CN108409996B - In-situ growth and haze control method of film surface hydrogen bond compound particles - Google Patents
In-situ growth and haze control method of film surface hydrogen bond compound particles Download PDFInfo
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- CN108409996B CN108409996B CN201810081965.6A CN201810081965A CN108409996B CN 108409996 B CN108409996 B CN 108409996B CN 201810081965 A CN201810081965 A CN 201810081965A CN 108409996 B CN108409996 B CN 108409996B
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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Abstract
The invention relates to a method for in-situ growth and haze control of hydrogen bond compound particles on the surface of a film, which comprises the steps of pretreating a base film, introducing a hydrogen bond donor on the surface of the base film, then sequentially and alternately depositing a hydrogen bond acceptor and particles with the hydrogen bond donor, or pretreating the base film, introducing the hydrogen bond acceptor on the surface of the base film, then sequentially and alternately depositing the particles with the hydrogen bond donor and the hydrogen bond acceptor, wherein the particles with the hydrogen bond donor are particles with the hydrogen bond donor attached to the surface, which are formed by combining excessive hydrogen bond donors and hydrogen bond acceptors through hydrogen bonding, the particles with the hydrogen bond donor on the surface of the base film grow in situ along with the increase of the alternation times, and the haze control is. The hydrogen bond compound particles which are in hydrogen bond action with the surface of the film are attached to the surface of the finally prepared haze film, the haze is 0-98%, and the light transmittance is 80-93%. The method is simple and convenient, the process is reasonable, and the haze control effect is good.
Description
Technical Field
The invention belongs to the field of film preparation, and relates to an in-situ growth and haze control method for hydrogen bond composite particles on the surface of a film.
Background
Since light rays penetrate through the diffusion layer and pass through the medium with the refractive index different from that of the medium, a plurality of refraction, reflection and scattering phenomena occur to light, and therefore the diffusion film which can correct the light rays into a uniform surface light source to achieve optical diffusion is widely applied to a backlight light source part of a liquid crystal display module at present. It can be applied to the occasions where soft and dazzling light is needed.
The existing diffusion membrane is mainly prepared by a blade coating method, specifically, a polyethylene glycol terephthalate (PET) base membrane is coated and attached with a polymethyl methacrylate (PMMA) blade, and a curing agent is used for curing. Although the method is convenient to operate, the method is difficult to be applied to irregular surfaces, the haze is difficult to regulate, and the method cannot be applied to foldable devices or wearable devices due to the requirement of blade coating on the rigidity of the base material.
The in-situ growth method is a new method for preparing composite materials, which takes a certain material as a substrate, and utilizes a chemical or physical method to graft, polymerize, singly load and deposit on the substrate to combine another functional body, so that the composite materials combine the advantages of the two, and realize the perfect combination of the functional body and the substrate. The method has the following characteristics: (1) the bonding fastness is high, and the crystal is 'crystallized' on a substrate to realize in-situ growth, which is different from common physical bonding; (2) the product performance is excellent, and the problem of poor compatibility between the matrix and the functional body is avoided; (3) the product is multifunctional, and can combine the advantages of both the substrate and the functional body, and improve the defect of single function of the substrate. At present, the in-situ growth method has wide application in the fields of chemical industry, machinery, telecommunication, textile and the like, and is mainly used for manufacturing a hydrophobic interface, enhancing surface raman, performing antibacterial treatment, performing patterned growth and the like.
Therefore, the development of a film haze control method which is suitable for surfaces or substrates with various shapes and sizes and is convenient to control the haze has a great application prospect.
