silanol-terminated polydiorganosiloxane, and (G) cyclic siloxazane are such that less than 2 molar equivalents of (G) cyclic siloxazane per mole of (F) bis-silanol-terminated polydiorganosiloxane and 0.5 molar equivalents of (B) bis-acryloyloxy-alkane per mole of (G) cyclic siloxazane are used, then each R in the aminosiloxane ester copolymer formula will have an end group represented by E may be a hydroxyl group as described above. Additionally, the amount of (B) bis-acryloyloxy-alkane may be less than 0.5 molar equivalents of (G) cyclic siloxazane to avoid residual acrylate functionality present in the copolymer, thereby allowing R E Some of the groups are of the above formula H2N-R A is an amino functional group of R E A part of the group may be hydroxyl.

[0053] or, for each mole of (F) bis-silanol-terminated polydiorganosiloxane, greater than 2 molar equivalents of (G) cyclic siloxazane, E is expressed as above by the formula H2N-R A Alternatively, the copolymers produced by this process may contain, in the same molecule, an amino functional group of R E is an amino functional group, and R E One example is where R is a hydroxyl group. E The amount of amino functional groups in the copolymer is E Based on the total molar amount of

[0054] The starting material (F), a bis-silanol-terminated polydiorganosiloxane, and the starting material (B), a bis-acryloyloxy-alkane, may be prepared by a process that includes combining the starting material (F), a bis-acryloyloxy-alkane, present in amounts such that the molar ratio of (F):(B) ranges from 2:1 to 1:1.1, alternatively from 2:1 to 1:1.05, alternatively from 2:1 to 1:1. Alternatively, the molar ratio of (F):(B) may be at least 1:1, alternatively at least 1.1:1, alternatively at least 1.3:1, while the ratio may be up to 2:1, alternatively up to 1.8:1, alternatively up to 1.5:1.

[0055] The starting material (F) has the formula

[0056] [ka] bis-silanol-terminated polydiorganosiloxanes of the formula: 1 and the subscript a are as defined above. Examples of starting materials (F) include bis-silanol terminated polydimethylsiloxanes, which are known in the art and are commercially available, for example, from DSC under the trade name XIAMETER™ OHX. Bis-silanol-terminated polydiorganosiloxanes suitable for use as starting material (F) may be prepared by methods known in the art, such as by hydrolysis and condensation of the corresponding organohalosilanes, or by equilibration of cyclic polydiorganosiloxanes.

[0057] The starting material (G) has the formula

[0058] [ka] where subscript c is 0 or 1, and each R 8 is an independently selected monovalent hydrocarbon radical of 1 to 18 carbon atoms, and each R 9 is independently selected from the group consisting of hydrogen and alkyl groups of 1 to 15 carbon atoms. 9are independently selected from the group consisting of hydrogen and alkyl groups of 1 to 15 carbon atoms, alternatively 1 to 12 carbon atoms, alternatively 1 to 6 carbon atoms. Suitable alkyl groups are exemplified by branched saturated monovalent hydrocarbyl groups of 6 or more carbon atoms including methyl, ethyl, propyl (e.g., iso-propyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, heptyl, octyl, nonyl, and decyl, as well as cycloalkyl groups such as cyclopentyl and cyclohexyl. Alternatively, R 9 Each alkyl group in may be methyl. Alternatively, each R 9 can be a hydrogen atom. Alternatively, at least one R 9 can be an alkyl group such as methyl.

[0059] Each R 8 R is an independently selected monovalent hydrocarbon group having 1 to 18 carbon atoms. The monovalent hydrocarbon group is exemplified by alkyl groups, aryl groups, and aralkyl groups. Alternatively, the monovalent hydrocarbon group may be an alkyl group. 8 An example of this is the aforementioned R 9 Examples include:

[0060] Examples of suitable cyclic siloxazanes include: formula

[0061] [ka] 1,1,3,3,-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane, and formula

[0062] [ka] Examples of such cyclononanes include 1,1,3,3,5,5-hexamethyl-2,4-dioxa-9-aza-1,3,5-trisilacyclononane.

[0063] Cyclic siloxazanes may be prepared by the hydrosilylation reaction of allyl-functional amines with SiH-terminated siloxane oligomers in the presence of a hydrosilylation reaction catalyst and a hydrosilylation reaction accelerator, as described in U.S. Provisional Patent Application No. 62 / 940,414, filed Nov. 26, 2019, to Rekken et al., which is incorporated herein by reference.

[0064] In the above process, (B) bis-acryloyloxy-alkane, (F) bis-silanol-terminated polydiorganosiloxane, and (G) cyclic siloxazane may be combined simultaneously or in any order in step 1). Without wishing to be bound by theory, it is believed that when starting materials (B), (F) and (G) are combined simultaneously, (G) cyclic siloxazane first reacts with the silanol groups of starting material (B) to form a terminal primary amino functional polydiorganosiloxane in situ, which then undergoes aza-Michael addition with (B) bis-acryloyloxy-alkane. The inventors have surprisingly found that (B) bis-acryloyloxy-alkane does not readily react with the secondary amine functional group of cyclic siloxazane. Alternatively, in step 1), starting material (G), the cyclic siloxazane, and starting material (F), the bis-silanol-terminated polydiorganosiloxane, may be combined to form the amino-functional polyorganosiloxane, and then starting material (B), the bis-acryloyloxy-alkane, may be added. Without wishing to be bound by theory, it is believed that (G) the cyclic siloxazane does not readily react with (B) the bis-acryloyloxy-alkane. The process for forming (A) the terminal primary amino-functional polyorganosiloxane may include i) combining starting materials including (G) the cyclic polysiloxazane described above, (F) the bis-silanol-terminated polydiorganosiloxane described above, and optionally ii) recovering (A) the primary amino-functional polyorganosiloxane. This process may be carried out by selecting a bis-silanol-terminated polydiorganosiloxane corresponding to the starting material (F) described above for use in the process, as described in U.S. Provisional Patent Application Serial No. 62 / 940414, filed November 26, 2019, to Rekken et al.

[0065] Step 1) in the process for forming a primary amino-functional polyorganosiloxane (combining the starting materials including (G) and (F)) may be carried out by any convenient means such as mixing, optionally with heating. Mixing and heating may be carried out using any convenient means such as charging the starting materials to a vessel such as a stirred jacketed batch reactor or a reactive distillation apparatus having a jacketed reboiler, the jacket being capable of being heated and cooled by passing steam / water or a heat transfer fluid through the jacket. The process may be carried out at a temperature of at least 50°C, alternatively at least 85°C, alternatively at least 90°C. Alternatively, the heating in step 1) may be carried out at 50°C to 150°C, alternatively at 85°C to 150°C, alternatively at 90°C to 150°C. The process is carried out for a time sufficient to form (A) a terminal primary amino-functional polyorganosiloxane. In step i), one of the (G) cyclic siloxazane and the (F) bis-silanol-terminated polydiorganosiloxane may be added continuously or incrementally to a vessel containing the other of (F) and (G). Such addition may be performed manually or using a metering device. The process of forming the (A) primary amino-functional polyorganosiloxane (A) described above may optionally further include one or more additional steps. The process may optionally further include step iii) of adding one or more additional starting materials to the reaction mixture in step i). Alternatively, step iii) may be performed during and / or after step i) and before step ii). The additional starting materials may be selected from the group consisting of acidic pre-catalysts, aminoalkyl-functional alkoxysilanes, endblockers, solvents, and combinations of two or more thereof, as described above for starting material (D), as described in U.S. Provisional Patent Application No. 62 / 940,414 to Rekken et al., filed November 26, 2019. The resulting primary amino-functional polyorganosiloxane may be used in the above-described process to make the above-described aminosiloxane ester copolymer.

[0066] In the above-mentioned process for making aminosiloxane ester copolymers, the method may optionally include one or more additional steps. The process may further include 2) recovering the aminosiloxane ester copolymer (during and / or after step 2). The recovery may be performed by any convenient means, such as stripping and / or distillation with heating and optionally reduced pressure, and / or removing the catalyst (C), for example, by stripping and / or distillation, neutralization, and / or adsorption, if a catalyst is used. Furthermore, those skilled in the art will recognize that in the above-mentioned process, when (G) cyclic siloxazanes are used, alcohols are not used as (C) catalysts and (D) solvents when cyclic siloxazanes are present, so as to avoid the reaction of the alcohol with the cyclic siloxazane to produce alkoxy-functional amino-functional alkoxysilanes or siloxanes.

[0067] Emulsions containing copolymers The copolymers described above may be incorporated into an emulsion. The emulsion may include (I) a liquid continuous phase comprising water, and (II) a discontinuous phase dispersed in the liquid continuous phase, the discontinuous phase comprising the aminosiloxane ester copolymer described above. The amount of copolymer added to the emulsion may vary and is not limited. However, the amount may typically range from 1 to 70%, alternatively 2 to 60% copolymer / emulsion weight ratio. Water (and additional starting materials, if present) may constitute the remainder of the emulsion up to 100%.

