A low-irritation long-acting polyurethane-hydroxyphthalein mosquito repellent

Abstract

The application discloses a low-irritation long-acting polyurethane-hydroxypiperidine mosquito repellent, and the mass composition of the efficacy component is as follows: 3-8 parts of polyurethane-2, 5-20 parts of hydroxypiperidine, 20-50 parts of polyhydric alcohol and 3-9 parts of fatty acid ester. The strong hydrogen bond is formed by the large number of IPDI groups in the polyurethane-2 and the piperidine groups in the hydroxypiperidine, and the hydroxyl groups, amino acid groups contained in the polyurethane and the cutin layer on the surface of the skin are well combined, so that the invisible and long-lasting mosquito repellent film can be formed on the surface of the skin, the greasy feeling of the traditional mosquito repellent is eliminated, the persistence and diffusivity of the hydroxypiperidine are improved, and the mosquito repellent effect is enhanced.

Description

Technical Field

[0001] This invention relates to a mosquito repellent, specifically a low-irritation, long-lasting polyurethane-hydroxypiperate mosquito repellent. Background Technology

[0002] Mosquitoes, belonging to the family Culicidae in the order Diptera, are small flying insects with piercing-sucking mouthparts. There are approximately 3,000 species worldwide. Females typically feed on blood, while males feed on plant sap. Blood-sucking female mosquitoes are intermediate hosts for dengue fever, malaria, yellow fever, filariasis, Japanese encephalitis, and other pathogens. Mosquitoes are found on every continent except Antarctica. The genera Anopheles, Aedes, and Culex are the most well-known. Mosquito saliva contains a substance that dilates blood vessels and has anticoagulant properties, making it easier for blood to flow to the bite site. Mosquito bites can cause mild swelling, itching, and redness, or more serious diseases, thus, research into mosquito control has been ongoing.

[0003] Currently, the most widely used mosquito repellents are DEET and IR3535. In recent years, it has been found that picaridin (also known as isobutyl hydroxyethylpiperidine carboxylate) has a similar mosquito-repelling effect to DEET, but is more effective than IR3535 and has better safety. At a 10% concentration, the mosquito-repelling effect can last for 8-10 hours, and at a 15% concentration, it can maintain the effect for up to 14 hours. Its safety has been recommended by the American Academy of Pediatrics for use in all individuals over 2 months of age. It has a significant disruptive effect on the nervous system of insects, effectively preventing insects from approaching. High concentrations of picaridin are colorless, transparent, viscous liquids with a noticeably oily feel.

[0004] However, when used alone, picaridin has limitations in both persistence and spread. Therefore, improving the mosquito-repellent effect of picaridin has been a key research direction in this field. Currently available products are mostly ethanol-based sprays, which are easy to use, but their safety is poor. After the ethanol evaporates, a high concentration of picaridin remains on the skin, failing to fundamentally solve the subsequent greasy feeling. While emulsified systems can enhance the residual texture by adding oils, this may increase the absorption of the mosquito repellent, affecting its effectiveness or the safety of the formulation.

[0005] CN102266270A discloses a mosquito repellent with hydroxylamine as the active ingredient. The weight percentages of its components are: 5-25% hydroxylamine, 10-80% organic matter, 0.1-10% organic acid, 0.1-1% fragrance, and the balance being water. This invention uses solvents such as ethanol and isopropanol, which can easily cause irritation to the user's mucous membranes, and as an aqueous emulsion, it is difficult to achieve good formulation stability. Summary of the Invention

[0006] The purpose of this invention is to overcome at least one deficiency of the prior art and provide a low-irritation, long-lasting polyurethane-hydroxypiperate mosquito repellent.

[0007] The technical solution adopted in this invention is:

[0008] This invention provides a low-irritation, long-lasting polyurethane-hydroxypiperate mosquito repellent, the active ingredient of which is composed of: 3-8 parts polyurethane-2, 5-20 parts hydroxypiperate, 20-50 parts polyol, and 3-9 parts fatty acid ester.

[0009] In some instances, the mass ratio of polyurethane-2 to hydroxypiperate is 1:(0.5 to 4).

