CN115040427A - Hand sanitizer with slow release effect and preparation method thereof - Google Patents

Hand sanitizer with slow release effect and preparation method thereof Download PDF

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CN115040427A
CN115040427A CN202210633888.7A CN202210633888A CN115040427A CN 115040427 A CN115040427 A CN 115040427A CN 202210633888 A CN202210633888 A CN 202210633888A CN 115040427 A CN115040427 A CN 115040427A
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polyvinyl alcohol
amino acid
hand sanitizer
release effect
colloidal particles
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CN115040427B (en
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周耘
卢绮华
林俊达
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Full Core Biotechnology Macau Co ltd
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    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8129Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers or esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers, e.g. polyvinylmethylether
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Abstract

The invention relates to a hand sanitizer with a slow release effect, which comprises the following components in parts by mass: 5-7 parts of polyvinyl alcohol colloidal particles containing amino acid, 2-4 parts of rosemary, 20-25 parts of sodium lauroyl methyl aminopropionate, 10-13 parts of cocamidopropyl betaine, 4-6 parts of sodium laureth sulfate, an auxiliary agent and water; the amino acid is selected from one or more of glycine, alanine, isoleucine, proline and aspartic acid. The cross-linked polyvinyl alcohol colloidal particles are wrapped with various amino acids, and can be isolated from other components in the hand sanitizer, so that when the product is idle, the amino acids and the rosemary are ensured to exist independently, and the amino acids and the rosemary do not influence each other; when the product is used, the polyvinyl alcohol colloidal particles gradually deform or break along with the mechanical force action of the palm of a user, so that the experience of consumers can be increased, and the amino acid functional substances in the polyvinyl alcohol colloidal particles can be released instantly, so that the effect of moistening the skin is achieved when the product is used.

Description

Hand sanitizer with slow release effect and preparation method thereof
Technical Field
The invention belongs to the field of personal cleaning, and particularly relates to a hand sanitizer with a slow release effect and a preparation method thereof.
Background
Rosemary is originally produced from Mediterranean sea, and has excellent antioxidant, refreshing, sterilizing and other effects. Rosemary has strong oxidation resistance, is a natural substance, and has good safety. The antioxidant mechanism is caused by the effects of the components of rosmanol, carnosol and rosemary dialdehyde in the rosemary extract. Compared to other artificially prepared antioxidants, rosemary is a favored target for daily chemical manufacturers due to its strong antioxidant properties (reported to be about 5 times as potent as BHT and BHA), natural non-toxicity, and wide source.
The amino acid component is another material preferred by daily chemical manufacturers. Amino acids also have an important effect on human skin: the amino acid can enhance skin immunity, regulate water content and pH value of skin, and balance surface oil. The amino acid can improve the anti-allergy capability of sensitive skin, and can generate a chelation reaction with divalent metal ions in the skin to prevent excessive divalent metal ions from generating a crosslinking effect with collagen in the skin, so that enough collagen fibers and elastic fibers are maintained, the skin is kept smooth, fine and elastic, and wrinkles are prevented from being generated. Amino acids also have the function of enhancing the lymphatic system, which can improve the skin's anti-allergic ability and metabolize aging cells in the body, so amino acids are essential substances for skin health.
For the above reasons, daily chemical manufacturers wish to apply the above two natural ingredients to personal care products, such as hand washing lotion and facial cleanser, in order to provide functional effects to the products while having no irritation to the digestive tract, respiratory tract and skin. However, amino acid and rosemary are natural organic matters, and the amino acid and the rosemary coexist in the formula for a long time, so that unstable phenomena such as product layering and too fast deterioration are easily caused, and the functionality is greatly reduced. Therefore, daily chemical manufacturers hope that in daily chemical products, rosemary and amino acid can exist relatively independently when the products are idle; when in use, the two can exert the effect at the same time.
Therefore, a technical solution is needed to solve the above-mentioned problems.
Disclosure of Invention
The invention discloses a hand sanitizer, which contains cross-linked polyvinyl alcohol colloidal particles, wherein various amino acids are wrapped in the colloidal particles and can be isolated from other components in the hand sanitizer, so that when a product is idle, the amino acids and rosemary are ensured to exist independently, and are not influenced by each other; when the product is used, the polyvinyl alcohol colloidal particles gradually deform or break along with the mechanical force of the palm of a user, so that the amino acid functional substances in the polyvinyl alcohol colloidal particles are released instantly, and the effect of moistening the skin is achieved when the product is used.