[0068] water The water is generally not limited and can be utilized undiluted (i.e., free of any carrier vehicle / solvent) and / or pure (i.e., free or substantially free of minerals and / or other impurities). For example, the water can be treated or untreated prior to making the emulsions described above. Examples of processes that can be used to purify the water include distillation, filtration, deionization, and combinations of two or more thereof, whereby the water can be deionized, distilled, and / or filtered. Alternatively, the water can be untreated (e.g., tap water, i.e., water from a municipal water system, or well water used without further purification). Alternatively, the water can be purified prior to use in making the emulsions.

[0069] Additional starting materials The above-described emulsions may further comprise additional starting materials selected from the group consisting of (H) surfactants, (I) acid compounds, (J) acid anhydrides, (K) thickeners, (L) stabilizers, (M) preservatives, and combinations of two or more of (H), (I), (J), (K), (L), and (M).

[0070] The copolymers described above may be self-emulsifying (i.e., a separate surfactant is optional). However, if a surfactant is used, it may be anionic, cationic, nonionic, or amphoteric, or a combination of two or more thereof. The amount of surfactant may be from 2% to 25%, based on the total weight of all starting materials in the emulsion.

[0071] (H) Surfactant The anionic surfactant may be selected from alkali metal sulforicinates, sulfonated glyceryl esters of fatty acids, salts of sulfonated monohydric alcohol esters, amides of aminosulfonic acids, sulfonation products of fatty acid nitriles, sulfonated aromatic hydrocarbons, condensation products of naphthalenesulfonic acid and formaldehyde, sodium octahydroanthracenesulfonate, sodium lauryl sulfate, alkali metal alkyl sulfates, alkyl ether sulfates having at least 8 carbon atoms, alkylaryl ether sulfates, alkylaryl sulfonates having at least 8 carbon atoms, alkylbenzenesulfonic acids, salts of alkylbenzenesulfonic acids, sulfate esters of polyoxyethylene alkyl ethers, amine salts or sodium or potassium salts of alkylnaphthylsulfonic acids, and combinations thereof.Suitable anionic surfactants are commercially available from various sources, including sodium lauryl sulfate available under the trade name CALIMULSE™ SLS from Pilot. Other anionic surfactants commercially available from TDCC include alkyldiphenyloxide disulfates available under the tradename DOWFAX™, dioctyl sulfosuccinates available under the tradename TRITON™ GR, phosphate esters available under the tradenames TRITON™ H-55, H-65, QS-44, or XQS-20, sulfates and sulfonates available under the tradenames TRITON™ QS-15 and TRITON™ XN-45S.

[0072] The cationic surfactant may be selected from dodecylamine acetate, octadecylamine acetate, acetates of amines of tallow fatty acid, homologues of aromatic amines with fatty acids, fatty amides derived from aliphatic diamines, fatty amides derived from aliphatic diamines, fatty amides derived from disubstituted amines, derivatives of ethylenediamine, quaternary ammonium compounds, salts of quaternary ammonium compounds, alkyltrimethylammonium hydroxide, dialkyldimethylammonium hydroxide, coconut oil, methylpolyoxyethylenecocoammonium chloride, dipalmitoylethylhydroxyethylmonium methosulfate, amide derivatives of amino alcohols, amine salts of long chain fatty acids, and combinations thereof. Cationic surfactants are commercially available from a variety of sources, including dialkylmethyl quaternary ammonium compounds (e.g., cetrimonium chloride) under the trade name ARQUAD™ from Akzo Nobel, ADOGEN™ cationic surfactants from Evonik, TOMAH™ cationic surfactants from Tomah Products, Inc. (Milton, Wisconsin, USA), and VARIQUAT™ cationic surfactants from Sea-Land Chemical Company (Westlake, Ohio, USA).

[0073] The non-ionic surfactants may be selected from alkylphenol alkoxylates, ethoxylated and propoxylated fatty alcohols, alkyl and hydroxyalkyl polyglucosides, sorbitan derivatives, N-alkyl glucamides, alkylene oxide block copolymers, such as block copolymers of ethylene oxide, propylene oxide and / or butylene oxide, fatty alcohol polyglycol ethers, polyhydroxy and polyalkoxy fatty derivatives, amine oxides, silicone polyethers, various polymeric surfactants. Non-ionic surfactants are commercially available, for example, alkylphenol alkoxylates available under the trade name ECOSURF™ EH, secondary alcohol ethoxylates, nonylphenol ethoxylates, and ethylene oxide / propylene oxide copolymers available under the trade name TERGITOL™, and specialty alkoxylates such as amine ethoxylates and octylphenol ethoxylates available under the trade name TRITON™, all from TDCC. Alternatively, the non-ionic surfactant may be Trideceth-6 or Trideceth-12, available, for example, under the tradename SYNPERONIC™ from Croda or LUTENSOL™ from BASF. Alternatively, the non-ionic surfactant may be a fatty alcohol polyglycol ether, such as, for example, GENAPOL™ UD050 and GENAPOL™ UD110, available commercially from Clariant, Frankfurt, Germany.

[0074] The nonionic surfactant may also be a silicone polyether (SPE). The silicone polyether as emulsifier may have a pitchfork structure in which polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted to a siloxane backbone, or the SPE may have an ABA block copolymer structure in which A represents the polyether portion and B represents the siloxane portion of the ABA structure. Suitable silicone polyethers include DSC's Dow Silicones™ 5329. Alternatively, the nonionic surfactant may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters, and silicone glycosides. Such silicone surfactants are known in the art and are described, for example, in U.S. Pat. No. 4,122,029 to Gee et al., U.S. Pat. No. 5,387,417 to Rentsch, and U.S. Pat. No. 5,811,487 to Schulz et al.

[0075] Suitable amphoteric surfactants include alkyl (C12-14) betaines, betaines such as cocoamidopropyl betaine, cocoamidopropyl dimethyl-hydroxysulfobetaine, dodecyl betaine, hexadecyl betaine, and tetradecyl betaine, sultaines such as cocamidopropyl hydroxysultaine, lecithin, hydrogenated lecithin, cocoamphodiacetate, cocoiminodipropionate, and dodecyliminodipropionate.

[0076] The emulsion may be formed as a water-in-oil emulsion (w / o) containing a water-in-oil surfactant (which may then be inverted by adding more water). The water-in-oil surfactant may be non-ionic and may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters, and silicone glycosides, as described above. Alternatively, if the emulsion is an oil-in-water emulsion (o / w), the emulsion may include a non-ionic surfactant known in the art for preparing o / w emulsions. Suitable non-ionic surfactants for this embodiment are exemplified by polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monooleates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycols, polypropylene glycols, ethylene glycols, ethoxylated trimethylnonanols, and polyoxyalkylene glycol-modified polysiloxane surfactants, as described above.

[0077] (I) Acid compound Acid compounds may be optionally added to the emulsion described herein to adjust pH.Suitable acids include acetic acid, formic acid, propionic acid, and combinations thereof.Suitable acids for adjusting pH are disclosed in, for example, U.S. Patent No. 6,180,117.

[0078] Method for producing emulsion Emulsions may be prepared by batch, semi-continuous, or continuous processes using conventional equipment. For example, the mixing of starting materials to form emulsions may occur using equipment such as batch equipment with high shear and high speed dispersers, including those manufactured by Charles Ross & Sons (NY), Hockmeyer Equipment Corp. (NJ), batch mixing equipment such as those sold under the trade name Speedmixer (trademark), high shear batch equipment, including Banbury type (CW Brabender Instruments Inc., NJ) and Henschel type (Henschel mixers America, TX). Illustrative examples of continuous mixers / compounders include single-screw, twin-screw, and multi-screw extruders, co-rotating extruders, twin counter-rotating extruders, two-stage extruders, twin-screw rotating continuous mixers, dynamic or static mixers, or combinations of these devices, such as those manufactured by Krupp Werner & Pfleiderer Corp (Ramsey, NJ) and Leistritz (NJ).

[0079] The above starting materials may be combined under any suitable conditions to form an emulsion. For example, any acid compound may be added at the end of the process, i.e., once the desired dilution level is reached, to simplify the mixing process and keep the emulsion viscosity low during handling.

[0080] hair care The copolymers and emulsions containing the copolymers are useful in hair care compositions, each as described above. The hair care compositions may be conditioners and / or leave-in hair treatments, such as styling products. The hair care compositions may be used for purposes such as styling (e.g., curl retention) and / or conditioning the hair fiber.

[0081] In using the hair care composition according to the present invention, conventional methods for conditioning hair may be used. For example, an effective amount of the composition for conditioning the hair is applied to the hair. Such an effective amount generally ranges from 0.5 g to 50 g, alternatively from 1 g to 20 g. Application to the hair typically involves working the composition through the hair so that most or all of the hair is in contact with the product. This method for conditioning the hair includes the steps of applying an effective amount of the hair care composition to the hair and then working the composition through the hair. These steps can be repeated as many times as desired to achieve the desired conditioning effect.

