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CN113480852B - Liquid silicone nipple and preparation method thereof - Google Patents

Liquid silicone nipple and preparation method thereof Download PDF

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Publication number
CN113480852B
CN113480852B CN202110898830.0A CN202110898830A CN113480852B CN 113480852 B CN113480852 B CN 113480852B CN 202110898830 A CN202110898830 A CN 202110898830A CN 113480852 B CN113480852 B CN 113480852B
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cyclodextrin
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chitosan
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CN113480852A (en
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邹坚强
沈海能
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Shenzhen Fufa Century Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04Polysiloxanes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61JCONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a liquid silicone nipple and a preparation method thereof. The liquid silica gel nipple is prepared from the following raw materials, by weight, 60-80 parts of liquid silica gel, 0.04-0.06 part of vulcanizing agent, 15-25 parts of chitosan, 5-10 parts of maltodextrin, 5-10 parts of beta-cyclodextrin, 10-20 parts of hydrophobic fumed silica, 5-10 parts of fumed nano titanium dioxide, 1-2 parts of hydroxyl silicone oil and 80-100 parts of acetic acid aqueous solution. According to the liquid silica gel nipple, chitosan is under the combined action of maltodextrin and beta-cyclodextrin, so that the chitosan is not easy to run off in the nipple washing process, and the gas-phase nano titanium dioxide and hydrophobic gas-phase silicon dioxide are combined to make the surface of the liquid silica gel nipple not easy to form water drops, so that the antibacterial property and the antibacterial durability of the liquid silica gel nipple are improved.

Description

Liquid silicone nipple and preparation method thereof
Technical Field
The invention relates to the field of food-grade liquid silica gel products, in particular to a liquid silica gel nipple and a preparation method thereof.
Background
The nipple is a tool used on a feeding bottle to help a baby suck milk, and at present, the requirements on the sanitation grade and the product quality of the nipple for the baby are higher and higher. The nipple is mainly composed of two types of latex and silica gel. The latex nipple is made of natural rubber, is rich in elasticity and very soft, tastes of infants sucked by the nipple are closer, but the latex nipple is sticky and aged after being used for a period of time, has short service life, can release a small amount of harmful chemical residues after being used for a long time, has low use safety and can cause adverse effects on the bodies of infants. And the latex nipple has poor smell, which can reduce the sucking liking of infants. The silica gel nipple is transparent, so that the content and the state of milk can be clearly seen, and the nipple can be adjusted and replaced in time according to the sucking condition of infants. The silica gel nipple is divided into a solid silica gel nipple and a liquid silica gel nipple. Because the liquid silica gel nipple is more transparent than solid silica gel, it is softer. In particular to a liquid silica gel nipple formed by high-temperature hot vulcanization, which has the characteristics of no peculiar smell, high temperature resistance, repeated boiling and disinfection, difficult aging, long service life and the like. Because the requirements on the sanitation grade of the nipple for the infant and the quality of the product are higher and higher at present, the liquid silica gel nipple becomes a nipple with wide application.
Although the liquid silica gel nipple molded by high-temperature hot vulcanization can be boiled for sterilization, the nipple does not have an antibacterial effect in the use process of infants. In addition, the milk contains nutrient substances such as high protein, high fat and the like, pathogenic microorganisms such as bacteria and the like are easy to breed, the nipple is in direct contact with the oral cavity of the infant, bacteria inside and outside the oral cavity are easy to adsorb on the nipple, and the infant is likely to have symptoms such as bacterial infection, allergy and the like. Therefore, how to improve the antibacterial effect of the nipple in the use process of the infant has an important role.