Disclosure of Invention
The invention aims to overcome the problems that the prior art can not be suitable for substrates with various shapes and the control of haze is difficult, and provides an in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film, which is suitable for surfaces or substrates with various shapes and sizes and is convenient to control the haze. According to the invention, through an in-situ growth method, hydrogen bond compound particles can be assembled on the surfaces of various substrates, and the change of haze and transparency can be regulated and controlled by controlling process conditions, so that a good optical diffusion effect is achieved. The invention has no requirements on the strength, shape and size of the substrate, has good application prospect, can be applied to wearable devices, anti-fingerprint films and self-repairing films, and has potential application prospect in the fields of biology, medicine transmission, slow release and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
the in-situ growth and haze control method of the hydrogen bond compound particles on the surface of the membrane comprises the steps of pretreating a base membrane, introducing a hydrogen bond donor on the surface of the base membrane, then sequentially and alternately depositing a hydrogen bond acceptor and particles with the hydrogen bond donor, or pretreating the base membrane, introducing the hydrogen bond acceptor on the surface of the base membrane, then sequentially and alternately depositing the particles with the hydrogen bond donor and the hydrogen bond acceptor, wherein the particles with the hydrogen bond donor are particles with the hydrogen bond donor attached to the surface, which are formed by combining excessive hydrogen bond donors and the hydrogen bond acceptor through hydrogen bonding, the particles with the hydrogen bond donor on the surface of the base membrane grow in situ along with the increase of the alternating times, and the haze control is realized by controlling. If the hydrogen bond donor does not participate in the assembly in the form of particles, although small particles can be formed, the rate of assembly and growth is too slow, resulting in reduced haze and failure to achieve control of haze.
As a preferred technical scheme:
the in-situ growth and haze control method of the hydrogen bond compound particles on the film surface comprises the following specific steps:
(1) pretreating a base film to introduce a hydrogen bond donor on the surface of the base film;
(2) immersing the basement membrane into a hydrogen bond receptor solution for 4-20 min, and then eluting the basement membrane;
(3) immersing the eluted basement membrane into hydrogen bond donor dispersion liquid for 4-20 min, and then eluting the basement membrane;
(4) sequentially and alternately repeating the steps (2) and (3) to obtain the haze film;
the hydrogen bond donor dispersion liquid is provided with hydrogen bond donor particles, and the step of eluting the basement membrane is to immerse the basement membrane into an aqueous solution with the pH value of 1-5 for 1min and repeat the above steps for more than three times; the hydrogen bond donor dispersion liquid, the hydrogen bond acceptor solution and the aqueous solution have the same pH. NMP or ethanol with pH of 1-5 can be selected as the elution solution, but the solvent of the aqueous solution has the best safety, speed and effect of assembly. The elution in the step (2) is mainly used for removing redundant hydrogen bond acceptors, so that the phenomenon that a great amount of direct flocculation is caused when hydrogen bond recombination is carried out with a hydrogen bond donor in the step (3) to cause particle shedding or pollute the solution is avoided. The elution in step (3) is to remove excess hydrogen bond donor to prevent flocculation during the next step of complexing with hydrogen bond acceptor. The more times of the alternating repetition, the higher the haze and the lower the transparency of the obtained haze film, and the number of the alternating repetition can be selected according to actual conditions.
In the method for in-situ growth and haze control of hydrogen bond complex particles on the surface of the film, in the step (1), the base film is a quartz film or a silicon-based film, and the pretreatment is oxidation treatment or plasma treatment.
In the method for in-situ growth and haze control of hydrogen bond composite particles on the surface of the film, in the step (1), the base film is a PET film, a PMMA film, a PVC film or a PC film, and the pretreatment is plasma treatment.
According to the in-situ growth and haze control method of the hydrogen bond compound particles on the surface of the membrane, the oxidation treatment is to immerse the base membrane into the piranha washing solution (a mixed solution of sulfuric acid and hydrogen peroxide in a volume ratio of 7-9: 3) for 30-60 min, and then wash the base membrane to be neutral by using deionized water. The washing function is to remove sulfuric acid and hydrogen peroxide on the surface and some impurities. After washing, if long-term storage is needed, the product can be dried by nitrogen, and can be taken out for use next time conveniently, and if the product is used directly, the product can not be dried.
The method for in-situ growth and haze control of the hydrogen bond complex particles on the surface of the membrane comprises the steps of treating a base membrane with oxygen plasma for 5 minutes, immersing the base membrane into 1mg/mL polydiallyldimethylammonium chloride (PDDA) solution for 20 minutes to obtain surface positive charges, and immersing the base membrane into 1mg/mL polymethacrylic acid (PMAA) solution for 20 minutes, wherein the number average molecular weight of the polydiallyldimethylammonium chloride is 100000-200000, and the number average molecular weight of the polymethacrylic acid is 6500. If long-term storage is needed, the product can be dried by nitrogen, and can be taken out for use next time conveniently, and if the product is used directly, the product can not be dried. The oxidation treatment or the plasma treatment of the invention is to introduce a hydrogen bond donor on the surface of the basement membrane, and the pretreatment mode of introducing a hydrogen bond acceptor on the surface of the basement membrane is to carry out the operation of the step (2) to connect excessive hydrogen bond acceptors to the hydrogen bond donor on the surface of the basement membrane after the oxidation treatment or the plasma treatment introduces the hydrogen bond donor on the surface of the basement membrane so as to achieve the purpose of introducing the hydrogen bond acceptors on the surface of the basement membrane.
