CN1792633A - Antibiosis layered board and preparation method thereof - Google Patents
Antibiosis layered board and preparation method thereof Download PDFInfo
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- CN1792633A CN1792633A CN 200510030990 CN200510030990A CN1792633A CN 1792633 A CN1792633 A CN 1792633A CN 200510030990 CN200510030990 CN 200510030990 CN 200510030990 A CN200510030990 A CN 200510030990A CN 1792633 A CN1792633 A CN 1792633A
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Abstract
An antibacterial composite plate used in electronic and computer areas is composed of a basic layer made of water-hardening cementing material, a transition layer made of polymer and concrete, and a surface layer made of high-molecular material and the antibacterial agent prepared from inorganic, organic and high-molecular antibacterial agents, diluent or coupling agent, block copolymer and super-disperser. It has high antistatic, fire-proof, mechanical and anticorrosion performance.
Description
Technical field
The present invention relates to a kind of composite sheet structure and preparation method thereof, composite sheet structure that particularly a kind of polymer material layer with corrosion-resistant, difficult combustion, anti-microbial property and inorganic material layer are compound and preparation method thereof.
Background technology
Along with rapid economy development, at present, the modern consumption theory of health forms gradually.Antibacterial product by universally acknowledged be cross-centennial environmental protection and health-oriented products, China anti-biotic material goods market presents situation in great demand, especially the sheet material that has corrosion resistant, difficult combustion, anti-microbial property is obtaining application widely aspect household electrical appliances, weaving, commodity, the building materials.
In the prior art, publication number is in the Chinese invention patent " a kind of antibiotic PLASTIC LAMINATED and manufacture method thereof " of CN1454776, providing a kind of is the fireprotection layer of base material to contain by resin impregnating paper, PLASTIC LAMINATED and manufacture method thereof at the surperficial bonding antibiotic layer of this base material, its antibiotic layer is to adhere to the bactericide silver ion, the melamine resin dipping decorative paper of zinc ion is a base material, by the nano-grade hydroxy apatite carrier, generate network structure integral body with the melamine resin reaction, thereby realization antibacterial action, but because its bactericide is to be attached to the melamine resin surface, therefore, in washability, aspects such as service life exist deficiency.
Publication number is in the Chinese invention patent " corrosion resistant clad plate with flame resisting construction and preparation method thereof " of CN 1654202, adopted first cast thermosetting resin to decorate overlay, reproduce the forming technique technology that pouring concrete strengthens basic unit and then makes composite sheet structure, sheet material has excellent performances such as corrosion-resistant, difficult combustion, but do not possess anti-microbial property, therefore, its range of application has been subjected to certain restriction.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, provide a kind of and not only have corrosion-resistant, flame retardant property, and the good composite plate of anti-microbial property and preparation method thereof.
Realize that the object of the invention technical scheme is: a kind of antibiosis layered board, it is basic unit with the hydraulic cementing materials, by the polymer concrete transition zone, be composited with the macromolecular material overlay, it is characterized in that: in the described macromolecular material overlay, contain 1～50 part of antiseptic, its main component is the inorganic antiseptic silver zeolite, active carbon of silver, silver silica gel, the silver bead, silver hydroxy-apatite based antimicrobials, the phosphoric acid titanium salt, nano-oxide, or organic compound antiseptic quaternary ammonium salt, the phenolic ether class, phenol, biguanides, the isothiazole class, pyroles, the organic metal class, imidazoles, pyridines, thiazoles, or polymer antibacterial agent shitosan class, poly-interior ureide derivative, the polypyridine class, polythiazole class and combination thereof.
