Preparation method of organosilicon-modified polyurethane sponge and its application as cosmetic material

Abstract

The present invention discloses a method for preparing a silicone-modified polyurethane sponge and its application as a beauty makeup material, the method comprising the following steps: 1) reacting diisocyanate, polyether polyol and dihydroxy-terminated polysiloxane to prepare an NCO-terminated silicone-modified polyurethane prepolymer as a foaming black material; 2) uniformly mixing water, color paste, filler and cage-type silsesquioxane as a foaming white material; 3) dispersing the black material and the white material at high speed, standing and foaming to obtain a silicone-modified polyurethane sponge. The silicone-modified polyurethane sponge prepared by the present invention has excellent color fixing and powder fixing effects, and at the same time, the expansion ratio after absorbing water is small, and it has good soft skin-friendliness and mechanical properties. Surprisingly, the beauty makeup egg prepared by the silicone-modified polyurethane does not get stuck during use, has a good makeup effect, and is easier to clean.

Description

Technical Field

[0001] The present invention relates to a modified polyurethane sponge, and in particular to a preparation method of an organosilicon-modified polyurethane sponge and an application of the sponge as a cosmetic material. Background Art

[0002] Beauty sponges are a popular makeup tool. The traditional production materials are divided into the following three types: 1. Styrene-butadiene rubber + natural rubber. The advantages are cheap, soft and skin-friendly. The disadvantages are that they absorb powder and have poor durability, and are usually used as disposable consumables. 2. Styrene-butadiene rubber. It feels soft and cottony, is skin-friendly, but absorbs powder particularly badly. 3. Nitrile rubber. It not only has a high production cost, but also has poor skin-friendliness and a hard touch, and is more suitable for use as a powder puff.

[0003] In recent years, with the development and utilization of high-performance materials, polyurethane makeup eggs have been widely welcomed by the market due to their high water absorption rate and no reaction residue, which makes them safer and more efficient. Considering the appearance and mechanical strength of makeup eggs, a certain amount of color paste and reinforcing fillers are usually added in the preparation of polyurethane sponges. However, the existing polyurethane makeup eggs have poor wrapping effect on color paste and reinforcing fillers, and often fade and powder fall off during use. In addition, foundation residue will remain on the surface of the makeup egg during makeup application, causing powder sticking and affecting the use effect. Summary of the invention

[0004] In order to solve the above technical problems, the present invention proposes a method for preparing a silicone modified polyurethane sponge and its application as a beauty makeup material. The bulk polymerization method is adopted to embed the main chain of silicone into the polyurethane macromolecular chain, and a silicone modified polyurethane prepolymer with -NCO end-capping is prepared by adjusting the ratio of diisocyanate and polysiloxane, and the molecular weight of polysiloxane, and the reaction process is simple and the polymerization efficiency is high; then the cage-type silsesquioxane is added to the white material, and the modified polyurethane prepolymer reacts with the white material, so that the color paste and filler are stably introduced into the sponge material, solving the problem of color fixation and powder fixation of the material; at the same time, the silicone material has good physiological inertness, softness and hydrophobicity, combined with the high strength of the polyurethane material, the obtained silicone modified polyurethane sponge has good softness, skin-friendlyness and mechanical properties, and the expansion ratio after water absorption is small, which is more conducive to use, and surprisingly, the beauty makeup egg made of the silicone modified polyurethane sponge provided by the present invention is used for makeup, and it is unexpectedly found that it has the characteristics of no powder sticking, good makeup effect, and the product is easy to clean.

[0005] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing a silicone-modified polyurethane sponge comprises the following steps:

[0007] 1) reacting diisocyanate, polyether polyol and dihydroxy-terminated polysiloxane to prepare -NCO-terminated organosilicon-modified polyurethane prepolymer as a foaming black material;

[0008] 2) mixing water, color paste, filler and cage-type silsesquioxane uniformly to obtain a foaming white material;

[0009] 3) After dispersing the black material and the white material at high speed, the material is allowed to stand for foaming to obtain a silicone-modified polyurethane sponge.

[0010] As a preferred embodiment, in step 1), the amount of polyether polyol and diisocyanate added is 1:(4-10) in terms of the molar ratio of OH to NCO;

[0011] Preferably, the added amount of dihydroxy-terminated polysiloxane and diisocyanate, calculated as the molar ratio of OH to NCO, is 1:(1.2-6), preferably 1:(1.2-4).

[0012] As a preferred embodiment, the reaction conditions in step 1) are: heating to 70-100° C. for 2-6 hours under an inert atmosphere; preferably heating to 80-90° C. for 3-4 hours;

[0013] Preferably, in step 1), the stirring speed is controlled to be 200-300 rpm / min.