According to the in-situ growth and haze control method of the hydrogen bond complex particles on the surface of the film, the hydrogen bond acceptor solution is a polyvinylpyrrolidone (PVPON) solution or a polyethylene oxide (PEO) solution.
According to the in-situ growth and haze control method of the hydrogen bond composite particles on the membrane surface, the solutes of the hydrogen bond donor dispersion liquid are a substance A and a substance B with the molar ratio of 0.1-0.8: 1; the substance A is polyvinylpyrrolidone (PVPON) or polyethylene oxide (PEO); the substance B is polyacrylic acid (PAA) and/or polymethacrylic acid (PMAA). When the molar ratio of the substance A to the substance B in the dispersion is large, the hydrogen bond donor particles in the dispersion are colloid particles with the particle size of 100-200 nanometers, and when the molar ratio of the substance A to the substance B in the dispersion is close to that of the substance B, the hydrogen bond donor particles can be separated out, and even flocculation precipitation can occur.
The in-situ growth and haze control method of the hydrogen bond compound particles on the surface of the film comprises the following steps of (1) controlling the concentration of a polyvinylpyrrolidone (PVPON) solution to be 0.1-1 wt%, controlling the pH value of the solution to be 1-5, and controlling the temperature of the solution to be 10-27 ℃;
the concentration of the polyethylene oxide (PEO) solution is 0.1-1 wt%, the pH of the solution is 1-5, and the temperature of the solution is 10-27 ℃;
the number average molecular weight of the polyvinylpyrrolidone (PVPON) is 10000-100000, the number average molecular weight of the polyethylene oxide (PEO) is 100000-600000, the number average molecular weight of the polyacrylic acid (PAA) is 8000-450000, and the number average molecular weight of the polymethacrylic acid (PMAA) is 4000-6500;
the concentration of the hydrogen bond donor solution is 0.1 wt%, the pH value is 1-5, and the temperature is 10-27 ℃.
The in-situ growth and haze control method of the hydrogen bond complex particles on the surface of the film is characterized in that the haze of the haze film is 0-98%, the haze is scattering transmittance/total transmittance or transmission scattering energy/total transmission energy, the light transmittance of the haze film is 80-93%, the light transmittance is total transmission light energy/incident light energy, the hydrogen bond complex particles which are in hydrogen bond action with the surface of the film are attached to the surface of the haze film, and the particle size of the hydrogen bond complex particles is 10 nm-1 μm. The haze and the light transmittance of the invention are tested according to GB/T2410-2008.
The invention mechanism is as follows:
the invention compounds a hydrogen bond acceptor and a hydrogen bond donor according to a molar ratio of 0.1-0.8: 1, compounds the hydrogen bond acceptor and the hydrogen bond donor to form hydrogen bond compound particles, and then redundant hydrogen bond donors which are not compounded exist in a solution, and the hydrogen bond donor is attached to the hydrogen bond compound particles to obtain the hydrogen bond compound particles with the hydrogen bond donor, firstly, the hydrogen bond donor is introduced on the surface of a membrane, then, excessive hydrogen bond acceptors are introduced to enable the hydrogen bond acceptors to form hydrogen bonds with the hydrogen bond donor, then adding hydrogen bond compound particles with hydrogen bond donors, wherein excessive hydrogen bond acceptors in the previous step react with the hydrogen bond donors on the surfaces of the particles to form hydrogen bonds to complete one-time assembly, and then, sequentially introducing hydrogen bond receptors and hydrogen bond compound particles with hydrogen bond donors, so that the hydrogen bond compound particles are assembled layer by layer, the particles grow in situ along with the assembly alternately, and the haze control is realized by regulating and controlling the process parameters of the assembly process. More particles are introduced in the process of alternating assembly, so that the particles can be continuously combined and grown, and at the moment, the surface of the membrane can be subjected to certain collapse to bury hydrogen bond receptors on the surface of the membrane, so that the membrane cannot be continuously assembled. Since the particle diameter of the film surface is equal to the wavelength of the irradiated light, the refraction phenomenon of the irradiated light at the film surface is the most severe, that is, the haze is the greatest. Therefore, the particle size of the film surface can be adjusted according to practical application to achieve the purpose of light transmission selection, for example, when the particle size of the film surface is 10-400 nm, the film has high haze in an ultraviolet band, high refractive index and low ultraviolet transmittance, and can be used as an ultraviolet protection material. Similarly, when the particle size of the particles on the surface of the film is 760nm, the film has high haze in an infrared band, high refractive index and low infrared transmittance, and can be used for heat insulation.
