Amino silicone oil emulsion, preparation method and application thereof, and hair care composition

Abstract

The invention relates to the field of amino silicon oil emulsions, in particular to an amino silicon oil emulsion and a preparation method and application thereof.The amino silicon oil emulsion is prepared from an amino silane coupling agent, cyclotetrasiloxane, a disiloxane end-capping reagent containing alkoxy, an emulsifier, a catalyst and water, and the emulsifier comprises a cationic emulsifier. The amino silicone oil emulsion disclosed by the invention is high in solid content, moderate in particle size, strong in stability, easier to spread uniformly on hair, excellent in film-forming property, beneficial to silicone deposition and excellent in care effect.

Description

Technical Field

[0001] This application relates to the field of amino silicone oil emulsions, and more particularly to amino silicone oil emulsions, their preparation methods and applications, and hair care compositions. Background Technology

[0002] Polydimethylsiloxanes with amino functional groups are long-chain organosilicon compounds containing repeating Si-O-Si bond units, typically characterized by their amine value (meq / g) and viscosity (mPa·s). In modern life, people's hair is increasingly exposed to sun exposure, environmental pollution, combing and stretching, hair dryers, curling irons, and dyeing and bleaching, resulting in varying degrees of damage. Currently, amino-based polydimethylsiloxanes with a viscosity exceeding 20,000 mPa·s and an amine value between 0.06 and 0.1 meq / g are more effective than dimethylsiloxanes in improving the hydrophobic properties of hair, thus giving hair an excellent soft and smooth feel.

[0003] Currently, there are two common methods for preparing amino silicone oil emulsions: one is bulk polymerization, which involves synthesizing amino silicone oil emulsions and then obtaining the emulsion through mechanical emulsification; the other is to directly obtain the emulsion by polymerization in the emulsion. However, traditional emulsion preparation methods have the following problems: (1) it is difficult to emulsify high-viscosity and high-amine-value amino polydimethylsiloxanes into small-particle-size, uniform, and stable emulsions; (2) the amino silicone oil emulsions obtained during emulsion polymerization are difficult to achieve high internal phase amino silicone oil viscosity, resulting in reduced film-forming properties and thus significantly reduced performance. Summary of the Invention

[0004] This application aims to at least partially solve one of the technical problems in the related art. To this end, this application provides an amino silicone oil emulsion, its preparation method and application, and a hair care composition. This amino silicone oil emulsion has a high solids content, strong stability, and moderate particle size, making it easier to spread evenly on the hair. It has excellent film-forming properties, which is conducive to silicone deposition, resulting in excellent hair care effects.

[0005] Therefore, the first aspect of this application provides an amino silicone oil emulsion. According to embodiments of this application, the raw materials of the amino silicone oil emulsion include: an aminosilane coupling agent, a cyclotetrameric dimethylsiloxane, an alkoxy-containing disiloxane end-capping agent, an emulsifier, a catalyst, and water, wherein the emulsifier includes a cationic emulsifier.

[0006] In the amino silicone oil emulsion according to the embodiments of this application, under the action of an emulsifier, the oil phase (aminosilane coupling agent, cyclotetrameric dimethylsiloxane, and alkoxy-containing disiloxane end-capping agent) can be dispersed in the aqueous phase to form a stable O / W emulsion. Under the catalysis of a catalyst, cyclotetrameric dimethylsiloxane undergoes ring-opening to generate a polysiloxane chain containing an active end group. This active end group undergoes a condensation reaction with the alkoxy group of the aminosilane coupling agent, linking the amino side into the main chain. At the same time, one end of the alkoxy-containing disiloxane end-capping agent condenses with the active chain end group to achieve end-capping and control the molecular weight, while the other end retains the alkoxy group as a crosslinking site. Subsequently, when the emulsion is applied to hair, the residual alkoxy group hydrolyzes upon contact with water on the hair surface to generate silanol groups (HO-Si-). The silanol groups then undergo a self-condensation reaction with the Si-OR or silanol groups of other molecular chains to form -Si-O-Si- crosslinking bonds, constructing a crosslinked network structure, thereby improving the stability and film-forming properties of the emulsion. Furthermore, amino silicone oil molecules have positively charged amino functional groups. When cationic emulsifiers dissociate in water, their hydrophilic ends carry a positive charge and come into contact with water, while their hydrophobic ends insert into the silicone oil droplets. This results in the latex particles being surrounded by a layer of positive charge, forming a stable positively charged layer. Since the amino groups on the amino silicone oil molecular chain also tend to be positively charged, they are compatible with the charge properties of the cationic emulsifier, thus forming a tight and strong adsorption layer, resulting in a more stable and finer emulsion. Simultaneously, cationic amino silicone oil emulsions can better adsorb onto the surface of most negatively charged hair, achieving excellent soft and smooth conditioning effects.

[0007] According to embodiments of this application, the alkoxy-containing disiloxane end-capping agent has the structure shown in Formula I: Formula I; wherein R1 is H or C1-C3 alkyl; R2 is C1-C3 alkyl or C1-C3 alkoxy.

