Super-breathable biodegradable organosilicone gel bra material and in-situ foaming forming preparation method thereof

Abstract

The invention discloses an ultra-breathable biodegradable organosilicone gel bra material and an in-situ foaming forming preparation method thereof, and belongs to the technical field of preparation of environment-friendly materials. The material adopts a two-component system, wherein a component A contains vinyl silicone oil, a platinum catalyst and plasma-treated starch particles; and the component B contains hydrogen-containing silicone oil, sodium bicarbonate microcapsules, a chitosan modified coupling agent and a ZPT / ellagic acid mildew-proof synergist. A through porous structure is formed through a gradient hot-pressing foaming process, and the problems that a traditional silica gel bra is poor in breathability, non-degradable and insufficient in antibacterial durability are solved. The material is large in air permeability, high in staphylococcus aureus antibacterial rate and high in biodegradation rate.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of ultra-permeable biodegradable organic silicone gel breast patch materials and its in-situ foaming forming preparation method, belong to environmental protection material preparation technical field. BACKGROUND

[0002] Traditional silicone gel breast patch material generally uses high crosslinking degree polydimethylsiloxane (PDMS) system, its molecular chain is densely stacked to form a continuous phase structure, which seriously limits the material's air permeability. According to industry standard test, the air permeability of commercially available products is usually less than 1000 g / m2·24h (38℃ / 90%RH conditions), this nearly closed moisture barrier environment is easy to form a high humidity microenvironment (relative humidity > 95%) at the skin interface when worn for a long time, not only causing stuffiness, but also providing a breeding ground for pathogenic microorganisms such as Staphylococcus aureus and Candida albicans. Clinical studies have shown that the total number of colonies can increase to 10 6 CFU / cm2 order of magnitude after continuous use for 7 days. To improve air permeability, existing technologies propose adding chemical foaming agents such as azodicarbonamide, but the foaming process and silicon hydrogen addition reaction are difficult to control simultaneously, resulting in isolated closed pore structures with pore diameters of 50-200 μm (pore connectivity <30%). The actual air permeability is only improved to 1200-1500 g / m2·24h, and the moisture export efficiency is low due to the pore wall barrier. Another technology attempts to introduce biodegradable components such as corn starch (addition amount 20-30wt%), which achieves a 6-month degradation rate of 40-50%. However, due to the poor interfacial compatibility between starch and silicone, the tensile strength of the material decreases from the initial 1.2MPa to 0.5-0.7MPa (decrease >40%), which cannot meet the mechanical requirements of repeated adhesion of breast patch products. In addition, some people use nano-silver ion antibacterial agents to solve the problem of microbial breeding, but the chloride ion (Cl- concentration about 35-65mM) in sweat will combine with Ag + to form AgCl precipitate, causing the antibacterial efficiency to decrease from 99% to less than 85% within 7 days, and there is a safety risk of heavy metal ion migration. As can be seen, the existing technical solutions have a difficult balance between air permeability improvement, biodegradable implementation, and long-term antibacterial maintenance: physical foaming easily leads to closed pore structures, biodegradable components weaken the mechanical strength, and traditional antibacterial agents face inactivation in sweat. The industry urgently needs to develop a breakthrough material system that combines through-pore design (air permeability >5000 g / m2·24h), enzyme-responsive controlled degradation (6-month degradation rate >60% and strength retention rate >80%), and long-term antibacterial performance in sweat environment (30-day antibacterial rate >99%). SUMMARY

[0003] In view of the defects of the prior art, the present application provides a preparation method of an ultra-permeable biodegradable organic silicone gel breast patch material, comprising the following steps:

[0004] (1) Preparation of A component: mix vinyl silicone oil, platinum catalyst, plasma-treated porous starch particles;

[0005] (2) Preparation of B component: mix hydrogen-containing silicone oil, microcapsule foaming agent, antibacterial interface modifier, slow-release mildew-resistant synergist;

[0006] (3) Mix and inject A component and B component into a mold according to the mass fraction ratio of each component;

[0007] (4) Gradient heat pressing and foaming: 60±2℃ for 10-15min, then 80±2℃ for 20-25min, pressure 0.5-1.0MPa;

[0008] (5) Demolding to obtain porous gel material.

[0009] Preferably, the platinum catalyst is selected from one of chloroplatinic acid, platinum-vinylsiloxane complex or platinum-divinyltetramethyldisiloxane complex.