The main means for regulating and controlling the haze of the film comprises the molar ratio of a substance A to a substance B in the hydrogen bond donor dispersion liquid, and the temperature, pH, concentration and alternate repetition times of the hydrogen bond donor dispersion liquid/hydrogen bond acceptor solution. Wherein the particle size of the film surface particles increases and the haze increases with increasing molar ratio of substance A and substance B, 0.2:1 being the molar ratio at which the haze is maximum for the PVPON/PAA system. The higher the solution/dispersion temperature, the more chain movement during particle assembly, the lower entanglement, and the lower the particle size and number of particles on the film surface, and thus the lower haze. With the increase of the pH value of the solution/dispersion, the ionization phenomenon of PAA or PMAA groups in the liquid is increased, the assembling effect is deteriorated due to the reduction of hydrogen bonding sites, the particle size of the particles on the surface of the film is reduced, and the haze is reduced. When the pH of the liquid is about 2.0, the carboxyl ionization of PAA or PMAA can be effectively inhibited, so that the haze can be regulated, when the pH is lower than 1.0, the particle size of the particles introduced once is large, the haze is not convenient to regulate, and when the pH is higher than 5.0, the particle size is too small, the hydrogen bond interaction is weak, and the assembly is difficult. As the solution/dispersion concentration increases, the particle assembly rate increases, the particle diameter of the particles on the film surface increases, and the haze increases. As the number of times of particle assembly on the film surface increases, the particle diameter increases, the number increases, and the haze increases.
Has the advantages that:
(1) the in-situ growth and haze control method of the hydrogen bond composite particles on the surface of the film is simple to operate, can be applied to various substrates and surfaces with different shapes, can be applied to wearable devices, and can obtain the needed haze by controlling the particle size through in-situ growth;
(2) the in-situ growth and haze control method for the hydrogen bond compound particles on the surface of the film can effectively realize the regulation and control of the haze of the film by controlling the in-situ growth of the hydrogen bond compound particles on the surface of the film, and the haze of the film prepared by the method is 0-98%, so that the regulation and control effect is good;
(2) the method for in-situ growth and haze control of the hydrogen bond compound particles on the surface of the film is simple and convenient, has reasonable process and has wide application prospect.
Drawings
FIG. 1 is a photograph under a metallographic microscope of a haze film prepared in example 3 of the present invention;
FIG. 2 is a photograph under a metallographic microscope of a film of the product obtained in comparative example 1.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film comprises the following steps:
(1) pre-treating;
and (2) immersing the quartz membrane into the piranha washing liquid for 45min, and washing the quartz membrane to be neutral by using deionized water, wherein the thickness of the quartz membrane is 1mm, the haze is 0%, the light transmittance is 93%, and the piranha washing liquid is a mixed solution of sulfuric acid and hydrogen peroxide in a volume ratio of 8: 3.
(2) Immersing the membrane obtained in the step (1) into a polyvinylpyrrolidone solution for 4min, and then immersing the membrane into a water solution with the pH value of 1 for three times; wherein the concentration of polyvinylpyrrolidone solution is 0.1 wt%, the pH of the solution is 1, the temperature of the solution is 10 deg.C, the number average molecular weight of polyvinylpyrrolidone is 100000, and the time for soaking in water solution is 1 min.
