Clothing sunscreen spray and preparation method thereof

Abstract

The invention provides a clothing sunscreen spray and a preparation method thereof, the clothing sunscreen spray comprises alcohol, a surfactant, a benzophenone-polyethylene glycol absorbent, modified titanium dioxide nanoparticles and water, the modified titanium dioxide nanoparticles are titanium dioxide nanoparticles grafted with polyacrylic acid, and the particle size of the modified titanium dioxide nanoparticles is 10-100 nm. The preparation method of the clothing sunscreen spray comprises the following steps: preparing a benzophenone-polyethylene glycol absorbent; preparing modified titanium dioxide nanoparticles; and preparing the clothes sunscreen spray. The sunscreen spray for the clothes is high in ultraviolet absorbance and light stability and has a good application prospect.

Description

Technical Field

[0001] The invention relates to the field of cosmetics, and mainly to a clothing sunscreen spray and a preparation method thereof. Background Art

[0002] Sunscreen technology has always been one of the important research directions in the field of cosmetics. Traditional sunscreen products mainly focus on the surface of the skin, and form a protective layer by adding sunscreen to block the damage of ultraviolet rays. However, these products have limited protective effects on clothing. The impact of ultraviolet rays on clothing is mainly reflected in the following aspects: 1. Fading. Ultraviolet rays can cause the color of clothing to fade, especially bright colors. This is because ultraviolet rays can destroy dye molecules, causing the color to become dull or uneven; 2. Fiber damage. Long-term exposure to ultraviolet rays may damage the fiber structure of clothing, causing the clothing to become fragile and easy to break. This damage is particularly evident in synthetic fibers (such as polyester and nylon); 3. Reduced strength. Ultraviolet rays can reduce the strength of clothing, making it more susceptible to damage when stretched or rubbed; 4. Aging. Ultraviolet rays accelerate the aging process of clothing, causing it to lose its original elasticity and softness, affecting wearing comfort; 5. Antibacterial properties. Certain ultraviolet rays may affect the antibacterial properties of clothing, causing bacteria to grow, thereby producing odors; 6. Reduced service life. Due to the influence of ultraviolet rays, the service life of clothing may be shortened, increasing the frequency and cost of replacement.

[0003] At present, the sunscreen products on the market cannot effectively prevent ultraviolet damage to clothing. Therefore, it is particularly important to develop a sunscreen spray that can directly act on clothing and effectively prevent ultraviolet damage. The research and development of clothing sunscreen spray combines sunscreen technology and cosmetic technology. Through special spray technology, the sunscreen ingredients are evenly distributed on the surface of clothing to form a sunscreen protective layer. This product has the advantages of easy use, uniform coverage, and good durability. It can prevent ultraviolet damage to clothing to a certain extent and extend the service life of clothing.

[0004] However, the current clothing sunscreen spray still cannot meet market demand and has the following shortcomings: 1. The ultraviolet absorption effect is not good enough, resulting in clothing being obviously damaged by ultraviolet rays, especially in areas with strong light, the impact is more obvious; 2. The light stability of the spray is insufficient. The spray will inevitably be exposed to ultraviolet rays during transportation and storage, resulting in a certain degree of photodegradation, which reduces its effectiveness.

[0005] In summary, it is necessary to develop a new technical solution to solve the defects and shortcomings in the existing technology. Summary of the invention

[0006] The invention provides a clothing sunscreen spray and a preparation method thereof. The clothing sunscreen spray has good ultraviolet absorption effect and strong light stability, has good sunscreen effect on clothing, and has good application prospects.

[0007] One object of the present invention is to provide a clothing sunscreen spray, the clothing sunscreen spray comprising the following components in mass fractions:

[0008]

[0009] Wherein, the structural formula of the benzophenone-polyethylene glycol absorbent is as follows:

[0010]

[0011] The modified titanium dioxide nanoparticles are titanium dioxide nanoparticles grafted with polyacrylic acid.

[0012] Furthermore, the surfactant is selected from one or more of polyglyceryl-3 methyl glucose distearate, glyceryl monostearate, and caprylic / capric triglyceride.

[0013] Furthermore, the particle size of the modified titanium dioxide nanoparticles is 10-100 nm.