[0008] According to embodiments of this application, the alkoxy-containing disiloxane end-capping agent includes at least one of 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane and 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane.

[0009] According to embodiments of this application, the aminosilane coupling agent comprises at least one of aminoethylaminoisobutylmethyldimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, 3-(N-cyclohexylamine)propylmethyldimethoxysilane, n-butylaminopropyltrimethoxysilane, N-(n-butyl)-3-aminopropyltriethoxysilane, and γ-aminopropylmethyldiethoxysilane; the catalyst comprises at least one of sodium hydroxide, potassium hydroxide, and tetramethylammonium chloride.

[0010] According to embodiments of this application, the cationic emulsifier includes at least one of hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, didodecyldimethylammonium bromide, benzalkonium chloride, fatty imidazoline, alkylpyridine halide, 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazoline, and polyoxyethylalkyl quaternary ammonium salt; the emulsifier further includes a nonionic emulsifier, which preferably includes fatty alcohol polyoxyethylene ether with an HLB value of 5 to 16.

[0011] According to an embodiment of this application, the mass ratio of the cationic emulsifier to the nonionic emulsifier is (1~7):(1~7); the nonionic emulsifier includes fatty alcohol polyoxyethylene ether with a carbon chain length of 12~14 and an ethoxy group number of 5~12.

[0012] According to embodiments of this application, the nonionic emulsifier includes at least one of isotretinoin polyoxyethylene ether-12 and isotretinoin polyoxyethylene ether-7.

[0013] According to an embodiment of this application, the content of the aminosilane coupling agent is 1% to 10% based on the total mass of the raw materials of the aminosilicone oil emulsion.

[0014] According to an embodiment of this application, based on the total mass of the raw materials of the amino silicone oil emulsion, the content of the cyclotetrameric dimethylsiloxane is 20% to 40%, and the content of the alkoxy-containing disiloxane end-capping agent is 0.02% to 2%.

[0015] According to an embodiment of this application, based on the total mass of the raw materials of the amino silicone oil emulsion, the content of the emulsifier is 2% to 14%; the mass ratio of the cationic emulsifier to the nonionic emulsifier is (1 to 7): (1 to 7).

[0016] According to an embodiment of this application, based on the total mass of the raw materials of the amino silicone oil emulsion, the catalyst content is 0.3% to 1%, and the water content is 34% to 76%.

[0017] According to embodiments of this application, the pH value of the amino silicone oil emulsion is 5.0~7.0.

[0018] The second aspect of this application provides a method for preparing the amino silicone oil emulsion described in the first aspect, comprising: mixing an aminosilane coupling agent, a cyclotetrameric dimethylsiloxane, an alkoxy-containing disiloxane end-capping agent, an emulsifier, a catalyst, and water, and obtaining the amino silicone oil emulsion through a ring-opening reaction. Therefore, the amino silicone oil emulsion prepared by this method has high solids content, strong stability, and moderate particle size, making it easier to spread evenly on hair and exhibiting excellent film-forming properties.

[0019] According to an embodiment of this application, the method further includes:

[0020] The aminosilane coupling agent, cyclotetrameric dimethylsiloxane, alkoxy-containing disiloxane end-capping agent, a portion of the emulsifier, and a portion of the water are mixed to obtain a pre-emulsion; The catalyst, the remaining emulsifier, and the remaining water are mixed to obtain a mixture; The mixture is combined with the preemulsion and subjected to a ring-opening reaction to obtain an intermediate emulsion. The pH of the intermediate emulsion is adjusted to 5.0~7.0 to obtain the amino silicone oil emulsion.

[0021] According to an embodiment of this application, the aminosilane coupling agent, cyclotetrameric dimethylsiloxane, alkoxy-containing disiloxane end-capping agent, a portion of the cationic emulsifier, a portion of the nonionic emulsifier, and a portion of the water are mixed to obtain the pre-emulsion; the catalyst, the remaining cationic emulsifier, the remaining nonionic emulsifier, and the remaining water are mixed to obtain the mixture; wherein the portion of the cationic emulsifier accounts for 40 wt% to 60 wt% of the total cationic emulsifier, and the portion of the nonionic emulsifier accounts for 40 wt% to 60 wt% of the total nonionic emulsifier.

[0022] According to an embodiment of this application, the pre-emulsion is added dropwise to the mixture over a period of 2 to 3 hours at a temperature of 60°C to 90°C; the ring-opening reaction takes 4 to 8 hours.

[0023] According to an embodiment of this application, the method further includes: adjusting the temperature of the intermediate emulsion to 30°C~40°C and the pH value to 5.0~7.0 to obtain the amino silicone oil emulsion.

[0024] A third aspect of this application provides a hair care composition comprising the amino silicone oil emulsion described in the first aspect. This hair care composition thus exhibits excellent film-forming, hair smoothness, shine, color protection, and damage repair effects.

[0025] A fourth aspect of this application provides a hair care method comprising: applying the amino silicone oil emulsion described in the first aspect or the hair care composition described in the third aspect to hair. Thereby, the amino silicone oil emulsion or hair care composition can provide film formation, hair smoothing, and damage repair effects.