(3) Immersing the membrane obtained in the step (2) into a hydrogen bond donor dispersion liquid for 20min, and then immersing the membrane into an aqueous solution with the pH value of 1 for three times; the hydrogen bond donor dispersion liquid is a mixed liquid of a polyvinylpyrrolidone solution and a polyacrylic acid solution, the molar ratio of hydrogen bond acceptor polyvinylpyrrolidone to hydrogen bond donor polyacrylic acid in the mixed liquid is 0.1:1, particles with hydrogen bond donor are dispersed in the mixed liquid, the particles with hydrogen bond donor are particles with hydrogen bond donor attached to the surface, the excessive hydrogen bond donor and hydrogen bond acceptor are combined through hydrogen bond action, the concentration of the polyvinylpyrrolidone solution is 0.55 wt%, the pH of the solution is 1, the temperature of the solution is 10 ℃, the concentration of the polyacrylic acid solution is 0.1 wt%, the pH is 1, the temperature is 10 ℃, the number average molecular weight of polyvinylpyrrolidone is 100000, and the number average molecular weight of polyacrylic acid is 8000.
(4) Sequentially and alternately repeating the steps (2) and (3) for 20 times to obtain the haze film;
the finally prepared haze film has the thickness of 10-15 mu m, and the haze is 80-82% and the light transmittance is 87-89% according to the test of GB/T2410-2008. The surface of the film is adhered with hydrogen bond compound particles which have hydrogen bond action with the surface of the film, and the particle size of the hydrogen bond compound particles is 100-400 nm.
Example 2
The in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film comprises the following steps:
(1) pre-treating;
and immersing the quartz membrane into the piranha washing liquid for 60min, and washing the quartz membrane to be neutral by using deionized water, wherein the thickness of the quartz membrane is 1mm, the haze is 5%, the light transmittance is 93%, and the piranha washing liquid is a mixed solution of sulfuric acid and hydrogen peroxide in a volume ratio of 9: 3.
(2) Immersing the membrane obtained in the step (1) into a polyoxyethylene solution for 20min, and then immersing the membrane into an aqueous solution with the pH value of 5 for three times; wherein the concentration of the polyoxyethylene solution is 0.5 wt%, the pH of the solution is 5, the temperature of the solution is 27 ℃, the number average molecular weight of the polyoxyethylene is 100000, and the time for each immersion in the aqueous solution is 1 min.
(3) Immersing the membrane obtained in the step (2) into a hydrogen bond donor dispersion liquid for 20min, and then immersing the membrane into an aqueous solution with the pH value of 5 for three times; the hydrogen bond donor dispersion liquid is a mixed liquid of a polyvinylpyrrolidone solution and a polymethacrylic acid solution, the molar ratio of a hydrogen bond acceptor polyvinylpyrrolidone to the hydrogen bond donor polymethacrylic acid in the mixed liquid is 0.8:1, particles with the hydrogen bond donor are dispersed in the mixed liquid, the particles with the hydrogen bond donor are particles with the hydrogen bond donor attached to the surface, the particles are formed by combining excessive hydrogen bond donors and hydrogen bond acceptors through hydrogen bonding, the concentration of the polyvinylpyrrolidone solution is 0.1 wt%, the pH of the solution is 5, the temperature of the solution is 27 ℃, the concentration of the polymethacrylic acid solution is 0.1 wt%, the pH of the solution is 5, the temperature of the solution is 27 ℃, the number average molecular weight of the polyvinylpyrrolidone is 10000, and the number average molecular weight of the polymethacrylic acid is.
(4) Sequentially and alternately repeating the steps (2) and (3) for 25 times to obtain the haze film;
the thickness of the finally prepared haze film is 2-5 microns, the haze is 20-30%, the light transmittance is 89-92%, hydrogen bond compound particles which are in hydrogen bond action with the surface of the film are attached to the surface of the film, the particle size of the hydrogen bond compound particles is 10-50 nm, and the test method of the haze and the light transmittance is the same as that of the embodiment 1.
Example 3
The in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film comprises the following steps:
(1) pre-treating;
and immersing the quartz membrane into the piranha washing liquid for 30min, and washing the quartz membrane to be neutral by using deionized water, wherein the thickness of the quartz membrane is 1mm, the haze is 3%, the light transmittance is 93.5%, and the piranha washing liquid is a mixed solution of sulfuric acid and hydrogen peroxide in a volume ratio of 7: 3.
