CN1243029A - Organic substrate double-layer film capable of photocatalytically purifying air and sterilizing, and preparation method thereof - Google Patents
Organic substrate double-layer film capable of photocatalytically purifying air and sterilizing, and preparation method thereof Download PDFInfo
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- CN1243029A CN1243029A CN 98103510 CN98103510A CN1243029A CN 1243029 A CN1243029 A CN 1243029A CN 98103510 CN98103510 CN 98103510 CN 98103510 A CN98103510 A CN 98103510A CN 1243029 A CN1243029 A CN 1243029A
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Abstract
The present invention relates to an organic substrate coated with double-film which can be photocatalysed to make air purification and sterilization and its preparation method. This organic substrate double-layer film is characterized by that on an organic substrate an inert oxide coating layer is applied, then a semiconductive photocatalyst coating layer is applied on the inert oxide coating layer, in which the thickness of the inert oxide coating layer is 0.1-100 micrometers, and the thickness of the semiconductive photo catalyst coating layer is 0.1-100 micrometers. Its preparation method includes the following steps: firstly, using rotary film-coating method to prepare inert oxide layer on the organic substrate surface, then also using the rotary film-coating method to prepare semiconductive coating layer on the inert oxide layer to obtain the invented product. Said film can effectively degrade organic dirt on the surface, and does not damage organic substrate.
Description
The invention belongs to the semiconductor light-catalyst technical field, particularly relate to duplicature and method for making thereof at the bottom of the organic group with photo-catalysis function.
In recent years, the research of the photocatalysis performance of semi-conducting material has obtained very big progress, and many semi-conducting materials are found degradation of organic substances, killing bacteria effectively as titanium dioxide, tin ash, tungstic acid, zinc oxide etc.; Semi-conducting material, especially titanium dioxide have obtained many-sided application study as water, gaseous-phase organic pollutant processing material and sterile material.Japan Patent JP 09,301,740 smear on the windshield of the window or the helmet Japan Patent JP09 with titanium deoxid film, 300,515 spread upon building material surface with titanium dioxide with adsorbent, binding agent is used as detergent, deodorant, bactericidal agent etc.Japan Patent JP09,290,165 processing that titanium dioxide is polluted in water as photocatalyst applications are in order to the organochlorine contamination thing in effective removal water.Japan Patent JP 10 43,539 utilizes titanium dioxide to prepare a kind of photochemical catalyst of removing nitrogen oxide.Japan Patent JP 09,294,919 is with semi-conductor nano particles and can launch that photoelectronic substrate is compound has made a kind of photochemical catalyst of removing pernicious gas and micronic dust in the air.Japan Patent JP09,299,937 are used to handle running water and gas with the semi-conductor nano particles appendix on optical fiber.
Smearing semi-conducting material at many material surfaces has carried out many researchs and has been considered to very effective in order to the organic matter in decontamination, deodorizing, sterilization, decomposition water and the gas phase as photochemical catalyst; Yet, surface at organic matter material or organic matter film, because semiconductor light-catalyst has photocatalytic oxidation to the organic matter material, make the surface of organic matter material or organic matter film be degraded or the variable color of going bad, be difficult to carry out so directly smear the work of semi-conducting material on organic matter material or organic matter film surface.
The objective of the invention is in order to overcome the limitation of the semiconductor light-catalyst film of development in the past, make it to be applied to the organic matter material or the effect of decontamination, deodorizing, sterilization, decomposing organic pollutant is played on organic matter film surface, but a kind of photocatalysis is provided, purify air and the organic group of sterilization at the bottom of duplicature and preparation method thereof.This duplicature surperficial organic dirt of can effectively degrading, and to the organic matter of substrate without any destruction.
But the method for making of the duplicature at the bottom of the organic group of PHOTOCATALYTIC AIR-PURIFYING of the present invention and sterilization is characterized in that: smear the indifferent oxide coating in the organic matter substrate, smear the semiconductor light-catalyst coating again on the indifferent oxide coating; Wherein the indifferent oxide coating layer thickness is 0.1～100 micron, and the semiconductor light-catalyst coating layer thickness is 0.1～100 micron.Its structure is as shown in Figure 1: 1 is the organic matter substrate, and 2 is the indifferent oxide film, and 3 is the semiconductor light-catalyst film.