A kind of preparation method of antibiosis layered board, it comprises the steps: that (1) adds filler, reinforcing material, toughening material, fire retardant in thermosetting resin, again through the curing system curing molding, makes the macromolecular material overlay; By weight, the ratio of each component is: 100 parts of resins, 10～250 parts of fillers, 0～100 part of reinforcing material, 0～100 part of toughening material, 10～200 parts of fire retardants, 1～50 part of curing agent; (2) be mixed and made into polymer concrete with thermosetting resin, hydraulic cementing materials, filler, solidify, on the macromolecular material overlay, form the polymer concrete transition zone through curing system; By weight, the ratio of each component is: 100 parts of thermosetting resins, 0～500 part of hydraulic cementing materials, 50～500 parts of fillers, 1～50 part of curing system; (3) it is cast-in-place on transition zone that hydraulic cementing materials, fine aggregate, coarse aggregate and reinforcing material mix the back, after maintenance, is made into composite sheet structure; By weight, the ratio of each component is: 100 parts of hydraulic cementing materials, 50～300 parts of fine aggregates, 50～500 parts of coarse aggregates, 0～70 part of reinforcing material; It is characterized in that: in described macromolecular material overlay preparation process, 1～50 part of inorganic antiseptic or organic compound antiseptic or polymer antibacterial agent and their combination have also been added in the thermosetting resin, wherein, inorganic antiseptic, polymer antibacterial agent carry out surface preparation earlier, and the method for described surface preparation is: itself and diluent, coupling agent or block copolymer or hyper-dispersant are at room temperature fully mixed to pulpous state or paste; Described coupling agent weight is 0.5～10% of antiseptic, and hyper-dispersant or block copolymer account for 1～20% of antiseptic weight.
Described coupling agent comprises organo-silicon coupling agent, titanate coupling agent, Organic Chromium coupling agent, aluminate coupling agent, boric acid ester coupler, zirconium ester coupling agent and combination thereof; Described diluent comprises substituted benzene, acetone, benzinum, atoleine, solvent naphtha.
In technical scheme of the present invention, adopt coupling agent, block copolymer or hyper-dispersant that inorganic antiseptic, polymer antibacterial agent are carried out preliminary treatment, be because these auxiliary agents have parents' characteristic, they make inorganic antiseptic, polymer antibacterial agent can with the organic resin good binding, reduce the agglomeration between trickle inorganic powder, it is uniformly dispersed, reaches the few high purpose of efficient of consumption.
Compared with prior art, the present invention has following advantage:
1, the present invention is base material with the hydraulic cementing materials, macromolecular material is an overlay, and in overlay, added antiseptic, make antimicrobial component can in time pass through the microbial reproduction of contact sterilization or inhibition material surface, and then reach long-term health, purpose of safety, have characteristics such as antibacterial effect is permanent, wash resistant, economy, convenience.
2, the antiseptic that uses in the composite sheet structure that the present invention relates to makes antiseptic be scattered in macromolecular material more equably through coupling agent preliminary treatment or the diffusing processing of oversubscription, and the antibiotic property effect obviously improves, and is better than existing similar sheet material.
3, the preparation technology of a kind of composite sheet structure with corrosion-resistant, difficult combustion, anti-microbial property provided by the present invention is feasible, easy to operate, no special equipment requirement, and production process is polluted less, will produce good society and economic benefit after applying.
Description of drawings
Fig. 1 is the structural representation of the described a kind of antibiosis layered board of the embodiment of the invention;
Fig. 2 is the blank test that is used for antibacterial tests, the long bacterium phenomenon photo of the water that carries disease germs (no composite plate);
Fig. 3 is the long bacterium phenomenon photo of composite plate when antibacterial tests that does not add antiseptic;
Fig. 4 is that antibiosis layered board by technical solution of the present invention preparation is at antibacterial tests duration bacterium phenomenon photo;
Wherein, [1] is the hydraulic cementing materials base material; [2] be the polymer concrete transition zone; [3] be the macromolecular material overlay.
The specific embodiment
Embodiment one:
Present embodiment selects for use silver oxide as antiseptic, earlier the antiseptic silver oxide is carried out the coupling agent preliminary treatment, with itself and diluent benzinum, organo-silicon coupling agent KH560, be mixed to paste, organo-silicon coupling agent KH560 accounts for 1% of silver oxide weight, under the room temperature condition, in ball mill, pulverized 30 minutes, it is mixed.