[0014] Another object of the present invention is to provide a method for preparing the above-mentioned clothing sunscreen spray, the method for preparing the clothing sunscreen spray comprising the following steps:

[0015] Preparation of benzophenone-polyethylene glycol absorbent:

[0016] S1, mixing polyethylene glycol and toluene and heating them under an inert atmosphere, adding sodium, and reacting to obtain a sodium polyethylene glycol toluene solution;

[0017] S2, mixing 2,4-dihydroxy-benzophenone, triethylamine and a solvent, adding chloroacetyl chloride under ice bath, and reacting to obtain 2-hydroxy-4-chloroacetate-benzophenone;

[0018] S3, under an inert atmosphere, mixing the 2-hydroxy-4-chloroacetate-benzophenone and a solvent, heating and stirring, and then adding a sodium polyethylene glycol toluene solution to react to obtain a benzophenone-polyethylene glycol absorbent;

[0019] Preparation of modified titanium dioxide nanoparticles:

[0020] The hydroxylated titanium dioxide is immersed in polyacrylic acid, and subjected to heating and ultrasonic reaction to obtain modified titanium dioxide nanoparticles;

[0021] To prepare a sunscreen spray for clothing:

[0022] The benzophenone-polyethylene glycol absorbent, modified titanium dioxide nanoparticles and other ingredients are mixed and stirred evenly to obtain a clothing sunscreen spray.

[0023] Furthermore, in step S1, the mass ratio of polyethylene glycol to sodium is (10-20):(0.05-0.15).

[0024] Furthermore, in step S2, the mass ratio of 2,4-dihydroxy-benzophenone, triethylamine and chloroacetyl chloride is (20-22):(9.6-12.8):(16-20).

[0025] Furthermore, in step S3, the molar ratio of the 2-hydroxy-4-chloroacetate-benzophenone and sodium polyethylene glycol is (2-3):1.

[0026] Furthermore, in step S1, the heating temperature is 110-120°C; in step S3, the heating temperature is 90-110°C.

[0027] Furthermore, the temperature of the heating and ultrasonic reaction is 60-70°C and the time is 90-180 minutes.

[0028] Furthermore, the mass ratio of the hydroxylated titanium dioxide to the polyacrylic acid is 1:(1-20).

[0029] The present invention has the following beneficial effects:

[0030] The clothing sunscreen spray provided by the present invention contains modified titanium dioxide nanoparticles in the UV light, which are prepared by grafting polyacrylic acid with hydroxylated titanium dioxide. On the one hand, by introducing polyacrylic acid groups on the surface of titanium dioxide nanoparticles, they can be cross-linked with benzophenone-polyethylene glycol absorbents through chemical bonds, thereby improving the dispersibility and compatibility with other components, which is beneficial to improving the ultraviolet absorption effect; on the other hand, the hydroxyl and carboxyl groups on the surface of the modified titanium dioxide nanoparticles can generate intermolecular forces with active groups such as hydroxyl groups in the benzophenone-polyethylene glycol absorbent, making the combination of the two more stable, thereby further improving the sunscreen effect and the stability of the product. DETAILED DESCRIPTION

[0031] In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. Unless otherwise stated, the raw materials, reactions and post-treatment methods shown in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0032] The words "preferred", "preferably", "more preferably", etc. in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0033] It should be understood that, except in any operating examples, or where otherwise indicated, all numbers indicating, for example, the amounts of ingredients used in the specification and claims should be understood to be modified in all cases by the term "about". Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that vary depending on the desired properties to be obtained by the present invention.

[0034] The following raw materials are used in the embodiments of the present invention:

[0035] Polyethylene glycol, molecular weight 2000, purchased from Taizhou Jiayin Chemical Co., Ltd.;

[0036] Polyglycerol-3 methyl glucose distearate, surfactant, brand name xyh001, purchased from Hubei Xinyuhong Biopharmaceutical Technology Co., Ltd.;

[0037] Glyceryl monostearate, surfactant, brand number Cl22023152, purchased from Wuhan Kemik Biopharmaceutical Technology Co., Ltd.;

[0038] Caprylic / capric triglyceride, surfactant, brand GTCC, purchased from Hubei Chengfeng Chemical Co., Ltd.;

[0039] Nano titanium dioxide, model YC-YT30GL, was purchased from Shanghai Yingcheng New Materials Co., Ltd.

[0040] The preparation method of hydroxylated titanium dioxide in the embodiment of the present invention comprises the following steps:

[0041] The nano-titanium dioxide was added into a sufficient amount of 6.5 wt % phosphoric acid solution, reacted in a water bath at 100° C. for 1 hour, washed with distilled water and dried to obtain hydroxylated titanium dioxide.