Wherein organic matter matrix material or the substrate of organic matter film are plastics, rubber, fiber or resin and organic coating, seal China ink etc.; Inert oxide material is the material with photochemistry and electrochemistry inertia, and as silica, aluminium oxide etc., its particle diameter is between 10 nanometer to 10 microns; Semiconductor light-catalyst is the material with photocatalytic activity, and as titanium dioxide, tin ash, zinc oxide, tungstic acid etc., its particle diameter is between 1 nanometer to 1 micron.
But the duplicature preparation method at the bottom of the organic group of PHOTOCATALYTIC AIR-PURIFYING of the present invention and sterilization carries out according to following steps:
The preparation of organic matter substrate surface indifferent oxide coating:
In advance indifferent oxide colloidal sol is diluted to 5～20% weight percent concentration, to dilute good indifferent oxide colloidal sol then films at the organic matter substrate surface with spin-coating method, then the film that coats is dried down at 30～70 ℃, repeat repeatedly to reach 0.1～100 micron up to the indifferent oxide coating layer thickness;
Wherein said organic matter substrate is organic matter material or organic matter film, as plastics, rubber, fiber or organic coating, seal China ink etc.; Inert oxide material is the material with photochemistry and electrochemistry inertia, as silica, aluminium oxide etc., its particle diameter is between 10 nanometer to 10 microns, can use commercially available Ludox, alumina sol etc., high concentration Ludox as Haiyang Chemical Plant, Qingdao's production, the Ludox that Nanjing inorganic chemical industry factory produces, the alumina sol that Inst., of Alunite Comprehensive Utilization, Zhejiang Prov. produces.
The preparation of coated semiconductor:
Prepare weight percent concentration in advance and be no more than 8% the semiconductor nano hydrosol, and in autoclave, the semiconductor Nano sol is carried out common crystallization and handle, the binding agent that in colloidal sol, adds net weight 0.4%～6.4% then, scribbled in step 1) with spin-coating method in the organic matter substrate of indifferent oxide coating and be coated with semiconductor film, then the film that coats is dried down at 30～70 ℃, or as above-mentioned step repeat repeatedly, reach 0.1～100 micron up to the semiconductor nano material coating layer thickness; At last the material that coats was toasted 1～8 hour down at 70～300 ℃.Crystallization the photochemical properties of titanium dioxide), the Ludox that adds net weight and be 5%～80% semiconductor net weight in semiconductor nano colloidal sol is as binding agent, film in the organic matter substrate that scribbles the indifferent oxide coating with spin-coating method, then the film that coats is dried down at 30～70 ℃, repeat repeatedly to reach 0.1～100 micron up to the semiconductor nano material coating layer thickness; With the duplicature of material at the bottom of but baking obtained the organic group of PHOTOCATALYTIC AIR-PURIFYING and sterilization in 1～8 hour under 70～300 ℃ that coats, prepared duplicature is transparent film at last.
Wherein said semi-conducting material is the material with photocatalytic activity, as its particle diameters such as titanium dioxide, tin ash, zinc oxide, tungstic acids between 1 nanometer to 1 micron.
The method for making of the semiconductor nano hydrosol can be with reference to " nature " (Nature) periodical, 91,353,737 article " based on the high efficiency solar cell of low expense of the colloidal titania film of dye sensitization ", " physical chemistry magazine " are (J.Phys.Chem.), 92,96,6829 article " optical physics of quantized zinc oxide colloid and photochemistry "; The semiconductor Nano sol is carried out that crystallization handles can be with reference to " investigation of materials magazine " (J.Mater.Res.), 98,13 (4), 844 article " titanium dioxide in liquid phase medium crystallization and crystallization the photochemical properties of titanium dioxide ".
But duplicature can be applicable to some organic matter goods of family and public arena (as household electrical appliance such as smoke exhaust ventilators on the duplicature surface at the bottom of the organic group of PHOTOCATALYTIC AIR-PURIFYING of the present invention and sterilization, furniture such as plastic seat, office appliance, communal facility, and various instruments surface, coating surface etc.) on, because the buffer action of indifferent oxide coating, avoided the photocatalysis of semi-conductor nano particles to the organic matter substrate, solve semiconductor nano photochemical catalyst in the past and can only be applied in a difficult problem under the non-organic matter material occasion, widened semiconductor nano photocatalyst applications scope greatly.