The invention aims to provide a hand sanitizer with a slow release effect, which is realized by the following technical means.
A hand sanitizer with a slow release effect comprises the following components in parts by mass:
Figure BDA0003681183300000021
auxiliary agent
Water;
the amino acid is selected from one or more of glycine, alanine, isoleucine, proline and aspartic acid.
The specific structure of the polyvinyl alcohol colloidal particle containing amino acid is a solid structure in which the amino acid is uniformly wrapped in spherical particles made of polyvinyl alcohol.
The surfactants are low-irritation surfactants, and have excellent suspending and solubilizing effects on rosemary and polyvinyl alcohol colloidal particles containing amino acid.
Further, the auxiliary agent is selected from one or more of propylene glycol, sodium chloride, essence and citric acid.
Further, the pH value of the hand sanitizer with the slow release effect is 6.5-7.0.
The invention also aims to provide a preparation method of the hand sanitizer with the slow release effect, which comprises the following steps:
preparation of polyvinyl alcohol colloidal particles containing amino acid:
s1, heating and stirring polyvinyl alcohol and oxalic acid under a catalyst system to obtain cross-linked polyvinyl alcohol;
s2, placing the crosslinked polyvinyl alcohol in a mixed solvent of water and glycerol, and stirring to obtain a crosslinked polyvinyl alcohol mixture;
s3, mixing the crosslinked polyvinyl alcohol mixture with the amino acid, adding a polyacrylate derivative, and stirring to obtain a dispersion liquid;
and S4, carrying out high-pressure atomization drying on the dispersion liquid to obtain the amino acid-containing polyvinyl alcohol colloidal particles.
In the above step S1, the catalyst is usually selected from strong acids, such as concentrated sulfuric acid, etc., and a part of the hydroxyl groups on the polyvinyl alcohol reacts with oxalic acid to form crosslinked polyvinyl alcohol. The obtained crosslinked polyvinyl alcohol can be primarily purified by means of catalyst removal, washing and the like. The obtained cross-linked polyvinyl alcohol has a complex structure, contains partial unreacted hydroxyl, and is easy to form intermolecular hydrogen bonds with groups in amino acid, so that the intermolecular force between the polyvinyl alcohol and the amino acid is enhanced; and the group reacting with oxalic acid forms a bridge bond to form a connection point of the network structure. The complex reticular structure is connected with different polyvinyl alcohol molecular chains, and has good film forming property and wrapping property.
The above-mentioned steps S2-S3 are physical blending steps, and the main purpose is to mix the crosslinked polyvinyl alcohol with the amino acid so that the amino acid is uniformly dispersed in the system. The polyacrylate derivative is added to facilitate the dispersion of the amino acid.
The above-mentioned step S4 is intended for granulation, and may be carried out by using an atomizing gun. By controlling the pressure and the caliber of the atomizing gun, the particle size of the formed polyvinyl alcohol colloidal particle containing amino acid can reach the optimal level, and the influence of over-coarse or over-fine on the use experience is avoided.
Further, the polyvinyl alcohol: oxalic acid: the mass ratio of the mixed solvent is 50 (3-5) to (200-250).
Furthermore, the mass ratio of the polyvinyl alcohol colloidal particles containing the amino acid to the amino acid is 100 (5-10).
Further, the polyacrylate derivative has the following structure:
Figure BDA0003681183300000031
wherein R and R' are independently selected from C1-C12 alkyl structures.
The acrylate derivative has a structure containing a branched chain and a longer branched chain, and has a better effect on the dispersion of amino acid. This is probably due to the deeper winding of both R and R' with amino acids; linear polyacrylate derivatives may not have the above characteristics.
Further, the amount of the polyacrylate derivative added is 0.5 to 1 wt% of the crosslinked polyvinyl alcohol mixture.
Further, the particle size of the amino acid-containing polyvinyl alcohol colloidal particles is 50-70 μm.