[0010] Preferably, the slow-release mildew-resistant synergist is composed of zinc pyrithione (ZPT) microcapsules and ellagic acid; the wall material of the ZPT microcapsules is polylactic acid-glycolic acid copolymer (PLGA), wherein the molar ratio of lactic acid to glycolic acid is 75:25-50:50.

[0011] Preferably, the mass ratio of the ZPT microcapsules to ellagic acid is 1:0.3, and pre-stirring is performed at 45±2℃ and 200rpm for 30min; the wall material of the ZPT microcapsules is polylactic acid-glycolic acid copolymer (PLGA75 / 25), the particle size is 1-5μm, and the drug loading capacity is ≥80%.

[0012] Preferably, the porous starch particles are selected from one of corn porous starch, cassava porous starch or potato porous starch, and are treated by argon plasma (power 100W, time 5min).

[0013] Preferably, the microcapsule foaming agent is polyurea-coated sodium bicarbonate microcapsule, the wall material is polyurea, the core material is sodium bicarbonate, and the wall thickness is 1-3μm.

[0014] Preferably, the vinyl silicone oil is selected from one of end-vinyl polydimethylsiloxane and side-chain vinyl polydimethylsiloxane, and the viscosity is 10000-20000mPa·s (25℃).

[0015] Preferably, the hydrogen-containing silicone oil is selected from one of end-hydrogen polydimethylsiloxane, side chain hydrogen-containing polydimethylsiloxane, with a hydrogen content of 0.3-0.8wt%; the antibacterial interface modifier is chitosan-g-g-aminopropyl triethoxysilane, wherein the degree of deacetylation of chitosan is ≥85%, and the grafting rate of g-aminopropyl triethoxysilane is 10-20%.

[0016] The application also provides a super-breathable biodegradable silicone gel chest patch material prepared by the above method, comprising the following components:

[0017] Vinyl silicone oil 100 parts by weight,

[0018] Hydrogen-containing silicone oil 3-8 parts by weight,

[0019] Platinum catalyst 50-200 ppm,

[0020] Porous starch particles 15-25 parts by weight,

[0021] Microcapsule foaming agent 3-10 parts by weight,

[0022] Antibacterial interface modifier: chitosan-g-g-aminopropyl triethoxysilane 2-5 parts by weight,

[0023] Slow-release mildew-resistant synergist 1.5-2.5 parts by weight.

[0024] Preferably, the viscosity of the vinyl silicone oil is 10000-20000 mPa·s (25℃)

[0025] The application has the following advantages:

[0026] ① The porous starch treated by plasma and the gradient foaming process synergistically form a network of through holes, greatly improving the air permeability, which is much higher than that of traditional silicone gel; ② The ZPT microcapsule and the pre-assembled ellagic acid maintain high antibacterial rate and high mildew resistance after 30 days of sweat soaking through ion chelation slow-release mechanism; ③ The chitosan modified coupling agent enhances the interface bonding between starch and silicone gel, so that the material maintains tensile strength under the premise of high degradation rate. The three synergistically solve the contradiction between air permeability, antibacterial durability and mechanical properties. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only a part of the embodiments of the application, and not all embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the application.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Methods and materials similar or equivalent to those described herein can be used in the practice of the present application. The preferred materials and methods are described herein, although any method and material similar or equivalent to those described herein can be used. The materials described or

[0029] The experimental methods in the following examples are all conventional methods unless otherwise specified. The experimental materials used in the following examples are all purchased from commercial channels unless otherwise specified. The porous starch particles are corn porous starch (porosity ≥ 70%, purchased from Shandong Zhucheng Xingmao), and the microcapsule foaming agent is polyurea-coated sodium bicarbonate microcapsule (core material ratio 80%, purchased from Zhejiang Ju Hua Group).

[0030] Example 1

[0031] Starch pretreatment:

[0032] Take 15.00 g of corn porous starch (Shandong Zhucheng Xingmao ZMS-30, porosity 75%) and place it in a plasma chamber. Wash it with argon gas for 3 times (-0.1 MPa→atmospheric pressure cycle), treat it with 100 W for 5 min, and take it out and stand for 15 min.