[0014] As a preferred embodiment, the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate;

[0015] Preferably, the polyether polyol is polyethylene glycol with a molecular weight of 200-5000, preferably 400-2000.

[0016] As a preferred embodiment, the dihydroxy-terminated polysiloxane has a structure as shown in the following formula I:

[0017]

[0018] Where X is C 1 -C 10 A linear or branched saturated hydrocarbon group or an ether-containing hydrocarbon group, R 1 and R 2 Each independently selected from C 1 -C 10 A linear or branched saturated alkyl or aryl group, wherein n is 0-50;

[0019] Preferably, in Formula I, X is C 3 -C5 A linear alkyl group or an ether-containing alkyl group, R 1 and R 2 Each is independently selected from methyl, ethyl, and propyl, and the value of n is 20-60.

[0020] As a preferred embodiment, in step 2), the mass ratio of water, color paste, filler and cage-type silsesquioxane is (50-1000):(1-25):(0.1-10):(0.5-20).

[0021] As a preferred embodiment, the filler is one or more of wollastonite powder, white carbon black, titanium dioxide, and talcum powder, preferably wollastonite powder with a particle size of 5-50 microns;

[0022] Preferably, the color paste is a pigment concentrate with a particle size of 1-300 nm, preferably 1-100 nm, and a solid content of 60-80%;

[0023] Preferably, the cage-type silsesquioxane is one or more of trisilanolphenyl-cage-type polysilsesquioxane, octa(aminophenyltrioxysilane), aminopropylheptyl-cage-type polysilsesquioxane, octaaminopropyl-cage-type polysilsesquioxane, and PSS-[3-(2-aminoethyl)amino]propyl-substituted heptaisobutyl.

[0024] As a preferred embodiment, in step 3), the mixing ratio of the black material and the white material is 100:(50-1000), preferably 100:(80-500), based on the mass ratio of the organosilicon-modified polyurethane prepolymer to water.

[0025] As a preferred embodiment, the high-speed dispersion conditions in step 3) are a rotation speed of 3000-6000 rpm / min, a time of 30-120 s, preferably a rotation speed of 4000-5000 rpm / min, and a time of 30-45 s;

[0026] Preferably, after the foaming in step 3) is completed, the mixture is dried at 70-110° C. for 2-8 hours, preferably at 90-100° C. for 4-6 hours.

[0027] An application of the organosilicon-modified polyurethane sponge prepared by the method described above as a cosmetic material.

[0028] The organosilicon-modified polyurethane sponge prepared by the present invention has excellent effects of fixing color and powder, and at the same time has a small expansion ratio after absorbing water, has good softness, skin-friendliness and mechanical properties, and surprisingly, the beauty egg prepared by the organosilicon-modified polyurethane does not get stuck during use, has a good makeup effect, and is easier to clean. DETAILED DESCRIPTION

[0029] The present invention is further described below by means of specific examples. The examples described in the present invention are only used to illustrate the present invention and do not limit the scope of the present invention.

[0030] The main raw material information involved in the following embodiments of the present invention is as follows:

[0031] Hexamethylene diisocyanate: Wanhua Chemical Group Co., Ltd.

[0032] Toluene diisocyanate: Wanhua Chemical Group Co., Ltd.

[0033] Isophorone diisocyanate: Wanhua Chemical Group Co., Ltd.

[0034] Diphenylmethane diisocyanate: Wanhua Chemical Group Co., Ltd.

[0035] Dicyclohexylmethane diisocyanate: Wanhua Chemical Group Co., Ltd.

[0036] Bishydroxy-terminated polysiloxane: molecular weight 1500-5000, Hubei Longsheng Sihai New Materials Co., Ltd., Shenzhen Jipeng Silicon Fluoride Materials Co., Ltd.

[0037] Polyethylene glycol (PEG): molecular weight 400-2000, Guangzhou David Chemical Co., Ltd.

[0038] Wollastonite powder: particle size 5-10 microns, Daye Jinpeng Friction Material Co., Ltd.

[0039] Silica: Degussa Silica A380, Guangzhou Jingyi New Materials Co., Ltd. Titanium dioxide: HN05, Hangzhou Hengna New Materials Co., Ltd.

[0040] Talc: 10000 mesh, Donghai County Fucai Mineral Products Co., Ltd.

[0041] Red paste: SK-103, Dongguan Guangsiyuan Polyurethane Materials Co., Ltd.

[0042] Octaaminopropyl-cage silsesquioxane:Xi'an Qiyue Biotechnology Co., Ltd.