The invention has the following beneficial effects:
1. the hand sanitizer with the slow release effect, which is obtained by the technical scheme of the invention, contains cross-linked polyvinyl alcohol colloidal particles, and various amino acids are wrapped in the colloidal particles and can be isolated from other components in the hand sanitizer, so that when a product is idle, the amino acids and rosemary can be ensured to exist independently, and the amino acids and the rosemary do not influence each other; when the product is used, the polyvinyl alcohol colloidal particles gradually deform or break along with the mechanical force action of the palm of a user, so that the consumer experience can be increased, and the amino acid functional substances in the polyvinyl alcohol colloidal particles can be released instantly, so that the effect of moistening the skin is exerted when the product is used.
2. The cross-linked polyvinyl alcohol colloidal particles in the technical scheme of the invention have a relatively complex structure, and on one hand, sufficient hydrogen bonds can be provided, so that the cross-linked polyvinyl alcohol colloidal particles can be more tightly combined with other substances, such as amino acid or glycerol; on the other hand, the gel has a large number of bridge bonds, a formed reticular structure is very large, the film forming property and the wrapping property are good, water in the formula is not easy to permeate into the colloidal particles, and the colloidal particles are not easy to swell.
Drawings
FIG. 1 shows the appearance of examples 1 to 3 and comparative examples 1 to 2 in both of sample A and sample B.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following examples and comparative examples are listed. The starting materials, reactions and work-up procedures presented in the examples and comparative examples are, unless otherwise stated, those commonly available on the market and well known to those skilled in the art.
In the high-pressure atomization drying adopted in the embodiment of the invention, the pressure of an atomization gun is about 1.3-1.4MPa, the diameter of the gun opening is about 1mm, the drying temperature is controlled at 60-70 ℃, and the average particle size of the cross-linked polyvinyl alcohol-containing colloidal particles obtained by the parameters is about 50-65 μm.
Examples
The components and the corresponding parts by mass of the hand sanitizer with sustained release effect in examples 1-3 are shown in table 1.
Table 1 examples 1-3 components and parts by weight of a hand sanitizer with sustained release
Figure BDA0003681183300000041
The preparation method of the polyvinyl alcohol colloidal particles containing the amino acid comprises the following steps:
s1, heating polyvinyl alcohol and oxalic acid (50:3, m/m) to 90 ℃ in a catalyst concentrated sulfuric acid (0.3 wt% of polyvinyl alcohol) system, stirring, removing water in the system to enable forward reaction to be complete as far as possible, then concentrating a solvent under reduced pressure, and passing through a column to elute catalyst residues to obtain crosslinked polyvinyl alcohol;
s2, placing the crosslinked polyvinyl alcohol into a mixed solvent of water and glycerol, and stirring (the ratio of the crosslinked polyvinyl alcohol to the water to the glycerol is 50:100:100) to obtain a crosslinked polyvinyl alcohol mixture;
s3, mixing the crosslinked polyvinyl alcohol mixture with the amino acids according to the calculated mass ratio, adding 0.5 wt% of polyisobutyl methacrylate (purchased from technical health chemical Co., Ltd.) of the crosslinked polyvinyl alcohol mixture, and uniformly stirring to obtain a dispersion liquid;
s4, carrying out high-pressure atomization drying on the dispersion liquid to obtain the amino acid-containing polyvinyl alcohol colloidal particles, wherein the specific ratio of each obtained amino acid in the amino acid-containing polyvinyl alcohol colloidal particles is finally measured, and is shown in Table 2.
TABLE 2 respective amino acid contents of amino acid-containing polyvinyl alcohol micelles in Table 1
Figure BDA0003681183300000042
Figure BDA0003681183300000051
After polyvinyl alcohol colloidal particles containing amino acid are prepared, all the components are sequentially added into a reaction kettle according to the mass parts in the table 1, the mixture is stirred for 30min at the temperature of 30 ℃, then the pH value is adjusted by citric acid, and the mixture is discharged from the bottom of the kettle to obtain the liquid soap products of examples 1-3.
Comparative example
Comparative examples 1-2 were set up based on example 1. The components and the corresponding parts by mass of the hand sanitizer of comparative examples 1-2 are shown in table 3.