[0010] In some instances, the mass ratio of polyurethane-2 to polyol is 1:(4–8).

[0011] In some instances, the mass ratio of polyurethane-2 to fatty acid ester is 1:(0.2 to 1.5).

[0012] In some instances, the polyol is selected from at least one of ethanol, 1,2-propanediol, 1,3-butanediol, and methylpropanediol.

[0013] In some instances, the polyol is a mixture of ethanol and 1,3-butanediol, with a mass ratio of ethanol to 1,3-butanediol of 0.65 to 0.7.

[0014] In some instances, the fatty acid ester is isononyl isononanoate.

[0015] In some examples, the active ingredient is characterized by the following composition by mass: 4-6 parts polyurethane-2, 15 parts hydroxyphenyl ester, 25 parts polyol, and 5 parts fatty acid ester.

[0016] In some instances, the average molecular weight of the polyurethane-2 is 1,000 to 200,000.

[0017] In some instances, the mosquito repellent also includes at least one of the following: antioxidants, fragrances, preservatives, neutralizers, emollients, free radical scavengers, deodorants, multivalent chelating agents, and solvents.

[0018] The beneficial effects of this invention are:

[0019] The polyurethane hydrochloride composite mosquito repellent of the present invention, due to the large number of IPDI groups in polyurethane-2, can form a strong hydrogen bond with the piperidine groups in hydrochloride. At the same time, because polyurethane contains hydroxyl and amino acid groups, it can bind well with the stratum corneum of the skin surface, forming an invisible and long-lasting mosquito repellent film on the skin surface, eliminating the greasy feeling of traditional mosquito repellents, prolonging the mosquito repellent effect, and reducing the transdermal absorption effect of hydrochloride. It not only improves the persistence and diffusion of hydrochloride, but also enhances the mosquito repellent effect. Attached Figure Description

[0020] Figure 1 The graphs show the mosquito repellent effects of comparative examples 1 to 14.

[0021] Figure 2 The graphs show the mosquito repellent effects of comparative examples 1-3 and comparative examples 15-26.

[0022] Figure 3 The graphs show the mosquito repellent effects of comparative examples 1-3 and comparative examples 27-32.

[0023] Figure 4 The graphs show the mosquito repellent effects of comparative examples 1-3 and comparative examples 33-50.

[0024] Figure 5 The figures show the mosquito repellent effects of Comparative Examples 1-3 and Examples 1-6. Detailed Implementation

[0025] The inventors discovered that polyurethane-2 contains a large number of IPDI groups, which can form strong hydrogen bonds with the piperidine groups in hydroxyl esters. Simultaneously, polyurethane-2 contains numerous hydroxyl and amino acid groups, providing excellent adhesion to the stratum corneum of the skin, thus forming an invisible, long-lasting, and skin-adhering mosquito-repellent film like a net. This structure helps hydroxyl esters to be efficiently adsorbed onto the microscopic spatial network structure formed by polyurethane-2. After spraying, a light and breathable film forms on the skin, eliminating the greasy feeling of traditional mosquito repellents and fixing it to the skin to prolong the mosquito-repellent effect and reduce the transdermal absorption of hydroxyl esters. Polyols can be interspersed within the microscopic spatial network structure, enhancing the hydrogen bonding effect while reducing the density of the structure. The added fatty acid esters in the system effectively reduce the stickiness of hydroxyl esters.

[0026] Additional common cosmetic ingredients:

[0027] The compositions according to the invention may also contain any conventional cosmetic ingredients, particularly selected from antioxidants, fragrances, preservatives, neutralizers, surfactants, solar filters, vitamins, moisturizers, self-tanning compounds, anti-wrinkle active ingredients, emollients, hydrophilic or lipophilic active ingredients, free radical scavengers, deodorants, multivalent chelating agents, and mixtures thereof.

[0028] The following disclosure provides many different implementations or examples for different ways of implementing the present invention.

[0029] All percentages in this invention are by weight and are based on 100% by weight of the cosmetic composition of this invention, unless otherwise stated.