[0043] Trisilanol phenyl-cage polysilsesquioxane: Shenzhen Lijing Biochemical Technology Co., Ltd.

[0044] Octa(aminophenyltrioxysilane): Shanghai MacLean Biochemical Technology Co., Ltd.

[0045] Aminopropylheptyl-cage polysilsesquioxane: Henan Weitixi Chemical Technology Co., Ltd.

[0046] PSS-[3-(2-aminoethyl)amino]propyl-substituted heptaisobutyl: Tianjin Xiensi Biochemical Technology Co., Ltd. Other raw materials and reagents were purchased from commercially available conventional products unless otherwise specified.

[0047] The main test methods involved in the following embodiments of the present invention are as follows:

[0048] <1> Color fixation / powder fixation: repeatedly rub the modified polyurethane sponge in a 10% sodium dodecyl sulfate solution for 10 minutes and observe the color change of the solution; if the color of the solution does not change after 10 minutes, it is recorded as "passed", if the color changes and the turbidity increases, it is recorded as "failed";

[0049] <2> Mechanical properties: The compression performance test was carried out using a WDW-5 micro-controlled electronic universal testing machine (Changchun Kexin Experimental Co., Ltd.) at room temperature, with a deformation of 80% and a compression speed of 15 mm / min.

[0050] The tensile strength test was carried out by cutting the elastomer with a standard cutter (5 mm in width), measuring the thickness of the elastomer with a CH-10-A thickness gauge produced by Zhejiang Linhai Instrument Factory, and testing the tensile strength of the elastomer with a 3340 Instron universal testing machine. The tensile test was carried out at room temperature with a test speed of 100 mm / min.

[0051] <3> Water absorption rate: The water absorption rate q is the weight of water absorbed by the unit weight of the absorbent material. Its expression is: q = (m2-m1) / m1

[0052] In the formula, m1 is the mass of the absorbent material before water absorption; m2 is the mass of the absorbent material after water saturation.

[0053] <4> 5% TD: The thermal stability test was conducted using a thermogravimetric analyzer model SDTA-854FTGA from Mettler, USA. The test was conducted under a nitrogen atmosphere with a temperature range of 30-800°C, a nitrogen flow rate of 10 mL / min, and an instrument heating rate of 10°C / min.

[0054] <5> Powder sticking test: cut the sponge into a cube with a length, width and height of 5 cm, with a mass of m1. Pat it on the foundation 10 times, dip it in the foundation, and the mass after dipping in the foundation is m2. Pat the sponge after dipping in the foundation on A4 paper 10 times, and the mass is m3 at this time. Sponge powder sticking rate = (m3-m1) / (m2-m1).

[0055] [Example 1]

[0056] (1) 20.16 g of hexamethylene diisocyanate, 12 g of PEG400 and 100 g of dihydroxy-terminated polysiloxane (relative molecular weight of 1000) were added to a reactor, and heated to 80° C. for reaction for 6 hours under stirring and nitrogen atmosphere to obtain an -NCO-terminated silicone-modified polyurethane prepolymer as a black material.

[0057] (2) 100 g of water, 1 g of color paste, 3 g of wollastonite powder, and 1.5 g of octaaminopropyl-cage polysilsesquioxane were mixed uniformly to prepare a white material.

[0058] (3) 30 g of the black material and 30 g of the white material were dispersed at a high speed of 4500 rpm / min for 35 seconds, and then allowed to stand for foaming. After the foaming was completed, the mixture was vacuum dried at 90° C. for 4 hours to obtain a silicone-modified polyurethane sponge.

[0059] [Example 2]

[0060] (1) 50.05 g of diphenylmethane diisocyanate, 8 g of PEG 800 and 50 g of dihydroxy-terminated polysiloxane (relative molecular weight of 2000) were added to a reactor, and heated to 80° C. for reaction for 6 hours under stirring and nitrogen atmosphere to obtain an -NCO-terminated silicone-modified polyurethane prepolymer as a black material.

[0061] (2) 100 g of water, 5 g of color paste, 15 g of talc, and 5 g of trisilanol phenyl-cage polysilsesquioxane were mixed uniformly to prepare a white material.

[0062] (3) 30 g of the black material and 45 g of the white material were dispersed at a high speed of 4500 rpm / min for 60 s, and then allowed to stand for foaming. After the foaming was completed, the mixture was vacuum dried at 90° C. for 4 hours to obtain a silicone-modified polyurethane sponge.

[0063] [Example 3]

[0064] (1) 70 g of toluene diisocyanate, 8 g of PEG 800 and 40 g of dihydroxy-terminated polysiloxane (relative molecular weight of 2500) were added to a reactor, and heated to 80° C. for reaction for 4 hours under stirring and nitrogen atmosphere to obtain an -NCO-terminated silicone-modified polyurethane prepolymer as a black material.