[0033] A component:

[0034] Add 100.00 g of vinyl-terminated PDMS (Lanxess Eckart VMS-050, viscosity 10000 mPa·s) to a 500 mL flask, inject 50 μL of platinum catalyst (Pt-DV™ DS, 3000 ppm stock solution) under a 40°C water bath, add the pretreated starch, and stir at 1500 rpm for 10 min (paddle blade distance from bottom 10 mm).

[0035] B component:

[0036] Add 3.00 g of hydrogen-containing side chain silicone oil (Wuhan Kanos HMS-301, hydrogen content 0.3 wt%) to a 250 mL brown bottle, add 5.00 g of sodium bicarbonate@polyurea microcapsule (Zhejiang Ju Hua JH-MC50), add 2.00 g of chitosan-g-KH550 (self-made: 90% deacetylation degree chitosan and 15% KH550 were reacted in ethanol at 60°C for 6 h and then vacuum dried, according to the mass ratio KH550: chitosan = 1:5), add 1.00 g of ZPT@PLGA7525 + 0.30 g of ellagic acid, and stir at 45°C / 500 rpm for 30 min.

[0037] Molding:

[0038] Mix A and B above (the experimental scale of examples and comparative examples can be scaled up according to the ratio described), manually stir 120 times → pour into the mold (100x100x3mm), heat pressing procedure: 60℃ / 15min (0.7MPa)→80℃ / 20min (0.7MPa)→demolding.

[0039] Example 2

[0040] Porous starch pretreatment:

[0041] Take 20.00g cassava porous starch (Guangxi Academy of Agricultural Sciences WPS-80, porosity 80%) and place it in a quartz culture dish, spread it into a single layer, and place it in a plasma cleaning machine (Institute of Microelectronics, Chinese Academy of Sciences TP-200 type). After closing the cabin door:

[0042] ① Turn on the vacuum pump to -0.1MPa, ② Introduce argon gas (purity 99.999%) to normal pressure, repeat 3 times, ③ Set parameters: power 100W, treatment time 5min, argon flow rate 20sccm (15-25sccm), ④ After treatment, stand for 15min and take out;

[0043] Preparation of A component (operation in fume hood):

[0044] In a 500mL four-necked flask, add 100g side chain vinyl PDMS (Dow Corning EG-3000, viscosity 15000mPa·s), fix the flask in a constant temperature water bath (Shanghai Jinghong HHS-21), heat to 40±1℃, use a microsyringe to suck 0.33mL platinum catalyst (Araldite H112284, 0.5wt% chloroplatinic acid isopropyl alcohol solution) and inject it along the wall of the flask, add the pretreated starch, insert a four-leaf paddle stirrer (IKAR W20), set 40℃ 1500rpm stirring for 15min, the paddle is 10mm from the bottom of the flask;

[0045] Preparation of B component (operation in the dark):

[0046] In a 250mL brown glass bottle, add 4.00g end-hydrogen-containing silicone oil (Momentive MHX-1107, hydrogen content 0.5wt%), add 5.00g sodium bicarbonate@polyurea microcapsule (Zhejiang Juohua JH-MC50), weigh 3.00g chitosan-g-KH550 (self-made: 90% deacetylated chitosan and 15% KH550 were reacted in ethanol at 60℃ for 6h and then vacuum dried, according to the mass ratio KH550: chitosan = 1:5), accurately weigh 1.50g ZPT@PLGA microcapsule (Shanghai Yuanye Biotechnology Co., Ltd. PLGA7525-ZPT) and 0.45g ellagic acid (Nanjing Daosi Biological Technology Co., Ltd. TY-001) and add them, place them in a magnetic stirrer (Shanghai Sile SL-202) in a 45℃ water bath, stir at 500rpm for 30min;

[0047] Mixing and casting:

[0048] Pour A, B components into plastic beaker (temperature maintained at 40℃), manually stir with flat paddle for 120 times (about 1 min), immediately pour into stainless steel mold (100x100x3mm, surface sprayed with mold release agent Dow Corning QZ-5119), scrape the surface flat, cover with porous PTFE film (pore 0.45μm);

[0049] Gradient heat pressing foaming:

[0050] Mold moved into heat press (Shanghai Yiheng DHG-9050), set program:

[0051] ① 60±0.5℃ for 12min, pressure 0.7MPa (heating rate 5℃ / min), ② switch to 80±0.5℃ for 22min, pressure maintained, naturally cool to 40℃ to open the mold, take out the gel piece and seal it in a PE bag.