Table 3 components and parts by mass of the hand washing solutions of example 1 and comparative examples 1 to 2
Figure BDA0003681183300000052
Wherein,
in comparative example 1:
the raw materials, the quality of the raw materials and the related preparation method of the amino acid-containing polyvinyl alcohol micelle (reference) are the same as those of the example 1, and only oxalic acid in the example 1 is replaced by acetic acid with equal quality, namely, the polyvinyl alcohol and the acetic acid are subjected to esterification reaction. The resulting polyvinyl alcohol is not the crosslinked polyvinyl alcohol described in example 1, and is more likely to be a linear structure.
The final measured specific ratios of the individual amino acids in the amino acid-containing polyvinyl alcohol micelles (reference) are also shown in table 2.
In comparative example 2:
various amino acids are directly added, and the total amount is 0.31 part; the mass ratio of glycine, alanine, isoleucine, proline and aspartic acid is 1.0:1.4:1.3:1.5: 1.0.
Test example
The hand washing solutions obtained in examples 1 to 3 and comparative examples 1 to 2 were subjected to stability tests. The specific method comprises the following steps: 200mL of each of the hand sanitizers of examples 1 to 3 and comparative examples 1 to 2 was put in a PE transparent bottle and sealed to prepare sample A. The same sample was then placed in a high temperature oven at 45 ℃ for 2 weeks to serve as sample B.
The experimenter was called 20 volunteers at the test center, and the samples were subjected to appearance observation and tried for two weeks. The record summarizes the sample appearance, as well as the trial experience. The resulting structures are shown in tables 4 and 5.
Wherein, the mode of trying the sample is as follows: the volunteers use the samples to wash hands in the morning, at noon and evening, about 1g of the samples are taken and placed in the hands, the hand centers are gently rubbed for 10S, and then the uniformly rubbed samples are coated on the two hands, so that the mechanical force of palm rubbing is utilized to break the colloidal particles and release amino acid.
TABLE 4 appearance of hand sanitizers obtained in examples 1-3 and comparative examples 1-2
Figure BDA0003681183300000061
While the appearance of the cleaning compositions of both sample a and sample B is shown in fig. 1, it can also be seen that the cleaning compositions of comparative examples 1-2 show a more pronounced change in appearance after storage for extended periods in a high temperature environment, whereas the cleaning compositions of examples 1-3 do not show such a change.
Table 5 experience on hand sanitizer testing obtained in example 1 and comparative examples 1-2
Figure BDA0003681183300000062
Figure BDA0003681183300000071
As can be seen from table 5, the samples a and B in example 1 have consistent user experience evaluation after undergoing the stability test in high temperature environment, which is caused by the good sustained release effect of the cross-linked polyvinyl alcohol micelle on the amino acid itself. When the modified polyvinyl alcohol gel is idle, the polyvinyl alcohol with the cross-linked structure provides a tough shell for the amino acid wrapped by the modified polyvinyl alcohol, and other components in the formula are difficult to permeate into colloidal particles even in a high-temperature water-rich environment, so that the performance of the amino acid cannot be negatively influenced, and the performance of the amino acid can be maintained for a long time. When the hand-washing powder is used, after the hand-washing powder is kneaded by the mechanical force of the palm of a volunteer, the cross-linked polyvinyl alcohol colloidal particles are broken, and the wrapped amino acid can be instantly released to the palm skin to play a role in cooperation with other components in the formula.
The sample B of comparative examples 1-2, however, showed significant changes in its physicochemical properties after being left at high temperatures for a long period of time: in comparative example 1, the polyvinyl alcohol colloidal particles have a lower degree of crosslinking, more linear structures than linear structures, but not body-type structures, so that the swelling phenomenon is generated when the polyvinyl alcohol colloidal particles are in a high-temperature water-rich environment for a long time, namely, the sizes of the polyvinyl alcohol colloidal particles become uneven and the texture becomes soft after a large amount of water in a formula is absorbed into the colloidal particles because the structure of the polyvinyl alcohol colloidal particles is too loose and the water easily permeates into the colloidal particles, so that a volunteer hardly experiences the pleasant feeling of breakage of the colloidal particles in hands; and along with the occurrence of the swelling phenomenon, a large amount of amino acid is also released into the formula, so that the deterioration is more easily caused, and the efficacy and performance of the amino acid are weakened in the hand washing process of volunteers. In the comparative example 2, the amino acid is directly contacted with all the components in the formula because no colloidal particles exist, so that the deterioration is easily caused in a high-temperature and water-rich environment, the appearance of the hand sanitizer is changed, and the efficacy performance of the amino acid is greatly weakened in the hand washing process of a volunteer.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (9)

1. The hand sanitizer with the slow release effect is characterized by comprising the following components in parts by mass:
Figure FDA0003681183290000011
the amino acid is selected from one or more of glycine, alanine, isoleucine, proline and aspartic acid.