[0065] (2) 100 g of water, 5 g of color paste, 10 g of titanium dioxide, and 0.5 g of octa(aminophenyltrioxysilane) were mixed evenly to prepare a white material.

[0066] (3) 30 g of the black material and 60 g of the white material were dispersed at a high speed of 5000 rpm / min for 55 s, and then allowed to stand for foaming. After the foaming was completed, the mixture was vacuum dried at 95° C. for 6 hours to obtain a silicone-modified polyurethane sponge.

[0067] [Example 4]

[0068] (1) 131.17 g of dicyclohexylmethane diisocyanate, 20 g of PEG 1000 and 80 g of dihydroxy-terminated polysiloxane (relative molecular weight of 4000) were added to a reactor, and heated to 80° C. for reaction for 7 hours under stirring and nitrogen atmosphere to obtain an -NCO-terminated silicone-modified polyurethane prepolymer as a black material.

[0069] (2) 100 g of water, 8 g of color paste, 30 g of white carbon black, and 12 g of aminopropylheptyl-cage polysilsesquioxane were uniformly mixed to prepare a white material.

[0070] (3) 30 g of black material and 50 g of white material were taken, dispersed at a high speed of 5000 rpm / min for 80 s, and then allowed to stand for foaming. After the foaming was completed, vacuum drying was performed at 100° C. for 4 hours to obtain a silicone-modified polyurethane sponge.

[0071] [Example 5]

[0072] (1) 177.86 g of isophorone diisocyanate, 10 g of PEG 2000 and 200 g of dihydroxy-terminated polysiloxane (relative molecular weight of 5000) were added to a reactor, and heated to 90° C. for reaction for 8 hours under stirring and nitrogen atmosphere to obtain an -NCO-terminated silicone-modified polyurethane prepolymer as a black material.

[0073] (2) 100 g of water, 8 g of color paste, 30 g of wollastonite powder, and 30 g of PSS-[3-(2-aminoethyl)amino]propyl-substituted heptaisobutyl] were mixed uniformly to prepare a white material.

[0074] (3) 30 g of the black material and 65 g of the white material were dispersed at a high speed of 5000 rpm / min for 110 s, and then allowed to stand for foaming. After the foaming was completed, the mixture was vacuum dried at 95° C. for 4 hours to obtain a silicone-modified polyurethane sponge.

[0075] [Comparative Example 1]

[0076] The organosilicon-modified polyurethane sponge was prepared in a method substantially the same as that in Example 1, except that no octaaminopropyl-cage polysilsesquioxane was added when preparing the white material in step (2).

[0077] [Comparative Example 2]

[0078] A polyurethane sponge was prepared in substantially the same manner as in Example 1, except that no dihydroxy-terminated polysiloxane was added in the preparation of the black material in step (1).

[0079] [Comparative Example 3]

[0080] A silicone-modified polyurethane sponge was prepared in substantially the same manner as in Example 1, except that in step (1), when preparing the black material, the amount of the dihydroxy-terminated polysiloxane was changed to 200 g.

[0081] The sponges prepared in Examples 1-5 and Comparative Examples 1-3 were respectively subjected to the performance tests shown in Table 1, and the test results are shown below.

[0082] Table 1. Performance test results

[0083]

[0084] The above is only a preferred embodiment of the present invention. It should be pointed out that ordinary technicians in this field can make several improvements and supplements without departing from the method of the present invention. These improvements and supplements should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a silicone-modified polyurethane sponge, characterized in that: The following steps are involved: 1) reacting diisocyanate with polyether polyol and dihydroxy-terminated polysiloxane to prepare -NCO-terminated organosilicon-modified polyurethane prepolymer as a foaming black material; the amount of dihydroxy-terminated polysiloxane added to diisocyanate is 1:(1.2-6) in terms of the molar ratio of OH to NCO; The dihydroxy-terminated polysiloxane has a structure as shown in the following formula I: Where X is C1-C 10 A linear or branched saturated hydrocarbon group or an ether-containing hydrocarbon group, R1 and R2 are each independently selected from C1-C 10 A linear or branched saturated alkyl or aryl group, wherein n is 0-50; 2) mixing water, color paste, filler and cage-type silsesquioxane uniformly to obtain a foaming white material; 3) After dispersing the black material and the white material at high speed, the material is allowed to stand for foaming to obtain a silicone-modified polyurethane sponge.