[0052] Example 3

[0053] Weigh 15.00g of corn porous starch (Zucheng Xingmao ZMS-30, porosity 75%) into the plasma chamber, wash with argon gas 3 times (-0.1MPa→atmospheric pressure cycle), 100W for 5min, take out and stand for 15min;

[0054] A component:

[0055] Add 100.00g of vinyl-terminated PDMS (Lanxing Eken VMS-050, viscosity 10000mPa·s) to a 500mL flask, inject 80μL of platinum catalyst (Pt-DV™ DS, 3000ppm stock solution) under a 40℃ water bath, add pretreated starch, stir at 1500rpm for 10min (paddle distance from bottom 10mm);

[0056] B component:

[0057] Add 7.00g of hydrogen-containing side chain silicone oil (Wuhan Kanos HMS-301, hydrogen content 0.3wt%) to a 250mL brown bottle, add 6.00g of sodium bicarbonate@polyurea microcapsule (Zhejiang Juhua JH-MC50), add 2.00g of chitosan-g-KH550 (self-made: 90% deacetylated chitosan and 15% KH550 reacted in ethanol at 60℃ for 6h, then vacuum dried, KH550:chitosan=1:5 by mass ratio), add 1.80g of ZPT@PLGA5050+0.54g of ellagic acid, stir at 45℃ / 500rpm for 30min;

[0058] Molding:

[0059] Mix component A and component B, stir manually 120 times → inject into a mold (100×100×3mm), and hot press program: 60℃ / 10min (0.5MPa) → 80℃ / 25min (0.5MPa) → demold.

[0060] Comparative Example 1 (difference from Example 1: starch is untreated)

[0061] Starch pretreatment:

[0062] 15.00 g of porous corn starch (ZMS-30, Xingmao, Zhucheng, Shandong, porosity 75%) was weighed (without plasma treatment).

[0063] Comparative Example 2 (difference from Example 1: single-stage foaming)

[0064] Same as Example 1, but the hot pressing procedure is changed to:

[0065] 80℃ / 35min(0.7MPa)→Demolding. (Cancel the 60℃ step)

[0066] Comparative Example 3 (difference from Example 1: no ellagic acid)

[0067] Changes to component B:

[0068] To a 250 mL brown bottle, 3.00 g of side chain hydrogenated silicone oil, 5.00 g of sodium bicarbonate@polyurea microcapsules, 2.00 g of chitosan-g-KH550, and 1.30 g of ZPT@PLGA7525 (without ellagic acid) were added and stirred at 45°C / 500 rpm for 30 min. The remaining contents were the same as in Example 1.

[0069] Comparative Example 4 (difference from Example 1: unmodified chitosan)

[0070] Changes to component B:

[0071] In a 250 mL brown bottle, 3.00 g of side chain hydrogenated silicone oil, 5.00 g of sodium bicarbonate@polyurea microcapsules, 2.00 g of ordinary chitosan (85% deacetylation degree), 1.00 g of ZPT@PLGA7525 + 0.30 g of ellagic acid were added and stirred at 45°C / 500 rpm for 30 min. The remaining reaction was the same as in Example 1.

[0072] Comparative Example 5 (difference from Example 1: excess hydrogenated silicone oil)

[0073] Changes to component B:

[0074] 250 mL brown bottle, 30.00 g side chain containing hydrogen silicone oil, 3.00 g sodium bicarbonate@polyurea microcapsule, 2.00 g chitosan-g-KH550, 1.00 g ZPT@PLGA7525+0.30 g tannic acid, 45℃ / 500rpm stirring for 30min, the rest is the same as example 1.

[0075] Comparative example 6: commercially available silica gel chest patch.

[0076] The products obtained in the examples and comparative examples were detected by the method described in Table 1, and the results are shown in Table 2.

[0077] Table 1 detection method

[0078]

[0079] Table 2 detection results

[0080]

[0081]