The patent with publication number CN105348817A discloses a method for preparing an antibacterial nipple by using plant extracts, wherein the plant extracts comprise fructus momordicae, gynostemma pentaphyllum, liquorice, green tea, andrographis paniculata and ganoderma lucidum, the plant extracts have antibacterial and antiviral properties, the smoking safety and taste of the nipple are improved, the effects of clearing away summer heat and improving immunity are achieved, amino acids and inorganic elements can be improved in the contact process of the nipple, and beneficial substances for human bodies are supplemented. However, the applicant finds that the antibacterial effect of the antibacterial nipple prepared from the plant extract is short, the plant extract is easy to lose in the nipple washing process, the nipple needs to be washed after each use, the antibacterial effect of the nipple is obviously reduced after multiple uses, and especially the antibacterial effect basically disappears after multiple high-temperature boiling, and the antibacterial durability is poor.
Disclosure of Invention
In order to improve the antibacterial property and the antibacterial durability of the nipple, the application provides a liquid silicone nipple and a preparation method thereof.
First aspect, this application provides a liquid silica gel nipple, adopts following technical scheme to realize:
the liquid silica gel nipple is prepared from the following raw materials, by weight, 60-80 parts of liquid silica gel, 0.04-0.06 part of vulcanizing agent, 15-25 parts of chitosan, 5-10 parts of maltodextrin, 5-10 parts of beta-cyclodextrin, 10-20 parts of hydrophobic fumed silica, 5-10 parts of fumed nano titanium dioxide, 1-2 parts of hydroxyl silicone oil and 80-100 parts of acetic acid aqueous solution.
By adopting the technical scheme, the chitosan is a product of natural polysaccharide chitin with partial acetyl removed, has multiple physiological functions of biodegradability, biocompatibility, nontoxicity, bacteriostasis, immunity enhancement and the like, is large molecules, is wound among molecules, and has active hydroxyl and amino, so that the chitosan is not easy to lose in the nipple washing process, and the antibacterial effect is good. Under the combined action of maltodextrin and beta-cyclodextrin, the chitosan not only improves the activity of chitosan, but also improves the antibacterial durability of chitosan. The reason for this is probably that the crystallinity and the adsorbability of chitosan are improved due to the combined influence of the gel structure of maltodextrin and the cavity structure of beta-cyclodextrin and the hydrogen bond action of chitosan, maltodextrin and beta-cyclodextrin, so that the antibacterial property and the antibacterial durability of the liquid silica gel nipple are improved. The antibacterial property and the antibacterial durability of the liquid silica gel nipple can be improved by adding the gas phase nano titanium dioxide, and the gas phase nano titanium dioxide has a large specific surface area and an antibacterial effect. The thermal stability and the heat resistance of the gas phase nano titanium dioxide are good, and the gas phase nano titanium dioxide and the hydrophobic gas phase silicon dioxide act together, so that water drops are not easily formed on the surface of the liquid silicon nipple, and the antibacterial property of the liquid silicon nipple after being washed for a long time and under high-temperature boiling is improved. In addition, the hydrophobic fumed silica, the fumed nano titanium dioxide and the hydroxyl silicone oil act together, so that the processing performance of the liquid silicone nipple is effectively improved, and the service life of the liquid silicone nipple is prolonged.
In the application, the liquid silica gel is food-grade silicone rubber.
Preferably, the shore hardness of the liquid silica gel is 50 ± 2 HA.
The test standard of the Shore hardness is GB/T531.1-2008. The liquid silica gel with the Shore hardness of 50 +/-2 HA HAs excellent flexibility and certain hardness, can improve the tolerance of the nipple, is not easy to be bitten by infants, and can also improve the resilience of the nipple. In addition, the nipple adopts food-grade silicon rubber, has excellent transparency, tear strength, rebound resilience, yellowing resistance, thermal stability, heat aging resistance and weather resistance, has moderate viscosity and is convenient to operate, thereby being an ideal nipple preparation raw material.
The liquid silica gel of the present application includes, but is not limited to, dongjue NE-9150.
In the present application, the vulcanizing agents include, but are not limited to, silica gel vulcanizing agent C-16, silica gel vulcanizing agent C-8, and silica gel vulcanizing agent C-15; preferably, the vulcanizing agent is a silica gel vulcanizing agent C-16.