[0082] In addition to the copolymers and / or emulsions described above, non-limiting examples of additives that may be incorporated into the hair conditioner composition include: (i) chelating agents, (ii) deposition agents such as cationic deposition aids, (iii) additional emulsifiers (e.g., nonionic), (iv) fragrances, (v) oils, (vi) pigments, (vii) preservatives, (viii) stabilizers, (ix) thickeners, and combinations thereof.

[0083] The hair care composition may contain at least one cationic deposition aid, or cationic deposition polymer. The cationic deposition aid may be present in an amount of 0.001% to 5%, alternatively 0.01% to 1%, or alternatively 0.02% to 0.5%, based on the total weight of all ingredients in the personal care product. The cationic deposition polymer may be a homopolymer or may be formed from two or more types of monomers. The molecular weight of the cationic deposition polymer may be at least 10,000, alternatively 5,000 to 10,000,000, alternatively 100,000 to 2,000,000. The cationic deposition polymer has cationic nitrogen containing groups such as quaternary ammonium or protonated amino groups, or mixtures thereof. The cationic charge density may be at least 0.1 meq / g, alternatively 0.8 meq / g or greater. The cationic charge density should not exceed 4 meq / g, alternatively less than 3, and alternatively less than 2 meq / g. The charge density can be measured using the Kjeldahl method and should be within the above limits at the desired pH of use, which may range from 3 to 9, alternatively 4 to 8. The cationic nitrogen-containing groups are generally present as substituents on a fraction of the total monomer units of the cationic deposition polymer. Thus, if the cationic deposition polymer is not a homopolymer, it can contain non-cationic spacer monomer units. Such polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition. Suitable cationic deposition aids include copolymers of vinyl monomers with cationic amine or quaternary ammonium functionality, such as (meth)acrylamides, alkyl and dialkyl (meth)acrylamides, alkyl (meth)acrylates, vinyl caprolactone, and vinyl pyrrolidine, with water-soluble spacer monomers. The alkyl and dialkyl substituted monomers may have alkyl groups of 1 to 7 carbon atoms, alternatively alkyl groups of 1 to 3 carbon atoms. Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol, and ethylene glycol.Cationic amines can be primary, secondary or tertiary amines, depending on the specific species and pH of the composition. Generally, secondary and tertiary amines, or quaternary amines can be used. Amine-substituted vinyl monomers and amines can be polymerized in amine form and then converted to ammonium by quaternization. Suitable cationic amino and quaternary ammonium monomers include, for example, vinyl compounds substituted with dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates, monoalkylaminoalkyl acrylates, monoalkylaminoalkyl methacrylates, trialkylmethacryloxyalkyl ammonium salts, trialkylacryloxyalkyl ammonium salts, diallyl quaternary ammonium salts, and vinyl quaternary ammonium monomers with cyclic cationic nitrogen-containing rings, such as pyridinium, imidazolium, and quaternized pyrrolidines, for example, alkyl vinylimidazoliums, and quaternized pyrrolidines, for example, alkyl vinylimidazoliums, alkyl vinylpyridiniums, alkyl vinylpyrrolidine salts. The alkyl portions of these monomers may be lower alkyl, such as alkyl groups of 1 to 4 carbon atoms, or alkyl groups of 1 to 2 carbon atoms. Amine-substituted vinyl monomers suitable for use herein include dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates, dialkylaminoalkyl acrylamides, and dialkylaminoalkyl methacrylamides. The cationic deposition aid may comprise a mixture of monomer units derived from amine and / or quaternary ammonium substituted monomers and / or compatible spacer monomers.Suitable cationic deposition aids include, for example: copolymers of 1-vinyl-2-pyrrolidine and 1-vinyl-3-methylimidazolium salts (e.g., the chloride salt) (referred to in the art by the Cosmetic, Toiletry, and Fragrance Association, "CTFA," as Polyquaternium-16), such as those available under the trade name LUVIQUAT (e.g., LUVIQUAT FC 370) from BASF Wyandotte Corp., Parsippany, NJ, USA; copolymers of 1-vinyl-2-pyrrolidine and dimethylaminoethyl methacrylate (referred to in the art by the CTFA as Polyquaternium-11), such as those available under the trade name GAFQUAT (e.g., GAFQUAT FC 370) from Gar Corporation, Wayne, NJ, USA; 755N); cationic diallyl quaternary ammonium-containing polymers, such as dimethyldiallyl ammonium chloride homopolymers and copolymers of acrylamide and dimethyldiallyl ammonium chloride, referred to in the art (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively; mineral acid salts of aminoalkyl esters of homopolymers and copolymers of unsaturated carboxylic acids having 3 to 5 carbon atoms, as described in U.S. Pat. No. 4,009,256 (Nowak Jr., et al.); and cationic polyacrylamides, as described in U.S. Pat. No. 5,543,074 (Hague et al.). Other cationic deposition aids that can be used include polysaccharide polymers, such as cationic cellulose derivatives and cationic starch derivatives. Cationic polysaccharide polymeric materials suitable for use in the compositions of the present invention include those of the formula -O(R. 15 -N+R 16 R 17 R 18 X-), where A is an anhydroglucose residue, such as a starch or cellulose anhydroglucose residue, and R 15 is an alkyleneoxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or a combination thereof; R 16 , R 17 , and R 18are independently alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each containing 18 or fewer carbon atoms, and the total number of carbon atoms in each cationic moiety (i.e., R 16 , R 17 , and R 18 (the total number of carbon atoms in X) may be up to 20, and X is an anionic counterion as described above. Cationic celluloses include the polymer iR™ and LR™ series of polymers available from Amerchol Corp. (Edison, NJ, USA) as salts of hydroxyethylcellulose reacted with trimethylammonium-substituted epoxides, referred to in the art (CTFA) as polyquaternium 10. Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethylcellulose reacted with lauryldimethylammonium-substituted epoxides, referred to in the art (CTFA) as polyquaternium 24. These materials are available from Amerchol Corp. (Edison, NJ, USA) under the trade name Polymer LM-200. Other cationic deposition aids that can be used include cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride (available in the Jaguar™ series from Celanese Corp.). Other materials include quaternary nitrogen-containing cellulose ethers such as those described in U.S. Pat. No. 3,962,418 (Birkofer), which is incorporated herein by reference, and copolymers of etherified cellulose and starch such as those described in U.S. Pat. No. 3,958,581 (Abegg et al.), which is incorporated herein by reference.

[0084] The hair care composition may contain various additional oils. As used herein, the term "oil" refers to any material that is substantially water insoluble. Suitable oils include, but are not limited to, natural oils such as coconut oil, hydrocarbons such as mineral oil and hydrogenated polyisobutene, fatty alcohols such as octyldodecanol and cetearyl alcohol (commercially available under the trade name Crodacol CS-50); esters such as C12-C15 alkyl benzoates, diesters such as propylene dipelargonate, triesters such as glyceryl trioctanoate, and silicones, particularly cyclomethicone and dimethicone, and combinations thereof. The hair care composition may also contain oils or mixtures of low and high viscosity oils. Suitable low viscosity oils have a viscosity of 5 to 100 mPa.s at 25°C and are represented by the structure R 20 CO-OR 21 [In the formula, R 20 CO represents a carboxylic acid group, and OR 21is an alcohol residue. Examples of these low viscosity oils include isotridecyl isononanoate, PEG-4 diheptanoate, isostearyl neopentanoate, tridecyl neopentanoate, cetyl octanoate, cetyl palmitate, cetyl ricinoleate, cetyl stearate, cetyl myristate, coco-dicaprylate / caprate, decyl isostearate, isodecyl oleate, isodecyl neopentanoate, isohexyl neopentanoate, octyl palmitate, dioctyl malate, tridecyl octanoate, myristyl myristate, octododecanol or mixtures of octyldodecanol, acetylated lanolin alcohol, cetyl acetate, isododecanol, polyglyceryl-3-diisostearate, or mixtures thereof. High viscosity surface oils generally have a viscosity of from 200 to 1,000,000 mPa.s, alternatively from 100,000 to 250,000 mPa.s at 25°C. Surface oils include castor oil, lanolin and lanolin derivatives, triisocetyl citrate, sorbitan sesquioleate, C10-18 triglycerides, caprylic / capric / triglycerides, coconut oil, corn oil, cottonseed oil, glyceryl triacetyl hydroxystearate, glyceryl triacetyl ricinoleate, glyceryl trioctanoate, hydrogenated castor oil, linseed oil, mink oil, olive oil, palm oil, illipe oil, rapeseed oil, soybean oil, sunflower seed oil, tallow, tricaprin, trihydroxystearin, triisostearin, trilaurin, trilinolein, trimyristin, triolein, tripalmitin, tristearin, walnut oil, wheat germ oil, cholesterol, or mixtures thereof. Alternatively, argan oil may be used. The recommended ratio of low viscosity oil to high viscosity oil in the oil phase is 1:15 to 15:1, alternatively 1:10 to 10:1. Alternatively, the personal care product may contain a mixture of 1% to 20% low viscosity oil and high viscosity oil.

