CN100334143C - Method for preparing titanium dioxide functional film from poly ethylene glycol terephthalate substrate surface - Google Patents

Method for preparing titanium dioxide functional film from poly ethylene glycol terephthalate substrate surface Download PDF

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Publication number
CN100334143C
CN100334143C CNB2005101109483A CN200510110948A CN100334143C CN 100334143 C CN100334143 C CN 100334143C CN B2005101109483 A CNB2005101109483 A CN B2005101109483A CN 200510110948 A CN200510110948 A CN 200510110948A CN 100334143 C CN100334143 C CN 100334143C
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film
titanium dioxide
polyethylene terephthalate
tio
base material
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CN1775833A (en
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张金龙
鲍兴旺
周立君
燕姗姗
陈锋
田宝柱
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East China University of Science and Technology
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East China University of Science and Technology
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Abstract

The present invention provides a method for preparing nanometer titanium dioxide photocatalysis thin films on a PET base material, which is characterized in that the method comprises the following steps: preparing water-phase nanometer titanium dioxide sol with a crystal phase of octahedrite by aging peroxidized titanic acid sol; adding a film forming auxiliary agent in the sol in order to obtain film coating liquid; finally, preparing a titanium dioxide thin film on the PET base material whose surface is treated in advance by a crystal pulling method. The nanometer titanium dioxide functional thin film prepared by the present invention can be used for practically applying PET materials to aseptic package, antisepsis fabric, antifogging drops and self-cleaning thin films. The thin film preparation method provided by the present invention has the advantages of low cost, simple operation and no environment pollution, and is suitable for industrial production.

Description

The polyethylene terephthalate substrate surface prepares the method for titanium dioxide functional film
Technical field
The invention belongs to technical field of function materials, relate to a kind of method for preparing transparent titanium dioxide function film at polyethylene terephthalate (PET) substrate surface with photocatalytic activity.
Background technology
Polyethylene terephthalate (PET) is owing to have good mechanical performance, electrical insulating property, chemical proofing, fatigue performance and crocking resistance etc., thereby be a kind of range of application material very widely, its purposes no longer is confined to fiber, but further be extended to fields such as all kinds of containers, wrapping material, film, film, engineering plastics, at present, PET is replacing aluminium, glass, pottery, paper, timber, iron and steel and other synthetic materialss more and more.
Along with development of science and technology and growth in the living standard, people more and more pay close attention to the functional performance that material itself is had, PET is as the wide material of range of application, to its surperficial study on the modification, hydrophobic modified to having anti-droplet as from material itself, self-cleaning function and give the focus that its antibacterial is research at present and practical application.
Titanium dioxide (TiO 2) film has good optical property and dielectric properties, as high refractive index, wide transmitted spectrum scope, abrasion resistance is good, chemical stability is good, thereby over nearly 40 years at optics, be subjected to extensive concern in photoelectronics and the person in electronics.What is more important is because TiO 2Be a kind of oxide semiconductor of broad stopband, it can directly utilize sunlight, and the ultraviolet source in the luminescent lamp produces very high photic activity, i.e. photocatalytic activity and photic Superhydrophilic.TiO 2The film light catalysis characteristics can decomposing organic matter, and is antifouling, sterilization, and functions such as deodorizing, and super hydrophilicity makes film surface prevent droplet, self-cleaning function makes TiO 2Film becomes a kind of very practical, and the Multifunction material that is concerned by people.Utilize TiO 2The photocatalytic activity of film and photic Superhydrophilic prepare antibiotic, the existing at home and abroad more patent of automatically cleaning material.As Chinese patent CN 1400185, CN 1493395 provides TiO respectively 2The application of film aspect automatically cleaning and anti-biotic material.But in the method for manufacturing thin film that these patents provided, prepared film must just can obtain having anatase crystal after high temperature (more than 400 ℃) is through calcining, promptly just have photic activity.Therefore in the method for manufacturing thin film that this class patent provides, its base material can only be a glass, and resistant to elevated temperatures inorganic materials such as pottery has limited TiO 2The application of film on thermo-labile base materials such as plastics.Though Chinese patent CN 1467305 provides a kind of magnetron sputtering method TiO at room temperature that utilizes 2The preparation method of film, but there is the equipment complexity in this method, cost height, base material such as need conduct electricity at particular requirement, thereby there is certain difficulty in production, and utilize the prepared TiO of this method 2The thin film crystallization degree is not high, is not suitable for being used as photocatalyst material.