[0030] All weights referred to in this invention are the weights of the effective substance. For substances in dispersion form, the weights referred to in this invention are the actual weights of the substance, excluding the weight of the carrier. That is, the weight of the substance in dispersion form as referred to in this invention = weight of the dispersion × content of solid components in the dispersion. For solid substances containing water of crystallization, the weights referred to in this invention are the weights after removing the water of crystallization.

[0031] The compositions according to the invention may also contain any conventional cosmetic ingredients, particularly selected from antioxidants, fragrances, preservatives, neutralizers, surfactants, solar filters, vitamins, moisturizers, self-tanning compounds, anti-wrinkle active ingredients, emollients, hydrophilic or lipophilic active ingredients, free radical scavengers, deodorants, multivalent chelating agents, and mixtures thereof.

[0032] Polyurethane-2 can be obtained by reacting one or more water-insoluble, non-aqueous isocyanates, preferably isophorone diisocyanate (IPDI) functionalized polyurethane prepolymer A1 with one or more amino functional compounds A2.

[0033] The polyurethane prepolymer A1 has terminal isocyanate groups, i.e., isocyanate groups are located at the ends of the prepolymer chains. Preferably, all chain ends of the polyurethane prepolymer have isocyanate groups. The water-insoluble and non-aqueous dispersible isocyanate-functionalized polyurethane prepolymer A1 used in this invention is substantially free of ionic groups and / or ion source groups, i.e., the content of ionic groups and / or ion source groups is suitably less than 15 milli-equivalents / 100g of polyurethane prepolymer A1), preferably less than 5 milli-equivalents, more preferably less than 1 milli-equivalent, and particularly preferably less than 0.1 milli-equivalents / 100g of polyurethane prepolymer A1. Here, water refers to deionized water without added surfactants.

[0034] The polyurethane prepolymers used in this invention may contain acidic ionic groups and / or ion-source groups, and the acid value of these polyurethane prepolymers is suitably below 30 mg KOH / g, preferably below 10 mg KOH / g. This acid value represents the mass (mg) of potassium hydroxide required to neutralize 1 g of a study sample (measured according to DIN EN ISO 211). The neutralized acid (i.e., the corresponding salt) naturally has no acid value or a low acid value.

[0035] Polyurethane-2 can also be prepared using polymeric polyols, such as polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols, and polyester polycarbonate polyols. These can be used alone or in mixtures to prepare the polyurethane of the present invention. The polymeric polyols are preferably polytetramethylene glycol polyether, polycarbonate polyols, and mixtures thereof, with polytetramethylene glycol polyether polyols being particularly preferred.

[0036] The polyurethane-2 used in this invention is preferably a linear molecule, but it can also be branched. The number-average molecular weight of the polyurethane used in this invention is preferably 1,000-200,000.

[0037] For ease of comparison, the abbreviations of some reagents or raw materials used in the examples of this invention are shown in Table 1:

[0038] Table 1

[0039]

[0040] In each embodiment and comparative example, 0.5 parts of LEXGARD H were added, and water was added to a total of 100 parts. Unless otherwise specified, all parts are by weight.

[0041] The polymer and polyol were stirred at high speed until homogeneous. While stirring, the hydroxylamine and fatty acid esters or other oils (if any) were added until homogeneous. Then, water, ethanol, and 1,2-hexanediol were added while stirring until homogeneous.

[0042] The components of Examples 1 to 6 are shown in Table 2. The copolymer used is C200F, and the fatty acid ester used is 99%.

[0043] Table 2

[0044] No. Copolymer Ethanol Hydroxypropyl ester Fatty acid ester 1,3-Butylene glycol Example 1 4 10 15 3 15 Example 2 4 10 15 5 15 Example 3 4 10 15 7 15 Example 4 6 10 15 3 15 Example 5 6 10 15 5 15 Example 6 6 10 15 7 15

[0045] The specific compositions of Comparative Examples 1 to 20 are shown in Table 3. The copolymer used in all comparative examples is C200F, and the fatty acid ester used in all comparative examples is 99%.

[0046] Table 3

[0047]

[0048]

[0049] The specific compositions of Comparative Examples 21–32 are shown in Table 4. The copolymer used in Comparative Examples 21–26 is 8100, the copolymer used in Comparative Examples 27–32 is VP / VA64, and the fatty acid ester used in all comparative examples is 99.