The application adopts the silica gel vulcanizing agent C-16, which is a vulcanizing agent of food-grade silicon rubber products, can avoid secondary vulcanization, has good yellowing resistance, and improves the use safety and transparency of liquid silica gel.
Preferably, the chitosan is formed by mixing carboxymethyl chitosan and hydroxypropyl chitosan according to a mass ratio of (4-8) to 1.
More preferably, the chitosan is prepared by mixing carboxymethyl chitosan and hydroxypropyl chitosan according to the mass ratio of 6: 1.
According to the liquid silicone nipple, carboxymethyl chitosan and hydroxypropyl chitosan are compounded, so that the antibacterial property of the liquid silicone nipple can be improved, and the effect is better when the mass ratio of the carboxymethyl chitosan to the hydroxypropyl chitosan is 6: 1. The reason is probably that the carboxymethyl chitosan is an amphoteric polyelectrolyte, and the carboxymethyl chitosan has stronger adsorption capacity and improves the antibacterial effect of the chitosan; and hydroxypropyl chitosan and hydroxypropyl-beta-cyclodextrin both have hydroxypropyl groups, so that the solubility of chitosan and beta-cyclodextrin is improved, and the combined action of chitosan, beta-cyclodextrin and maltodextrin is also improved, thereby improving the antibacterial durability of the liquid silicone nipple.
In the application, the substitution degree of the carboxymethyl chitosan is 60-65%, and the deacetylation degree is 85%.
In the present application, the deacetylation degree of hydroxypropyl chitosan is 80%.
The higher the deacetylation degree of chitosan, the smaller the relative molecular mass, and the more soluble the chitosan in water; the lower the degree of deacetylation of chitosan, the greater the relative molecular mass and the greater the viscosity. The carboxymethyl chitosan with the degree of substitution of 60% -65% and the degree of deacetylation of 85% and the hydroxypropyl chitosan with the degree of deacetylation of 80% jointly act, the deacetylation degree is appropriate, the solubility is good, the viscosity is low, the chitosan is favorable for forming a gel state, the dispersibility of the chitosan, beta-cyclodextrin and maltodextrin is good, the adsorption capacity of a system is improved, and therefore the antibacterial property and the antibacterial durability of the liquid silica gel nipple are improved.
Preferably, the beta-cyclodextrin is hydroxypropyl-beta-cyclodextrin and/or ethylenediamine-beta-cyclodextrin.
More preferably, the beta-cyclodextrin is formed by mixing hydroxypropyl-beta-cyclodextrin and ethylenediamine-beta-cyclodextrin according to the mass ratio of 1 (3-6).
Most preferably, the beta-cyclodextrin is formed by mixing hydroxypropyl-beta-cyclodextrin and ethylenediamine-beta-cyclodextrin according to the mass ratio of 1: 5.
The liquid silicone nipple is compounded by adopting the hydroxypropyl-beta-cyclodextrin and the ethylenediamine-beta-cyclodextrin, the ethylenediamine group in the ethylenediamine-beta-cyclodextrin has complexing capacity, the adsorption effect on bacteria can be further improved, the antibacterial property of the liquid silicone nipple is improved, the hydrogen bonding effect of the hydroxypropyl and the amino is stronger, the combined action of the beta-cyclodextrin, the chitosan and the maltodextrin is improved, the improvement of the cavity compounding capacity of the beta-cyclodextrin is facilitated, and the antibacterial durability of the liquid silicone nipple is improved. When the mass ratio of the hydroxypropyl-beta-cyclodextrin to the ethylenediamine-beta-cyclodextrin is 1:5, the antibacterial property and the antibacterial durability of the liquid silicone nipple are better.
Herein, the hydrophobic fumed silica has a specific surface area of 200. + -.30 m2The specific surface area is large, and the adsorption capacity is super strong.
Preferably, the gas phase nano titanium dioxide is mixed crystal type gas phase nano titanium dioxide.