Referring to accompanying drawing 1, preparing a kind of is basic unit with the hydraulic cementing materials, polymer concrete is a transition zone, macromolecular material is the antibiosis layered board of overlay, its method is: with its part by weight of hybrid resin of phenolic resins and epoxy resin is 1: 1,400 order talcum powder, carbon black, ammonium polyphosphate flame retardant, glass fibre, the fire retardant HBCD, the antiseptic silver oxide was by 100: 120: 1: 30: 1: 10: 3 weight are mixed and are stirred, add the curing agent diethylenetriamine then, it is 15% that its consumption accounts for the weight resin ratio, after pouring in the mould at room temperature spontaneous curing 20～40min after stirring into, under 90 ℃ of temperature, solidify 100min again, be prepared into macromolecular material overlay [3], thickness is 3mm.
Above-mentioned hybrid resin and diethylenetriamine and No. 425 portland cements are mixed with 1: 4 weight proportion make transition zone, wherein curing agent and hybrid resin ratio are the same, evenly be covered on the overlay, the about 2mm of thickness, place 10min down at 100 ℃, be prepared into polymer concrete transition zone [2].
With portland cement, coarse aggregate, fine aggregate, water by 1: 2: 4: 0.5 part by weight evenly mixes, and is cast-in-place on transition zone, place 12h under the room temperature after, steam curing 4～5h, being prepared into hydraulic cementing materials basic unit [1] thickness is 30mm.
Take out sheet material from mould, placed under room temperature 2～3 days, making a kind of is base material with the hydraulic cementing materials, and polymer concrete is a transition zone, and macromolecular material is the composite sheet structure of corrosion-resistant, the difficult combustion of having of overlay, anti-microbial property.
Embodiment two:
Present embodiment selects for use silver orthophosphate as antiseptic, earlier the antiseptic silver orthophosphate is carried out the oversubscription preliminary treatment of loosing, with itself and diluent acetone, hyper-dispersant, be mixed to paste, hyper-dispersant accounts for 1.5% of silver oxide weight, under the room temperature condition, in ball mill, pulverized 60 minutes, it is mixed.
Referring to accompanying drawing 1; preparing a kind of is basic unit with the hydraulic cementing materials; polymer concrete is a transition zone; macromolecular material is the antibiosis layered board of overlay; its method is: with unsaturated-resin and epoxy resin hybrid resin; its part by weight is 1: 1; 500 order kaolin; iron oxide yellow; ammonium polyphosphate flame retardant; polypropylene fibre; flame retardant brominated epoxy resin; the antiseptic silver orthophosphate was by 100: 100: 1: 40: 1: 20: 3 part by weight stir after mixing; adding curing system then is triethylamine; peroxide MEK and cobalt naphthenate; its part by weight is 1: 1: 1; it is 15% that its consumption accounts for the weight resin ratio; pour into after stirring in the mould behind 20 ℃ of following spontaneous curing 20～40min; under 70 ℃ of temperature, solidify 40min; be prepared into macromolecular material clad can protective layer [3], thickness is 3mm.
Above-mentioned thermosetting resin and curing system triethylamine, peroxide MEK and cobalt naphthenate and above-mentioned weight concrete ratio mixed with 1: 3 proportioning make transition zone, wherein triethylamine, peroxide MEK and cobalt naphthenate part by weight are 1: 1: 1, concrete component and ratio are the same, evenly be covered in the about 2mm of thickness on the overlay, under 70 ℃ of temperature, place 10min, be prepared into polymer concrete transition zone [2].
With portland cement, coarse aggregate, fine aggregate, water by 1: 2: 4: 0.5 part by weight evenly mixes, and is cast-in-place on intermediate layer, 20 ℃ down place 12h after, boiling water maintenance 4～5h, being prepared into hydraulic cementing materials basic unit [1] thickness is 30mm.