(2) Immersing the membrane obtained in the step (1) into a polyvinylpyrrolidone solution for 10min, and then immersing the membrane into a water solution with the pH value of 2 for three times; wherein the concentration of the polyvinylpyrrolidone solution is 1 wt%, the pH of the solution is 2, the temperature of the solution is 25 ℃, the number average molecular weight of the polyvinylpyrrolidone is 40000, and the time for soaking in the aqueous solution is 1min each time.
(3) Immersing the membrane obtained in the step (2) into a hydrogen bond donor dispersion liquid for 15min, and then immersing the membrane into a water solution with the pH value of 2 for three times; the hydrogen bond donor dispersion liquid is a mixed liquid of a polyvinylpyrrolidone solution and a polyacrylic acid solution, the molar ratio of hydrogen bond acceptor polyvinylpyrrolidone to hydrogen bond donor polyacrylic acid in the mixed liquid is 0.2:1, particles with hydrogen bond donor are dispersed in the mixed liquid, the particles with hydrogen bond donor are particles with hydrogen bond donor attached to the surface, the excessive hydrogen bond donor and hydrogen bond acceptor are combined through hydrogen bond action, the concentration of the polyvinylpyrrolidone solution is 1 wt%, the pH of the solution is 2, the temperature of the solution is 25 ℃, the concentration of the polyacrylic acid solution is 1 wt%, the pH is 2, the temperature is 25 ℃, the number average molecular weight of polyvinylpyrrolidone is 40000, and the number average molecular weight of polyacrylic acid is 450000.
(4) Sequentially and alternately repeating the steps (2) and (3) for 20 times to obtain the haze film;
the thickness of the finally prepared haze film is 10-15 microns, the haze is 91-92%, the light transmittance is 87-89%, the haze and light transmittance testing method is the same as that of the embodiment 1, hydrogen bond compound particles which are in hydrogen bond action with the surface of the film are attached to the surface of the film, the particle size of the hydrogen bond compound particles is 200-1000 nm, and a photograph under a metallographic microscope is shown in fig. 1.
Comparative example 1
The hydrogen bond recombination in situ growth method for the membrane surface is basically the same as that of the example 3, except that the hydrogen bond donor dispersion liquid is not used in the step (3), but the polyacrylic acid solution is used as that of the example 3.
The thickness of the finally prepared film is 5-10 microns, the haze is 45-50%, the light transmittance is 90-92%, the haze and light transmittance testing method is the same as that of the film in embodiment 1, hydrogen bond compound particles which are in hydrogen bond action with the surface of the film are attached to the surface of the film, the particle size of the hydrogen bond compound particles is 50-100 nm, a photograph under a metallographic microscope is shown in fig. 2, and compared with embodiment 3, it can be found that the in-situ assembly of the particles can be more rapidly carried out due to the existence of the hydrogen bond donor particles in the hydrogen bond donor dispersion liquid in embodiment 3, the haze of the particles can be more easily attached and grown, so that the haze can be more obviously improved in the same assembly times, the haze of the product film is greatly improved, and meanwhile, the loss of the transmittance can be controlled to be about 2%.
Example 4
The in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film comprises the following steps:
(1) pre-treating;
treating the quartz membrane by oxygen plasma for 5 minutes, immersing the quartz membrane into 1mg/mL poly (diallyldimethylammonium chloride) solution for 20 minutes, and then immersing the quartz membrane into 1mg/mL polymethacrylic acid solution for 20 minutes; wherein the number average molecular weight of the poly (diallyldimethylammonium chloride) is 100000, the number average molecular weight of the polymethacrylic acid is 6500, the thickness of the quartz film is 1mm, the haze is 1%, and the light transmittance is 93%.
(2) Immersing the membrane obtained in the step (1) into a polyvinylpyrrolidone solution for 12min, and immersing the membrane into a water solution with the pH value of 3 for three times; wherein the concentration of polyvinylpyrrolidone solution is 0.2 wt%, the pH of the solution is 3, the temperature of the solution is 15 deg.C, the number average molecular weight of polyvinylpyrrolidone is 10000, and the time for soaking in water solution is 1 min.