In the application, the weight ratio of anatase nano titanium dioxide to rutile nano titanium dioxide in the mixed crystal type gas phase nano titanium dioxide is 80: 20; the mixed crystal type gas phase nano titanium dioxide has the average particle size of 21nm and the specific surface area of 50m2/g。
The two structures of anatase nano titanium dioxide and rutile nano titanium dioxide in the mixed crystal type gas phase nano titanium dioxide are mixed, so that the TiO is enlarged2The defect density in the crystal lattice improves the capturing capacity of the gas phase nano titanium dioxide to bacteria, and is beneficial to improving the sterilization effect, weather resistance and ageing resistance of the gas phase nano titanium dioxide, thereby improving the antibacterial property and antibacterial durability of the liquid silica gel nipple.
In the present application, the number average molecular weight of the hydroxyl silicone oil is 2000.
Herein, the pH of the aqueous acetic acid solution is 4 to 5; preferably, the pH of the aqueous acetic acid solution is 4.
In a second aspect, the application provides a method for preparing a liquid silicone nipple, which adopts the following technical scheme:
a preparation method of a liquid silicone nipple comprises the following steps:
s1, adding chitosan, maltodextrin and beta-cyclodextrin into an acetic acid aqueous solution, and uniformly mixing to obtain a mixed solution;
s2, mixing the liquid silica gel, the hydrophobic fumed silica and the fumed nano titanium dioxide to obtain a mixture;
s3, mixing the mixed solution obtained in the step S1 with the mixed solution obtained in the step S2, adjusting the pH of the system to 8-12, and kneading to obtain a kneaded material;
and S4, adding hydroxyl silicone oil and a vulcanizing agent into the kneaded material obtained in the step S3, uniformly mixing, injecting into a baby nipple mould for forming, vulcanizing, cooling and demoulding to obtain the liquid silicone nipple.
The liquid silica gel nipple provided by the application is simple in preparation method, the prepared liquid silica gel nipple has excellent transparency, tear strength, resilience, yellowing resistance, thermal stability, thermal aging resistance and weather resistance, and meanwhile, the safety of the liquid silica gel nipple is high.
In this application, in the step S3, the pH adjusting agent is 4-6 wt% of an aqueous solution of edible calcium hydroxide; preferably, the pH adjusting agent is a 5 wt% aqueous solution of edible calcium hydroxide.
In this application, in the step S3, the pH value of the 5 wt% edible calcium hydroxide aqueous solution is adjusted to 10.
In the present application, in the step S3, the kneading temperature is 100-120 ℃; preferably, the kneading temperature is 110 ℃.
In the present application, in the step S3, the kneading time is 1 to 2 hours; preferably, the kneading time is 1.5 h; after the kneading is finished, the temperature needs to be reduced to room temperature before the kneading can be used in the step S4.
In summary, the present application has the following beneficial effects:
1. under the combined action of maltodextrin and beta-cyclodextrin, the gel structure of maltodextrin and the cavity structure of beta-cyclodextrin have common influence, and chitosan is a macromolecule, and is wound among chitosan molecules and has active hydroxyl and amino, so that the hydrogen bonding action of chitosan, maltodextrin and beta-cyclodextrin is stronger, the crystallinity and the adsorbability of chitosan are improved, and the chitosan is not easy to lose in the nipple washing process, thereby improving the antibacterial property and the antibacterial durability of the liquid silicone nipple. The gas-phase nano titanium dioxide and the hydrophobic gas-phase silicon dioxide act together, so that water drops are not easily formed on the surface of the liquid-state silica gel nipple, and the antibacterial property of the liquid-state silica gel nipple after being washed for a long time and under high-temperature boiling is improved.
2. According to the application, carboxymethyl chitosan and hydroxypropyl chitosan are compounded, the carboxymethyl chitosan is an amphoteric polyelectrolyte, the carboxymethyl chitosan has strong adsorption capacity, and the antibacterial effect of the chitosan is improved; and hydroxypropyl chitosan and hydroxypropyl-beta-cyclodextrin both have hydroxypropyl groups, so that the solubility of chitosan and beta-cyclodextrin is improved, and the combined action of chitosan, beta-cyclodextrin and maltodextrin is also improved, thereby improving the antibacterial durability of the liquid silicone nipple.