Summary of the invention
In order to utilize the preparation of simple operations method to have photic active transparent TiO at thermo-labile base material pet sheet face 2Film, it is antibiotic that the PET material is given, anti-droplet, functions such as automatically cleaning propose the present invention.
The invention provides a kind ofly under cold condition, prepare transparent TiO at thermo-labile base material pet sheet face 2The method of film is achieved through the following technical solutions:
A kind of polyethylene terephthalate substrate surface prepares the method for titanium dioxide functional film, it is characterized in that, described method comprises the steps:
(1) has the TiO of anatase crystal 2The preparation of colloidal sol:
A, H with 30% 2O 2The unformed white gels shape titanium hydroxide precipitation of dissolving obtains pertitanic acid solution under condition of ice bath, and it is 0.1～0.6M that its thin up is made the volumetric molar concentration of pertitanic acid solution;
B, with the solution of a step gained 80～120 ℃ of following ageings 3～24 hours, obtain the TiO of the controlled anatase crystal of crystallization degree 2Colloidal sol; The ageing temperature is preferably 100 ℃, and digestion time is preferably 6-12 hour;
Used unformed white gels shape titanium hydroxide is precipitated as neutral gel shape precipitation, can add alkali again as presoma behind hydrolysis reaction by alkyl titanate or inorganic titanium salt and transfer pH value to obtain to the neutral precipitation that generates.Selected alkyl titanate is that moieties is C 1-C 6Alkyl titanate, the present invention is preferably titanium ethanolate or isopropyl titanate, and inorganic titanium salt the present invention is preferably titanium sulfate or titanium tetrachloride.Selected accent pH value can be preferably NaOH solution or ammoniacal liquor in the present invention to neutral alkali.Gained white gels shape titanium hydroxide is deposited in uses H 2O 2Before the dissolving, must clean and remove other impurity, as reacted alcohols (alkyl titanate is as presoma), and SO 4 2-, Cl -(inorganic titanium salt is as presoma);
(2) add film coalescence aid in the TiO of step (1) gained 2In the colloidal sol, obtain having the TiO of anatase crystal 2Dissolved glue film liquid:
In order to improve water TiO 2The viscosity of colloidal sol, increasing the film forming properties of colloidal sol, used organic polymer as film coalescence aid is for can increase TiO 2The polymkeric substance of the viscosity of colloidal sol, as polyvinylpyrrolidone (PVP) (K-15, K-30), polyacrylamide (anionic, molecular weight are 400-1000 ten thousand), polyvinyl alcohol (molecular weight is 12-15 ten thousand), Natvosol (molecular weight is about 500,000) etc., the present invention preferentially selects polyvinylpyrrolidone (PVP) for use (K-30), add the film forming auxiliary agent concentration be controlled at the 0.05-1 grams per liter, the preferred 0.2-0.6 grams per liter of the present invention;
(3) surface treatment of PET base material:
At first use deionized water ultrasonic cleaning PET base material, after cleaning with outstanding water-ethanol, anhydrous propanone successively then, place the acetone soln of silane coupling agent to carry out surface treatment PET, take out after 5-30 minute, after dry 5-60 under 100-150 ℃ the air atmosphere minute, be used as and be coated with film base material;
Wherein, used silane coupling agent is γ-aminopropyl series, comprise γ-An Bingjisanyiyangjiguiwan (KH-550 silane coupling agent), N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan (TM-551 silane coupling agent), N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan (TM-552 silane coupling agent), N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane (TM-602 silane coupling agent) etc., the preferred γ-An Bingjisanyiyangjiguiwan of the present invention (KH-550 silane coupling agent);
The volumetric concentration of the acetone soln of above-mentioned silane coupling agent is 0.1%-10%, the preferred 1%-5% of the present invention, the acetone soln of silane coupling agent could be as the surface treatment liquid of PET after need placing for some time, and be 1 day-30 days storage period, the present invention preferred 5 days-10 days;
(4) will place the film liquid of step (2) gained through the PET base material that handled step (3), and form a wet film with crystal pulling method at the PET substrate surface, wherein, putting forward the film speed control is the 2-5 mm/second, and can regulate by the thickness of required film;
(5) will be attached to the wet film drying of PET substrate surface;
Wet film that step (4) obtains is earlier in drying at room temperature, and placing temperature again is that 100-150 ℃ baking oven is dry under air atmosphere, and be 30-120 minute time of drying, promptly gets required titanium dioxide functional film of the present invention.