[0026] Additional aspects and advantages of this application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of this application. Detailed Implementation

[0027] The embodiments of this application are described in detail below. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application.

[0028] It should be noted that the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. Furthermore, in the description of this application, unless otherwise stated, "multiple" means two or more.

[0029] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0030] To facilitate understanding of this application, certain technical and scientific terms are specifically defined below. Unless otherwise expressly defined elsewhere in this document, all other technical and scientific terms used herein have the meanings commonly understood by one of ordinary skill in the art to which this application pertains.

[0031] In this document, the terms “comprising” or “including” are open-ended expressions, meaning that they include the contents specified in this application but do not exclude other contents.

[0032] In this article, the term "HLB value" refers to the hydrophilic-lipophilic balance value.

[0033] This application provides an amino silicone oil emulsion in a first aspect. According to embodiments of this application, the raw materials for the amino silicone oil emulsion include: an aminosilane coupling agent, a cyclotetrameric dimethylsiloxane, an alkoxy-containing disiloxane end-capping agent, an emulsifier, a catalyst, and water, wherein the emulsifier includes a cationic emulsifier.

[0034] Since the surface of hair (cuticle) is mainly composed of keratin, under the pH value (slightly acidic) used in most hair care products, the carboxyl groups (-COOH) in keratin will ionize and become negatively charged. The amino groups (-NH2) in amino silicone oil will protonate under these weakly acidic conditions, forming positively charged ammonium ions (-NH3). +This generates strong electrostatic adsorption: the positively charged amino silicone oil is strongly attracted to the negatively charged hair surface, forming a strong silicone oil film. Under the action of an emulsifier, the oil phase (aminosilane coupling agent, cyclotetrameric dimethylsiloxane, and alkoxy-containing disiloxane end-capping agent) can be dispersed in the aqueous phase to form a stable O / W emulsion. Under the catalysis of a catalyst, cyclotetrameric dimethylsiloxane undergoes ring-opening to generate a polysiloxane chain containing active end groups. These active end groups undergo a condensation reaction with the alkoxy groups of the aminosilane coupling agent, linking the amino side into the main chain. Simultaneously, the alkoxy-containing disiloxane end-capping agent condenses with the active chain end group at one end to achieve end-capping and control the molecular weight, while retaining the alkoxy group at the other end as a crosslinking site. When the emulsion is applied to the hair, the residual alkoxy groups hydrolyze upon contact with moisture on the hair surface to generate silanol groups (HO-Si-). These silanol groups then undergo self-condensation reactions with Si-OR or silanol groups of other molecular chains to form -Si-O-Si- crosslinks, constructing a crosslinked network structure, thereby enhancing the stability and film-forming properties of the emulsion. Furthermore, amino silicone oil molecules have positively charged amino functional groups. After the cationic emulsifier dissociates in water, its hydrophilic end carries a positive charge and comes into contact with water, while its hydrophobic end inserts into the silicone oil droplet. This results in the latex particles being surrounded by a layer of positive charge, forming a stable positively charged layer. Since the amino groups on the amino silicone oil molecular chain also tend to be positively charged, they are compatible with the charge properties of the cationic emulsifier, thus forming a tight and strong adsorption layer, resulting in a more stable and finer emulsion. Simultaneously, cationic amino silicone oil emulsions can better adsorb onto the surface of most negatively charged hair, achieving excellent softening and smoothing effects.

[0035] According to embodiments of this application, the aminosilane coupling agent includes aminoethylaminoisobutylmethyldimethoxysilane (CAS: 23410-40-4), N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (CAS: 3069-29-2), 3-(N-cyclohexylamine)propylmethyldimethoxysilane (CAS: 120218-28-2), n-butylaminopropyltrimethoxysilane (CAS: 31024-56-3), N-(n-butyl)-3-aminopropyltriethoxysilane (CAS: 94047-95-7), and γ-aminopropylmethyldiethoxysilane (CAS: 3179-76-8), etc.

[0036] According to embodiments of this application, the alkoxy-containing disiloxane end-capping agent has the structure shown in Formula I: Formula I; Wherein, R1 is H or C1-C3 alkyl; R2 is C1-C3 alkyl or C1-C3 alkoxy. Specifically, the alkoxy-containing disiloxane end-capping agent includes at least one of 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane (CAS: 1118-15-6) and 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane (CAS: 18001-60-0).

[0037] According to embodiments of this application, the emulsifier further includes a nonionic emulsifier. To further enhance the emulsification effect, cationic and nonionic emulsifiers can be used in combination, which can make the resulting emulsion have better stability and be less prone to stratification.

[0038] In some embodiments, the mass ratio of the cationic emulsifier to the nonionic emulsifier is (1~7):(1~7). Exemplarily, the mass ratio of the cationic emulsifier to the nonionic emulsifier is 1:7, 1:5, 1:4, 1:2, 1:1, 2:1, 4:1, 5:1, or 7:1. This results in a more stable emulsion, less prone to stratification, and avoids excessive nonionic emulsifier addition leading to excessively large emulsion particle size, incomplete reaction, and demulsification / stratification.

