CN104086088A - Method of preparing glass with surface antibacterial property by photopolymerization - Google Patents
Method of preparing glass with surface antibacterial property by photopolymerization Download PDFInfo
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Abstract
A method of preparing glass with a surface antibacterial property by photopolymerization is disclosed. The invention relates to pretreatment of glass surfaces. Antibacterial property modification is performed by utilization of a silicone coupling agent and a photopolymerization method. The method of preparing the glass includes: hydroxylating a glass sheet in a solution comprising concentrated sulfuric acid having a concentration of 98% and hydrogen peroxide having a concentration of 30% in a volume ratio of 7:3; performing silanization to give glass surfaces a photopolymerization function; preparing a photopolymerization system of a quaternary ammonium salt photosensitive monomer; coating the silanized glass with the photopolymerization system; covering the glass with a mask; and exposing to obtain the surface antibacterial glass. The method of preparing the glass has characteristics of no need of heating, simple operation process, high efficiency, capability of achieving large-scale continuous preparation of the surface antibacterial glass, and capability of achieving control of the antibacterial specific surface area, and can be used in the fields of medical sanitary, environment protection, biotechnology, and the like.
Description
Technical field
The present invention relates to Glass Surface Modification to process, utilize silane coupling agent and photopolymerisable method to carry out antibacterial surface modification to it.
Background technology
Along with people's quality of life level improves, hygienic environment-protecting is more paid attention to.We are at any time contacting various bacteriophagees, especially in medical industry in daily life.So people are also more and more urgent to the demand of germ resistance material surface, especially glasswork.The main method that current people obtain antibacterial glass has two kinds: a kind of is to add antibacterial inorganic metal salt when producing glass, and sterilization effect is played in mineral ion stripping in glass when using glass with anti-microbial property; Another kind is at glass surface modification one deck, to have the coating of antibacterial effect, as decorated nanometer titanium dioxide layer etc.
In Improving Glass Manufacturing Processes, adding the inevitable shortcoming of antiseptic elements method is exactly along with the continuous stripping of antiseptic elements of time glass the inside, to cause the decline of its antibacterial effect.In the method for glass surface modification antimicrobial coating, there is two kinds of Physical and chemical methods: patent ZL-200820084346.4 to utilize the method for plasma spraying that titanium dioxide nano-particle is plated in to glass surface, utilize nano-TiO
2can play antibacterial effect to the performance of most of Photocatalytic Degradation of Organic; Patent CN-103172275A has introduced a kind of manufacture method of antibiotic glass touch panel, first be that glass substrate is cleaned and then modifies upper amino silicane coupling agent with acidic solution, finally immerse the solution that contains nano anti-biotic material (zinc oxide, titanium dioxide, copper, gold and silver or clay), although this method is the chemically modified to glass surface, but the bonding force dependence absorption of antimicrobial nano particle and glass surface is not covalent linkage when antibacterial modification, easily come off, be restricted work-ing life.The people such as Joerg C.Tiller are grafted to glass surface by (4-vinyl-N-alkyl pyridine bromide) mode with covalent linkage of gathering and have played antibacterial effect, but their method need to heat 75 ℃, react time consumption and energy consumption (Tiller, J.C. 24 hours; Liao, C.J.; Lewis, K.; Klibanov, A.M.Proc.Natl.Acad.Sci.2001,98 (11), 5981 – 5985.).
We have invented a kind of method that photopolymerization preparation has the glass of antibacterial surface performance.This method utilizes the features such as photopolymerization is efficient, environmental protection, low power consuming that the good quaternary ammonium salt of sterilization effect is fixed on to glass surface in the mode of covalent linkage; The feature of the partial exposure of photopolymerization is simultaneously given antimicrobial surface patterning, realizes the controlled of antimicrobial surface specific surface area.Can be used for health care, environment protection, biotechnology field.
Summary of the invention
The object of this invention is to provide a kind of method that photopolymerization preparation has the glass of antibacterial surface performance.