Take out sheet material from mould, placed 2～3 days down in 20 ℃, making a kind of is base material with the hydraulic cementing materials, and polymer concrete is a transition zone, and macromolecular material is the composite sheet structure of corrosion-resistant, the difficult combustion of having of overlay, anti-microbial property.
Embodiment three:
Present embodiment selects for use silver zeolite as antiseptic, earlier the antiseptic silver zeolite is carried out the diffusing preliminary treatment of oversubscription, and silver zeolite and toluene, hyper-dispersant are mixed to paste, and hyper-dispersant accounts for 2% of silver zeolite weight, under the room temperature condition, pulverizes 60 minutes in ball mill.
Referring to accompanying drawing 1; preparing a kind of is basic unit with the hydraulic cementing materials; polymer concrete is a transition zone; macromolecular material is the antibiosis layered board of overlay; its method is: with the hybrid resin of phenolic resins and unsaturated-resin; its part by weight is 1: 1; 400 order calcium carbonate; chrome yellow; fire retardant magnesium hydroxide; the polybutadiene dihydroxylic alcohols; the fire retardant chlorinated paraffin-70; the antiseptic silver zeolite was by 100: 120: 1: 30: 5: 15: 3 part by weight stir after mixing; add dimethylaniline and benzoyl peroxide then; its part by weight is 1: 1; its consumption accounts for weight resin ratio 10%; pour into after stirring in the mould behind 20 ℃ of following spontaneous curing 20～40min; under 100 ℃ of temperature, solidify 40min; be prepared into macromolecular material clad can protective layer [3], thickness is 3mm.
Above-mentioned thermosetting resin, dimethylaniline, benzoyl peroxide and above-mentioned concrete mixed with 1: 1 weight proportion make transition zone, wherein dimethylaniline and benzoyl peroxide part by weight are 1: 1, its weight quota accounts for 10% of hybrid resin, concrete component is the same, evenly be covered in the about 2mm of thickness on the overlay, under 100 ℃ of temperature, place 10min, be prepared into polymer concrete transition zone [2].
With aluminate cement, coarse aggregate, fine aggregate, water by 1: 2: 4: 0.5 part by weight evenly mixes, and is cast-in-place on transition zone, 20 ℃ down place 12h after, steam curing 4～5h is prepared into polymer concrete transition zone [1].Thickness is 30mm.
Take out sheet material from mould, placed 2～3 days down in 20 ℃, making a kind of is base material with the hydraulic cementing materials, and polymer concrete is a transition zone, and macromolecular material is the composite sheet structure of corrosion-resistant, the difficult combustion of having of overlay, anti-microbial property.
The antibiosis layered board that the technical scheme that is provided by the foregoing description one, two, three prepares has good antibacterial performance.Referring to accompanying drawing 2,3 and 4, Fig. 2 is the blank test that is used for antibacterial tests, the long bacterium phenomenon photo of the water that carries disease germs (no composite plate); Fig. 3 is the long bacterium phenomenon photo of composite plate when antibacterial tests that does not add antiseptic; Fig. 4 is by the antibiosis layered board of the technical solution of the present invention preparation long bacterium phenomenon photo when the antibacterial tests.Antibacterial tests is according to the GB15979-2002 standard, and as seen from Figure 2, the water that carries disease germs demonstrates long bacterium phenomenon through containing under the agar of nutrient solution after cultivating 24 hours under 37 ℃; As seen from Figure 3, the composite plate that does not add antiseptic demonstrates long bacterium phenomenon through testing under above-mentioned identical condition; As seen from Figure 4, under above-mentioned identical condition, test, do not demonstrate long bacterium phenomenon on the composite plate by the antibiosis layered board of technical solution of the present invention preparation.
