Waterproof eyeliner capable of being torn and pulled and preparation method of waterproof eyeliner

Abstract

The invention relates to the field of colored cosmetics, and particularly discloses a tearable waterproof eyeliner and a preparation method thereof. The waterproof eyeliner capable of being torn and pulled comprises a container and eyeliner liquid contained in the container, and the eyeliner liquid is prepared from, by weight, 5-10 parts of 1, 3-butanediol; 0.5 to 1 part of phenoxyethanol; 0.5 to 1 part of caprylyl glycol; 30 to 40 parts of water; 2-3 parts of glycerol; 30 to 35 parts of color paste; 2 parts of acrylic resin; 10 to 15 parts of polyurethane resin; and 10 to 15 parts of styrene / isoprene / acrylic resin. The eyeliner prepared by the invention can quickly form a film on the skin of a human body, has a certain thickness, can completely tear off the eyeliner only by rubbing one corner of the eyeliner and then tearing the eyeliner, and also has excellent waterproof and oil-resistant effects.

Description

Technical Field

[0001] The present application relates to the technical field of color cosmetics, and more specifically, to a tearable waterproof eyeliner and a preparation method thereof. Background Art

[0002] Liquid eyeliner is a product that uses special raw materials to evenly disperse pigments in water and is applied to the root of eyelashes through a brush to form a thin line with a beauty effect. Its characteristics are smooth brush strokes, easy coloring, quick drying, and long-lasting non-smudged, thus helping users to easily draw delicate eyeliners and enhance the overall makeup effect. Compared with other types of eyeliner products, such as eyeliner pens and eyeliner gels, liquid eyeliner has a more precise and long-lasting makeup effect.

[0003] In order to achieve waterproof and oil-resistant effects, existing liquid eyeliners usually add a large amount of film-forming agents to maintain the makeup effect, but this makes it difficult to remove makeup. And as people's demand for more diverse makeup effects increases, traditional liquid eyeliners that are difficult to remove can no longer meet advanced needs such as quick changes in makeup. Summary of the invention

[0004] In order to solve the above technical problems, the present application provides a tearable waterproof eyeliner and a preparation method thereof.

[0005] In the first aspect, the present application provides a tearable waterproof eyeliner, which adopts the following technical solution: A tearable waterproof eyeliner comprises a container and an eyeliner liquid contained in the container, wherein the raw materials used for the eyeliner liquid include the following components in parts by weight: 1,3-Butanediol 5-10 parts; Phenoxyethanol 0.5-1 part; Caprylyl glycol 0.5-1 part; 30-40 parts water; 2-3 parts of glycerin; Color paste 30-35 parts; 2 parts of acrylic resin; 10-15 parts of polyurethane resin; Styrene / isoprene / acrylic resin 10-15 parts.

[0006] Preferably, the weight ratio of the polyurethane resin to the styrene / isoprene / acrylic resin is 1:1.

[0007] By adopting the above technical solution, the present application combines polyurethane resin and styrene / isoprene / acrylic resin as a film-forming agent, which can make the eyeliner liquid form a film quickly on human skin and have a certain thickness. When removing makeup, you only need to rub a corner of the eyeliner and then tear it off to completely tear off the eyeliner. The film-forming agent also brings excellent waterproof and oil-resistant effects to the eyeliner liquid. In addition, the film-forming agent also has good compatibility with the color powder contained in the color paste in the eyeliner liquid, reducing the risk of pigment particles agglomerating to increase the particle size and improving the overall stability of the eyeliner liquid.

[0008] Among them, polyurethane resin refers to a type of polymer containing a characteristic unit of carbamate in the main chain, which has the elasticity of rubber, the strength of plastic and excellent processing performance, so that the eyeliner can have a certain thickness and tearability; styrene / isoprene / acrylic resin is a polymer copolymerized by styrene, isoprene, acrylic acid and / or acrylate, which provides excellent waterproof and oil-resistant properties for the eyeliner. Therefore, the present application optimizes the ratio between polyurethane resin and styrene / isoprene / acrylic resin, so that the tearable waterproof eyeliner can have a certain thickness, tearability and waterproof and oil-resistant capabilities at the same time. And it has been proved by experiments that when the weight ratio of polyurethane resin and styrene / isoprene / acrylic resin is 1:1, the tearability and waterproof and oil-resistant properties of the eyeliner reach the best balance.

[0009] Preferably, the monomer residue of the polyurethane resin is less than 50 ppm and the molecular weight is 4000-150000.