[0085] Among the additional oils, mineral oils, such as liquid paraffin or liquid petroleum oil, animal oils, such as perhydrosqualene, or vegetable oils, such as sweet almond, calophyllum, palm, castor, avocado, jojoba, olive or cereal germ oil, may be added to the hair care composition containing the copolymer described above.For example, it is also possible to use esters of lanolin acid, oleic acid, lauric acid, stearic acid or myristic acid; alcohols, such as oleyl alcohol, linoleyl or linolenyl alcohol, isostearyl alcohol or octyl dodecanol; or acetyl glycerides, octanoates, decanoates or ricinoleates of alcohols or polyalcohols.Alternatively, it is also possible to use hydrogenated oils, such as hydrogenated castor oil, palm oil or coconut oil, or hydrogenated tallow, that are solid at 25°C; mono-, di-, tri- or sucroglycerides; lanolin; or aliphatic esters, that are solid at 25°C.

[0086] A thickener may be added to provide a convenient viscosity. For example, 500 mm at 25° C. 2 / s~25,000mm 2 / s, or 3,000 to 7,000 mm 2A viscosity of 1000 / s is usually suitable. Suitable thickening agents are exemplified by sodium alginate, gum arabic, polyoxyethylene, guar gum, hydroxypropyl guar gum, ethoxylated alcohols such as laureth-4 or polyethylene glycol 400, cellulose derivatives exemplified by methylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, polypropylhydroxyethylcellulose, hydroxyethylcellulose, starch and starch derivatives exemplified by hydroxyethylamylose and starch amylose, locust bean gum, electrolytes exemplified by sodium chloride and ammonium chloride, and sugars such as fructose and glucose, and sugar derivatives such as PEG-120 methyl glucose diolate, or a mixture of two or more of these. Alternatively, the thickening agent is selected from cellulose derivatives, sugar derivatives, and electrolytes, or from a combination of two or more of the above thickening agents exemplified by a combination of a cellulose derivative and any electrolyte, and a combination of a starch derivative and any electrolyte. Thickeners are commercially available, for example hydroxyethyl cellulose is available from TDCC under the trade name Cellosize™ Hydroxyethyl Cellulose PCG-10 Europe. 2 / s~25,000mm 2 The thickener may be used in the hair care composition in an amount sufficient to provide a viscosity of from 0.05% to 10%, alternatively from 0.05% to 5%, based on the total weight of the hair care composition.

[0087] Stabilizers can be used in the aqueous phase of hair care compositions containing the copolymers described above. Suitable aqueous phase stabilizers can include, alone or in combination, one or more electrolytes, polyols, alcohols such as ethyl alcohol, and hydrocolloids. Typical electrolytes are alkali metal and alkaline earth salts, especially chloride salts, borates, citrates, and sulfates of sodium, potassium, calcium, and magnesium, as well as aluminum chlorohydrates, and polyelectrolytes, especially hyaluronic acid and sodium hyaluronate. When the stabilizer is an electrolyte or includes an electrolyte, it can amount to about 0.1% to 5%, or alternatively 0.5% to 3% by weight of the total composition. Hydrocolloids include gums such as xanthan gum or veegum, and thickeners such as carboxymethylcellulose. Polyols such as glycerin, glycol, and sorbitol can also be used. Alternative polyols are propylene glycol, sorbitol, and butylene glycol. If a large amount of polyol is used, it is not necessary to add electrolytes. However, it is typical to use a combination of electrolytes, polyols and hydrocolloids to stabilize the aqueous phase, such as magnesium sulfate, butylene glycol and xanthan gum.

[0088] The hair care composition may optionally further comprise a chelating agent, such as tetrasodium ethylenediaminetetraacetic acid (tetrasodium EDTA), available commercially under the tradename Versene 220.

[0089] The hair care composition may optionally further comprise an additional emulsifier, which may be a non-ionic emulsifier, for example, PEG-100 stearate and glyceryl stearate.

[0090] The hair care composition may optionally further comprise a preservative. Examples of suitable preservatives include phenoxyethanol and methylisothiazolinone, which are commercially available as Neolone PE Preservative.

[0091] The hair care compositions can also be in the form of aerosols in combination with propellants such as carbon dioxide, nitrogen, nitrous oxide, volatile hydrocarbons such as butane, isobutane, or propane, and chlorinated or fluorinated hydrocarbons such as dichlorodifluoromethane and dichlorotetrafluoroethane or dimethyl ether.

[0092] When selecting the components of the hair care composition described above, a particular component described herein may have more than one function, so there may be overlap in the types of components.For example, hydroxyethyl cellulose may be useful as a colloid stabilizer and thickener.When additional components are added to the hair care composition, the additional components are different from each other.

[0093] Alternatively, hair care products are (I) the copolymer described above, or an emulsion of the copolymer described above, (II) Water; Optionally (ix) a thickening agent (e.g., hydroxyethyl-cellulose); (v) oils, such as fatty alcohols (e.g., cetearyl alcohol); Optionally, (iii) other emulsifiers (e.g., PEG-100 stearate and glyceryl stearate); optionally (vii) a preservative, and optionally (ii) a cationic deposition aid, and Optionally, (i) it may be a hair conditioner that includes a chelating agent (eg, tetrasodium ethylenediaminetetraacetate).

[0094] Alternatively, the emulsions described above may be used as leave-in hair treatment compositions (eg, as styling aids). EXAMPLES

[0095] The following examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention as set forth in the claims. The specific starting materials used in the examples are set forth in Table 1 below, followed by characterization and evaluation procedures also used in the examples.

[0096] [Table 1]

[0097] As used herein, XIAMETER™ brand materials are commercially available from DSC.

[0098] In this Reference Example 1, the copolymer was prepared as follows: A terminal primary amino-functional polyorganosiloxane and a bis-(acryloyloxy)alkane were combined and mixed for 30 minutes under an inert atmosphere (i.e., oxygen content <3%). The resulting mixture was heated to 80-90°C for 1 hour. The mixture was then heated to 90-120°C and optionally stirred for a period of time (A hours in Table 2 below). The mixture was then heated to 130°C-150°C and optionally stirred for a period of time (B hours in Table 2 below). Examples 1p and 1q demonstrated that even if residual acrylate remained after heating, the acrylate was consumed over a period of days or weeks, even at ambient temperature. The resulting copolymer was then: 1 H NMR, 13 C NMR, 29 Characterized by a combination of Si NMR, IR, rheometry (viscosity), and / or GPC. Evaluation of storage modulus (G') and loss modulus versus frequency ωrad / s showed no crossover in the most acrylate-rich example (1a), indicating little or no crosslinking of the polymer.

[0099] [Table 2] 1 indicates that sample 1p was mixed for an additional 4 days at ambient temperature.2 indicates that 1q of sample was mixed for an additional 25 days at ambient temperature. 3 The sample shows that when first tested it had a viscosity of 702 and after aging for two years it had a viscosity of 4572. The data in Table 1 demonstrates that copolymers can be produced without a catalyst according to the method of the present invention as exemplified by the procedure of Reference Example 1. The storage and loss modulus data showed that the copolymers are linear and do not suffer from the crosslinking drawbacks that are an issue with the amine-containing hydrocarbon polymers that use an aza-Michael addition reaction with a bis(acryloyloxy)alkane to form the polymer backbone of the comparative example.

[0100] In this Comparative Example 2, TAS4 was combined with BAA1. These two liquids were miscible when mixed at ambient temperature for 30 minutes, and then a catalytic amount of 2,6-lutidine, about 400 ppm, was added. The resulting reaction mixture was heated at 80° C. for 2 hours, then at 90° C. for 5.5 hours to obtain a clear solution, which was cooled to ambient temperature and stirred. However, within 24 hours, the mixture collapsed, yielding a suspension of solid polymerized acrylate and amino-terminated polydimethylsiloxane.

[0101] In this Comparative Example 3, Comparative Example 2 was repeated and split into two batches with the addition of DBU catalyst to one of them. Within 30 hours, both mixtures had disintegrated to give suspensions of solid polymerized acrylate and amino-terminated polydimethylsiloxane.

[0102] Comparative Examples 2 and 3 showed that when a terminal primary amino-functional polyorganosiloxane with too high a DP was used, it was not possible to form a copolymer under the conditions tested.

[0103] In this Reference Example 4, the copolymer was prepared as follows: A terminal primary amino-functional polyorganosiloxane and a bis-(acryloyloxy)-alkane were combined and mixed for 30 minutes under an inert atmosphere (i.e., oxygen content <3%). A catalyst (2,6-lutidine) was added, and the resulting mixture was heated to 90°C for 1 hour. The mixture was then heated to 110°C and optionally stirred for a period of time (mixing time A hours in Table 3 below). The mixture was then heated to 140°C-150°C and optionally stirred for a period of time (mixing time B hours in Table 3 below). If residual acrylate is still present in the resulting product, it will be consumed over time under ambient conditions. The resulting copolymer was then 1 H NMR, 13 C NMR, 29 Characterized by a combination of Si NMR, IR, rheometry (viscosity), and / or GPC.