[0050] Table 4

[0051] No. Copolymer Ethanol Hydroxypropyl ester Fatty acid ester 1,3-Butylene glycol Comparative Example 21 6 10 15 3 15 Comparative Example 22 6 10 15 5 15 Comparative Example 23 6 10 15 7 15 Comparative Example 24 8 10 15 3 15 Comparative Example 25 8 10 15 5 15 Comparative Example 26 8 10 15 7 15 Comparative Example 27 20 15 15 3 15 Comparative Example 28 20 15 15 5 15 Comparative Example 29 20 15 15 7 15 Comparative Example 30 25 15 15 3 15 Comparative Example 31 25 15 15 5 15 Comparative Example 32 25 15 15 7 15

[0052] The specific compositions of Comparative Examples 33–44 are shown in Table 5. The copolymer used in all comparative examples is C200F, the fatty acid ester used in Comparative Examples 33–38 is DC345, and the fatty acid ester used in Comparative Examples 39–44 is GTCC.

[0053] Table 5

[0054] No. Copolymer Ethanol Hydroxypropyl ester Fatty acid ester 1,3-Butylene glycol Comparative Example 33 4 10 15 3 15 Comparative Example 34 4 10 15 5 15 Comparative Example 35 4 10 15 7 15 Comparative Example 36 6 10 15 3 15 Comparative Example 37 6 10 15 5 15 Comparative Example 38 6 10 15 7 15 Comparative Example 39 4 10 15 3 15 Comparative Example 40 4 10 15 5 15 Comparative Example 41 4 10 15 7 15 Comparative Example 42 6 10 15 3 15 Comparative Example 43 6 10 15 5 15 Comparative Example 44 6 10 15 7 15

[0055] The components of Comparative Examples 45-50 are shown in Table 6. The difference from Examples 1-6 is that 1,3-butanediol is replaced with glycerol, the copolymer used is C200F, and the fatty acid ester used is 99.

[0056] Table 6

[0057] No. Copolymer Ethanol Hydroxypropyl ester Fatty acid ester Glycerin Comparative Example 45 4 10 15 3 15 Comparative Example 46 4 10 15 5 15 Comparative Example 47 4 10 15 7 15 Comparative Example 48 6 10 15 3 15 Comparative Example 49 6 10 15 5 15 Comparative Example 50 6 10 15 7 15

[0058] Formula stability and skin feel assessment

[0059] The formulation stability and skin sensitivity evaluation of each embodiment and comparative example are shown in Table 7.

[0060] Table 7

[0061]

[0062]

[0063]

[0064] The data in Table 4 show that comparative examples 1 to 14 can effectively reduce the greasiness of the formula. Compared with the common ethanol system, the addition of 1,3-butanediol can reduce the amount of ethanol used, but it cannot significantly improve the greasiness of the formula.

[0065] Comparative examples 15-20 show that a low polyurethane-2 content makes it difficult to maintain formulation stability, while a high content can actually increase the oiliness.

[0066] Comparative Examples 21–26 show that, compared to Polyurethane-2, Polyurethane-35 has poor stability and tends to clump, and has a slightly more greasy feel when used.

[0067] Comparative Examples 27–32 show that, compared to polyurethane-2, the VP / VA copolymer has poor stability and is difficult to stabilize even at higher content. It also has a slightly stronger oily feel than the ethanol system and significantly worse water resistance.

[0068] Comparative Examples 33-44 show that, compared with the Examples, the formulation of isononyl isononanoate has better stability and less greasiness, while DC345 and CTCC have slightly worse stability.

[0069] Comparative Examples 45-50 show that, compared to the Examples, the use of glycerin resulted in a more greasy feeling than the use of 1,3-butanediol.

[0070] Overall, Embodiments 2 and 5 of the present invention are the best.