[0010] Preferably, the polyurethane resin is prepared by the following method: Under the protection of inert gas, 10-15 parts by weight of polyether diol, 20-30 parts by weight of isophorone diisocyanate and 2-4 parts of dibutyltin oxide are mixed and pre-emulsified by heat preservation, and then 10-20 parts by weight of isododecane are added, the oil bath is heated to 70-80°C, stirred and reacted for 1.5-2h, and then 8-12 parts by weight of 1,4-butanediol are added and heated and reacted for 1.5-2h, then the temperature is lowered and triethylamine is added for neutralization, and then 50-60 parts by weight of water are poured into it while stirring to obtain a polyurethane resin.

[0011] Preferably, the molecular weight of the polyether diol is 500-1000.

[0012] Since the polyurethane raw materials used in general commercial cosmetics are only used as film-forming agents, they will form a hydrophilic film, and the affinity with other raw materials in the eyeliner is slightly low, and it is impossible to achieve the effect of making the eyeliner have a certain thickness and tearability. However, the present application adopts the above technical solution, selects a polyether diol with good affinity with the other components in the eyeliner as a reaction monomer, controls its molecular weight, and optimizes the reaction conditions, so that the mixed slurry has a moderate viscosity during the reaction process, which is convenient for the full mixing of the components, and makes the residual reaction monomer in the final polyurethane resin controlled below 50ppm, the molecular weight is between 4000-150000, and has good compatibility with the other components in the eyeliner, so that the eyeliner can have a certain thickness and tearability. In addition, the present application uses isododecane, which has a relatively fast evaporation rate, as a diluent, which can make the eyeliner liquid form a film quickly, and isododecane can be used in cosmetics, while other diluents commonly used in the preparation of polyurethane resins, such as ethyl acetate and N,N-dimethylformamide, are not applicable in cosmetics and have extremely slow evaporation rates. The specific principle is shown in the figure below: Among them, R 1 isophorone, R 2 For polyether.

[0013] Preferably, the styrene / isoprene / acrylic resin is prepared by the following method: a. 20-30 parts by weight of styrene, 10-20 parts by weight of isoprene and 12-18 parts by weight of methyl methacrylate and / or acrylic acid are mixed and added to 30-40 parts by weight of water for pre-emulsification to obtain an emulsion; b. 90-110 parts by weight of water, 0.8-1 parts by weight of sodium bicarbonate and 0.8-1 parts by weight of disodium decanol polyether-6 sulfosuccinate are mixed and heated to 75-80 ° C in an oil bath, followed by adding 18-25 parts by weight of the pre-emulsion and heating to 80-85 ° C, adding 5-6 parts by weight of the initiator, and reacting for 10-15 minutes after the emulsion turns blue; c. The remaining pre-emulsion is added dropwise to the product obtained in step b at a rate of 1-2 parts by weight / min, and 1-2 parts by weight of initiator is added every 10-20 minutes until all the pre-emulsion is added dropwise, and then the mixture is kept in an oil bath at 90-95°C for 4-5 hours, and then the temperature is lowered to 50-60°C, and sodium bicarbonate is added for neutralization to obtain a styrene / isoprene / acrylic resin.

[0014] Preferably, the initiator comprises ammonium persulfate, ammonium bisulfite solution and water in a weight ratio of (2-3):(1-1.5):(50-80).

[0015] Preferably, the monomer residue of the styrene / isoprene / acrylic resin is less than 50 ppm.

[0016] By adopting the above technical scheme, the present application adopts styrene with higher affinity with other components in the eyeliner as a reaction raw material and copolymerizes with isoprene, methyl methacrylate and / or acrylic acid to obtain styrene / isoprene / acrylic resin. The synthesis principle is free radical polymerization of emulsion. Free radical polymerization is an important polymerization reaction mode, which mainly undergoes three stages: chain initiation, chain growth and chain termination. In the chain initiation stage, ammonium persulfate is decomposed by heat to produce free radicals. These free radicals are highly active and can quickly react with monomer molecules to start the polymerization process; the chain growth stage is the process in which free radicals continuously react with monomer molecules to form polymer chains; and in the chain termination stage, the interaction between free radicals causes the active chain to disappear and form stable polymer molecules. After GC-MS detection, the residual monomer substance of the styrene / isoprene / acrylic resin prepared by the present application is below 50ppm, which meets the specifications for cosmetic raw materials.