Table 1 is the antibiosis layered board specimen 1 by the embodiment of the invention one, two and three technical scheme preparation
#, 2
#With 3
#The test result of corrosion-resistant, fire-retardant, the anti-microbial property that has.As shown in Table 1, antibiosis layered board is except that can be antibiotic, also have excellent corrosion-resistant, fire resistance, therefore, this composite sheet structure has very high cost performance, can be widely used in field such as chemistry, chemical industry, pharmacy and other to analysis and test place corrosion-resistant, fire-retardant, antibiotic, ornamental and that mechanical property requirements is high, and demanding kitchen guarding's occasions such as water-fast, resistance tocrocking, ornamental and scrubbing resistance.
Table 1:
| Performance | Medium or method | 1 # | 2 # | 3 # |
| Corrosion-resistant | Hydrochloric acid (37wt%, 40 ℃) | 0.8570％ | 0.8650％ | 0.8630％ |
| Sulfuric acid (75wt%, 70 ℃) | 0.8210％ | 0.8010％ | 0.8340％ | |
| NaOH (40wt%, 70 ℃) | 0.7321％ | 0.7541％ | 0.7611％ | |
| Methyl alcohol (40 ℃) | 0.0098％ | 0.013％ | 0.0092％ | |
| Toluene (70 ℃) | 0.0419％ | 0.0435％ | 0.0400％ | |
| Method of testing is pressed GB11547-1989 | ||||
| Fire-retardant | Vertical combustion/GB4609-84 | The FV-0 level | The FV-0 level | The FV-0 level |
| Oxygen index (OI)/ASTM-D2863 | 32 | 32.5 | 32.5 | |
| Antibiotic | Adopt the running water that carries disease germs with reference to GB15979-2002 bacterium source | Not long bacterium | Not long bacterium | Not long bacterium |
Claims (4)
1, a kind of antibiosis layered board, it is basic unit with the hydraulic cementing materials, by the polymer concrete transition zone, be composited with the macromolecular material overlay, it is characterized in that: in the described macromolecular material overlay, contain 1～50 part of antiseptic, its main component is the inorganic antiseptic silver zeolite, active carbon of silver, silver silica gel, the silver bead, silver hydroxy-apatite based antimicrobials, the phosphoric acid titanium salt, nano-oxide, or organic compound antiseptic quaternary ammonium salt, the phenolic ether class, phenol, biguanides, the isothiazole class, pyroles, the organic metal class, imidazoles, pyridines, thiazoles, or polymer antibacterial agent shitosan class, the polycaprolactam ureas, the polypyridine class, polythiazole class and combination thereof.
2, a kind of preparation method of antibiosis layered board, it comprises the steps: that (1) adds filler, reinforcing material, toughening material, fire retardant in thermosetting resin, again through the curing system curing molding, makes the macromolecular material overlay; By weight, the ratio of each component is: 100 parts of resins, 10～250 parts of fillers, 0～100 part of reinforcing material, 0～100 part of toughening material, 10～200 parts of fire retardants, 1～50 part of curing agent; (2) be mixed and made into polymer concrete with thermosetting resin, hydraulic cementing materials, filler, solidify, on the macromolecular material overlay, form the polymer concrete transition zone through curing system; By weight, the ratio of each component is: 100 parts of thermosetting resins, 0～500 part of hydraulic cementing materials, 50～500 parts of fillers, 1～50 part of curing system; (3) it is cast-in-place on transition zone that hydraulic cementing materials, fine aggregate, coarse aggregate and reinforcing material mix the back, after maintenance, is made into composite sheet structure; By weight, the ratio of each component is: 100 parts of hydraulic cementing materials, 50～300 parts of fine aggregates, 50～500 parts of coarse aggregates, 0～70 part of reinforcing material; It is characterized in that: in described macromolecular material overlay preparation process, 1～50 part of inorganic antiseptic or organic compound antiseptic or polymer antibacterial agent and their combination have also been added in the thermosetting resin, wherein, inorganic antiseptic, polymer antibacterial agent carry out surface preparation earlier, and the method for described surface preparation is: itself and diluent, coupling agent or block copolymer or hyper-dispersant are at room temperature fully mixed to pulpous state or paste; Described coupling agent weight is 0.5～10% of antiseptic, and hyper-dispersant or block copolymer account for 1～20% of antiseptic weight.