The present invention be take glass as base material, and silane coupling agent is intermediate, by photopolymerisable method, the quaternary ammonium salt of the photopolymerization of different chain length is fixed on glassly in the mode of covalent linkage, obtains a kind of antibacterial surface glass.The method comprises the following steps:
(1), hydroxylation glass: sheet glass is immersed in respectively to supersound process 5-20 minute in deionized water, ethanol, acetone, dries up then with nitrogen and put into " anthropophagy's acid " solution (98% vitriol oil and 30% hydrogen peroxide volume ratio 7:3) immersion 1-24 hour.
(2), silanized glass: (ratio of organic solvent and MPS is the organic solvent solution of preparation γ-methacryloxypropyl trimethoxy silane (MPS): 10mL organic solvent: 5-20mg MPS, with second acid for adjusting pH value, be 3-5), hydroxylation glass in step (1) is immersed to 1-24 hour.Methoxyl group hydrolysis and the hydroxyl dehydrating condensation of glass surface of MPS obtain silanized glass.
(3), the Photopolymer System of preparation different chain length quaternary ammonium salt photosensitive monomer, be coated onto on silanized glass, cover mask, with ultraviolet lamp (300-500nm) exposure 1-10min.Product immerses in solvent ultrasonic, and unexposed portion comes off and obtains final product.
(4), in step (3), product is done antibacterial test.
This preparation method of the present invention is fixed on glass obtained antibacterial surface glass by the photo polymerization monomer with anti-microbial property in the mode of covalent linkage by means of the light polymerization process of high-efficiency environment friendly.Antibiotic glass feature:
1, whole process is chemically modified, and antibacterial modified post polymerization thing is fixed on glass surface in the mode of covalent linkage, rather than simply applies, and high being not easy of bonding strength is cleaned.
2, mask is controlled the pattern of polymkeric substance after glass surface solidifies, and different polymkeric substance pattern specific surface areas is different, and realization is adjustable controlled to glass surface germ resistance.
3, the antibacterial modification of photocuring quaternary ammonium salt used is autonomous synthetic photopolymerizable monomer, and glass surface QAS polymer demonstrates good germ resistance, and the gram-negative/positive bacterias such as intestinal bacteria, streptococcus aureus are had to good restraining effect.
4, can produce continuously in a large number, the proportion relation of solvent and quaternary ammonium salt directly affects solidification effect and then affects antibacterial effect.
Accompanying drawing explanation
Fig. 1: antibiotic glass preparation process schematic diagram
Embodiment
Long chain quaternary photosensitive monomer with
for example, called after nQAS.
Embodiment 1:
(1), sheet glass is immersed in respectively in deionized water, ethanol, acetone to supersound process 5 minutes, with nitrogen, dries up then and put into " anthropophagy's acid " solution (98% vitriol oil and 30% hydrogen peroxide volume ratio 7:3) immersion 5 hours.
(2), silanized glass: (ratio of toluene and silane coupling agent is the toluene solution of preparation γ-methacryloxypropyl trimethoxy silane (MPS): 10mL toluene: 5mg silane coupling agent, with second acid for adjusting pH value, be 3.5), hydroxylation glass in step (1) is immersed to 2 hours.Methoxyl group hydrolysis and the hydroxyl dehydrating condensation of glass surface of MPS obtain silanized glass.
(3), configuration long chain quaternary photosensitive monomer Photopolymer System (6QAS-46wt.%, 2-hydroxy-2-methyl-1-phenyl-1-acetone-3wt.%, Viscoat 295-0.5wt.%, 1,6-hexanediyl ester-0.5wt.%, ethanol-25wt.%, methyl alcohol-25wt.%], be coated onto on silanized glass, cover mask, pointolite ultraviolet lamp (320-500nm) exposure 60 seconds, light intensity 35mW/cm
2.Product immerses in ethanol ultrasonic, and unexposed portion comes off and obtains final product.