[0017] Generally, acrylic resin raw materials used in commercially available cosmetics have certain waterproof and oil-resistant properties, but they may have compatibility issues with the color powder contained in the color paste in the eyeliner, causing the pigment particles to have the risk of agglomeration and increase in particle size. The styrene / isoprene / acrylic resin prepared in the present application has better compatibility with the pigment particles, can improve the overall stability of the eyeliner, and thus enhance the various properties of the eyeliner.

[0018] Preferably, the color paste comprises 1,3-butanediol, phenoxyethanol, silicone resin, water, styrene / acrylic resin and color powder in a weight ratio of (5-6):(1-2):(0.5-1):(50-65):(5-7):(25-30).

[0019] Wherein, the color powder includes one or more of carbon black, titanium dioxide and red iron oxide.

[0020] By adopting the above technical solution, the present application homogenizes 1,3-butanediol, phenoxyethanol, silicone resin, water, styrene / acrylic resin and color powder with a homogenizer at a certain speed for 30-40 minutes to fully disperse the color powder and prepare a premixed color paste.

[0021] In a second aspect, the present application provides a method for preparing a tearable waterproof eyeliner, which adopts the following technical solution: A method for preparing a tearable waterproof eyeliner, comprising the following steps: 1,3-Butanediol, phenoxyethanol, caprylyl glycol, water, glycerin, color paste, acrylic resin, polyurethane resin and styrene / isoprene / acrylic resin are mixed and stirred for 20-30 minutes to obtain an eyeliner liquid base, which is then combined with a container to obtain a tearable waterproof eyeliner.

[0022] Through the above technical solution, the tearable waterproof eyeliner prepared by the present application can be applied after waiting for 0.5-1min, and when you want to change the makeup effect later, you only need to tear it off to remove the makeup, which improves the convenience of changing makeup. In order to reduce the damage to the skin during tearing and increase the ease of tearing, before using the eyeliner, you can first use a base pen to evenly apply it on the outer area of ​​the eyelashes, and then apply eyeliner liquid on the basis of the base.

[0023] The substrate pen comprises a container and a substrate liquid contained in the container, and the substrate liquid is prepared by the following method: 13-15 parts by weight of plasticizer, 50-60 parts by weight of silicone oil, 0.5-1 parts by weight of silicone film-forming agent, 15-20 parts by weight of filling powder and 0.2-0.3 parts by weight of antioxidant are mixed and heated to form a uniform suspension, and then filled into a mold, frozen and plasticized, placed at -18°C for 15-30 minutes, and then combined with a container to obtain a base pen.

[0024] Wherein, the plasticizer is one or more of polyethylene wax, candelilla wax and microcrystalline wax.

[0025] The silicone oil is one or more of phenyl trimethicone, dimethicone and methyl trimethicone.

[0026] The silicon film-forming agent is an acrylic acid (ester)-polydimethylsiloxane methacrylate copolymer.

[0027] The filler powder is silica and / or mica.

[0028] The antioxidant is tocopheryl acetate.

[0029] In summary, this application has the following beneficial technical effects: 1. The present application uses a certain ratio of polyurethane resin and styrene / isoprene / acrylic resin as a film-forming agent. The film-forming agent can make the eyeliner quickly form a film on human skin with a certain thickness. To remove makeup, you only need to rub a corner of the eyeliner and then tear it off to completely tear off the eyeliner. The film-forming agent also brings excellent waterproof and oil-resistant effects to the eyeliner. 2. The present application uses a polyurethane resin and a styrene / isoprene / acrylic resin as a film-forming agent. The film-forming agent has good compatibility with the color powder contained in the color paste in the eyeliner, reduces the risk of pigment particles agglomerating to increase the particle size, and improves the overall stability of the eyeliner. 3. The present application adopts polyether diol as a reaction monomer, controls its molecular weight, and optimizes the reaction conditions, so that the prepared polyurethane resin can make the eyeliner liquid have a certain thickness and tearability compared with the polyurethane resin used in existing commercial cosmetics; 4. The present application uses styrene as a reaction raw material to copolymerize with isoprene, methyl methacrylate and / or acrylic acid to prepare styrene / isoprene / acrylic resin. Compared with the acrylic resin raw materials used in existing commercial cosmetics, it has better compatibility with pigment particles, can improve the overall stability of the eyeliner, and thus improve the various performances of the eyeliner. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a photo of the finished product of the tearable waterproof eyeliner prepared by the present application; Figure 2 This is a schematic diagram of the skin coated with a base pen; Figure 3 This is a schematic diagram of the effect after applying eyeliner on a large scale on the base; Figure 4 This is a diagram showing the effect on the skin after the eyeliner is torn off. DETAILED DESCRIPTION

[0031] The present application is further described in detail below in conjunction with embodiments.