3, the preparation method of a kind of antibiosis layered board according to claim 2 is characterized in that: described coupling agent comprises organo-silicon coupling agent, titanate coupling agent, Organic Chromium coupling agent, aluminate coupling agent, boric acid ester coupler, zirconium ester coupling agent and combination thereof.
4, the preparation method of a kind of antibiosis layered board according to claim 2 is characterized in that: described diluent comprises substituted benzene, acetone, benzinum, atoleine, solvent naphtha.
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| CN100439597C (en) * | 2006-11-21 | 2008-12-03 | 朱运彬 | Process for preparing fruit and vegetable fresh-keeping paper made from tourmaline |
| CN102267153A (en) * | 2011-04-28 | 2011-12-07 | 朱奎 | Antimicrobial flame-retardant composite plate |
| CN104890317A (en) * | 2015-06-24 | 2015-09-09 | 浙江天成医药包装有限公司 | Medicinal composite membrane |
| CN109679187A (en) * | 2018-12-24 | 2019-04-26 | 上海大觉包装制品有限公司 | A kind of high-efficiency antimicrobial antistatic degradable environmental protection stone plastic film material and preparation method thereof |
| CN111975899A (en) * | 2020-08-24 | 2020-11-24 | 湖南省春龙竹艺有限公司 | Antibacterial mosquito-repelling bamboo summer sleeping mat and preparation process thereof |
| CN114467973A (en) * | 2022-01-07 | 2022-05-13 | 台山市新建业（药用）五金包装有限公司 | Nano-silver antibacterial material for food-grade and/or medical-grade packaging material and preparation method thereof |
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| JP4387097B2 (en) * | 2002-11-29 | 2009-12-16 | 株式会社シナネンゼオミック | Antibacterial agent for concrete, concrete composition and concrete product |
| CN2647534Y (en) * | 2003-10-10 | 2004-10-13 | 周意人 | Antibiotic board |
| CN1539898A (en) * | 2003-11-03 | 2004-10-27 | 吉林省纳米技术应用工程（集团）股份 | Method of producing Nano Functional agent for protecting stone surface and water proof, soil repellent and antibacterial dimension stone |
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| CN100439597C (en) * | 2006-11-21 | 2008-12-03 | 朱运彬 | Process for preparing fruit and vegetable fresh-keeping paper made from tourmaline |
| CN102267153A (en) * | 2011-04-28 | 2011-12-07 | 朱奎 | Antimicrobial flame-retardant composite plate |
| CN102267153B (en) * | 2011-04-28 | 2013-11-06 | 温州市金誉建设监理有限公司 | Antimicrobial flame-retardant composite plate |
| CN104890317A (en) * | 2015-06-24 | 2015-09-09 | 浙江天成医药包装有限公司 | Medicinal composite membrane |
| CN109679187A (en) * | 2018-12-24 | 2019-04-26 | 上海大觉包装制品有限公司 | A kind of high-efficiency antimicrobial antistatic degradable environmental protection stone plastic film material and preparation method thereof |
| CN111975899A (en) * | 2020-08-24 | 2020-11-24 | 湖南省春龙竹艺有限公司 | Antibacterial mosquito-repelling bamboo summer sleeping mat and preparation process thereof |
| CN111975899B (en) * | 2020-08-24 | 2021-06-15 | 湖南省春龙竹艺有限公司 | Antibacterial mosquito-repelling bamboo summer sleeping mat and preparation process thereof |
| CN114467973A (en) * | 2022-01-07 | 2022-05-13 | 台山市新建业（药用）五金包装有限公司 | Nano-silver antibacterial material for food-grade and/or medical-grade packaging material and preparation method thereof |
| CN114467973B (en) * | 2022-01-07 | 2024-05-14 | 台山市新建业（药用）五金包装有限公司 | Nano silver antibacterial material for food-grade and/or medical-grade packaging materials and preparation method thereof |
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| CN100411867C (en) | 2008-08-20 |
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