(4), in step (3), product is done antibacterial test, concrete antibacterial test step: 100 μ L are contained to the colibacillary PBS buffering suspension of 0.1mol (pH value is 7.0, and cell concn is 1011/mL) and join in the aseptic Erlenmeyer flask of the yeast/dextrose bouillon that fills 50ml.Stirring velocity by suspension at 200rpm, at the temperature of 37 ℃, incubation is 8 hours, carries out the cultivation of bacterial cell.By centrifugation (2700rpm, 10 minutes), washing, bacterial cell is suspended in distilled water the most at last.The cell concn of the suspension of this bacterium is 106/mL, simultaneously, use chromatographic spray and at a constant spray velocity to the antibiotic glass of preparing and do not carry out antibacterial modified glass and spray, prepare the glass that contains identical initial cell quantity.Glass is placed on after being dried in air and is placed in culture dish, add the sealing of growth agar, and further at 37 ℃, cultivate 15 hours.The colony number of growing in not carrying out antibacterial modified glass is as criterion numeral, the antibiotic rate using the ratio of the epontic colony number of antibiotic glass and criterion numeral as antibiotic glass.(with reference to GB: ISO22196-2007, reference: Tiller, J.C.; Liao, C.J.; Lewis, K.; Klibanov, A.M.Proc.Natl.Acad.Sci.2001,98 (11), 5981 – 5985.).Experimental result shows, its 15 hours sterilizing rates are 98.7%.
Embodiment 2:
(1), sheet glass is immersed in respectively in deionized water, ethanol, acetone to supersound process 10 minutes, with nitrogen, dries up then and put into " anthropophagy's acid " solution (98% vitriol oil and 30% hydrogen peroxide volume ratio 7:3) immersion 1 hour.
(2), silanized glass: (ratio of toluene and silane coupling agent is the toluene solution of preparation γ-methacryloxypropyl trimethoxy silane (MPS): 10mL toluene: 10mg silane coupling agent, with second acid for adjusting pH value, be 3), hydroxylation glass in step (1) is immersed to 1 hour.Methoxyl group hydrolysis and the hydroxyl dehydrating condensation of glass surface of MPS obtain silanized glass.
(3), configuration long chain quaternary photosensitive monomer Photopolymer System (7QAS-20wt.%, 1-hydroxyl-cyclohexyl-phenyl ketone-1wt.%, 1,6-hexylene glycol double methacrylate-2wt.%, methylene dichloride-77wt.%), be coated onto on silanized glass, cover mask, pointolite ultraviolet lamp (320-500nm) exposure 60 seconds, light intensity 40mW/cm
2.Product immerses in ethanol ultrasonic, and unexposed portion comes off and obtains final product.
(4), product antibacterial test in step (3), testing method is identical with embodiment 1, tests and shows that its 15 hours antibiotic rates are 98.9%.
Embodiment 3:
(1), sheet glass is immersed in respectively in deionized water, ethanol, acetone to supersound process 15 minutes, with nitrogen, dries up then and put into " anthropophagy's acid " solution (98% vitriol oil and 30% hydrogen peroxide volume ratio 7:3) immersion 5 hours.
(2), silanized glass: (ratio of toluene and silane coupling agent is the toluene solution of preparation γ-methacryloxypropyl trimethoxy silane (MPS): 10mL toluene: 5mg silane coupling agent, with second acid for adjusting pH value, be 4), hydroxylation glass in step (1) is immersed to 10 hours.Methoxyl group hydrolysis and the hydroxyl dehydrating condensation of glass surface of MPS obtain silanized glass.
(3), configuration long chain quaternary photosensitive monomer Photopolymer System (8QAS-70wt.%, 2; 4; 6-trimethylbenzoyl phosphinic acid ethyl ester-1.5wt.%; 1-hydroxyl-cyclohexyl-phenyl ketone-1.5wt.%, two contracting propylene glycol double methacrylate-0.1wt.%, ethanol-26.9wt.%); be coated onto on silanized glass; cover mask, area source ultraviolet lamp exposure 200 seconds, light intensity 30mW/cm
2.Product immerses in methylene dichloride ultrasonic, and unexposed portion comes off and obtains final product.