[0032] Material Source Unless otherwise specified, the raw materials used in this application are all commercially available products, including: Acrylic resin, purchased from Hubei Jusheng Technology Co., Ltd., model SS-22, CAS number 25035-69-2; Silicone resin, purchased from Shenzhen Jipeng Silicone Fluoride Materials Co., Ltd., model SH-1053, composition is methylphenyl polysilicone resin, CAS number is 67763-03-5; Styrene / acrylic resin, CAS No. 9010-92-8, purchased from Wuhan Kamik Technology Co., Ltd., solid content 40%, daily chemical grade; Disodium decyl polyether-6 sulfosuccinate, CAS No. 68311-03-5, purchased from Jinjinle Chemical Co., Ltd.; Polyether diol, specifically polyethylene glycol ether, CAS No. 25322-68-3, was purchased from Sinopharm Shanghai Test.

[0033] Preparation Example 1.1.1 The preparation method of polyurethane resin comprises the following steps: Under the protection of dry nitrogen, 10 kg of dehydrated polyethylene glycol ether with a molecular weight of 500, 30 kg of isophorone diisocyanate and 2 kg of dibutyltin oxide were added to a reactor and mixed and stirred. The mixture was kept warm at 40°C for 30 minutes. Then, 20 kg of isododecane was added, the oil bath was heated to 70°C, and the mixture was stirred and reacted for 2 hours. Then, 8 kg of 1,4-butanediol was added and the mixture was kept warm for 2 hours. The mixture was then cooled to 35°C and triethylamine was added for neutralization to obtain a polymer. The polymer was then slowly poured into 50 kg of water while stirring to obtain a polyurethane resin with a monomer residue of less than 50 ppm and a number average molecular weight of 4000.

[0034] Preparation Example 1.1.2 The preparation method of polyurethane resin comprises the following steps: Under the protection of dry nitrogen, 15 kg of dehydrated polyethylene glycol ether with a molecular weight of 1000, 20 kg of isophorone diisocyanate and 4 kg of dibutyltin oxide were added to a reactor and mixed and stirred. The mixture was kept warm at 50°C for 15 minutes. Then, 10 kg of isododecane was added, the oil bath was heated to 80°C, and the mixture was stirred for 1.5 hours. Then, 12 kg of 1,4-butanediol was added and kept warm for 1.5 hours. The mixture was then cooled to 40°C and triethylamine was added for neutralization to obtain a polymer. The polymer was then slowly poured into 60 kg of water while stirring to obtain a polyurethane resin with a monomer residue of less than 50 ppm and a number average molecular weight of 150,000.

[0035] Preparation Example 1.2.1 The difference from Preparation Example 1.1.2 is that the molecular weight of the polyethylene glycol ether is 200, and the rest is the same as Preparation Example 1.1.2.

[0036] Preparation Example 1.2.2 The difference from Preparation Example 1.1.2 is that the molecular weight of the polyethylene glycol ether is 5000, and the rest is the same as Preparation Example 1.1.2.

[0037] Preparation Example 1.3.1 The difference from Preparation Example 1.1.2 is that after isododecane is added, the oil bath is heated and stirred for reaction for 1 hour, and after 1,4-butanediol is added, the temperature is kept for reaction for 0.5 hour. The rest is the same as Preparation Example 1.1.2.

[0038] Preparation Example 1.3.2 The difference from Preparation Example 1.1.2 is that after isododecane is added, the oil bath is heated and stirred for reaction for 2.5 hours, and after 1,4-butanediol is added, the temperature is kept warm for reaction for 3 hours. The rest is the same as Preparation Example 1.1.2.

[0039] Comparative Preparation Example 1 The difference from Preparation Example 1.1.2 is that polyethylene glycol ether is replaced by ethylene glycol, and the rest is the same as Preparation Example 1.1.2.