Beneficial effect
Utilize the titanium deoxid film of the method for the invention preparation that good perviousness is arranged in visible-range, show that this film is transparent.The size of the Titanium particles in the film is the 5-15 nanometer, and by single, the anatase octahedrite phase composite that crystallization degree is good, the gauge control of film is the 80-200 nanometer, thereby utilizes the titanium deoxid film of the method for the invention preparation can show very strong photic activity under uv irradiating.
Description of drawings
Fig. 1 is the TiO with anatase crystal of the present invention under the different ageing 2X-ray diffraction (XRD) figure of colloidal sol gained powder after drying at room temperature.
Fig. 2 scribbles TiO for blank PET material and surface 2The visible light transmissivity figure of the PET material of film.
Fig. 3 scribbles TiO for surface of the present invention 2The photocatalytic activity result of the PET material of film.
Fig. 4 scribbles TiO for surface of the present invention 2The Superhydrophilic result of the PET material of film.
Table 1 and table 2 scribble TiO for surface of the present invention 2The fungicidal activity result of the PET material of film.
Embodiment
Below with specific embodiment the present invention is described, embodiment comprises material preparation embodiment of the present invention and material application test embodiment of the present invention.
Preparation embodiment
TiO with anatase crystal 2The preparation of dissolved glue film liquid
With a certain amount of titanium tetrachloride (TiCl 4) dropwise join in the deionized water, constantly stir and obtain transparent TiOCl 2Solution, the volumetric molar concentration 0.1-1.0M of Ti in the solution is then with this solution ammoniacal liquor (NH 4OH) it is neutral transferring PH, obtains white titanium hydroxide precipitation.Cl is removed in this washing of precipitate for several times -, under condition of ice bath, be dissolved in 30% hydrogen peroxide (H then 2O 2) obtain orange pertitanic acid solution, H 2O 2With the mol ratio of Ti be H 2O 2/ Ti=10-30, the volumetric molar concentration that this solution with water is diluted to Ti is 0.1-0.6M, at 100 ℃ of ageing 3-24 hours, can obtain having the anatase titanium oxide sol of different crystallization degrees then.Get small portion colloidal sol and be scattered in the big furnace pot, it is obtained corresponding powder in drying at room temperature, be used to do X-ray diffraction (XRD) test, characterize the prepared TiO of the present invention 2The crystal formation of colloidal sol.Test result is seen Fig. 1, shows the prepared TiO of the present invention 2Colloidal sol is single anatase crystal.At last, add the film coalescence aid stirring and obtained coating liquid in 30-60 minute in the anatase titanium oxide with different crystallization degrees of gained, adjuvant used is polyvinylpyrrolidone (PVP), and concentration is 0.4g/L.
The transparent TiO of PET substrate surface 2The preparation of film
With deionized water ultrasonic cleaning PET base material, use ethanol then respectively successively, acetone cleans, cleaning finish treat surface drying after, it is that the acetone soln of 1% silane coupling agent carries out surface treatment that PET is placed volumetric concentration, took out after 5-30 minute under 100-150 ℃ air atmosphere dry 5-60 minute, after the cooling with its vertical TiO that inserts with anatase crystal 2In the dissolved glue film liquid, form a wet film with crystal pulling method at the PET substrate surface, pull rate is 2.5 mm/second, at last with wet film 120 ℃ of dryings, promptly getting surface-coated has transparent TiO 2The PET material of film.Tested blank PET base material with the ultra-violet absorption spectrum instrument, surface treated PET material and surface scribble TiO 2The visible light transmissivity of the PET material of film.Test result is seen Fig. 2, shows to scribble TiO 2The PET material of film is almost consistent with blank PET base material in the transmitance at visible light place, and good transparency is arranged.