(4), product antibacterial test in step (3), testing method is identical with embodiment 1, tests and shows that its 15 hours antibiotic rates are 99.6%.
Embodiment 4:
(1), sheet glass is immersed in respectively in deionized water, ethanol, acetone to supersound process 5 minutes, with nitrogen, dries up then and put into " anthropophagy's acid " solution (98% vitriol oil and 30% hydrogen peroxide volume ratio 7:3) immersion 20 hours.
(2), silanized glass: (ratio of toluene and silane coupling agent is the toluene solution of preparation γ-methacryloxypropyl trimethoxy silane (MPS): 10mL toluene: 20mg silane coupling agent, with second acid for adjusting pH value, be 4), hydroxylation glass in step (1) is immersed to 5 hours.Methoxyl group hydrolysis and the hydroxyl dehydrating condensation of glass surface of MPS obtain silanized glass.
(3), configuration long chain quaternary photosensitive monomer Photopolymer System (9QAS-9wt.%, 2-hydroxy-2-methyl-1-phenyl-1-acetone-0.3wt.%; 2; 4; 6-trimethylbenzoyl phosphinic acid ethyl ester-0.4wt.%; 1-hydroxyl-cyclohexyl-phenyl ketone-0.3wt.%; Viscoat 295-3.3wt.%; 1; 6-hexanediyl ester-3.3wt.%, two contracting propylene glycol double methacrylate-3.4wt.%, ethanol-80wt.%); be coated onto on silanized glass; cover mask, area source ultraviolet lamp exposure 200 seconds, light intensity 50mW/cm
2.Product is immersed in the water ultrasonic, and unexposed portion comes off and obtains final product.
(4), product antibacterial test in step (3), testing method is identical with embodiment 1, tests and shows that its 15 hours antibiotic rates are 99.7%.
Embodiment 5:
(1), sheet glass is immersed in respectively in deionized water, ethanol, acetone to supersound process 15 minutes, with nitrogen, dries up then and put into " anthropophagy's acid " solution (98% vitriol oil and 30% hydrogen peroxide volume ratio 7:3) immersion 20 hours.
(2), silanized glass: (ratio of toluene and silane coupling agent is the toluene solution of preparation γ-methacryloxypropyl trimethoxy silane (MPS): 10mL toluene: 20mg silane coupling agent, with second acid for adjusting pH value, be 5), hydroxylation glass in step (1) is immersed to 24 hours.Methoxyl group hydrolysis and the hydroxyl dehydrating condensation of glass surface of MPS obtain silanized glass.
(3), configuration long chain quaternary photosensitive monomer Photopolymer System (12QAS-59wt.%, 2-hydroxy-2-methyl-1-phenyl-1-acetone-10wt.%, tripropylene glycol double methacrylate-1wt.%, ethanol-10wt.%, methyl alcohol-10wt.%, methylene dichloride-10wt.%), be coated onto on silanized glass, cover mask, pointolite ultraviolet lamp (320-500nm) exposure 600 seconds, light intensity 45mW/cm
2.Product immerses in acetone ultrasonic, and unexposed portion comes off and obtains final product.
(4), product antibacterial test in step (3), testing method is identical with embodiment 1, tests and shows that its 15 hours antibiotic rates are 99.9%.
Embodiment 6:
(1), sheet glass is immersed in respectively in deionized water, ethanol, acetone to supersound process 20 minutes, with nitrogen, dries up then and put into " anthropophagy's acid " solution (98% vitriol oil and 30% hydrogen peroxide volume ratio 7:3) immersion 24 hours.
(2), silanized glass: (ratio of toluene and silane coupling agent is the toluene solution of preparation γ-methacryloxypropyl trimethoxy silane (MPS): 10mL toluene: 15mg silane coupling agent, with second acid for adjusting pH value, be 3.5), hydroxylation glass in step (1) is immersed to 20 hours.Methoxyl group hydrolysis and the hydroxyl dehydrating condensation of glass surface of MPS obtain silanized glass.