[0040] Preparation Example 2.1 The preparation method of styrene / isoprene / acrylic resin comprises the following steps: a. 20kg of styrene, 20kg of isoprene and 12kg of methyl methacrylate were mixed and added to 40kg of water for pre-emulsification to obtain an emulsion; 2kg of ammonium persulfate, 1.5kg of a 70% concentration of ammonium bisulfite solution and 50kg of water were stirred and mixed to obtain an initiator; b. 90kg of water, 1kg of sodium bicarbonate and 0.8kg of disodium decyl polyether-6 sulfosuccinate were mixed into a reactor as a substrate and dissolved by stirring at 300rpm. After the oil bath was heated to 75°C, 18kg of pre-emulsion was added and the temperature was raised to 80°C. Then, 6kg of initiator was added and the emulsion was allowed to react for 10min after the emulsion turned blue. c. The remaining pre-emulsion was added dropwise to the product obtained in step b at a rate of 1 kg / min, and 1 kg of initiator was added every 20 min until all the pre-emulsion was added. The mixture was then kept in an oil bath at 90°C for 5 h, and then cooled to 50°C, and sodium bicarbonate was added for neutralization to obtain a styrene / isoprene / acrylic resin with a monomer residue of less than 50 ppm.

[0041] Preparation Example 2.2 The preparation method of styrene / isoprene / acrylic resin comprises the following steps: a. 30kg of styrene, 10kg of isoprene and 18kg of acrylic acid were mixed and added to 30kg of water for pre-emulsification to obtain an emulsion; 3kg of ammonium persulfate, 1kg of a 70% concentration of ammonium bisulfite solution and 80kg of water were stirred and mixed to obtain an initiator; b. 110kg of water, 0.8kg of sodium bicarbonate and 1kg of disodium decanol polyether-6 sulfosuccinate were mixed into a reactor as a substrate and stirred at 300rpm to dissolve. After the oil bath was heated to 80°C, 25kg of pre-emulsion was added and the temperature was raised to 85°C, and then 5kg of initiator was added. After the emulsion turned blue, the reaction lasted for 15min. c. The remaining pre-emulsion was added dropwise to the product obtained in step b at a rate of 2 kg / min, and 2 kg of initiator was added every 10 min until all the pre-emulsion was added. The mixture was then kept in an oil bath at 95°C for 4 h, then cooled to 60°C, and sodium bicarbonate was added for neutralization to obtain a styrene / isoprene / acrylic resin having a monomer residue of less than 50 ppm.

[0042] Preparation Example 2.3 The difference from Preparation Example 2.2 is that the initiator is replaced with a sodium persulfate solution obtained by stirring and mixing 4 kg of sodium persulfate and 80 kg of water, and the rest is the same as Preparation Example 2.2.

[0043] Comparative Preparation Example 2 The difference from Preparation Example 2.2 is that styrene is replaced by isooctyl acrylate, and the rest is the same as Preparation Example 2.2.

[0044] Example 1.1 A method for preparing a tearable waterproof eyeliner comprises the following steps: S1. 5 kg 1,3-butanediol, 2 kg phenoxyethanol, 0.5 kg silicone resin, 65 kg deionized water, 5 kg styrene / acrylic resin and 30 kg carbon black were mixed and homogenized at a speed of 5000 rpm for 30 min to obtain a color paste; S2. 5 kg of 1,3-butanediol, 1 kg of phenoxyethanol, 0.5 kg of caprylyl glycol, 40 kg of deionized water, 2 kg of glycerol, 35 kg of the color paste prepared in step S1, 2 kg of acrylic resin, 10 kg of the polyurethane resin prepared in Preparation Example 1.1.1 and 15 kg of the styrene / isoprene / acrylic resin prepared in Preparation Example 2.1 were mixed and stirred at a rotation speed of 300 rpm for 20 min to obtain an eyeliner liquid, and then combined with a container to obtain a tearable waterproof eyeliner.

[0045] Example 1.2 A method for preparing a tearable waterproof eyeliner comprises the following steps: S1. 6 kg of 1,3-butanediol, 1 kg of phenoxyethanol, 1 kg of silicone resin, 50 kg of deionized water, 7 kg of styrene / acrylic resin and 25 kg of titanium dioxide and carbon black (10 kg of titanium dioxide and 15 kg of carbon black) were mixed and homogenized at a speed of 5000 rpm for 40 min to obtain a color paste; S2. 10 kg of 1,3-butanediol, 0.5 kg of phenoxyethanol, 1 kg of caprylyl glycol, 30 kg of deionized water, 3 kg of glycerol, 30 kg of the color paste prepared in step S1, 2 kg of acrylic resin, 15 kg of the polyurethane resin prepared in Preparation Example 1.1.2 and 10 kg of the styrene / isoprene / acrylic resin prepared in Preparation Example 2.2 were mixed and stirred at a rotation speed of 300 rpm for 30 min to obtain an eyeliner liquid, and then combined with a container to obtain a tearable waterproof eyeliner.