[0104] [Table 3] 1 indicates that instead of heating as above, sample 4a was held at 90° C. for 13 hours. After heating there was a significant amount of residual acrylate, but after standing for 22 months the viscosity of the material had increased. 2 Sample 4f had too high a viscosity to be measured with the same equipment used for the other samples. Sample 4f became fibrous after aging for 21 months. Sample 4f had MW=389,121, Mn=41462, and PD=9.39.

[0105] In this Example 5, 45.00 g (113 mmol) of bis(aminopropyl)tetrasiloxane, 1,13-diamino-4,4,6,6,8,8,10,10-octamethyl-5,7,9-trioxa-4,6,8,10-tetrasilatridecane, was added to a 250 mL reaction flask equipped with a magnetic stir bar and a thermocouple. The flask was inerted and 19.74 g (87 mmol) of BAA1 was added over 15 minutes under a N2 flow. Due to the exotherm of the reaction, the temperature of the mixture rose from about 22° C. to 39° C. and the clear, colorless liquid became significantly viscous. The mixture was stirred at ambient temperature for about 8 more hours. 1 H, 13 C, and 29 Si NMR analysis confirmed that the acrylate (BAA1) had been consumed. GPC showed that the weight average molecular weight of this material was 4130 g / mol. This example demonstrated that the process to (AB)n copolymers using siloxane oligomers (DP=2) can be carried out using the method of the present invention without external heating. A significant exotherm was observed and the product produced was viscous (4150 mPa s) compared to products produced using TAA with DP=16 or DP=44.

[0106] (AB) nA three-component single reactor process for producing copolymers was developed. The process involved the addition of bis-silanol-terminated polydiorganosiloxane, bis-acryloyloxy-alkane, and cyclic siloxazane (1,1,3,3,-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane) as shown in Scheme 1 below to form copolymers such as those described in Reference Examples 1 and 4. Without wishing to be bound by theory, it is believed that the cyclic siloxazane first reacts with the bis-silanol-terminated polydiorganosiloxane to form a bis(aminopropyl)siloxane in situ, which then undergoes aza-Michael 1,4-addition with the bis-acryloyloxy-alkane. Surprisingly, the bis-acryloyloxy-alkane used under the conditions tested did not readily react with the secondary amine present in the cyclic siloxazane. When the cyclic siloxazane and the bis-acryloyloxy-alkane were combined in a mixture, no reaction was observed when heated to 60° C. for about 3 hours in the presence of 1.2% 2,6-lutidine catalyst. The cyclic siloxazane begins to react with the bis-silanol-terminated polydiorganosiloxane and is quickly completed within 6 to 8 hours at ambient temperature and less at elevated temperatures, as disclosed in International Publication WO 2021 / 108068, which corresponds to U.S. Provisional Patent Application No. 62 / 940414, filed November 26, 2019, to Rekken et al. Without wishing to be bound by theory, it is believed that the method provided herein involves the initial addition of the cyclic siloxazane to the bis-silanol-terminated polydiorganosiloxane, followed by an aza-Michael addition, as shown in Scheme 1 below.

[0107] Scheme 1. (Top) Addition of cyclic siloxazane did not readily react with bis-acryloyloxy-alkane. (Bottom) In the mixture, bis-silanol-terminated polydiorganosiloxane reacts with cyclic siloxazane and subsequently with bis-acryloyloxy-alkane, regardless of the order of addition.

[0108] [ka]

[0109] In this Example 6, 80.1 g (25.6 mmol) of OH-PDMS was added to a 250 mL 3-neck reaction flask equipped with a gas inlet, an air-cooled condenser fed to an oil bubbler, a glass stopper, and a magnetic stir bar. While mixing, 4.51 g (19.9 mmol) of BAA1 was added to the mixing OH-PDMS and stirred for about 5 minutes. The atmosphere was inerted to less than 0.3% oxygen. 10.4 g (54.9 mmol) of 1,1,3,3,-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane was then added to the mixture, resulting in a mild exotherm indicating reaction. After the exotherm subsided, the mixture was stirred at ambient temperature for 2 hours, when the mixture became significantly viscous, and then the pot temperature was slowly increased to 80° C. over 1 hour, then heated at 80° C. for 3 hours, then at 120° C. for 3 hours, then at 70° C. for 2 hours. 1 H and 29 Si NMR spectroscopy and viscosity measurements supported the formation of a material similar to that in Example 1i.

[0110] When a cyclic siloxazane is combined with a bis-silanol-terminated polydiorganosiloxane such that there are less than 2 moles of cyclic siloxazane (Y) per mole of silanol (X) on the bis-silanol-terminated polydiorganosiloxane and the moles of bis-acryloyloxy-alkane (Z) are equal to half the moles of cyclic siloxazane (Y), the copolymer is terminated with SiOH functional groups (rather than having primary aminopropyl groups) (AB), as shown in Scheme 2. n A copolymer was formed. When the copolymer is used in a hair care composition, Z may be selected to be less than Y / 2 to minimize or avoid the possibility of residual acrylate in the copolymer, thereby resulting in a small amount of amino-functional end (AB) in the mixture. n Copolymers can be produced that have a silanol end at one end and an amino functionality at the other end, (AB) n Copolymers may contain residual amino functional ends (AB).n The amount of copolymer can be 0 to <100%, alternatively 0 to 50%, alternatively 0 to 5%.

[0111] [ka]

[0112] In this Example 7, 80.1 g (25.6 mmol) of OH-PDMS was added to a 250 mL three-necked reaction flask equipped with a gas inlet, an air-cooled condenser fed to an oil bubbler, a glass stopper, and a magnetic stir bar. While mixing, 4.51 g (19.9 mmol) of BAA1 was added to the mixing OH-PDMS and stirred for about 10 minutes. The atmosphere was inerted to less than 0.3% oxygen. Then, 7.81 g (41.2 mmol) of 1,1,3,3,-tetramethyl-2-oxa-7-aza-1,3-disilacycloheptane was added to the mixture, resulting in a mild exotherm indicating the reaction. After the exotherm subsided, the mixture was stirred at ambient temperature for 1.5 hours, at which point the mixture became significantly viscous, and the pot temperature was then increased to 60°C and stirred for 1.5 hours, then heated at 80°C for 6 hours to give a polymer with a viscosity of 755 mPa s and an average molecular weight of 19940 g / mol. 1 H, 13 C and 29 Si It was also characterized by NMR spectroscopy.

[0113] In this Comparative Example 8, the synthesis of the derivative polymers of Reference Examples 1 and 4 was attempted under similar conditions using alkanediol di(meth)acrylates BAA4 and BAA5 instead of alkanediol acrylate. The conversion was very slow, taking several weeks to complete even 50% conversion. Neither alkanediol (meth)acrylate BAA4 nor BAA5, when combined with either TAS1 or TAS2, undergoes complete conversion, even when TAS is used at either 30% or 100% molar excess. Furthermore, the addition of a catalyst, DBU (about 2000 ppm), slightly improved the conversion rate, but complete conversion could not be achieved even in a multi-week time frame with heating to 120°C. Furthermore, the initiation of the process was not comparable, as inerting the reaction flask and heating to 60°C for less than one hour resulted in polymerization of the methacrylate moieties and their separation from the polyorganosiloxane matrix, as initiated by the formation of a cloudy white solid. Without a process to remove the methacrylate moieties in the product, these copolymers are not suitable for any personal care applications due to the skin sensitizing properties of the methacrylate-functional starting materials.

[0114] In this Example 9, emulsions of the copolymer samples prepared as described above were prepared using the starting materials and amounts shown in Table 4 below. Amounts are in weight percent. The samples were prepared as follows: The copolymer, surfactant, and water were added to a 100 DAC cup. These starting materials were speed mixed in a Speed ​​Mixer at 3500 RPM twice for 30 seconds each time. The resulting mixture was diluted stepwise with the remaining amount of water, speed mixed at 3500 RPM for 30 seconds between each successive water dilution step. Acetic acid was added to the mixture, and the ingredients were speed mixed at 3500 RPM for an additional 30 seconds.

[0115] [Table 4]

[0116] In this Example 10, emulsions of the copolymer samples prepared as described above were prepared using the starting materials and amounts shown in Table 5 below. The samples were prepared as follows: The copolymer, surfactant, and water were added to a 100 DAC cup. These starting materials were speed mixed in a Speed ​​Mixer at 3500 RPM twice for 30 seconds each time. The resulting mixture was diluted stepwise with the remaining amount of water, speed mixed at 3500 RPM for 30 seconds between each successive water dilution step. A non-ionic surfactant was used to make the emulsion. The surfactants used were S1 and S2 from Table 6.

[0117] [Table 5]

[0118] In this Example 11, anionic, cationic, and nonionic surfactants were used to prepare emulsions. The starting materials used are shown in Table 6.

[0119] [Table 6]

[0120] Emulsion samples were prepared using the starting materials listed in the following amounts in Tables 7-8. The amount of each starting material is in parts by weight unless otherwise specified. Table 7 shows the nonionic emulsions. Table 8 shows the anionic and cationic emulsions.