3. The liquid silicone nipple is compounded by adopting the hydroxypropyl-beta-cyclodextrin and the ethylenediamine-beta-cyclodextrin, the ethylenediamine group in the ethylenediamine-beta-cyclodextrin has complexing capacity, the adsorption effect on bacteria can be further improved, the antibacterial property of the liquid silicone nipple is improved, the hydrogen bonding effect of the hydroxypropyl and the amino is stronger, the combined action of the beta-cyclodextrin, the chitosan and the maltodextrin is improved, the improvement of the cavity compounding capacity of the beta-cyclodextrin is facilitated, and the antibacterial durability of the liquid silicone nipple is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials used in the present application are commercially available, and the raw materials not mentioned in each example and comparative example are purchased from national drug group chemical agents, ltd.
Examples
Examples 1-14 provide a liquid silicone nipple, which is described below using example 1 as an example.
The liquid silicone nipple provided in example 1 includes the following steps:
s1, adding 150g of carboxymethyl chitosan, 50g of maltodextrin and 50g of hydroxypropyl-beta-cyclodextrin into 800g of acetic acid aqueous solution with the pH value of 4, and uniformly mixing to obtain mixed solution;
s2, mixing 600g of liquid silica gel, 100g of hydrophobic fumed silica and 50g of fumed nano titanium dioxide to obtain a mixture;
s3, mixing the mixed solution obtained in the step S1 with the mixed solution obtained in the step S2, adjusting the pH value of the system to 10 by using 5 wt% of edible calcium hydroxide aqueous solution, placing the mixture into a vacuum kneader, kneading the mixture for 1.5 hours under vacuum negative pressure in the vacuum kneader and heating to 110 ℃, and cooling to 25 ℃ after the kneading is finished to obtain a kneaded material;
s4, adding 10g of hydroxyl silicone oil and 0.4g of vulcanizing agent into the kneaded material obtained in the step S3, uniformly mixing, injecting into a baby nipple mould for forming, vulcanizing, cooling and demoulding to obtain a liquid silicone nipple;
wherein the model of the liquid silica gel is Dongjue NE-9150, the Shore hardness is 50 +/-2 HA, and the Murray purchased from Shenzhen is science and technology Co., Ltd;
the vulcanizing agent is a silica gel vulcanizing agent C-16 purchased from Shenzhen, Shenbang, New Polymer Material Co., Ltd;
the deacetylation degree of the carboxymethyl chitosan is 85 percent, and the carboxymethyl chitosan is purchased from Wuhankemike biological medicine technology limited company;
maltodextrin is MC-maltodextrin, purchased from Jinan Shuang chen environmental protection science and technology Limited company;
hydroxypropyl-beta-cyclodextrin type 21-010, available from Shandong Pingyu chemical Co., Ltd
The hydrophobic fumed silica has model number of WACKER HDK H20 and specific surface area of 200 + -30 m2(ii) per gram, purchased from Wake, Germany;
the gas phase nanometer titanium dioxide is anatase nanometer titanium dioxide with model VK-TA18, average particle diameter of 20nm, and specific surface area of 60-90m2(ii)/g, purchased from Xuancheng crystal-like new materials, Inc.;
the hydroxyl silicone oil was purchased from Guangdong Wengjiang chemical Co., Ltd, having a product number of PB09815 and a number average molecular weight of 2000.
Examples 2-5, which differ from example 1 only in that: the quality of each prepared raw material of the liquid silica gel nipple is different, and the liquid silica gel nipple is specifically shown in table 1.