[0071] Evaluation of mosquito repellent effect

[0072] The test was conducted according to standard GB / T 13917.9-2009, Indoor Efficacy Tests and Evaluation of Sanitary Insecticides for Pesticide Registration, Part 9. A 5cm × 5cm skin area was drawn on the back of each hand of four qualified individuals (half male, half female, numbered 1#, 2#, 3#, and 4#). One hand served as a blank control, while the other hand was sprayed with the mosquito repellent liquid of this invention at a dosage of 15 μL / cm². 2Expose 4cm x 4cm of skin, covering the rest. Two hours after applying the mosquito repellent, place your hand in the mosquito cage for 2 minutes and observe whether any mosquitoes come to suck your blood. Repeat this test every hour thereafter. After 8 hours, test every 0.5 hours, recording the number of mosquitoes landing. If even one mosquito comes to suck your blood, the mosquito repellent is considered ineffective. Results are as follows... Figures 1-5 As shown.

[0073] Depend on Figure 1 The data shows that the mosquito-repellent effect of the solvent-solubilized system is only related to the content of the mosquito repellent hydroxylamine.

[0074] Depend on Figure 2 The data shows that polyurethane-2 can effectively improve the mosquito repellency effect, while polyurethane-35, due to its poor formula stability, is not conducive to maintaining the mosquito repellency effect.

[0075] Depend on Figure 3 The data shows that using VP / VA polymers not only fails to effectively improve the mosquito repellency effect, but also, due to the poor stability and water resistance of the formula, it is not conducive to maintaining the mosquito repellency effect.

[0076] Depend on Figure 4 The data shows that using polyurethane-2 effectively improves the mosquito repellency retention effect, while DC345 and GTCC, due to their slightly lower formulation stability, show only a smaller improvement compared to the example. The mosquito repellency effect of the glycerin system is consistent with the example.

[0077] Depend on Figure 5 The data shows that the application of the polyurethane-2 system in the embodiments can effectively prolong the mosquito-repellent effect, even approaching the formulation with a higher concentration of mosquito repellent.

[0078] In summary, among all the embodiments, Embodiments 2 and 5 show the best overall effect. They not only effectively prolong the mosquito repellent time but also provide an excellent user experience.

[0079] The above is a further detailed description of the present invention and should not be considered as a limitation on the specific implementation of the present invention. For those skilled in the art, simple deductions or substitutions without departing from the concept of the present invention are all within the protection scope of the present invention.

Claims

1. A low-irritation, long-lasting polyurethane-hydroxypiperate mosquito repellent, characterized in that, The active ingredient has the following composition by mass: 3-8 parts polyurethane-2, 5-20 parts hydroxyphenyl ester, 20-50 parts polyol, and 3-9 parts fatty acid ester. The polyol is a mixture of ethanol and 1,3-butanediol, with a mass ratio of ethanol to 1,3-butanediol of (0.65-0.7):

1. The fatty acid ester is isononyl isononanoate.

2. The low-irritation, long-lasting polyurethane-hydroxypiperate mosquito repellent according to claim 1, characterized in that, The mass ratio of polyurethane-2 to hydroxyl ester is 1:(0.5-4).

3. The low-irritation, long-lasting polyurethane-hydroxypiperate mosquito repellent according to claim 1, characterized in that, The mass ratio of polyurethane-2 to polyol is 1:(4-8).

4. The low-irritation, long-lasting polyurethane-hydroxypiperate mosquito repellent according to claim 1, characterized in that, The mass ratio of polyurethane-2 to fatty acid ester is 1:(0.2~1.5).

5. The low-irritation, long-lasting polyurethane-hydroxypiperate mosquito repellent according to any one of claims 1 to 4, characterized in that, Its active ingredient composition is as follows: 4-6 parts polyurethane-2, 15 parts hydroxyl ester, 25 parts polyol, and 5 parts fatty acid ester.

6. The low-irritation, long-lasting polyurethane-hydroxypiperate mosquito repellent according to any one of claims 1 to 4, characterized in that, The average molecular weight of the polyurethane-2 is 1,000 to 200,000.

7. The low-irritation, long-lasting polyurethane-hydroxypiperate mosquito repellent according to any one of claims 1 to 4, characterized in that, The mosquito repellent also includes at least one of the following: antioxidants, fragrances, preservatives, neutralizers, emollients, free radical scavengers, deodorants, multivalent chelating agents, and solvents.

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