[0039] According to embodiments of this application, the cationic emulsifier includes at least one of hexadecyltrimethylammonium chloride (CAS: 112-02-7), docosyltrimethylammonium chloride (CAS: 17301-53-0), bis(dodecyl)dimethylammonium bromide (CAS: 3282-73-3), benzalkonium chloride (CAS: 63449-41-2), aliphatic imidazoline, alkylpyridine halide, 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazoline, and polyoxyethylalkyl quaternary ammonium salt.

[0040] Specifically, the substituted pyridine halides may include alkyl pyridine halides, such as hexadecylpyridine chloride, hexadecylpyridine bromide, etc. Aliphatic imidazolines include 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazoline (CAS: 504-74-5). Alkyl pyridine halides include hexadecylpyridine chloride (CAS: 123-03-5).

[0041] According to embodiments of this application, the nonionic emulsifier includes fatty alcohol polyoxyethylene ethers with an HLB value of 5 to 16, preferably fatty alcohol polyoxyethylene ethers with a carbon chain length of 12 to 14 and an ethoxy group number of 5 to 12, such as at least one of isotridecyl alcohol polyoxyethylene ether-12 (CAS: 9043-30-5) and isotridecyl alcohol polyoxyethylene ether-7 (CAS: 9043-30-5).

[0042] According to embodiments of this application, the catalyst includes at least one of sodium hydroxide, potassium hydroxide, and tetramethylammonium chloride. This allows for the effective catalysis of ring-opening of cyclotetrameric dimethylsiloxane to generate a polysiloxane chain containing active end groups. The active end groups undergo a condensation reaction with the alkoxy groups of the aminosilane coupling agent, linking the amino side into the main chain. Simultaneously, one end of the alkoxy-containing disiloxane end-capping agent condenses with the active chain end group to achieve end-capping.

[0043] According to embodiments of this application, the content of the aminosilane coupling agent is 1% to 10% based on the total mass of the raw materials of the aminosilicone oil emulsion. Exemplarily, the content of the aminosilane coupling agent is 1%, 2%, 4%, 5%, 6%, 8%, or 10%. Therefore, the aminosilicone oil exhibits superior adsorption strength, adsorption amount, and the characteristics of the final film formed on the hair surface.

[0044] According to embodiments of this application, based on the total mass of the raw materials of the amino silicone oil emulsion, the content of the cyclotetrameric dimethylsiloxane is 20%~40%, and the content of the alkoxy-containing disiloxane end-capping agent is 0.02%~2%. Exemplarily, the content of the cyclotetrameric dimethylsiloxane is 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, or 40%, and the content of the alkoxy-containing disiloxane end-capping agent is 0.02%, 0.1%, 0.5%, 1%, 1.5%, or 2%. The cyclotetrameric dimethylsiloxane serves as the main monomer for polymerization, providing the polysiloxane backbone, while the alkoxy-containing disiloxane end-capping agent achieves end-capping through reaction with the polymerizable active end groups. When both components meet the above ratio, the polymerized product can have both good degree of polymerization, dispersibility, and relatively high molecular weight. The resulting emulsion has better film-forming properties and stability. When used to care for hair, it can improve the softness, shine, combability, and color protection of hair, and is conducive to silicone deposition, making it less likely to cause oily and heavy hair.

[0045] According to embodiments of this application, the content of the emulsifier is 2% to 14% based on the total mass of the raw materials of the amino silicone oil emulsion. For example, the content of the emulsifier is 2%, 4%, 5%, 6%, 8%, 10%, 12%, or 14%. This allows for efficient dispersion of the oil phase into small, uniform droplets, forming a stable O / W emulsion. It avoids problems such as droplet aggregation, large particle size, and easy stratification at high temperatures. The resulting emulsion has moderate viscosity, and when used for hair care, it can improve hair softness, shine, combability, and color retention, which is beneficial for silicone deposition.

[0046] According to embodiments of this application, based on the total mass of the raw materials of the amino silicone oil emulsion, the catalyst content is 0.3%~1%, and the water content is 34%~76%. Exemplarily, the catalyst content is 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%, and the water content is 34%, 40%, 50%, 60%, 70%, or 76%. Therefore, this amino silicone oil emulsion has a high solids content and moderate particle size, making it easier to spread evenly on the hair, exhibiting excellent film-forming properties, which is beneficial for silicone deposition and provides excellent conditioning effects. Furthermore, the emulsion has strong stability and does not easily separate after standing at 50°C for 3 months.

[0047] According to embodiments of this application, the pH value of the amino silicone oil emulsion is 5.0 to 7.0. Exemplarily, the pH value of the amino silicone oil emulsion is 5.0, 5.5, 6.0, 6.5, or 7.0. Therefore, the amino silicone oil emulsion exhibits high stability.