Effect of the present invention:
The present invention selected for use high-grade car coating with the pigment reducing yellow G as the degraded species:
In order to observe the effect of duplicature, the present invention prepares three kinds of multi-form films:
1, in substrate, coats earlier degraded species reducing yellow G film, and then be coated with titanium dioxide membrane-membrane a in the above
2, in substrate, coat earlier degraded species reducing yellow G film, and then prepare double-deck membrane-membrane b in the above
3, in substrate, prepare the duplicature film earlier, and then on film, smear degraded species reducing yellow G-film c
Employed film all shone one day under sunshine in the measure of merit.Test result is as shown in the table:
| Before the illumination | After the illumination | |
| Film a film b film c | Film a film b film c | |
| Reducing yellow G | ○???○???○ | ×???○???× |
Zero: the color no change; *: fade fully.
As can be seen from the above table: the duplicature of the present invention surperficial organic dirt of can effectively degrading, shown in the effect of film c: the dirt that is in behind the illumination certain hour on the duplicature is degraded fully, and to the organic matter of substrate without any destruction, shown in film b: the organic matter that is in the duplicature bottom is not subjected to photocatalytic degradation and destroys.
The present invention is described in detail below in conjunction with drawings and Examples:
Fig. 1-double membrane structure schematic diagram of the present invention
Drawing is described as follows:
1 is the organic matter substrate, and 2 is the indifferent oxide film, and 3 is the semiconductor light-catalyst film.
Embodiment 1:
1, in advance Ludox is diluted to 8% weight percent concentration, films at resin surface with spin-coating method diluting good Ludox, then the film that coats is put into baking oven 70 ℃ of oven dry down, repeating several to thickness by above-mentioned steps is about 40 microns;
2, prepare the nano titania hydrosol of 5% weight percent concentration in advance, and in autoclave, it is carried out crystallization and handle, add net weight then in the colloidal sol and be 1.5% Ludox as binding agent, on the resin base that scribbles silica based coating, be coated with titanium dioxide film with spin-coating method, then with the film that coats 70 ℃ of oven dry down, by above-mentioned steps repeat 4 times to the semiconductor light-catalyst thickness be about 10 microns; At last the material that coats was toasted 4 hours down at 200 ℃.Obtaining at last with the resin is substrate 3, but scribbles the duplicature at the bottom of the organic group of catalytic purification air that the titanium dioxide optical catalyst coating 1 of the silica indifferent oxide film 2 of 40 micron thickness and 10 micron thickness forms and sterilization thereon.
Embodiment 2, Ludox is diluted to 20% weight percent concentration in advance, to dilute good Ludox then films at resin surface with spin-coating method, then the film that coats is put into baking oven 50 ℃ of oven dry down, repeating several to thickness by above-mentioned steps is about 100 microns;
Prepare the nano titania hydrosol of 5% weight concentration in advance, and in autoclave, it is carried out crystallization and handle, in colloidal sol, add net weight and be 1% Ludox as binding agent, on spin-coating method is at the bottom of scribbling the polyester paint-based of silica based coating, be coated with titanium dioxide film, then the film that coats is dried down at 50 ℃, repeating to be coated with semiconductor light-catalyst film to thickness for several times by above-mentioned steps is 20 microns; At last the material that coats was toasted 8 hours down at 70 ℃.Obtaining with polyester coating at last is substrate 3, but scribbles the duplicature at the bottom of the organic group of catalytic purification air that the titanium dioxide optical catalyst coating 1 of the silica indifferent oxide film 2 of 100 micron thickness and 20 micron thickness forms and sterilization on it.
Embodiment 3, Ludox is diluted to 5% weight percent concentration in advance, to dilute good Ludox then films at frosting with spin-coating method, then the film that coats is put into baking oven 30 ℃ of oven dry down, the film that makes by above-mentioned steps is about 0.1 micron;
Prepare the nano titania hydrosol of 1% weight percent concentration in advance, and in autoclave, it is carried out crystallization and handle, in colloidal sol, add net weight and be 0.05% Ludox as binding agent, on the plastic-substrates that scribbles silica based coating, be coated with titanium dioxide film with spin-coating method, then the film that coats is dried down at 30 ℃, repeating to be coated with semiconductor light-catalyst film to thickness for several times by above-mentioned steps is about 0.1 micron; At last the material that coats was toasted 3 hours down at 300 ℃.Obtaining at last with plastics is substrate 3, but scribbles the duplicature at the bottom of the organic group of catalytic purification air that the titanium dioxide optical catalyst coating 1 of the silica indifferent oxide film 2 of 0.1 micron thickness and 0.1 micron thickness forms and sterilization on it.