[0046] Example 1.3 A method for preparing a tearable waterproof eyeliner, which is different from that of Example 1.2 in that: in step S2, the weight ratio of polyurethane resin to styrene / isoprene / acrylic resin is 1:1, wherein the polyurethane resin is 15 kg, and the styrene / isoprene / acrylic resin is 15 kg, and the rest is the same as Example 1.2.

[0047] Examples 2.1-2.4 A method for preparing a tearable waterproof eyeliner, which is different from Example 1.2 in that: in step S2, the polyurethane resin prepared in Preparation Example 1.1.2 is replaced by the polyurethane resins prepared in Preparation Examples 1.2.1-1.3.2 respectively, and the rest is the same as Example 1.2.

[0048] Example 3.1 A method for preparing a tearable waterproof eyeliner, which differs from Example 1.2 in that: in step S2, the styrene / isoprene / acrylic resin prepared in Preparation Example 2.2 is replaced by the styrene / isoprene / acrylic resin prepared in Preparation Example 2.3, and the rest is the same as Example 1.2.

[0049] Comparative Example 1.1 The difference from Example 1.2 is that in step S2, no polyurethane resin is added, the amount of styrene / isoprene / acrylic resin is 25 kg, and the rest is the same as Example 1.2.

[0050] Comparative Example 1.2 The difference from Example 1.2 is that in step S2, no styrene / isoprene / acrylic resin is added, the amount of polyurethane resin used is 25 kg, and the rest is the same as Example 1.2.

[0051] Comparative Example 2.1 The difference from Example 1.2 is that in step S2, the polyurethane resin is a commercially available polyurethane resin, that is, the polyurethane resin prepared in Comparative Preparation Example 1, and the rest is the same as Example 1.2.

[0052] Comparative Example 2.2 The difference from Example 1.2 is that in step S2, the styrene / isoprene / acrylic resin uses a commercially available acrylic resin, that is, the acrylic resin prepared in Comparative Preparation Example 2, and the rest is the same as Example 1.2.

[0053] Comparative Example 3.1 The difference from Example 1.2 is that in step S2, the weight ratio of polyurethane resin to styrene / isoprene / acrylic resin is 1:0.5, wherein the polyurethane resin is 15 kg and the styrene / isoprene / acrylic resin is 7.5 kg, and the rest is the same as Example 1.2.

[0054] Comparative Example 3.2 The difference from Example 1.2 is that in step S2, the weight ratio of polyurethane resin to styrene / isoprene / acrylic resin is 1:2, wherein the polyurethane resin is 15 kg and the styrene / isoprene / acrylic resin is 30 kg, and the rest is the same as Example 1.2.

[0055] Performance Testing 1. Waterproofness: The eyeliners prepared in the above embodiments and comparative examples were drawn on the skin and then rinsed with water at the same flow rate for 3 minutes after drying. The color fading of the pigment was observed. If there was no color fading, the water resistance was judged to be strong; if there was slight color fading, the water resistance was judged to be relatively strong; if most of the color fading was judged to be weak.

[0056] 2. Oil resistance: Apply the eyeliner prepared in the above embodiments and comparative examples on a glass slide, and after drying to form a film, soak it in a beaker containing isononyl isononanoate for 30 minutes, and observe the color fading of the pigment. If there is no fading or bleeding, it is judged as strong; if there is slight fading or bleeding, it is judged as relatively strong; if most of the fading or bleeding occurs, it is judged as weak.

[0057] 3. Ease of tearing: The eyeliners prepared in the above embodiments and comparative examples were used to make makeup. After drying and forming a film, they were directly torn off to observe whether they could be completely torn off.

[0058] 4. Skin feel after application: Make up with the eyeliners prepared in the above embodiments and comparative examples and record the skin feel experience.

[0059] The above performance tests are recorded in Table 1.