[0042] Example 1

[0043] A clothing sunscreen spray, comprising the following components in mass fractions:

[0044]

[0045] The preparation method of the clothing sunscreen spray comprises the following steps:

[0046] Preparation of benzophenone-polyethylene glycol absorbent:

[0047] S1. Blend polyethylene glycol and toluene in a mass ratio of 1:6 and heat to 115° C. under nitrogen protection, add sodium (the mass ratio of polyethylene glycol to sodium is 10:0.15), react for 24 hours until the solution turns dark brown, remove the remaining sodium, and obtain a sodium polyethylene glycol toluene solution;

[0048] S2, 2,4-dihydroxy-benzophenone, triethylamine and tetrahydrofuran were blended in a mass ratio of 21:10:36, and a mixed solution of chloroacetyl chloride and tetrahydrofuran (the mass ratio of 2,4-dihydroxy-benzophenone, chloroacetyl chloride and tetrahydrofuran was 21:18:36) was added dropwise under an ice bath, and the mixture was added for 2 hours, and the mixture was reacted for 6 hours. Ice water was added to precipitate the mixture, and the mixture was washed with a saturated sodium bicarbonate solution to obtain a yellow oily product. The product was dried to obtain a yellow powder, which was recrystallized with 95wt% ethanol and dried to obtain slightly yellow needle-shaped crystals, i.e., 2-hydroxy-4-chloroacetate-benzophenone;

[0049] S3, under nitrogen protection, the 2-hydroxy-4-chloroacetate-benzophenone and a sufficient amount of toluene are blended, heated to 100 ° C and stirred until dissolved, and then a sodium polyethylene glycol toluene solution (the molar ratio of 2-hydroxy-4-chloroacetate-benzophenone and sodium polyethylene glycol is 2.4:1) is added to react for 12 hours, and a viscous substance is precipitated, the upper toluene solution is removed, ether is added for precipitation, and vacuum drying is performed to obtain a benzophenone-polyethylene glycol absorbent;

[0050] Preparation of modified titanium dioxide nanoparticles:

[0051] The hydroxylated titanium dioxide was immersed in polyacrylic acid (the mass ratio of hydroxylated titanium dioxide to polyacrylic acid was 1:5), heated to 65°C for ultrasonic reaction for 90 minutes, washed and dried to obtain modified titanium dioxide nanoparticles;

[0052] To prepare a sunscreen spray for clothing:

[0053] According to the above mass fractions, the benzophenone-polyethylene glycol absorbent, modified titanium dioxide nanoparticles, alcohol, and surfactant (the mass ratio of polyglycerol-3 methyl glucose distearate, monostearate glyceryl, caprylic acid / capric acid triglyceride is 1:1:1) are blended and stirred evenly to obtain a clothing sunscreen spray.

[0054] Example 2

[0055] A clothing sunscreen spray, comprising the following components in mass fractions:

[0056]

[0057] The preparation method of the clothing sunscreen spray comprises the following steps:

[0058] Preparation of benzophenone-polyethylene glycol absorbent:

[0059] S1. Blend polyethylene glycol and toluene in a mass ratio of 1:6 and heat to 115° C. under nitrogen protection, add sodium (the mass ratio of polyethylene glycol to sodium is 10:0.15), react for 24 hours until the solution turns dark brown, remove the remaining sodium, and obtain a sodium polyethylene glycol toluene solution;

[0060] S2, 2,4-dihydroxy-benzophenone, triethylamine and tetrahydrofuran were blended in a mass ratio of 21:10:36, and a mixed solution of chloroacetyl chloride and tetrahydrofuran (the mass ratio of 2,4-dihydroxy-benzophenone, chloroacetyl chloride and tetrahydrofuran was 21:18:36) was added dropwise under an ice bath, and the mixture was added for 2 hours, and the mixture was reacted for 6 hours. Ice water was added to precipitate the mixture, and the mixture was washed with a saturated sodium bicarbonate solution to obtain a yellow oily product. The product was dried to obtain a yellow powder, which was recrystallized with 95wt% ethanol and dried to obtain slightly yellow needle-shaped crystals, i.e., 2-hydroxy-4-chloroacetate-benzophenone;

[0061] S3, under nitrogen protection, the 2-hydroxy-4-chloroacetate-benzophenone and a sufficient amount of toluene are blended, heated to 100 ° C and stirred until dissolved, and then a sodium polyethylene glycol toluene solution (the molar ratio of 2-hydroxy-4-chloroacetate-benzophenone and sodium polyethylene glycol is 2.4:1) is added to react for 12 hours, and a viscous substance is precipitated, the upper toluene solution is removed, ether is added for precipitation, and vacuum drying is performed to obtain a benzophenone-polyethylene glycol absorbent;

[0062] Preparation of modified titanium dioxide nanoparticles:

[0063] The hydroxylated titanium dioxide was immersed in polyacrylic acid (the mass ratio of hydroxylated titanium dioxide to polyacrylic acid was 1:5), heated to 70°C for ultrasonic reaction for 90 minutes, washed and dried to obtain modified titanium dioxide nanoparticles;

[0064] To prepare a sunscreen spray for clothing:

[0065] According to the above mass fractions, the benzophenone-polyethylene glycol absorbent, modified titanium dioxide nanoparticles, alcohol, and surfactant (the mass ratio of polyglycerol-3 methyl glucose distearate, monostearate glyceryl, caprylic acid / capric acid triglyceride is 1:2:2) are blended and stirred evenly to obtain a clothing sunscreen spray.