Embodiment 4, alumina sol is diluted to 8% weight percent concentration in advance, to dilute good alumina sol then films at epoxy resin surface with spin-coating method, then the film that coats is put into baking oven 50 ℃ of down oven dry, by above-mentioned steps repeat 3 times to thickness be about 30 microns;
Prepare the nano titania hydrosol of 8% weight percent concentration in advance, and in autoclave, it is carried out crystallization and handle, in colloidal sol, add net weight then and be 6.4% Ludox as binding agent, in the epoxy resin substrate that scribbles silica based coating, be coated with titanium dioxide film with spin-coating method, then the film that coats is dried down at 30 ℃, repeating to be coated with semiconductor light-catalyst film to thickness for several times by above-mentioned steps is about 100 microns; At last the material that coats was toasted 3 hours down at 250 ℃.Obtaining at last with epoxy resin is substrate 3, but scribbles the duplicature at the bottom of the organic group of catalytic purification air that the titanium dioxide optical catalyst coating 1 of the aluminium dioxide indifferent oxide film 2 of 30 micron thickness and 100 micron thickness forms and sterilization thereon.
Claims (10)
1. but duplicature at the bottom of the organic group of PHOTOCATALYTIC AIR-PURIFYING and sterilization is characterized in that smearing the indifferent oxide coating in the organic matter substrate, smears the semiconductor light-catalyst coating again on the indifferent oxide coating; Wherein the indifferent oxide coating layer thickness is 0.1～100 micron, and the semiconductor light-catalyst coating layer thickness is 0.1～100 micron.
But 2, duplicature at the bottom of the organic group of a kind of PHOTOCATALYTIC AIR-PURIFYING as claimed in claim 1 and sterilization is characterized in that described indifferent oxide coating is silica, aluminum oxide coating layer.
3, as claim 1, but the duplicature at the bottom of the organic group of 2 described a kind of PHOTOCATALYTIC AIR-PURIFYING and sterilization is characterized in that described indifferent oxide particle diameter is between 10 nanometer to 10 microns.
But 4, duplicature at the bottom of the organic group of a kind of PHOTOCATALYTIC AIR-PURIFYING as claimed in claim 1 and sterilization is characterized in that described semiconductor light-catalyst is titanium dioxide, tin ash, zinc oxide, tungstic acid.
But 5, duplicature at the bottom of the organic group of a kind of PHOTOCATALYTIC AIR-PURIFYING as claimed in claim 1 and sterilization is characterized in that at the bottom of the described organic group be organic matter material or organic matter film.
6. but duplicature at the bottom of the organic group of a kind of PHOTOCATALYTIC AIR-PURIFYING as claimed in claim 5 and sterilization is characterized in that described organic matter material or organic matter film are plastics, rubber, fiber, resin or organic coating, Yin Mo.
But 7, the method for making of duplicature at the bottom of a kind of organic group for preparing described PHOTOCATALYTIC AIR-PURIFYING of claim 1 and sterilization is characterized in that carrying out according to following steps:
1) preparation of organic group basal surface indifferent oxide coating:
In advance indifferent oxide colloidal sol is diluted to 5～20% weight percent concentration, to dilute good indifferent oxide colloidal sol then films at the organic matter substrate surface with spin-coating method, then the film that coats is dried down at 30～70 ℃, or repeat repeatedly to reach 0.1～100 micron up to the indifferent oxide coating layer thickness by above-mentioned steps;
2) preparation of coated semiconductor:
Prepare weight percent concentration in advance and be no more than 8% the semiconductor nano hydrosol, and in autoclave, the semiconductor Nano sol is carried out common crystallization and handle, the binding agent that in colloidal sol, adds net weight 0.4%～6.4% then, scribbled in step 1) with spin-coating method in the organic matter substrate of indifferent oxide coating and be coated with semiconductor film, then the film that coats is dried down at 30～70 ℃, or as above-mentioned step repeat repeatedly, reach 0.1～100 micron up to the semiconductor nano material coating layer thickness; At last the material that coats was toasted 1～8 hour down at 70～300 ℃.