TABLE 1 EXAMPLES 1-5 preparation of liquid Silicone Nipples raw materials weight/g
Figure BDA0003198996920000061
Example 6 differs from example 2 only in that: carboxymethyl chitosan and the like are replaced by hydroxypropyl chitosan, the deacetylation degree of the hydroxypropyl chitosan is 80 percent, and the hydroxypropyl chitosan is purchased from Wuhankemike biological medicine technology company Limited.
Example 7 differs from example 2 only in that: the chitosan is formed by mixing carboxymethyl chitosan and hydroxypropyl chitosan according to the mass ratio of 4: 1.
Example 8, which differs from example 7 only in that: the chitosan is prepared by mixing carboxymethyl chitosan and hydroxypropyl chitosan according to the mass ratio of 6: 1.
Example 9, which differs from example 7 only in that: the chitosan is formed by mixing carboxymethyl chitosan and hydroxypropyl chitosan according to the mass ratio of 8: 1.
Example 10, which differs from example 8 only in that: hydroxypropyl-beta-cyclodextrin and the like are replaced by mono- (6-ethylenediamine-6-deoxidation) -beta-cyclodextrin with the CAS number of 60984-63-6, and the hydroxypropyl-beta-cyclodextrin and the like are purchased from Jiangtai Tahua chemical industry Co., Ltd.
Example 11, which differs from example 8 only in that: the beta-cyclodextrin is prepared by mixing hydroxypropyl-beta-cyclodextrin and mono- (6-ethylenediamine-6-deoxidation) -beta-cyclodextrin according to the mass ratio of 1: 3.
Example 12 differs from example 11 only in that: the beta-cyclodextrin is prepared by mixing hydroxypropyl-beta-cyclodextrin and mono- (6-ethylenediamine-6-deoxidation) -beta-cyclodextrin according to the mass ratio of 1: 5.
Example 13, which differs from example 11 only in that: the beta-cyclodextrin is prepared by mixing hydroxypropyl-beta-cyclodextrin and mono- (6-ethylenediamine-6-deoxidation) -beta-cyclodextrin according to the mass ratio of 1: 6.
Example 14 differs from example 12 only in that: the gas phase nanometer titanium dioxide is mixed crystal type gas phase nanometer titanium dioxide with model number of AEROXIDE P25, wherein the weight ratio of anatase nanometer titanium dioxide to rutile nanometer titanium dioxide is 80:20, the average particle diameter is 21nm, and the specific surface area is 50m2(iv)/g, purchased from Germany winning the Chuangdegaseite.
Comparative example
Comparative example 1, which differs from example 1 only in that: the mass of hydroxypropyl-beta-cyclodextrin is replaced by MC-maltodextrin.
Comparative example 2, which differs from example 1 only in that: the mass of MC-maltodextrin is replaced by hydroxypropyl-beta-cyclodextrin.
Comparative example 3, which differs from example 1 only in that: the hydrophobic fumed silica is replaced by hydrophilic fumed silica with the model of WACKER
Figure BDA0003198996920000072
N20, specific surface area 200 +/-30 m2,/g, purchased from Wake, Germany.
Comparative example 4, which differs from example 1 only in that: carboxymethyl chitosan, etc. was replaced by Galla chinensis extract, having a cat # SR01336, purchased from Saisenann ran bioengineering, Inc.
Comparative example 5, which differs from example 1 only in that: the carboxymethyl chitosan and the gas phase nano titanium dioxide are replaced by liquid silica gel with the model of Dongjue NE-9150 in equal mass.
Performance test
The following performance tests were performed on the liquid silicone nipples provided in examples 1-14 and comparative examples 1-5 of the present application.