(3), configuration long chain quaternary photosensitive monomer Photopolymer System (12QAS-57wt.%, 1-hydroxyl-cyclohexyl-phenyl ketone-2wt.%, Viscoat 295-1wt.%, ethanol-40wt.%), be coated onto on silanized glass, cover mask, pointolite ultraviolet lamp (320-500nm) exposure 600 seconds, light intensity 40mW/cm
2.Product immerses in ethanol ultrasonic, and unexposed portion comes off and obtains final product.
(4), product antibacterial test in step (3), testing method is identical with embodiment 1, just changes intestinal bacteria into streptococcus aureus, tests and shows that its 15 hours antibiotic rates are 99.9%.
Claims (5)
1. photopolymerization preparation has the method for the glass of anti-microbial property, comprises the following steps:
(1) hydroxylation glass: sheet glass is immersed in respectively to supersound process 5-20 minute in deionized water, ethanol, acetone, dries up then and put into " anthropophagy's acid " solution with nitrogen and soak 1-24 hour;
(2) silanized glass: the organic solvent solution of preparation γ-methacryloxypropyl trimethoxy silane MPS, the ratio of organic solvent and MPS is: 10mL organic solvent: 5-20mg MPS, with second acid for adjusting pH value, be 3-5, hydroxylation glass in step (1) is immersed to 1-24 hour; Methoxyl group hydrolysis and the hydroxyl dehydrating condensation of glass surface of MPS obtain silanized glass;
(3) preparation quaternary ammonium salt photosensitive monomer Photopolymer System, is coated onto on silanized glass, covers mask, with ultraviolet lamp 300-500nm exposure 1-10min suggestion, supplements light intensity; Product immerses in solvent ultrasonic, and unexposed portion comes off and obtains final product.
Photopolymer System described in step (3):
(a) monomer is different chain length quaternary ammonium salt photosensitive monomer, and the massfraction that accounts for system is 20%-70%,
Quaternary ammonium salt photosensitive monomer:
n>=2 wherein, R'=CH
3or H, X=Cl, Br or I, R
1, R
2, R
3group is
1≤m≤15 wherein,
p>=2 wherein,
r wherein
4=CH
3or C
2h
5,
r wherein
5=H, CH
3, OH, Cl, Br or I,
it is 0.1%-10% that linking agent accounts for system quality mark; It is 1%-10% that initiator accounts for system quality mark; The massfraction that solvent accounts for system is 30%-80%.
2. according to the preparation method of claim 1, it is characterized in that:
Linking agent is 1, 6-hexanediyl ester, three contracting tripropylene glycol diacrylates, polyethyleneglycol diacrylate, propylene glycol diacrylate, three contracting tripropylene glycol dimethacrylates, ethylene glycol dimethacrylate, tetraethylene-glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, the third oxidation Viscoat 295, Viscoat 295, pentaerythritol triacrylate, ethoxyquin Viscoat 295, trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate, two-trimethylolpropane tetra-acrylate, and one or more mixing in tetramethylolmethane five/six acrylate.
3. according to the preparation method of claim 1, it is characterized in that:
Initiator is 2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2, 4, 6-trimethylbenzoyl phosphinic acid ethyl ester, 2-hydroxy-methyl phenyl-propane-1-ketone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-hydroxyl-4'-(2-hydroxy ethoxy)-2-methyl phenyl ketone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio group) phenyl]-1-acetone, 2-phenyl benzyl-2-dimethyl amine-1-(4-morpholine benzyl phenyl) butanone, isopropyl thioxanthone, 2, 4-diethyl thioxanthone, EHA, one or more mixing in EDMAB.
4. according to the preparation method of claim 1, it is characterized in that:
Solvent is one or more mixing in ethanol, methyl alcohol, propyl alcohol, propyl carbinol, methylene dichloride.