[0048] A second aspect of this application provides a method for preparing the amino silicone oil emulsion described in the first aspect, comprising: An aminosilane coupling agent, cyclotetrameric dimethylsiloxane, disiloxane end-capping agent, cationic emulsifier, nonionic emulsifier, catalyst, and water are mixed, and the aminosilicone oil emulsion is obtained through a ring-opening reaction. Therefore, the aminosilicone oil emulsion prepared by this method has high solids content, strong stability, and moderate particle size, making it easier to spread evenly on hair and exhibiting excellent film-forming properties.

[0049] According to an embodiment of this application, the method further includes: The aminosilane coupling agent, cyclotetrameric dimethylsiloxane, alkoxy-containing disiloxane end-capping agent, a portion of the emulsifier, and a portion of the water are mixed to obtain a pre-emulsion; The catalyst, the remaining emulsifier, and the remaining water are mixed to obtain a mixture; The mixture is combined with the preemulsion and subjected to a ring-opening reaction to obtain an intermediate emulsion. The pH of the intermediate emulsion is adjusted to 5.0~7.0 to obtain the amino silicone oil emulsion; The cationic emulsifier accounts for 40 wt% to 60 wt% (e.g., 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%) of the total cationic emulsifier, and the nonionic emulsifier accounts for 40 wt% to 60 wt% (e.g., 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%) of the total nonionic emulsifier.

[0050] In some specific embodiments, the aminosilane coupling agent, cyclotetrameric dimethylsiloxane, alkoxy-containing disiloxane end-capping agent, a portion of the cationic emulsifier, a portion of the nonionic emulsifier, and a portion of the water are mixed to obtain a pre-emulsion; the catalyst, the remaining cationic emulsifier, the remaining nonionic emulsifier, and the remaining water are mixed to obtain a mixture.

[0051] By adding cationic and nonionic emulsifiers in two stages, the oil phase is better dispersed in the aqueous phase, forming a stable emulsion system that is less prone to stratification and also facilitates polymerization.

[0052] Specifically, an aminosilane coupling agent, cyclotetrameric dimethylsiloxane, disiloxane end-capping agent, partially cationic emulsifier, partially nonionic emulsifier, and water can be mixed to form a stable O / W preemulsion by applying mechanical shear force.

[0053] Specifically, the mixing method between the mixture and the preemulsion is not particularly limited; they can be mixed directly or added dropwise to the preemulsion.

[0054] Specifically, the pre-emulsion is added dropwise to the mixture at a temperature of 60°C to 90°C for 2 to 3 hours. This achieves a better mixing effect.

[0055] Specifically, the ring-opening reaction can be carried out under heat preservation conditions for a reaction time of 4 to 8 hours. This facilitates the efficient progress of the polymerization reaction.

[0056] Specifically, the pH of the emulsion obtained by the ring-opening reaction can be adjusted at 30-40℃, for example, by adjusting the pH of the emulsion to 5.0-7.0, in order to improve its stability and particle size.

[0057] According to specific embodiments of this application, the obtained amino silicone oil emulsion can be subjected to mechanical shearing, filtration, and other operations to obtain the target amino silicone oil emulsion for subsequent testing, production, and other applications.

[0058] A third aspect of this application provides a hair care composition comprising the amino silicone oil emulsion described in the first aspect. This hair care composition thus exhibits excellent film-forming, hair smoothness, shine, color protection, and damage repair effects. In some embodiments, the hair care composition may be a conditioner, shampoo, hair mask, etc.

[0059] A fourth aspect of this application provides a hair care method comprising: applying the amino silicone oil emulsion described in the first aspect or the hair care composition described in the third aspect to hair. Thereby, the amino silicone oil emulsion or hair care composition can provide film formation, hair smoothing, and damage repair effects.

[0060] The following will explain the solution of this application with reference to embodiments. Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be considered as limiting the scope of this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in the art or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0061] Example 1 In this embodiment, the amino silicone oil emulsion was prepared according to the following method: 1. Formula The formulation of the amino silicone oil emulsion is shown in Table 1, wherein the mass ratio of isomeric 13 alcohol polyoxyethylene ether-12 and isomeric 13 alcohol polyoxyethylene ether-7 is 0.46:8.68, and hexadecyltrimethylammonium chloride is provided in the form of an aqueous solution with a concentration of 30 wt%.

[0062] The specific preparation method is as follows: (1) Mix the aminosilane coupling agent and the disiloxane end-capping agent in a beaker to obtain material A. In another beaker, mix 50% cationic emulsifier, 50% nonionic emulsifier and 50% water to obtain material B. Mix material A and material B under stirring for 20 min, and homogenize at 10000 rpm for 5 min to obtain emulsion D. (2) Add the remaining cationic emulsifier, nonionic emulsifier, water and all KOH to the flask to obtain material C. Add emulsion D dropwise to material C at 85°C while stirring, for 2 hours. Then keep the reaction at this temperature for 5 hours. Cool down to 30°C and add glacial acetic acid to neutralize the emulsion to pH 6.8. Homogenize the obtained emulsion at 10,000 rpm for 5 minutes using a homogenizer. Filter the emulsion through a 180-mesh filter to obtain an amino silicone oil emulsion.