[0066] Example 3

[0067] A clothing sunscreen spray, comprising the following components in mass fractions:

[0068]

[0069] The preparation method of the clothing sunscreen spray comprises the following steps:

[0070] Preparation of benzophenone-polyethylene glycol absorbent:

[0071] S1. Blend polyethylene glycol and toluene in a mass ratio of 1:6 and heat to 115° C. under nitrogen protection, add sodium (the mass ratio of polyethylene glycol to sodium is 10:0.15), react for 24 hours until the solution turns dark brown, remove the remaining sodium, and obtain a sodium polyethylene glycol toluene solution;

[0072] S2, 2,4-dihydroxy-benzophenone, triethylamine and tetrahydrofuran were blended in a mass ratio of 21:10:36, and a mixed solution of chloroacetyl chloride and tetrahydrofuran (the mass ratio of 2,4-dihydroxy-benzophenone, chloroacetyl chloride and tetrahydrofuran was 21:18:36) was added dropwise under an ice bath, and the mixture was added for 2 hours, and the mixture was reacted for 6 hours. Ice water was added to precipitate the mixture, and the mixture was washed with a saturated sodium bicarbonate solution to obtain a yellow oily product. The product was dried to obtain a yellow powder, which was recrystallized with 95wt% ethanol and dried to obtain slightly yellow needle-shaped crystals, i.e., 2-hydroxy-4-chloroacetate-benzophenone;

[0073] S3, under nitrogen protection, the 2-hydroxy-4-chloroacetate-benzophenone and a sufficient amount of toluene are blended, heated to 100 ° C and stirred until dissolved, and then a sodium polyethylene glycol toluene solution (the molar ratio of 2-hydroxy-4-chloroacetate-benzophenone and sodium polyethylene glycol is 2.4:1) is added to react for 12 hours, and a viscous substance is precipitated, the upper toluene solution is removed, ether is added for precipitation, and vacuum drying is performed to obtain a benzophenone-polyethylene glycol absorbent;

[0074] Preparation of modified titanium dioxide nanoparticles:

[0075] The hydroxylated titanium dioxide was immersed in polyacrylic acid (the mass ratio of hydroxylated titanium dioxide to polyacrylic acid was 1:5), heated to 65°C for ultrasonic reaction for 100 minutes, washed and dried to obtain modified titanium dioxide nanoparticles;

[0076] To prepare a sunscreen spray for clothing:

[0077] According to the above mass fractions, the benzophenone-polyethylene glycol absorbent, modified titanium dioxide nanoparticles, alcohol, and surfactant (the mass ratio of polyglycerol-3 methyl glucose distearate, monostearate glyceryl, caprylic / capric triglyceride is 1:1:3) are blended and stirred evenly to obtain a clothing sunscreen spray.

[0078] Comparative Example

[0079] The difference between this comparative example and Example 1 is that the modified titanium dioxide nanoparticles are replaced by a physical mixture of hydroxylated titanium dioxide and polyacrylic acid in a mass ratio of 1:5.

[0080] Test Example 1

[0081] The ultraviolet absorption effects of Examples 1-3 and Comparative Example were tested.

[0082] Test method:

[0083] The molar extinction coefficient of UV absorbers is an important indicator for measuring their UV absorption effect. Therefore, the UV absorption intensity of different samples at their respective maximum UV absorption wavelengths was measured using a spectrophotometer. According to the Lamber-Beer law, the molar extinction coefficient of the corresponding sample was obtained.

[0084] Test results:

[0085] Table 1 UV absorption test results

[0086] sample <![CDATA[Molar extinction coefficient (L·mol -1 ·cm -1 )]]> Example 1 18650 Example 2 18470 Example 3 18260 Comparative Example 11092

[0087] The test results are shown in Table 1. It can be seen that the ultraviolet absorption effect of Examples 1-3 is better than that of the comparative example. This is because the comparative example replaces the modified titanium dioxide nanoparticles with a physical mixture of hydroxylated titanium dioxide and polyacrylic acid in a mass ratio of 1:5, and does not introduce polyacrylic acid groups on the surface of the titanium dioxide nanoparticles. The dispersion is poor, the compatibility with other components is insufficient, and it cannot be cross-linked with the benzophenone-polyethylene glycol absorber. Therefore, the ultraviolet absorption effect is reduced.