Experimental example 1
The surface scribbles TiO 2The photocatalytic activity of the PET material of film
Surface of the present invention scribbles TiO 2The photocatalytic activity of the PET material of film characterizes the photocatalytic activity of gained film by photocatalytic degradation rhodamine B solution.Method is that the surface is scribbled TiO 2The PET material of film vertically places 5mgL is housed -1In the silica tube of rhodamine B solution, and it is 25 centimetres apart from light source center.Different samples are all placed under 300 watts the high voltage mercury lamp and rhodamine B solution to be carried out the photocatalytic degradation reaction in illumination 0-180 minute, get part rhodamine B solution at set intervals, measure its absorbancy with Cary100 ultra-violet absorption spectrum instrument then and change, characterize surface of the present invention with this and scribble TiO in the maximum absorption wave strong point 2The photocatalytic activity of the PET material of film.
The surface of preparation embodiment preparation is scribbled TiO 2The PET material of film detects with aforesaid method, and measurement result is seen Fig. 3.Show that the prepared surface of the present invention scribbles TiO 2The photocatalytic activity of the PET material of film can change with the crystallization degree of the prepared anatase sol of the present invention, and the crystallization degree of anatase sol depends on the digestion time of pertitanic acid solution.
Experimental example 2
The surface scribbles TiO 2The Superhydrophilic of the PET material of film
The surface scribbles TiO 2The PET material Superhydrophilic of film adopts the contact angle of measurement water droplet on material to characterize its photic Superhydrophilic.Concrete testing method is as follows: the surface that will prepare embodiment 2 preparations scribbles TiO 2The PET material of film places one or two moon of dark air, and water reaches the 50-70 degree at this lip-deep contact angle, and the black lamp that then material is placed on 125 watts shines different time down, measures the size of water contact angle.The centre wavelength of this black lamp is 365 nanometers, and sample places on the flat board apart from about 25 centimeters of black lamp.It is the JC98A contact angle measurement that contact angle is measured used instrument.Test result is seen Fig. 4, and illumination is after 10 minutes, and water scribbles TiO on the surface 2Contact angle on the PET material of film has dropped to below 5 degree, illustrates that surface of the present invention scribbles TiO 2The PET material of film has good photic Superhydrophilic, can be used as anti-droplet, the automatically cleaning material.
Experimental example 3
The surface scribbles TiO 2The fungicidal activity of the PET material of film
The surface scribbles TiO 2The change that the fungicidal activity of the PET material of film adopts the pad pasting irradiation to calculate illumination front and back thalline quantity characterizes its fungicidal activity.Concrete grammar is as follows: test strain adopts intestinal bacteria 8099 and streptococcus aureus ATCC65388, and its store method and bacterium liquid making method can be with reference to the methods of appendix A in the QB/T2509-2003 standard.With 1 * 10 6It is the sample surfaces of 5 centimetres of 5 cm x that bacterium drop about CFU adds to through sterilising treatment, size, adds a cover the layer of polyethylene film simultaneously on the surface that drips bacterium liquid, and bacterium liquid is fully contacted with product surface.With this sample place ultraviolet light intensity be 1 milliwatt/centimetre 2(365 nanometer) located to shine 45 minutes.After finishing the sterilization normal saline solution of sample surfaces with 10 milliliters washed repeatedly, the bacterium liquid that will wash gained again drips in media surface after through dilution in various degree, cultivates 24 hours for 36 ℃.Simultaneously, at no TiO 2The pet sheet face of film carries out identical contrast experiment.Test result sees Table 1 and table 2, illumination after 45 minutes the killing rate for intestinal bacteria and streptococcus aureus all reach more than 95%, illustrate that surface of the present invention scribbles TiO 2The PET material of film has good fungicidal activity.