[0060] Table 1 Performance test results project Waterproof Oil resistance Difficulty of tearing Apply skin feeling Example 1.1 powerful powerful Easier generally Example 1.2 Strong Strong easy generally Example 1.3 powerful powerful easy generally Example 2.1 Strong Strong Easier generally Example 2.2 Strong Strong Easier generally Example 2.3 Strong Strong Easier generally Example 2.4 Strong Strong Easier generally Example 3.1 weak weak easy generally Comparative Example 1.1 Strong weak / generally Comparative Example 1.2 weak weak Easier generally Comparative Example 2.1 Strong Strong / generally Comparative Example 2.2 weak weak easy generally Comparative Example 3.1 weak weak Easier generally Comparative Example 3.2 Strong Strong weak generally 5. Compatibility of film-forming agent and color paste: The polyurethane resin prepared in Preparation Example 1.1.1, the styrene / isoprene / acrylic resin prepared in Preparation Example 2.1 and the color paste prepared in Step S1 of Example 1.1 were mixed in a weight ratio of 3:3:4, and the viscosity and particle size were tested at a temperature of 50°C at the initial time, 1 day, 3 day, 7 day, 14 day and 28 day, and the change rate of 28d viscosity and particle size was calculated; at the same time, the commercially available acrylic resin prepared in Comparative Preparation Example 2 in a weight ratio of 6:4 and the color paste prepared in Step S1 of Example 1.1 were mixed as a control group, and the results are shown in Table 2.

[0061] Table 2 Color paste compatibility comparison results As can be seen from Table 1, the eyeliners prepared in Examples 1.1-1.3 of the present application have almost no fading in the experiments of water resistance and oil resistance, or have slight fading, and the degree of tearing is relatively easy, and there is no obvious abnormality in the skin feel of application. This shows that the present application can make the eyeliner have a certain thickness, tearability, and water resistance and oil resistance by using a specific polyurethane resin and styrene / isoprene / acrylic resin in a certain ratio as a film-forming agent. Among them, when the weight ratio of polyurethane resin and styrene / isoprene / acrylic resin is 1:1, tearability and water resistance and oil resistance reach the best balance, which are the best effects. At the same time, it can be seen from the changes in the particle size of the toner pigment and the viscosity of the mixed liquid in Table 2 that the film-forming agent of the present application has excellent compatibility with the color paste, reduces the risk of pigment particles agglomerating to increase the particle size, and improves the stability of the overall eyeliner liquid.

[0062] The difference between Examples 2.1-2.4 and Example 1.2 is that the molecular weight of the polyether diol in the preparation method of the polyurethane is not within the scope of the present application and the reaction time is different. As can be seen from Table 1, Examples 2.1-2.4 are all worse than Example 1.2 in terms of the ease of tearing, which shows that the present application can enhance the affinity between the polyurethane and the other components in the eyeliner by optimizing the molecular weight and process parameters of the polyether diol, thereby further improving the tearability of the eyeliner. In addition, since commonly used diluents such as ethyl acetate cannot be used in cosmetics, they are not illustrated in the specific embodiments of the present application.

[0063] The difference between Example 3.1 and Example 1.2 is that the initiators in the preparation method of styrene / isoprene / acrylic resin are different. As can be seen from Table 1, Example 3.1 is inferior to Example 1.2 in terms of waterproof and oil-resistant properties. This shows that the present application optimizes the initiator in the preparation method of styrene / isoprene / acrylic resin, which can further improve the effect of styrene / isoprene / acrylic resin in eyeliner liquid, thereby further improving the waterproof and oil-resistant properties of eyeliner.

[0064] The difference between Comparative Examples 1.1-1.2 and Example 1.2 is that only one of polyurethane resin and styrene / isoprene / acrylic resin is used as a film-forming agent. It can be seen from Table 1 that when only styrene / isoprene / acrylic resin is used as a film-forming agent, the eyeliner is not tearable; when only polyurethane resin is used as a film-forming agent, the eyeliner does not have good waterproof and oil-resistant properties. This shows that the present application can make the eyeliner have both tearability and waterproof and oil-resistant properties by using a combination of polyurethane resin and styrene / isoprene / acrylic resin as a film-forming agent.

[0065] The difference between Comparative Examples 2.1-2.2 and Example 1.2 is that commercially available polyurethane resin or commercially available acrylic resin is used. As can be seen from Table 1, when Comparative Example 2.1 uses commercially available polyurethane resin, the eyeliner is not tearable; when Comparative Example 2.2 uses commercially available acrylic resin, the eyeliner has poor waterproof and oil-resistant properties. In addition, combined with the changes in the particle size of the toner pigment and the viscosity of the mixed liquid in Table 2, it can be seen that when commercially available acrylic resin is used, the compatibility with the toner contained in the color paste is poor, causing the pigment particles to agglomerate, affecting the overall stability of the eyeliner liquid.

[0066] The difference between Comparative Examples 3.1-3.2 and Example 1.2 is that the ratio of polyurethane resin and styrene / isoprene / acrylic resin is not within the scope of the present application. As can be seen from Table 1, Comparative Examples 3.1-3.2 are inferior to Example 1.2 in terms of tearability and waterproof and oil-resistant properties. Experimental data show that the present application optimizes the ratio of polyurethane resin and styrene / isoprene / acrylic resin to enable the eyeliner to have good tearability and waterproof and oil-resistant properties.