[0063] Example 2-20 The amino silicone oil emulsion was prepared according to the method of Example 1, except that the formulation is shown in Table 1 and the pH value of the amino silicone oil emulsion is shown in Table 2.

[0064] Example 21 The amino silicone oil emulsion was prepared according to the method of Example 1, except that no nonionic emulsifier was added.

[0065] Example 22 The amino silicone oil emulsion was prepared according to the method of Example 1, except that the cationic emulsifier hexadecyltrimethylammonium chloride was replaced with dioctadecyldimethylammonium chloride.

[0066] Example 23 The amino silicone oil emulsion was prepared according to the method of Example 1, except that the nonionic emulsifiers isomeric 13 alcohol polyoxyethylene ether-12 and isomeric 13 alcohol polyoxyethylene ether-7 were replaced with dodecyl alcohol polyoxyethylene ether-7.

[0067] Comparative Example 1 An amino silicone oil emulsion was prepared according to the method in Example 1, except that no capping agent was added.

[0068] Comparative Example 2 An amino silicone oil emulsion was prepared according to the method of Example 1, except that the capping agent 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane was replaced with hexamethyldisiloxane.

[0069] Table 1 Formula

[0070] Test case 1. The following performance tests were performed on the amino silicone oil emulsions prepared in each embodiment and comparative example: (1) Solid content test: Place the sample in an infrared moisture analyzer and heat it to 105°C. The volatile components will evaporate from the sample. Weigh the remaining sample to obtain its solid content.

[0071] (2) Test of internal phase silicone oil content: Isopropanol (mass ratio of 3:1 to emulsion) was added to the sample to demulsify, the silicone oil in the sample was extracted, its weight was weighed, and the silicone oil content in the sample was calculated.

[0072] (3) Particle size test: Particle size was measured using a Malvern particle size analyzer.

[0073] (4) Film-forming property test: Place a Teflon ring with an inner diameter of 40 mm on a flat glass plate. Weigh 2.5 g of the emulsion to be tested into the ring, place it on the glass plate, pop any air bubbles with a toothpick, and dry it in a 35°C oven, ensuring the glass plate is on a flat surface to form a film of uniform thickness. After drying, a film of approximately 0.5 mm thickness is obtained. Observe and score the integrity, flexibility, and stickiness of the film. The better the integrity, the higher the flexibility, and the lower the stickiness, the higher the score. Five people will be responsible for scoring.

[0074] The test results are shown in Table 2.

[0075] Table 2

[0076] 2. Hair care compositions (conditioners) were prepared based on the amino silicone oil emulsions obtained in the various embodiments and comparative examples, and their formulations are shown in Table 3.

[0077] Table 3

[0078] The specific preparation steps are as follows: (1) Mix the raw materials of phase A and heat to 75-80℃. Stir and dissolve evenly, then homogenize at 6000rpm for 3min. (2) Slowly cool down to 50-55℃, add phase B raw material, and homogenize at 6000rpm for 2min; (3) Add the C phase raw material to neutralize, stir evenly, and make the pH value of the reactants 4.0-6.0; (4) Add phase D raw materials and stir evenly to obtain hair care composition.

[0079] The effects of the prepared hair care composition were tested: 1) Treatment of external hair Cleaning: Select hair strands from the same batch for treatment. First, soak the hair in ether in a well-ventilated environment for four hours, repeat twice, and then air dry. Next, place the hair in a 0.5% K12 (sodium dodecyl sulfate) aqueous solution at a temperature of 50-60℃ for 2 hours, repeat twice, rinse with tap water until no foam remains, and then air dry.

[0080] Damaged Hair: Damaged hair was created by bleaching cleaned natural hair strands. The hair strands were immersed in a solution of 30% hydrogen peroxide and 25% ammonia (33.5:1 ratio) for 30 minutes. The hair was then thoroughly rinsed with deionized water and soaked in a 0.5% K12 aqueous solution at 50-60°C for 2 hours, repeated twice, rinsing with deionized water until no foam remained. Afterward, the hair strands were placed in a large beaker of deionized water for 1 hour, removed, and rinsed further under running deionized water. Before further treatment (i.e., before the next washing and conditioning step), the bleached hair strands were conditioned at 23°C and 50% humidity for 12 hours and combed before use.

[0081] 2) Shampooing and conditioning procedures: Wet the damaged hair strands with tap water (at a low flow rate, keep the tap running throughout the test to maintain a consistent flow rate). Weigh 2g of standard shampoo (formula shown in Table 4), apply it evenly to the hair strands, massage for 1 minute, then rinse for 1 minute until no more foam appears. Weigh 2g of the hair care composition, apply the conditioner evenly to the hair, about 1g on each side, massage for 1 minute (30 seconds on the front, 30 seconds on the back), leave for 2 minutes, then rinse for 1 minute. Allow the hair to air dry after rinsing.