Table 1 intestinal bacteria (8099) antibacterial tests result
Numbering 0min viable count (individual) 45min viable count (individual) Sterilizing rate (%)
Contrast PE 2.28×10 5 1.68×10 5 26.3
Base material 2.28×10 5 1.98×10 5 13.2
Base material+photocatalysis membrana 2.28×10 5 7.00×10 3 96.9
Table 2 streptococcus aureus (ATCC6538) antibacterial tests result
Numbering 0min viable count (individual) 45min viable count (individual) Sterilizing rate (%)
Contrast PE 1.54×10 5 5.10×10 5 6.9
Base material+photocatalysis membrana 1.54×10 5 6.00×10 2 99.6

Claims (5)

1, a kind of polyethylene terephthalate substrate surface prepares the method for titanium dioxide functional film, it is characterized in that, described method comprises the steps:
(1) has the TiO of anatase crystal 2The preparation of colloidal sol:
A, H with 30% 2O 2The unformed white gels shape titanium hydroxide precipitation of dissolving obtains pertitanic acid solution under condition of ice bath, and with its thin up, the volumetric molar concentration that makes pertitanic acid solution is 0.1～0.6M;
B, with the solution of a step gained 80～120 ℃ of following ageings 3～24 hours, obtain the TiO of the controlled anatase crystal of crystallization degree 2Colloidal sol;
(2) add film coalescence aid in the TiO of step (1) gained 2In the colloidal sol, obtain having the TiO of anatase crystal 2Dissolved glue film liquid:
The used organic polymer as film coalescence aid is to be selected from a kind of in polyvinylpyrrolidone, polyacrylamide, polyvinyl alcohol, the Natvosol, wherein: polyvinylpyrrolidone is K-15, K-30, polyacrylamide is an anionic, molecular weight is 400～1,000 ten thousand, polyvinyl alcohol is that molecular weight is 12～150,000, and Natvosol is that molecular weight is 500,000;
The concentration of film coalescence aid is 0.05～1 grams per liter;
(3) surface treatment of polyethylene terephthalate base material:
At first use deionized water ultrasonic cleaning polyethylene terephthalate base material, after cleaning with dehydrated alcohol, anhydrous propanone successively then, place the acetone soln of silane coupling agent to carry out surface treatment the polyethylene terephthalate base material, take out after 5～30 minutes, after under 100～150 ℃ the air atmosphere dry 5～60 minutes, be used as and be coated with film base material;
Wherein, used silane coupling agent is γ-aminopropyl series, comprise and be selected from γ-An Bingjisanyiyangjiguiwan, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan, a kind of in N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane;
The volumetric concentration of the acetone soln of above-mentioned silane coupling agent is 0.1%～10%, and the acetone soln of silane coupling agent could be as the surface treatment liquid of polyethylene terephthalate base material after need placing for some time, and be 1～30 day storage period;
(4) will place the film liquid of step (2) gained through the polyethylene terephthalate base material that handled step (3),
Form a wet film with crystal pulling method at the polyethylene terephthalate substrate surface, wherein, putting forward the film speed control is the 2-5 mm/second;
(5) will be attached to the wet film drying of polyethylene terephthalate substrate surface, promptly get required titanium dioxide functional film.
2, polyethylene terephthalate substrate surface as claimed in claim 1 prepares the method for titanium dioxide functional film, it is characterized in that, the ageing temperature among described method steps (1) b is 100 ℃, and digestion time is 6-12 hour.
3, polyethylene terephthalate substrate surface as claimed in claim 1 prepares the method for titanium dioxide functional film, it is characterized in that, film coalescence aid is polyvinylpyrrolidone K-30 in the described method steps (2), and the concentration of film coalescence aid is 0.2～0.6 grams per liter.
4, polyethylene terephthalate substrate surface as claimed in claim 1 prepares the method for titanium dioxide functional film, it is characterized in that, in the described method steps (3), silane coupling agent is a γ-An Bingjisanyiyangjiguiwan, the volumetric concentration of the acetone soln of silane coupling agent is 1%～5%, and be 5～10 days its storage period before as surface treatment liquid.
5, polyethylene terephthalate substrate surface as claimed in claim 1 prepares the method for titanium dioxide functional film, it is characterized in that, described method steps (5) is, the wet film that step (4) obtains is first in drying at room temperature, placing temperature again is that 100～150 ℃ baking oven is dry under air atmosphere, be 30～120 minutes time of drying, promptly gets required titanium dioxide functional film.
CNB2005101109483A 2005-11-30 2005-11-30 Method for preparing titanium dioxide functional film from poly ethylene glycol terephthalate substrate surface Expired - Fee Related CN100334143C (en)

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CN101220231B (en) * 2007-12-26 2010-06-16 华东理工大学 Bi-component titanium dioxide film forming liquid
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