1. Preparing a bacterial solution with antibacterial performance: adding Candida albicans (ATCCY0109) and Staphylococcus aureus (ATCC25923) into sterile physiological saline to obtain a mixture containing Candida albicans and Staphylococcus aureus with concentration of 1 × 105CFU/mL bacterial liquid;
and (3) testing the antibacterial rate: placing sterilized liquid silicone nipples of examples 1-14 and comparative examples 1-5 (wherein examples 1-14 and comparative examples 1-4 are experimental groups, and comparative example 5 is a control group) in a mixed solution of 1mL of the bacterial liquid and 49mL of 5 wt% protein sterile deionized water solution, culturing for 8h in an incubator at 35 ℃, testing the colony numbers of Candida albicans and Staphylococcus aureus in the mixed solution after soaking the liquid silicone nipples of examples 1-14 and comparative examples 1-5, setting 3 groups of parallel groups for each liquid silicone nipple, and averaging the results; among them, the number of colonies corresponding to examples 1 to 14 and comparative examples 1 to 4 was counted as the number of colonies of the test group, the number of colonies corresponding to comparative example 5 was counted as the number of colonies of the control group, and the antibacterial ratio (%) (number of colonies of the control group-number of colonies of the test group)/number of colonies of the control group × 100%, and the test results were shown in table 2.
Table 2 test data of antibacterial property
Figure BDA0003198996920000071
Figure BDA0003198996920000081
2. Durability of antibacterial
Test A: the liquid silicone nipples of examples 1 to 14 and comparative examples 1 to 5 were washed with water daily and then placed in water at 30 ℃ to be soaked for 12 hours, the operation was repeated once a day until 6 months later, the treated liquid silicone nipples of examples 1 to 14 and comparative examples 1 to 5 were taken out, sterilized after drying, and the antibacterial rate was measured according to the above-described antibacterial property method, and the test results are shown in table 3.
And (3) testing B: the liquid silicone nipples of examples 1 to 14 and comparative examples 1 to 5 were rinsed with water every day and placed in water at 100 ℃ to cook for 1 hour, and this operation was repeated once a day until 30 days later, and the treated liquid silicone nipples of examples 1 to 14 and comparative examples 1 to 5 were taken out, dried, sterilized, and tested for antibacterial efficiency according to the above-described antibacterial property method, and the test results are shown in table 3.
TABLE 3 test data for antimicrobial durability
Figure BDA0003198996920000082
Figure BDA0003198996920000091
The following detailed description of the present application is provided for the test data of tables 2 and 3.
From the experimental data of the example 1 and the comparative example 4, the antibacterial property of chitosan is stronger than that of the gallnut extract, and chitosan is macromolecular, intertwined among molecules and has active hydroxyl and amino, so that the chitosan is not easy to run off in the nipple washing process, and the antibacterial property and the antibacterial durability of the liquid silicone nipple are improved.
From the experimental data of example 1 and comparative examples 1-2, it can be seen that the antibacterial rate and the antibacterial durability of candida albicans and staphylococcus aureus are significantly improved, especially the antibacterial durability, by the combined action of maltodextrin and beta-cyclodextrin.
From the experimental data of the example 1 and the comparative example 3, it can be known that the hydrophobic fumed silica and the fumed nano titanium dioxide act together, so that water drops are not easily formed on the surface of the liquid silicone nipple, and the antibacterial rate of the liquid silicone nipple after being washed for a long time and under high-temperature boiling is improved.
From the experimental data of the embodiments 2 and 6-7, it can be known that the antibacterial property of the liquid silicone nipple can be improved by compounding the carboxymethyl chitosan and the hydroxypropyl chitosan, and the antibacterial durability is also improved to a certain extent; from the experimental data of examples 7-9, it can be seen that when the mass ratio of carboxymethyl chitosan to hydroxypropyl chitosan is 6:1, the antibacterial property and antibacterial durability of the liquid silicone nipple are better. Because the carboxymethyl chitosan is an amphoteric polyelectrolyte, the carboxymethyl chitosan has stronger adsorption capacity, and the antibacterial effect of the chitosan is improved; and hydroxypropyl chitosan and hydroxypropyl-beta-cyclodextrin both have hydroxypropyl groups, so that the solubility of chitosan and beta-cyclodextrin is improved, and the combined action of chitosan, beta-cyclodextrin and maltodextrin is also improved, thereby improving the antibacterial durability of the liquid silicone nipple.