5. according to the preparation method of claim 1, it is characterized in that described in step (3) Light Curing mask.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105712638A (en) * | 2015-12-07 | 2016-06-29 | 华南理工大学 | Ultraviolet-cured polyacrylate superhydrophilic coating for glass and preparation method thereof |
| CN106188419A (en) * | 2016-07-25 | 2016-12-07 | 东南大学 | Graft polymers and the preparation method of antibacterial soft lens based on surface grafting |
| CN108793772A (en) * | 2018-04-25 | 2018-11-13 | 成都思博特科技有限公司 | A kind of preparation method of anti-fog bacteriostatic coating |
| CN108996916A (en) * | 2018-09-05 | 2018-12-14 | 成都中建材光电材料有限公司 | A kind of method of quartz inside pipe wall plated film |
| CN109161885A (en) * | 2017-11-14 | 2019-01-08 | 西南交通大学 | A kind of antibacterial functionalized method of modifying of aluminum alloy surface |
| CN114042482A (en) * | 2021-03-04 | 2022-02-15 | 杭州安誉科技有限公司 | Low-adsorption antibacterial centrifuge tube and application thereof |
| CN114196053A (en) * | 2021-12-14 | 2022-03-18 | 赛宁(苏州)生物科技有限公司 | Surface modification method of plastic centrifuge tube for extracting biological sample |
| CN114200659A (en) * | 2021-09-26 | 2022-03-18 | 吉林大学 | Hydrophilic antibacterial glass slide with bionic structure and preparation method thereof |
| CN115028374A (en) * | 2022-04-28 | 2022-09-09 | 华北制药股份有限公司玻璃分公司 | Antibacterial glass and preparation method thereof |
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| CN105712638B (en) * | 2015-12-07 | 2018-06-22 | 华南理工大学 | Glass cures polyacrylate super-hydrophilic coating and preparation method thereof with ultraviolet light |
| CN105712638A (en) * | 2015-12-07 | 2016-06-29 | 华南理工大学 | Ultraviolet-cured polyacrylate superhydrophilic coating for glass and preparation method thereof |
| CN106188419A (en) * | 2016-07-25 | 2016-12-07 | 东南大学 | Graft polymers and the preparation method of antibacterial soft lens based on surface grafting |
| CN109161885A (en) * | 2017-11-14 | 2019-01-08 | 西南交通大学 | A kind of antibacterial functionalized method of modifying of aluminum alloy surface |
| CN108793772A (en) * | 2018-04-25 | 2018-11-13 | 成都思博特科技有限公司 | A kind of preparation method of anti-fog bacteriostatic coating |
| CN108996916B (en) * | 2018-09-05 | 2021-06-08 | 成都中建材光电材料有限公司 | Method for coating inner wall of quartz tube |
| CN108996916A (en) * | 2018-09-05 | 2018-12-14 | 成都中建材光电材料有限公司 | A kind of method of quartz inside pipe wall plated film |
| CN114042482A (en) * | 2021-03-04 | 2022-02-15 | 杭州安誉科技有限公司 | Low-adsorption antibacterial centrifuge tube and application thereof |
| CN114042482B (en) * | 2021-03-04 | 2022-07-08 | 杭州安誉科技有限公司 | Low-adsorption antibacterial centrifuge tube and application thereof |
| CN114200659A (en) * | 2021-09-26 | 2022-03-18 | 吉林大学 | Hydrophilic antibacterial glass slide with bionic structure and preparation method thereof |
| CN114196053A (en) * | 2021-12-14 | 2022-03-18 | 赛宁(苏州)生物科技有限公司 | Surface modification method of plastic centrifuge tube for extracting biological sample |
| CN114196053B (en) * | 2021-12-14 | 2023-02-10 | 赛宁(苏州)生物科技有限公司 | Surface modification method of plastic centrifuge tube for extracting biological sample |
| CN115028374A (en) * | 2022-04-28 | 2022-09-09 | 华北制药股份有限公司玻璃分公司 | Antibacterial glass and preparation method thereof |
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