2. The method for preparing the organosilicon-modified polyurethane sponge according to claim 1, characterized in that: In step 1), the amount of polyether polyol and diisocyanate added is 1:(4-10) in terms of the molar ratio of OH to NCO.

3. The method for preparing the organosilicon-modified polyurethane sponge according to claim 2, characterized in that: In step 1), the added amount of dihydroxy-terminated polysiloxane and diisocyanate, calculated by the molar ratio of OH to NCO, is 1:(1.2-4).

4. The method for preparing the organosilicon-modified polyurethane sponge according to claim 2, characterized in that: The reaction conditions in step 1) are: heating to 70-100° C. for 2-6 hours under an inert atmosphere.

5. The method for preparing the organosilicon-modified polyurethane sponge according to claim 4, characterized in that: The reaction conditions in step 1) are: heating to 80-90° C. for 3-4 hours under an inert atmosphere.

6. The method for preparing the organosilicon-modified polyurethane sponge according to claim 4, characterized in that: In step 1), the stirring speed is controlled to be 200-300 rpm / min.

7. The method for preparing the organosilicon-modified polyurethane sponge according to any one of claims 1 to 6, characterized in that: The diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.

8. The method for preparing the organosilicon-modified polyurethane sponge according to claim 7, characterized in that: The polyether polyol is polyethylene glycol with a molecular weight of 200-5000.

9. The method for preparing the organosilicon-modified polyurethane sponge according to claim 8, characterized in that: The polyether polyol is polyethylene glycol with a molecular weight of 400-2000.

10. The method for preparing the organosilicon-modified polyurethane sponge according to claim 1, characterized in that: In formula I, X is a C3-C5 linear alkyl group or an ether-containing alkyl group, R1 and R2 are independently selected from methyl, ethyl, and propyl, and n is 20-60.

11. The method for preparing the organosilicon-modified polyurethane sponge according to any one of claims 1 to 6, characterized in that: In step 2), the mass ratio of water, color paste, filler and cage-type silsesquioxane is (50-1000):(1-25):(0.1-10):(0.5-20).

12. The method for preparing the organosilicon-modified polyurethane sponge according to claim 11, characterized in that: The filler is one or more of wollastonite powder, white carbon black, titanium dioxide, and talc powder.

13. The method for preparing the organosilicon-modified polyurethane sponge according to claim 12, characterized in that: The filler is wollastonite powder with a particle size of 5-50 microns.

14. The method for preparing the organosilicon-modified polyurethane sponge according to claim 12, characterized in that: The color paste is a concentrated pigment paste with a particle size of 1-300 nm and a solid content of 60-80%.

15. The method for preparing the organosilicon-modified polyurethane sponge according to claim 14, characterized in that: The color paste is a concentrated pigment paste with a particle size of 1-100 nm and a solid content of 60-80%.

16. The method for preparing the organosilicon-modified polyurethane sponge according to claim 12, characterized in that: The cage-type silsesquioxane is one or more of trisilanolphenyl-cage-type polysilsesquioxane, octa(aminophenyltrioxysilane), aminopropylheptyl-cage-type polysilsesquioxane, octaaminopropyl-cage-type polysilsesquioxane, and PSS-[3-(2-aminoethyl)amino]propyl-substituted heptaisobutyl.

17. The method for preparing the organosilicon-modified polyurethane sponge according to any one of claims 1 to 6, characterized in that: In step 3), the mixing ratio of the black material and the white material is 100:(50-1000) based on the mass ratio of the organosilicon-modified polyurethane prepolymer to water.

18. The method for preparing the organosilicon-modified polyurethane sponge according to claim 17, characterized in that: In step 3), the mixing ratio of the black material and the white material is 100:(80-500) based on the mass ratio of the organosilicon-modified polyurethane prepolymer to water.

19. The method for preparing the organosilicon-modified polyurethane sponge according to claim 17, characterized in that: In step 3), the high speed dispersion conditions are a rotation speed of 3000-6000 rpm / min and a time of 30-120 s.

20. The method for preparing the organosilicon-modified polyurethane sponge according to claim 19, characterized in that: In step 3), the high-speed dispersion conditions are a rotation speed of 4000-5000 rpm / min and a time of 30-45 s.

21. The method for preparing the organosilicon-modified polyurethane sponge according to claim 19, characterized in that: Step 3) After the foaming is completed, dry at 70-110°C for 2-8h.

22. The method for preparing the organosilicon-modified polyurethane sponge according to claim 21, characterized in that: Step 3) After the foaming is completed, dry at 90-100°C for 4-6 hours.

23. Use of the organosilicon-modified polyurethane sponge prepared by the method according to any one of claims 1 to 22 as a cosmetic material.

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