[0067] The embodiments of this specific implementation method are all preferred embodiments of the present application, and are not intended to limit the protection scope of the present application. Therefore, all equivalent changes made based on the structure, shape, and principle of the present application should be included in the protection scope of the present application.

Claims

1. A tearable waterproof eyeliner, comprising a container and an eyeliner liquid contained in the container, characterized in that: The raw materials used for the eyeliner liquid include the following components in parts by weight: 1,3-Butanediol 5-10 parts; Phenoxyethanol 0.5-1 part; Caprylyl glycol 0.5-1 part; 30-40 parts water; 2-3 parts of glycerin; Color paste 30-35 parts; 2 parts of acrylic resin; 10-15 parts of polyurethane resin; Styrene / isoprene / acrylic resin 10-15 parts.

2. The tearable waterproof eyeliner according to claim 1, characterized in that: The weight ratio of the polyurethane resin to the styrene / isoprene / acrylic resin is 1:

1.

3. The tearable waterproof eyeliner according to claim 1, characterized in that: The monomer residue of the polyurethane resin is less than 50 ppm and the molecular weight is 4,000-150,000.

4. The tearable waterproof eyeliner according to claim 3, characterized in that: The polyurethane resin is prepared by the following method: Under the protection of inert gas, 10-15 parts by weight of polyether diol, 20-30 parts by weight of isophorone diisocyanate and 2-4 parts of dibutyltin oxide are mixed and pre-emulsified by heat preservation, and then 10-20 parts by weight of isododecane are added, the oil bath is heated to 70-80°C, stirred and reacted for 1.5-2h, and then 8-12 parts by weight of 1,4-butanediol are added and heated and reacted for 1.5-2h, then the temperature is lowered and triethylamine is added for neutralization, and then 50-60 parts by weight of water are poured into it while stirring to obtain a polyurethane resin.

5. The tearable waterproof eyeliner according to claim 4, characterized in that: The molecular weight of the polyether diol is 500-1000.

6. The tearable waterproof eyeliner according to claim 1, characterized in that: The styrene / isoprene / acrylic resin is prepared by the following method: a. 20-30 parts by weight of styrene, 10-20 parts by weight of isoprene and 12-18 parts by weight of methyl methacrylate and / or acrylic acid are mixed and added to 30-40 parts by weight of water for pre-emulsification to obtain an emulsion; b. 90-110 parts by weight of water, 0.8-1 parts by weight of sodium bicarbonate and 0.8-1 parts by weight of disodium decanol polyether-6 sulfosuccinate are mixed and heated to 75-80 ° C in an oil bath, followed by adding 18-25 parts by weight of the pre-emulsion and heating to 80-85 ° C, adding 5-6 parts by weight of the initiator, and reacting for 10-15 minutes after the emulsion turns blue; c. The remaining pre-emulsion is added dropwise to the product obtained in step b at a rate of 1-2 parts by weight / min, and 1-2 parts by weight of initiator is added every 10-20 minutes until all the pre-emulsion is added dropwise, and then the mixture is kept in an oil bath at 90-95°C for 4-5 hours, and then the temperature is lowered to 50-60°C, and sodium bicarbonate is added for neutralization to obtain a styrene / isoprene / acrylic resin.

7. The tearable waterproof eyeliner according to claim 6, characterized in that: The initiator comprises ammonium persulfate, ammonium bisulfite solution and water in a weight ratio of (2-3): (1-1.5): (50-80).

8. The tearable waterproof eyeliner according to claim 6, characterized in that: The monomer residue of the styrene / isoprene / acrylic resin is less than 50 ppm.

9. The tearable waterproof eyeliner according to claim 1, characterized in that: The color paste includes 1,3-butylene glycol, phenoxyethanol, silicone resin, water, styrene / acrylic resin and color powder in a weight ratio of (5-6): (1-2): (0.5-1): (50-65): (5-7): (25-30).

10. A method for preparing the tearable waterproof eyeliner according to claim 1, characterized in that: The following steps are involved: 1,3-Butanediol, phenoxyethanol, caprylyl glycol, water, glycerin, color paste, acrylic resin, polyurethane resin and styrene / isoprene / acrylic resin are mixed and stirred for 20-30 minutes to obtain an eyeliner liquid, which is then combined with a container to obtain a tearable waterproof eyeliner.

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