[0088] Test Example 2

[0089] The light stability of Examples 1-3 and Comparative Examples was tested.

[0090] Test method:

[0091] Using an ultraviolet spectrophotometer, the sample was exposed to sunlight for two weeks under sealed conditions, and then the ratio of the integrated area of ​​the ultraviolet absorption spectrum in the range of 200-400nm before and after irradiation was tested respectively, and the residual rate of ultraviolet absorption effect was calculated to examine the photostability of the sample.

[0092] Generally speaking, the photostability is good if the residual rate of ultraviolet light absorption effect is above 95%, average if it is between 95% and 90%, and poor if it is between 90% and 70%.

[0093] Test results:

[0094] Table 2 Light stability test results

[0095] sample UV absorption effect residual rate (%) Photostability Example 1 99.4 better Example 2 98.3 better Example 3 96.8 better Comparative Example 83.1 Poor

[0096] The test results are shown in Table 2. It can be seen that Examples 1-3 have better photostability than the comparative example. This is because the comparative example replaces the modified titanium dioxide nanoparticles with a physical mixture of hydroxylated titanium dioxide and polyacrylic acid in a mass ratio of 1:5. The compatibility and synergy between the components are weakened, and a more stable structure cannot be formed, thereby reducing the photostability.

[0097] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0098] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A clothing sunscreen spray, characterized in that: The clothing sunscreen spray comprises the following components in mass fractions: Wherein, the structural formula of the benzophenone-polyethylene glycol absorbent is as follows: The modified titanium dioxide nanoparticles are titanium dioxide nanoparticles grafted with polyacrylic acid.

2. The clothing sunscreen spray according to claim 1, characterized in that: The surfactant is selected from one or more of polyglyceryl-3 methyl glucose distearate, glyceryl monostearate, caprylic / capric triglyceride.

3. The clothing sunscreen spray according to claim 1, characterized in that: The particle size of the modified titanium dioxide nanoparticles is 10-100 nm.

4. The method for preparing the clothing sunscreen spray according to any one of claims 1 to 3, characterized in that: The preparation method of the clothing sunscreen spray comprises the following steps: Preparation of benzophenone-polyethylene glycol absorbent: S1, mixing polyethylene glycol and toluene and heating them under an inert atmosphere, adding sodium, and reacting to obtain a sodium polyethylene glycol toluene solution; S2, mixing 2,4-dihydroxy-benzophenone, triethylamine and a solvent, adding chloroacetyl chloride under ice bath, and reacting to obtain 2-hydroxy-4-chloroacetate-benzophenone; S3, under an inert atmosphere, mixing the 2-hydroxy-4-chloroacetate-benzophenone and a solvent, heating and stirring, and then adding a sodium polyethylene glycol toluene solution to react to obtain a benzophenone-polyethylene glycol absorbent; Preparation of modified titanium dioxide nanoparticles: The hydroxylated titanium dioxide is immersed in polyacrylic acid, and subjected to heating and ultrasonic reaction to obtain modified titanium dioxide nanoparticles; To prepare a sunscreen spray for clothing: The benzophenone-polyethylene glycol absorbent, modified titanium dioxide nanoparticles and other ingredients are mixed and stirred evenly to obtain a clothing sunscreen spray.

5. The method for preparing the clothing sunscreen spray according to claim 4, characterized in that: In step S1, the mass ratio of polyethylene glycol to sodium is (10-20):(0.05-0.15).

6. The method for preparing the clothing sunscreen spray according to claim 4, characterized in that: In step S2, the mass ratio of 2,4-dihydroxy-benzophenone, triethylamine and chloroacetyl chloride is (20-22):(9.6-12.8):(16-20).

7. The method for preparing the clothing sunscreen spray according to claim 4, characterized in that: In step S3, the molar ratio of the 2-hydroxy-4-chloroacetate-benzophenone and sodium polyethylene glycol is (2-3):

1.

8. The method for preparing the clothing sunscreen spray according to claim 4, characterized in that: In step S1, the heating temperature is 110-120°C; in step S3, the heating temperature is 90-110°C.

9. The method for preparing the clothing sunscreen spray according to claim 4, characterized in that: The temperature of the heating and ultrasonic reaction is 60-70° C. and the time is 90-180 min.

10. The method for preparing the clothing sunscreen spray according to claim 4, characterized in that: The mass ratio of the hydroxylated titanium dioxide to the polyacrylic acid is 1:(1-20).

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