[0121] [Table 7]

[0122] [Table 8]

[0123] In Tables 7 and 8, "ND" means not detected.

[0124] In Table 7, emulsion EM12 was prepared as follows: 2g of copolymer P1, 1g of surfactant S1 and 0.7g of water (D1) were added to a 20DAC cup. These starting materials were speed mixed in a Speed ​​Mixer at 3500 RPM twice for 30 seconds each time. 0.1g of 10% acetic acid solution (A1) was added to the cup and the contents of the cup were speed mixed at 3500 RPM for 30 seconds. The resulting mixture was diluted stepwise with water until the final translucent / transparent microemulsion was fluid (having a water-like viscosity). 0.5g of water was added at each step and the contents of the cup were speed mixed in between.

[0125] In Table 7, emulsion EM16 was prepared as follows: 3.59 g of copolymer P3, 0.13 g of surfactant S1, 0.12 g of surfactant S2, and 0.36 g of water were added to a 20DAC cup. These starting materials were speed mixed in a Speed ​​Mixer at 3500 RPM twice for 30 seconds each time. Water was added incrementally to the cup with speed mixing between each successive water dilution step until the total water content was 2.15 g and the resulting emulsion was flowable.

[0126] In Table 7, emulsion sample 17 was prepared as follows: 3.6 g of copolymer P2, 0.13 g of surfactant S1, 0.12 g of surfactant S2, and 0.35 g of water were added to a 20DAC cup. These starting materials were speed mixed in a Speed ​​Mixer at 3500 RPM twice for 30 seconds each time. Water was added incrementally to the cup with speed mixing between each successive water dilution step until the total water content was 2.15 g and the resulting emulsion was flowable.

[0127] In Table 7, emulsions EM21-EM24 were prepared as follows: Copolymer, surfactant S5 and water (D1) were added to a 100DAC cup. These starting materials were speed mixed in a SpeedMixer (Flaktek SpeedMixer DAC 330-100 SE) at 3500 RPM for 1 minute. The resulting mixture was diluted stepwise with the remaining amount of water (D1) and speed mixed at 3500 RPM for 30 seconds between each successive water dilution step. A 10% acetic acid solution (A1) was added to the cup and the contents of the cup were speed mixed at 3500 RPM for 30 seconds. Surfactant S2 was then added to the cup and the contents of the cup were speed mixed at 3500 RPM for 30 seconds.

[0128] In Table 7, emulsion EM25 was prepared as follows: 3.01 g of copolymer P7, 0.15 g of surfactant S1, 0.12 g of S2, and 0.33 g of water were added to a 20DAC cup. These starting materials were speed mixed in a Speed ​​Mixer at 3500 RPM twice for 30 seconds each time. Water was added incrementally to the cup with speed mixing between each successive water dilution step until the total water content was 1.72 g and the emulsion was flowable.

[0129] In Table 8, emulsion EM13 was prepared as follows: 2g of copolymer P1, 0.29g of surfactant S1 and 2.23g of anionic surfactant S3 were added to a 20DAC cup. These starting materials were mixed in a Speed ​​Mixer at 3500 RPM twice for 30 seconds each time. 0.1g of 10% acetic acid solution (A1) was added to the cup and the contents of the cup were mixed at 3500 RPM for 30 seconds. The resulting mixture was diluted stepwise with water until the final translucent / transparent microemulsion was fluid (having a water-like viscosity). 0.5g of water was added at each step and the contents of the cup were mixed at high speed in between.

[0130] In Table 8, emulsion EM14 was prepared as follows: 4.8 g of copolymer P1, 0.24 g of surfactant S1, and 0.76 g of anionic surfactant S3 were added to a 20DAC cup. These starting materials were speed mixed in a Speed ​​Mixer at 3500 RPM twice for 30 seconds each time. Water was added incrementally to the cup (total of 2.21 g), with speed mixing between each successive water dilution, until the resulting emulsion was fluid.

[0131] In Table 8, emulsion EM15 was prepared as follows: 3.6g of copolymer P3, 0.19g of surfactant S1, 0.13g of surfactant S2, and 0.36g of water were added to a 20DAC cup. These starting materials were high-speed mixed in a SpeedMixer (Flaktek SpeedMixer DAC 150.1 FVZ-K) at 3500 RPM twice for 30 seconds each time. Water was added stepwise to the cup until the total water content was 1.67g. The resulting product was high-speed mixed between each successive water dilution step. 0.42g of cationic surfactant S4 was added to the cup, and the contents of the cup were high-speed mixed at 3500 RPM for 30 seconds.

[0132] In Table 8, emulsion EM18 was prepared as follows: 3.56g of copolymer P1, 0.2g of surfactant S1, 0.18g of surfactant S2, and 0.57g of water were added to a 20DAC cup. These starting materials were speed mixed in a Speed ​​Mixer at 3500 RPM twice for 30 seconds each time. Water was added incrementally to the cup until the total water content was 1.58g. The resulting product was speed mixed between each successive water dilution step. 0.4g of cationic surfactant S4 was added to the cup, and the contents of the cup were speed mixed at 3500 RPM for 30 seconds.

[0133] Particle size of macroemulsions (e.g., EM14-EM18 and EM25) was measured with a Malvern Mastersizer 3000. A small amount of emulsion (<1 wt%) was first diluted with DI water. This diluted emulsion was then dripped onto the Hydro LV attachment of the Mastersizer until obscuration reached 5%-8%. Particle size analysis was then performed using a custom SOP for particle sizes below 10 μm.

[0134] The particle size of the microemulsions (e.g., EM12 and EM13) was measured with a Microtrac™ Nanotrac Wave particle size analyzer. Background scattering data was collected by adding DI water to the sample chamber. A small amount of emulsion (<1 wt%) was separately diluted with DI water. This diluted emulsion was then dropped into the sample chamber of the particle size analyzer. Particle size analysis was then performed using a custom SOP. No particle size was detected for samples EM21-24, likely because the actual size was below the detection limit of the instrument.

[0135] In this Reference Example 12, emulsion samples EM19 and EM20 were prepared as follows using the starting materials and amounts shown in Table 9 below. Amounts are in parts by weight. Copolymer, surfactant, and first water were added to a 20 DAC cup. These starting materials were speed mixed in a SpeedMixer (Flaktek SpeedMixer DAC 150.1 FVZ-K) at 3500 RPM twice for 30 seconds each time. Acetic acid (10%) and dilution water were added stepwise to the above mixture, speed mixing between each successive water dilution step.

[0136] [Table 9]

[0137] In this Comparative Example 13, an amino silicone emulsion (EM11) was prepared as follows: 57.5g of bis-diisopropanolamino-PG-propyldisiloxane / bis-vinyldimethicone copolymer, 2.4g of T Maz-20, and 6g of water were added to a 100DAC cup. These starting materials were speed mixed in a SpeedMixer (Flaktek SpeedMixer DAC 150.1 FVZ-K) at 3500 RPM twice for 30 seconds each time. 12g of water was added to the cup, and the contents of the cup were speed mixed in the Speed ​​Mixer at 3500 RPM. An additional 22g of water was added to the cup, and the contents of the cup were speed mixed in the Speed ​​Mixer at 3500 RPM.

[0138] In this Example 14, a rinse-off hair conditioner formulation (CF) was prepared using the emulsion prepared above and the starting materials shown in Table 10 below.

[0139] [Table 10]

[0140] Samples of rinse-off hair conditioner formulations were prepared as follows, using the amounts of each starting material shown in Table 11 below: Deionized water was added to a mixing vessel and heated to 70°C. Hydroxyethylcellulose was dispersed with moderate agitation until completely dissolved. Heat was reduced to 60°C and cetearyl alcohol, PEG-100 stearate and glyceryl stearate and silicone (if present) were added. The conditioner was mixed for 3 minutes, after which tetrasodium EDTA was added and mixed for 3 minutes. When the temperature had fallen below 40°C, phenoxyethanol was added. Lost water was replaced and the resulting formulation was mixed for an additional 5 minutes. The final pH of all conditioner formulations was approximately 5.

[0141] For the silicone emulsion, the emulsion was added last along with the phenoxyethanol.

[0142] [Table 11]

[0143] [Table 12]

[0144] In Table 11, qs is "sufficient amount."

[0145] A study was conducted to evaluate the ease of combing wet and dry of hair treated with rinse-off hair conditioner formulations (CF1-CF13 above) as follows: Slightly bleached Caucasian hair from International Hair Importers was used to test the rinse-off hair conditioner formulations. Each tress weighed 2 grams. Each tress was rinsed for 30 seconds under running tap water at 40° C. A pipette was used to apply 0.4 grams of a solution containing 9 percent sodium lauryl sulfate and lathered throughout each tress for 30 seconds. The tress was then rinsed for 1 minute under running water. Excess water was removed from each tress by passing the tress between the index and middle fingers of the hand. The tress was then treated with one of the rinse-off conditioner formulations of Examples CF1-CF13 at 0.4 g of formulation / g of hair by massaging the formulation into the wet / damp hair for 1 minute. The tress was then rinsed with tap water at 40°C for 30 seconds. Excess water was removed by pulling the tress through the index and middle fingers of the hand. The tress was placed on a tray covered with paper towels and allowed to dry overnight at room temperature. The rinse-off hair conditioner samples prepared as described in Reference Example 14 above were tested according to the coefficient of friction, INSTRON COMBING, INSTRON WET COMBING, and INSTRON DRY COMBING methods described below. The results are shown in Table 12 below.