But 8, the method for making of duplicature at the bottom of the organic group of a kind of PHOTOCATALYTIC AIR-PURIFYING as claimed in claim 7 and sterilization is characterized in that described indifferent oxide is silica, aluminium oxide.
But 9, the method for making of duplicature at the bottom of the organic group of a kind of PHOTOCATALYTIC AIR-PURIFYING as claimed in claim 7 and sterilization is characterized in that described semi-conducting material is titanium dioxide, tin ash, zinc oxide, tungstic acid.
But 10, the method for making of duplicature at the bottom of the organic group of a kind of PHOTOCATALYTIC AIR-PURIFYING as claimed in claim 7 and sterilization, it is characterized in that described inert oxide material particle diameter between 10 nanometer to 10 microns, the semiconductor light-catalyst particle diameter is between 1 nanometer to 1 micron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98103510A CN1104938C (en) | 1998-07-29 | 1998-07-29 | Organic substrate double-layer film capable of photocatalytically purifying air and sterilizing, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98103510A CN1104938C (en) | 1998-07-29 | 1998-07-29 | Organic substrate double-layer film capable of photocatalytically purifying air and sterilizing, and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1243029A true CN1243029A (en) | 2000-02-02 |
| CN1104938C CN1104938C (en) | 2003-04-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN98103510A Expired - Lifetime CN1104938C (en) | 1998-07-29 | 1998-07-29 | Organic substrate double-layer film capable of photocatalytically purifying air and sterilizing, and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100406124C (en) * | 2006-08-22 | 2008-07-30 | 北京大学 | Planar photocatalytic device and its preparing method |
| CN102458625A (en) * | 2009-05-18 | 2012-05-16 | 迪博因特技术公司 | Coated membranes for enthalpy exchange and other applications |
| CN103007936A (en) * | 2012-12-28 | 2013-04-03 | 青岛信锐德科技有限公司 | Air purifier material, preparation method and use of air purifier material |
| CN106238059A (en) * | 2016-07-13 | 2016-12-21 | 中国科学院化学研究所 | A kind of remove the composite photo-catalyst of arsenic from underwater, preparation method, method for purifying water and system |
| CN107228431A (en) * | 2016-03-23 | 2017-10-03 | 刘胜瑞 | A kind of preparation method of purification factor generator |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4997576A (en) * | 1989-09-25 | 1991-03-05 | Board Of Regents, The University Of Texas System | Materials and methods for photocatalyzing oxidation of organic compounds on water |
-
1998
- 1998-07-29 CN CN98103510A patent/CN1104938C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100406124C (en) * | 2006-08-22 | 2008-07-30 | 北京大学 | Planar photocatalytic device and its preparing method |
| CN102458625A (en) * | 2009-05-18 | 2012-05-16 | 迪博因特技术公司 | Coated membranes for enthalpy exchange and other applications |
| CN103007936A (en) * | 2012-12-28 | 2013-04-03 | 青岛信锐德科技有限公司 | Air purifier material, preparation method and use of air purifier material |
| CN103007936B (en) * | 2012-12-28 | 2014-07-09 | 青岛信锐德科技有限公司 | Air purifier material, preparation method and use of air purifier material |
| CN107228431A (en) * | 2016-03-23 | 2017-10-03 | 刘胜瑞 | A kind of preparation method of purification factor generator |
| CN107228431B (en) * | 2016-03-23 | 2019-12-03 | 刘胜瑞 | A kind of preparation method of purification factor generator |
| CN106238059A (en) * | 2016-07-13 | 2016-12-21 | 中国科学院化学研究所 | A kind of remove the composite photo-catalyst of arsenic from underwater, preparation method, method for purifying water and system |
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| Publication number | Publication date |
|---|---|
| CN1104938C (en) | 2003-04-09 |
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Owner name: CHEMISTRY INSTITUTE, CHINESE ACADEMY OF SCIENCES Free format text: FORMER OWNER: INST. OF PHOTOGRAPHIC CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20030411 |
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Effective date of registration: 20030411 Address after: 100080 No. 2 North First Street, Haidian District, Beijing, Zhongguancun Patentee after: Institute of Chemistry, Chinese Academy of Sciences Address before: 100101 Beijing city Chaoyang District Datun Road No. 3 Patentee before: Photosensitive Chemical Inst., China Academy of Sciences |
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