[0082] Table 4

[0083] The standard shampoo preparation steps are as follows: (1) Mix the raw materials of phase A and heat to 80°C, stirring to dissolve; (2) After dispersing phase B, add it to the mixture obtained in step (1) and continue stirring for 30 minutes; (3) Cool down to below 50℃, add C phase raw material, and stir evenly; (4) Add the D phase raw material and stir evenly to obtain standard shampoo.

[0084] 3) Sorting tests Combing force was measured on wet and dry hair using a 2g, 20cm length bundle of damaged hair after washing and conditioning. Combing force was measured using a dynamic combing instrument (TECHNO HASHIMOTO CO.,LTD. model: SK-7AII). First, wet and dry combing forces were measured along the measurement section on an untreated hair bundle (i.e., the prepared damaged hair bundle, without washing and conditioning). Then, the hair bundle was treated with shampoo and hair care composition, and force absorption during the combing process was measured. The reported measurements are the reduction in combing force (work) along the measurement section between the treated and untreated hair bundles, averaged from five hair bundles, and the reduction in combing force is recorded as a percentage, i.e., the degree of combing improvement.

[0085] 4) Softness and gloss test To evaluate the softness of hair strands, their tactile properties were assessed by experts (trained panel members). In each case, hair strands were compared in pairs, for example, shampoo-treated hair was compared to untreated hair. The detailed steps were as follows: a) Two strands of similarly damaged hair were considered a pair; b) One strand was washed and air-dried as a control, while the other was washed and conditioned as a test group; c) Three pairs of hair strands were evaluated, and five panel members were involved; d) Based on the above hair strand evaluation, scores were assigned. The scoring rule was that hair strands that were softer and shinier than the control group received higher scores.

[0086] 5) Deposition of Si in hair The amount of Si deposited on the hair surface (silicone deposition) was measured in ppm: Using energy dispersion X The amount of silicone deposited on the hair surface was determined using a METEK (XEPOS) X-ray fluorescence spectrometer. Specifically, 0.10-0.15 g (accurate to 0.0001 g) of hair sample was accurately weighed into a polytetrafluoroethylene digestion vessel, 9 mL of nitric acid was added (a blank sample was prepared simultaneously), and the sample was allowed to stand for 60 min. Then, the sample was placed on a heater and heated at 120 °C for 30 min. After cooling, high-temperature digestion was performed. After digestion, the silicon content was determined using an inductively coupled plasma atomic emission spectrometer.

[0087] To determine the effectiveness of the silicone deposition, the silica content in ppm was first measured as a blank value on cleaned hair strands. Subsequently, the same hair strands were treated by washing and conditioning with the shampoo and hair care compositions listed in Table 4. The Si content in ppm was measured again as a sample value. The amount of deposited Si, i.e., sample value minus blank value, was obtained by subtraction. Centered measurements were performed on both the front and back sides of each hair strand. The reported results are the average of the three hair strands.

[0088] 3. Color protection / color measurement: A hair cleaning composition containing amino silicone oil emulsion was prepared, and its color protection effect was tested, as follows: Using Byk Gardner's Spectro Guide colorimeter measures color on a smooth surface of a hair strand and records the color parameters L, a, b (Lab color space).

[0089] Dyed hair will change color after being washed with a hair care composition. This color change can be described by the ΔE value, which is defined as: Where L0, a0, and b0 are the color values ​​of untreated dyed hair strands, and L1, a1, and b1 are the colors of hair strands after shampooing, prepared as a 5% aqueous solution using a hair cleaning composition containing amino silicone oil emulsion (formulation shown in Table 5). A low ΔE value indicates less color change or enhanced durability.

[0090] The results are shown in Table 6.

[0091] Table 5

[0092] Preparation steps: (1) Mix the raw materials of phase A and heat to 80°C, stirring to dissolve; (2) After dispersing phase B, add it to the mixture obtained in step (1) and continue stirring for 30 minutes; (3) Cool down to below 50℃, add C phase raw material, and stir evenly; (4) Add the D phase raw material and stir evenly. (5) Add phase E raw material to obtain hair cleaning composition.

[0093] Table 6

[0094] As shown in Tables 2 and 6, compared with Comparative Examples 1-2, the amino silicone oil emulsion provided in this application has a higher solid content and better film-forming properties. When used in hair care products, it is easier to spread evenly, which is conducive to silicone deposition. It can achieve the same conditioning function with less amino silicone oil emulsion added. At the same time, it can significantly improve the dry and wet combability of hair, ensure the softness and luster of hair, achieve the effects of hair damage repair, and have good color protection effect.

[0095] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0096] Although embodiments of this application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting this application. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of this application.

Claims

1. An amino silicone oil emulsion, characterized in that, The raw materials for the amino silicone oil emulsion include: aminosilane coupling agent, cyclotetrameric dimethylsiloxane, alkoxy-containing disiloxane end-capping agent, emulsifier, catalyst, and water, wherein the emulsifier includes cationic emulsifier.