[0146] [Table 13]

[0147] [Table 14]

[0148] Comparative Example 1 was a control and contained no copolymer and a comparative amino-terminated silicone. Comparative Examples 2 and 3 contained a commercial amino silicone instead of the copolymer of the present invention.

[0149] The results in Table 12 show that all inventive examples containing copolymers made with terminal primary amino functional siloxanes performed significantly better than the control CF1 in both dry and wet combing. Most inventive copolymers performed comparable to the comparative commercial amino silicones, while CF13 outperformed the other polymers in dry combing. For COF, all samples performed better than the control CF1.

[0150] In this Reference Example 15, hair care compositions CF17-CF23 were prepared and evaluated for styling / curl retention as follows. CF17-23 were prepared by simply diluting the emulsion in deionized water with thorough stirring at room temperature. Samples CF17-CF23 had the amounts of starting materials in Table 13 below. Amounts are in parts by weight.

[0151] Tests to evaluate the styling and curl retention effects of the formulations of Examples CF17-CF23 were performed as follows: Slightly bleached Caucasian hair from International Hair Importers was used for testing. Each tress weighed 2 grams. Each tress was rinsed for 30 seconds under running tap water at 40°C. Using a pipette, 0.4 grams of a solution containing 9 percent sodium lauryl sulfate was applied and lathered throughout each tress for 30 seconds. The tress was then rinsed for 1 minute under running water. Excess water was removed from each tress by passing the tress between the index and middle fingers of the hand. The tress was then treated with one of the samples CF17-CF21 at 0.15 g of formulation / g of hair by massaging the formulation into the wet / damp hair for 1 minute. The tress was tightly wound on curlers and left in a 45°C oven overnight. The next day, the tress was removed from the oven and allowed to cool to room temperature for 30 minutes. The curlers were carefully removed from the tresses and the tresses were hung in a humidity chamber at 25° C. and 80% relative humidity for a total of 5 hours. The percent curl retention was calculated based on the length of the tress before incubation in the humidity chamber. The results in Table 13 show that hair treated with CF20 and CF21 provided improved curl retention compared to comparative examples CF17 and CF18, and was comparable to the best silicone product (CF19).

[0152] [Table 15] In Table 13, qs means "sufficient amount." a Used in the comparative examples and available from DSC under the trade name DOWSIL™ CE-7080 Smart Style.

[0153] [Table 16]

[0154] CF21 contains a copolymer with a higher degree of polymerization (DP) and performs equally well as comparative sample CF19.However, the polymer used in CF19 is known to contain high levels of cyclomethicone (>0.1%), which is of concern in personal care applications.The polymer used in CF20 and CF21 has low levels of cyclomethicone (<0.1%) even after aging at room temperature for 2 years.The inventors have surprisingly found that the copolymer of the present invention has the advantage of low cyclomethicone content, especially in the sample with a longer DP siloxane.When using a shorter DP siloxane in the copolymer (CF20-EM19 with 44DP siloxane), curl retention effect is also observed compared to the control.

[0155] In this Reference Example 16, hair manageability was evaluated as follows: Curly hair purchased from International Hair was washed with 9% SLS for 30 seconds and treated with 0.15g of CF17, CF22, or CF23 per gram of hair. The tresses were left at room temperature and 50% relative humidity and the manageability factor was measured using RUMBA by Bossa Nova after 3 and 21 hours with and without combing. The results in Table 15 below show that the tresses treated with the inventive example (CF23) had higher hair manageability compared to the control in all conditions. Compared to the comparative example CF22, the hair treated with CF23 showed significantly improved manageability after 21 hours.

[0156] [Table 17]

[0157] The test methods used herein are described below.

[0158] 29 Si NMR and 13 C NMR spectroscopy can be used to characterize the hydrocarbon groups in the polydiorganosiloxane (e.g., R 8 and / or R 9The content of R groups such as 29 Si NMR spectra should be obtained using the methodology outlined by Taylor et al. in Chapter 12, pages 347-417, Section 5.5.3.1, The Analytical Chemistry of Silicones, edited by A. Lee Smith, Chemical Analysis Vol 112, John Wiley & Sons, Inc. (1991). In this chapter, the authors discuss the general parameters specific to obtaining quantitative NMR spectra of silicon nuclei. Each NMR spectrometer differs in terms of electronics, capabilities, sensitivity, frequency, and operating procedures. 29 Si and 13 The instrument manual of the spectrometer used must be consulted in order to tune, shim and calibrate a pulse sequence sufficient for quantitative 1D measurements of C nuclei.

[0159] The key output of an NMR analysis is the NMR spectrum. In the absence of a standard, a signal-to-noise ratio of 10:1 or greater (signal height to average baseline noise) is recommended to be considered quantitative. A properly acquired and processed NMR spectrum results in signals that can be integrated using any commercially available NMR processing software package.

[0160] From these integrals, the weight percent of the total R group content is 29 From the Si NMR spectrum, the compound of the following formula (I M )·(U M )=G M ;(I M(R) )·(U M(R’) )=G M(R) ;(I D )·(U D )=G D ;(I D(R) )·(U D(R) )=G D(R) ;U R / U M(R) =Y R’ ;U R / U D(R) =Y R’’; Y R’’ · [G M(R) / (G M +G M(R) +G D +G D(R) )·100]=W R’ ; Y R’’’ · [G D(R) / (G M +G M(R) +G D +G D(R) )·100]=W R’’ ; and W R’ +W R’’ = Total W R where I is the integral signal of the indicated siloxy group, U is the unit molecular weight of the indicated siloxy group, G is a placeholder representing units in grams, W is the weight percent of the indicated siloxy unit, Y is the ratio value of the specified siloxy unit, R is as above, R' represents the R group from M(R) alone, and R ’’ " represents the R group from the D(R) group only.

[0161] 1 H-NMR was evaluated using a Varian 400 MHz Mercury NMR Spectrometer. Samples were prepared by dissolving the analyte in CDCl3, which consisted of at least 60% but not more than 90% by mass. The determination of complete conversion of the acrylate moiety was made when the vinyl proton signal was indistinguishable from the baseline.

[0162] Using FTIR, (AB) nThe concentration of unreacted acrylate present in the copolymer can be determined. FTIR analysis was performed using a PerkinElmer FTIR Spectrometer Frontier. Samples were prepared by diluting the polymer with tetrachloroethylene and mixing with a vortex action. Once mixed, the sample was pipetted into an FTIR sample cell that had a fixed gap between two NaCl salt plates. The sample cell was then placed in the FTIR instrument and scanned 16 times to obtain the final spectrum.

[0163] Rheometry can be used to measure the viscosity of the copolymer. Viscosity measurements were performed on a Brookfield DV-III Ultra Programmable Rheometer fitted with a CPE-44Y standard sample cup with an integrated CPE-52 cone and temperature probe, and calibrated to measure the kinematic viscosity of amino silicone polymers as described in the manual. Approximately 0.4 mL of sample was poured into the center of the sample cup, and the sample cup was set in place for the measurement. The appropriate RPM value was determined by ensuring the cup temperature was 25° C. and checking the % torque and adjusting the RPM value if necessary.

[0164] GPC can be used to measure the number average molecular weight (Mn) and weight average molecular weight (Mw) of the copolymers. Measurements were performed using the system described in the table below. Samples were prepared in 20 mL scintillation vials at 10 mg / mL concentration and capped with acetic anhydride. Samples were shaken for 2 hours using a wrist shaker and then filtered through a 0.45 μm PTFE syringe filter into a 2 mL GC vial. Samples were placed on the autosampler and data collection was started. Data collection was performed over a 30 minute period and the data was processed and analyzed against polystyrene standards ranging from 580 to 2,750,000 daltons.

[0165] [Table 18]

[0166] COEFFICIENT OF FRICTION is an industry standard method for measuring the reduction in frictional properties of a treatment on hair and correlates to sensory metrics of smoothness and softness. For testing in a temperature and humidity controlled room, a Diastron MTT175 tensile tester was used, fitted with a 50g normal force on a rubber probe. Three hair tresses per treatment and five measurements per tress were tested to obtain friction data both with and against the hair cuticle. Coefficient of Friction (COF)=F / N, where F is the force applied outwards and N is the normal force. The same hair tresses as for the combing test were used to measure the coefficient of friction in the dry state.