From the experimental data of examples 8 and 10-11, it can be known that the antibacterial property, especially the antibacterial durability, of the liquid silicone nipple can be improved by compounding hydroxypropyl-beta-cyclodextrin and ethylenediamine-beta-cyclodextrin. Because the ethylenediamine group in the ethylenediamine-beta-cyclodextrin has complexing ability, the adsorption effect on bacteria can be further improved; the stronger the hydrogen bond action of the hydroxypropyl and the amino, the better the combined action of the beta-cyclodextrin, the chitosan and the maltodextrin, and the improvement of the composite capacity of the cavity of the beta-cyclodextrin, thereby improving the antibacterial durability of the liquid silica gel nipple. From the experimental data of examples 11 to 13, it is known that the antibacterial property and antibacterial durability of the liquid silicone nipple are better when the mass ratio of hydroxypropyl- β -cyclodextrin to ethylenediamine- β -cyclodextrin is 1: 5.
From the experimental data of examples 13-14, it can be seen that the mixed crystal type gas phase nano titanium dioxide increases TiO2The defect density in the crystal lattice improves the capturing capacity of the gas phase nano titanium dioxide to bacteria, and is beneficial to improving the sterilization effect, weather resistance and ageing resistance of the gas phase nano titanium dioxide, thereby improving the antibacterial property and antibacterial durability of the liquid silica gel nipple.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (9)

1. The nipple is characterized in that the nipple is prepared from the following raw materials, by weight, 60-80 parts of liquid silica gel, 0.04-0.06 part of vulcanizing agent, 15-25 parts of chitosan, 5-10 parts of maltodextrin, 5-10 parts of beta-cyclodextrin, 10-20 parts of hydrophobic fumed silica, 5-10 parts of fumed nano titanium dioxide, 1-2 parts of hydroxyl silicone oil and 80-100 parts of acetic acid aqueous solution.
2. The liquid silicone nipple of claim 1, wherein the chitosan is formed by mixing carboxymethyl chitosan and hydroxypropyl chitosan according to a mass ratio of (4-8) to 1.
3. The liquid silicone nipple of claim 2, wherein the chitosan is formed by mixing carboxymethyl chitosan and hydroxypropyl chitosan according to a mass ratio of 6: 1.
4. The liquid silicone nipple of claim 1, wherein the vapor phase nano titanium dioxide is a mixed crystal type vapor phase nano titanium dioxide.
5. The liquid silicone nipple of claim 1, wherein the beta-cyclodextrin is hydroxypropyl-beta-cyclodextrin and/or ethylenediamine-beta-cyclodextrin.
6. The liquid silicone nipple of claim 5, wherein the beta-cyclodextrin is formed by mixing hydroxypropyl-beta-cyclodextrin and ethylenediamine-beta-cyclodextrin according to a mass ratio of 1 (3-6).
7. The liquid silicone nipple of claim 6, wherein the beta-cyclodextrin is formed by mixing hydroxypropyl-beta-cyclodextrin and ethylenediamine-beta-cyclodextrin in a mass ratio of 1: 5.
8. A liquid silicone teat as claimed in any one of claims 1 to 7 wherein the liquid silicone HAs a Shore hardness of 50 ± 2 HA.
9. The method for preparing a liquid silicone nipple according to any one of claims 1-8, comprising the steps of:
s1, adding chitosan, maltodextrin and beta-cyclodextrin into an acetic acid aqueous solution, and uniformly mixing to obtain a mixed solution;
s2, mixing the liquid silica gel, the hydrophobic fumed silica and the fumed nano titanium dioxide to obtain a mixture;
s3, mixing the mixed solution obtained in the step S1 with the mixed solution obtained in the step S2, adjusting the pH of the system to 8-12, and kneading to obtain a kneaded material;
and S4, adding hydroxyl silicone oil and a vulcanizing agent into the kneaded material obtained in the step S3, uniformly mixing, injecting into a baby nipple mould for forming, vulcanizing, cooling and demoulding to obtain the liquid silicone nipple.
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