2. The hand sanitizer with slow release effect according to claim 1, wherein the auxiliary agent is selected from one or more of propylene glycol, sodium chloride, essence and citric acid.
3. The hand sanitizer with slow release effect according to claim 1, wherein the pH of the hand sanitizer with slow release effect is 6.5-7.0.
4. A method of preparing a hand sanitizer with sustained release as claimed in any of claims 1 to 3, wherein the method of preparing a hand sanitizer with sustained release comprises the steps of:
preparation of polyvinyl alcohol colloidal particles containing amino acid:
s1, heating and stirring polyvinyl alcohol and oxalic acid under a catalyst system to obtain cross-linked polyvinyl alcohol;
s2, placing the crosslinked polyvinyl alcohol in a mixed solvent of water and glycerol, and stirring to obtain a crosslinked polyvinyl alcohol mixture;
s3, mixing the crosslinked polyvinyl alcohol mixture with the amino acid, adding a polyacrylate derivative, and stirring to obtain a dispersion liquid;
and S4, carrying out high-pressure atomization drying on the dispersion liquid to obtain the amino acid-containing polyvinyl alcohol colloidal particles.
5. The method for preparing a hand sanitizer with sustained release effect according to claim 4, wherein the polyvinyl alcohol: oxalic acid: the mass ratio of the mixed solvent is 50 (3-5) to (200-250).
6. The preparation method of the hand sanitizer with the slow release effect according to claim 4, wherein the mass ratio of the amino acid-containing polyvinyl alcohol micelle to the amino acid is 100 (5-10).
7. The method for preparing a hand sanitizer with sustained release effect according to claim 4, wherein the polyacrylate derivative has the following structure:
Figure FDA0003681183290000021
wherein R and R' are independently selected from C1-C12 alkyl structures.
8. The method for preparing a hand sanitizer with sustained release effect according to claim 4, wherein the polyacrylate derivative is added in an amount of 0.5 to 1 wt% of the crosslinked polyvinyl alcohol mixture.
9. The method for preparing a hand sanitizer with sustained release effect according to claim 4, wherein the particle size of the amino acid-containing polyvinyl alcohol micelle is 50 to 70 μm.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016222612A (en) * 2015-06-01 2016-12-28 昭和電工株式会社 Cosmetic and skin external preparation
CN108125857A (en) * 2018-01-10 2018-06-08 威莱(广州)日用品有限公司 A kind of novel quick defoaming bacteriostatic hand sanitizer and preparation method thereof
CN110960444A (en) * 2020-01-06 2020-04-07 浙江神英科技股份有限公司 Slow-release lasting antibacterial hand sanitizer and preparation method thereof
CN112168729A (en) * 2020-10-13 2021-01-05 禹州森茂迷迭香生物科技有限公司 Rosemary disinfection hand sanitizer and preparation method thereof
CN112972281A (en) * 2021-03-02 2021-06-18 上海应用技术大学 Disinfectant-grade hand sanitizer containing salicylic acid microcapsules and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016222612A (en) * 2015-06-01 2016-12-28 昭和電工株式会社 Cosmetic and skin external preparation
CN108125857A (en) * 2018-01-10 2018-06-08 威莱(广州)日用品有限公司 A kind of novel quick defoaming bacteriostatic hand sanitizer and preparation method thereof
CN110960444A (en) * 2020-01-06 2020-04-07 浙江神英科技股份有限公司 Slow-release lasting antibacterial hand sanitizer and preparation method thereof
CN112168729A (en) * 2020-10-13 2021-01-05 禹州森茂迷迭香生物科技有限公司 Rosemary disinfection hand sanitizer and preparation method thereof
CN112972281A (en) * 2021-03-02 2021-06-18 上海应用技术大学 Disinfectant-grade hand sanitizer containing salicylic acid microcapsules and preparation method thereof

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