[0167] An INSTRON Model 4464 running BlueHill 2 software was also used to measure conditioning performance by wet combing and dry combing ease. The test used an INSTRON strain gauge equipped to measure the force required to comb the hair. Conditioning performance was based on the ability of a particular hair treatment formulation, such as a shampoo or hair conditioner, to reduce the force required to comb the hair with an INSTRON strain gauge. The force was reported as the average comb load (ACL). The lower the number of ACL values, the greater the conditioning benefits imparted by the formulation being tested.

[0168] According to the INSTRON WET COMBING method, the hair was first wetted by immersion in distilled water, then the tress was detangled by combing it three times. The tress was then re-tangled by immersing it three times in distilled water. Excess water was removed from the tress by passing it between the index and middle fingers of the hand twice. The tress was placed on a hanger and combed with an INSTRON comb. The re-tangling and combing were repeated until all data points were collected. The average combing force of three tresses was measured for each treatment.

[0169] The hair was detangled by combing the tress three times according to the INSTRON DRY COMBING method. The tress was then retangled by rotating it three times clockwise and three times counterclockwise. The tress was placed on a hanger and combed with an INSTRON comb. The retangling and INSTRON combing were repeated until all data points were collected. The average combing force of three tresses was measured for each treatment.

[0170] Industrial Applicability The copolymers described herein may have one or more of the following advantages: low cyclic polyorganosiloxane content (<0.05% octamethylcyclotetrasiloxane), stability after aging as evidenced by low cyclic content after aging, little or no crosslinking, and potential biodegradability. Additionally, the copolymers may be miscible with organic solvents and some oils. Without wishing to be bound by theory, it is believed that the use of copolymers in which subscript a is at least 44, alternatively 44-200, alternatively 44-84, may provide improved curl retention when formulated into hair styling compositions. Without wishing to be bound by theory, it is believed that copolymers in which subscript a is at least 44, alternatively 44-200, alternatively 44-84, may provide improved curl retention when formulated into hair styling compositions. While not wishing to be bound by theory, it is believed that copolymers in which subscript a is at least 44, alternatively 44-200, alternatively 44-84, may provide improved curl retention when formulated into hair styling compositions. D It is further believed that may improve the performance of the copolymer on hair, particularly for the dry comb test described above. As shown by the examples above, the copolymers of the present invention also provide significantly better wet combing performance than amino-terminated silicone polymers, using the wet comb test described above.

[0171] The copolymers described herein are useful in hair care applications and may provide one or more styling benefits such as increased curl retention, improved hair manageability, and / or improved hair orientation and / or hair conditioning as evidenced by improved dry and / or wet combing performance and improved coefficient of friction.

[0172] Definitions and Use of Terms All amounts, ratios, and percentages are by weight unless otherwise indicated by the context of the specification. The amounts of all starting materials in the composition total 100% by weight. The Summary and Abstract are incorporated herein by reference. The articles "a," "an," and "the" each refer to one or more, unless otherwise indicated. The singular includes the plural, unless otherwise indicated. The terms "comprising" and "comprise" are used herein in their broadest sense to mean and encompass the ideas of "including," "include," "consist(ing) essentially of," and "consist(ing) of." The use of "for example," "eg," "such as," and "including" to list examples is not limited to only the examples listed. Thus, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to," and includes other similar or equivalent examples. The disclosure of a range includes the range itself and any subsumed within the range, as well as the endpoints. Similarly, the disclosure of a Markush group includes the entire group, as well as any individual members and subgroups subsumed therein. For example, the disclosure of the Markush group "hydrogen atom, alkyl group, alkenyl group, or aryl group" includes the individual members alkyl, the subgroups alkyl and aryl, and any other individual members and subgroups subsumed within the Markush group. Abbreviations are as defined in Table 7 below.

[0173] [Table 19]

Claims

1. formula: 【Chemistry 1】 [In the formula, each R １ are independently selected monovalent hydrocarbon radicals of 1 to 12 carbon atoms, and each R Ｅ are independently hydroxyl and a group of formula H ２ N-R Ａ -, and each R Ａ are independently divalent hydrocarbon radicals of 1 to 12 carbon atoms, and each R ２ is independently selected from the group consisting of hydrogen and methyl, and each R Ｄ are independently selected divalent hydrocarbon radicals of 2 to 20 carbon atoms, each subscript a independently having a value such that 0≦a<220 and each subscript b independently having a value such that 1≦b≦100; 1. An aminosiloxane ester copolymer comprising:

2. One or more of conditions i) to vii) are satisfied, where condition i) is that subscript a is between 2 and 200, condition ii) is that subscript b is between 2 and 20, and condition iii) is that each R Ｄ has 3 to 12 carbon atoms; proviso iv) is that each R ２ is hydrogen, and condition v) is that each R １ is an alkyl group of 1 to 6 carbon atoms; and proviso vi) that each R Ａ is an alkyl group of 1 to 6 carbon atoms; and proviso vii) that the copolymer has a number average molecular weight of >1,000 g / mol to 250,000 g / mol as measured by gel permeation chromatography. The copolymer of claim 1.

3. 10. A process for preparing the copolymer of claim 1, wherein each R Ｅ is an amino functional group, and said process comprises (A) Formula 【Chemistry 2】 wherein each R １ is an independently selected monovalent hydrocarbon radical of 1 to 12 carbon atoms, and each R Ａ are independently divalent hydrocarbon radicals of 1 to 12 carbon atoms, and the subscript a has a value such that 0≦a<220; and (B) Formula 【Transformation 3】 Bis-acryloyloxy-alkanes of the formula: Ｄ includes combining a starting material including a bis-acryloyloxy-alkane, which is a divalent hydrocarbon radical of 2 to 20 carbon atoms; A process for preparing a copolymer, wherein starting material (A) and starting material (B) are present in amounts such that the molar ratio of (A):(B) ranges from 2:1 to 1:1.

1.

4. 10. A process for preparing the copolymer of claim 1, said process comprising: １） (B) Formula 【Chemistry 4】 Bis-acryloyloxy-alkanes of the formula: Ｄ is a bis-acryloyloxy-alkane, which is a divalent hydrocarbon radical of 2 to 20 carbon atoms; (F) formula 【Transformation 5】 bis-silanol-terminated polydiorganosiloxanes of the formula: １ is an independently selected monovalent hydrocarbon radical of 1 to 12 carbon atoms, and the subscript a has independently a value such that 0≦a<220; (G) formula 【Transformation 6】 wherein the subscript c is 0 or 1; and each R ８ are independently selected monovalent hydrocarbon radicals of 1 to 18 carbon atoms, and each R ９ are independently selected from the group consisting of hydrogen and alkyl groups of 1 to 15 carbon atoms; A process for preparing a copolymer comprising combining starting materials comprising:

5. 5. The process of claim 3 or claim 4, wherein (B) the bis-acryloyloxy-alkane is selected from the group consisting of 1,3-butanediol diacrylate, 1,4-butanediol diacrylate; 1,6-hexanediol diacrylate; 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, and combinations of two or more of 1,3-butanediol diacrylate, 1,4-butanediol diacrylate; 1,6-hexanediol diacrylate; 1,9-nonanediol diacrylate, and 1,10-decanediol diacrylate.

6. 5. The process of claim 3 or claim 4, further comprising adding during step 1) additional starting materials selected from the group consisting of (C) a catalyst, (D) a solvent, (E) an acrylate polymerization inhibitor, and combinations of two or more of (C), (D), and (E).

7. 5. The process of claim 3 or claim 4, wherein one or both of conditions (a) and (b) are met, condition (a) being that the combining in step 1) comprises mixing and heating the starting materials at a temperature from 0° C. to 180° C., and condition (b) being that the combining in step 1) is conducted for 1 to 48 hours.

8. 2) The process of claim 3 or claim 4, further comprising recovering the copolymer during and / or after step 1).

9. 5. The process of claim 4, wherein said method uses less than 2 molar equivalents of (G) cyclic siloxazane per mole of (F) bis-silanol-terminated polydiorganosiloxane.

10. 5. The process of claim 4, wherein the method employs at least 2 molar equivalents of (G) cyclic siloxazane per mole of (F) bis-silanol-terminated polydiorganosiloxane.

11. An emulsion, (I) a liquid continuous phase comprising water; (II) a discontinuous phase dispersed in the liquid continuous phase, the discontinuous phase comprising the aminosiloxane ester copolymer of claim 1 or claim 2.

12. 12. The emulsion of claim 11, wherein the emulsion further comprises additional starting materials selected from the group consisting of (H) surfactants, (I) acid compounds, (J) acid anhydrides, (K) thickeners, (L) stabilizers, and combinations of two or more of (H), (I), (J), (K), and (L).

13. 10. A method for producing an emulsion, comprising mixing under shear starting materials comprising the copolymer of claim 1 or claim 2, water, and optionally one or more starting materials selected from the group consisting of (H) surfactants, (I) acid compounds, (J) acid anhydrides, (K) thickeners, and (L) stabilizers.

14. 3. Use of the copolymer of claim 1 or claim 2 in a hair care composition.

15. 15. The use according to claim 14, wherein the hair care composition is a conditioner or styling product.

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