2. The amino silicone oil emulsion according to claim 1, characterized in that, The alkoxy-containing disiloxane end-capping agent has the structure shown in Formula I: Equation I; Wherein, R1 is H or C1-C3 alkyl; R2 is C1-C3 alkyl or C1-C3 alkoxy; Preferably, the alkoxy-containing disiloxane end-capping agent includes at least one of 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane and 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane.

3. The amino silicone oil emulsion according to claim 1, characterized in that, The aminosilane coupling agent includes at least one of aminoethylaminoisobutylmethyldimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, 3-(N-cyclohexylamine)propylmethyldimethoxysilane, n-butylaminopropyltrimethoxysilane, N-(n-butyl)-3-aminopropyltriethoxysilane, and γ-aminopropylmethyldiethoxysilane. The catalyst includes at least one of sodium hydroxide, potassium hydroxide, and tetramethylammonium chloride.

4. The amino silicone oil emulsion according to claim 1, characterized in that, The cationic emulsifier includes at least one of hexadecyltrimethylammonium chloride, docosyltrimethylammonium chloride, didodecyldimethylammonium bromide, benzalkonium chloride, fatty imidazoline, alkylpyridine halide, polyoxyethylalkyl quaternary ammonium salt, and 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazoline. The emulsifier further includes a nonionic emulsifier, which preferably includes a fatty alcohol polyoxyethylene ether with an HLB value of 5 to 16.

5. The amino silicone oil emulsion according to claim 4, characterized in that, The nonionic emulsifier includes fatty alcohol polyoxyethylene ethers with a carbon chain length of 12-14 and an ethoxy group number of 5-12; Preferably, the nonionic emulsifier includes at least one of isotretinoin polyoxyethylene ether-12 and isotretinoin polyoxyethylene ether-7.

6. The amino silicone oil emulsion according to claim 1, characterized in that, Based on the total mass of the raw materials of the aminosilicone oil emulsion, the content of the aminosilane coupling agent is 1% to 10%.

7. The amino silicone oil emulsion according to claim 1, characterized in that, Based on the total mass of the raw materials of the amino silicone oil emulsion, the content of the cyclotetrameric dimethylsiloxane is 20% to 40%, and the content of the alkoxy-containing disiloxane end-capping agent is 0.02% to 2%.

8. The amino silicone oil emulsion according to claim 4 or 5, characterized in that, Based on the total mass of the raw materials of the amino silicone oil emulsion, the content of the emulsifier is 2% to 14%; The mass ratio of the cationic emulsifier to the nonionic emulsifier is (1~7):(1~7).

9. The amino silicone oil emulsion according to claim 1, characterized in that, Based on the total mass of the raw materials of the amino silicone oil emulsion, the catalyst content is 0.3%~1% and the water content is 34%~76%.

10. The amino silicone oil emulsion according to claim 1, characterized in that, The pH value of the amino silicone oil emulsion is 5.0~7.

0.

11. A method for preparing the amino silicone oil emulsion according to any one of claims 1-10, characterized in that, include: The aminosilane coupling agent, cyclotetrameric dimethylsiloxane, alkoxy-containing disiloxane end-capping agent, emulsifier, catalyst and water are mixed and the aminosilicone oil emulsion is obtained by ring-opening reaction.

12. The method according to claim 11, characterized in that, The method further includes: The aminosilane coupling agent, cyclotetrameric dimethylsiloxane, alkoxy-containing disiloxane end-capping agent, a portion of the emulsifier, and a portion of the water are mixed to obtain a pre-emulsion; The catalyst, the remaining emulsifier, and the remaining water are mixed to obtain a mixture; The mixture is combined with the preemulsion and subjected to a ring-opening reaction to obtain an intermediate emulsion. The pH of the intermediate emulsion is adjusted to 5.0~7.0 to obtain the amino silicone oil emulsion.

13. The method according to claim 12, characterized in that, The aminosilane coupling agent, cyclotetrameric dimethylsiloxane, alkoxy-containing disiloxane end-capping agent, a portion of the cationic emulsifier, a portion of the nonionic emulsifier, and a portion of the water are mixed to obtain the pre-emulsion; The catalyst, the remaining cationic emulsifier, the remaining nonionic emulsifier, and the remaining water are mixed to obtain the mixture; The cationic emulsifier accounts for 40 wt% to 60 wt% of the total cationic emulsifier, and the nonionic emulsifier accounts for 40 wt% to 60 wt% of the total nonionic emulsifier.

14. The method according to claim 12 or 13, characterized in that, The preemulsion is added dropwise to the mixture over a period of 2 to 3 hours at a temperature of 60°C to 90°C. The ring-opening reaction takes 4 to 8 hours.

15. The method according to claim 12, characterized in that, The method further includes: The temperature of the intermediate emulsion is adjusted to 30℃~40℃ and the pH value is adjusted to 5.0~7.0 to obtain the amino silicone oil emulsion.

16. A hair care composition, characterized in that, include: The amino silicone oil emulsion is prepared according to any one of claims 1-10 or by any one of claims 11-15.

17. A hair care method, characterized in that, include: Apply the amino silicone oil emulsion according to any one of claims 1-10 or the hair care composition according to claim 16 to the hair.

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