[0082] The present application realizes technical breakthrough through triple synergistic mechanism: the high connectivity pore network is constructed by the synergistic effect of plasma activated porous starch and gradient foaming process, which makes the air permeability break through 5000g / m2·24h, which is more than 400% higher than traditional silica gel; the interface modifier chitosan-g-KH550 enhances the interface bonding force between starch and silica gel through silane coupling, which realizes 6 months of enzyme degradation of >65% while maintaining >80% of strength retention rate, overcoming the industry problem of mechanical attenuation of degradable materials; the ZPT-tannic acid chelation slow-release system continuously releases active components in the sweat environment, and the antibacterial rate against pathogenic bacteria is still >99% after 30 days, and the pH response characteristics of the PLGA wall material (sweat pH = 4.5-6.5 to accelerate release) significantly improve the time effectiveness of antibacterial. The data of comparative examples confirms that canceling any key technology (such as starch activation, step foaming or synergistic antibacterial) will cause a 20-50% drop in core performance, especially the antibacterial attenuation (86.2% vs 99.4%) of comparative example 3 and the strength collapse (45% vs 87%) of comparative example 4 highlight the irreplaceability of the synergistic effect of the present scheme, which successfully solves the industry contradiction between air permeability, degradability and long-acting antibacterial.

[0083] Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, the scope of which is defined by the appended claims and their equivalents.

[0084] The above describes the present application and its embodiments, which are not limited, and only one of the embodiments of the present application is shown, and the practical application is not limited thereto. In general, if a person skilled in the art is inspired thereby, without departing from the purpose of the present application, similar modes and embodiments are not created by creative design, and all should belong to the protection scope of the present application.

Claims

1. A method for in-situ foamed molding of a super gas permeable biodegradable silicone gel breast patch material, characterized by: It comprises the following steps: (1) Preparation of A component: mix vinyl silicone oil, platinum catalyst, plasma-treated porous starch particles; (2) Preparation of B component: mix hydrogen-containing silicone oil, microcapsule foaming agent, antibacterial interface modifier, slow-release mildew-resistant synergist; (3) Mix A component and B component and inject into mold; (4) Gradient heat pressing and foaming: 60±2℃ for 10-15min, then 80±2℃ for 20-25min, pressure 0.5-1.0MPa; (5) Demolding to obtain porous gel material.

2. The method of claim 1, wherein: The platinum catalyst is selected from one of chloroplatinic acid, platinum-vinylsiloxane complex or platinum-divinyltetramethyldisiloxane complex.

3. The method of claim 1, wherein: The slow-release mildew-resistant synergist is composed of zinc pyrithione microcapsule and ellagic acid; the wall material of the ZPT microcapsule is polylactic acid-hydroxyacetic acid copolymer, and the molar ratio of lactic acid to hydroxyacetic acid is 75:25-50:

50.

4. The method of claim 3, wherein: The mass ratio of the ZPT microcapsule to ellagic acid is 1:0.3, and the pre-stirring is carried out at 45±2℃ and 200rpm for 30min; the wall material of the ZPT microcapsule is polylactic acid-hydroxyacetic acid copolymer, the particle size is 1-5μm, and the drug loading is ≥80%.

5. The method of claim 1, wherein: The porous starch particles are selected from one of corn porous starch, cassava porous starch or potato porous starch, and are treated by argon plasma.

6. The method of claim 1, wherein: The microcapsule foaming agent is polyurea-coated sodium bicarbonate microcapsule, the wall material is polyurea, the core material is sodium bicarbonate, and the wall thickness is 1-3μm.

7. The method of claim 1, wherein: The vinyl silicone oil is selected from one of end-vinyl polydimethylsiloxane and side-chain vinyl polydimethylsiloxane, and the viscosity is 10000-20000mPa·s.

8. The method of claim 1, wherein: The hydrogen-containing silicone oil is selected from one of end-hydrogen-containing polydimethylsiloxane and side-chain hydrogen-containing polydimethylsiloxane, and the hydrogen content is 0.3-0.8wt%; the antibacterial interface modifier is chitosan-g-γ-aminopropyl triethoxysilane, wherein the deacetylation degree of chitosan is ≥85%, and the grafting rate of γ-aminopropyl triethoxysilane is 10-20%.

9. A super gas permeable biodegradable silicone gel breast patch material prepared by the method of any one of claims 1-8, characterized by: It comprises the following components: vinyl silicone oil 100 parts by weight, hydrogen-containing silicone oil 3-8 parts by weight, platinum catalyst 50-200ppm, porous starch particles 15-25 parts by weight, microcapsule foaming agent 3-10 parts by weight, antibacterial interface modifier: chitosan-g-γ-aminopropyl triethoxysilane 2-5 parts by weight, slow-release mildew-resistant synergist 1.5-2.5 parts by weight.

10. The material of claim 9, wherein: The viscosity of the vinyl silicone oil is 10000-20000mPa·s.

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