(3) Immersing the membrane obtained in the step (2) into a hydrogen bond donor dispersion liquid for 8min, and then immersing the membrane into an aqueous solution with the pH value of 3 for three times; the hydrogen bond donor dispersion liquid is a mixed liquid of a polyoxyethylene solution and a polyacrylic acid/polymethacrylic acid mixed solution, the molar ratio of hydrogen bond acceptor polyoxyethylene to hydrogen bond donor polyacrylic acid/polymethacrylic acid in the mixed liquid is 0.45:1, hydrogen bond donor particles are dispersed in the mixed liquid, the hydrogen bond donor particles are particles with hydrogen bond donors attached to the surfaces, the particles are formed by bonding excessive hydrogen bond donors and hydrogen bond acceptors through hydrogen bonding, the concentration of the polyoxyethylene solution is 0.1 wt%, the pH of the solution is 3, the solution temperature is 15 ℃, the polyacrylic acid concentration of the polyacrylic acid/polymethacrylic acid mixed solution (the mass ratio of the polyacrylic acid to the polymethacrylic acid is 1: 1) is 0.1 wt%, the pH is 3, the temperature is 15 ℃, the number average molecular weight of polyoxyethylene is 600000, the number average molecular weight of polyacrylic acid is 450000, and the number average molecular weight of the.
(4) Sequentially and alternately repeating the steps (2) and (3) for 30 times to obtain the haze film;
the thickness of the finally prepared haze film is 5-8 microns, the haze is 40-45%, the light transmittance is 88-90%, hydrogen bond compound particles which are in hydrogen bond action with the surface of the film are attached to the surface of the film, the particle size of the hydrogen bond compound particles is 50-200 nm, and the test method of the haze and the light transmittance is the same as that of the embodiment 1.
Example 5
The in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film comprises the following steps:
(1) pre-treating;
treating the quartz membrane by oxygen plasma for 5 minutes, immersing the quartz membrane into 1mg/mL poly (diallyldimethylammonium chloride) solution for 20 minutes, and then immersing the quartz membrane into 1mg/mL polymethacrylic acid solution for 20 minutes; wherein the number average molecular weight of the poly (diallyldimethylammonium chloride) is 200000, the number average molecular weight of the polymethacrylic acid is 6500, the thickness of the quartz film is 1mm, the haze is 4%, and the light transmittance is 92%.
(2) Immersing the membrane obtained in the step (1) into a polyvinylpyrrolidone solution for 16min, and immersing the membrane into a water solution with the pH value of 4 for three times; wherein the concentration of polyvinylpyrrolidone solution is 0.6 wt%, the pH of the solution is 4, the temperature of the solution is 18 deg.C, the number average molecular weight of polyvinylpyrrolidone is 50000, and the time for soaking in the aqueous solution is 1 min.
(3) Immersing the membrane obtained in the step (2) into a hydrogen bond donor dispersion liquid for 10min, and then immersing the membrane into a water solution with the pH value of 4 for three times; the hydrogen bond donor dispersion liquid is a mixed liquid of a polyvinylpyrrolidone solution and a polyacrylic acid solution, the molar ratio of hydrogen bond acceptor polyvinylpyrrolidone to hydrogen bond donor polyacrylic acid in the mixed liquid is 0.6:1, particles with hydrogen bond donor are dispersed in the mixed liquid, the particles with hydrogen bond donor are particles with hydrogen bond donor attached to the surface, the excessive hydrogen bond donor and hydrogen bond acceptor are combined through hydrogen bond action, the concentration of the polyvinylpyrrolidone solution is 0.2 wt%, the pH of the solution is 4, the temperature of the solution is 18 ℃, the concentration of the polyacrylic acid solution is 0.1 wt%, the pH is 4, the temperature is 18 ℃, the number average molecular weight of polyvinylpyrrolidone is 80000, and the number average molecular weight of polyacrylic acid is 400000.
(4) Repeating the steps (2) and (3) for 40 times in turn to obtain the haze film;
the thickness of the finally prepared haze film is 3-6 microns, the haze is 30-40%, the light transmittance is 90-91%, hydrogen bond compound particles which are in hydrogen bond action with the surface of the film are attached to the surface of the film, the particle size of the hydrogen bond compound particles is 80-250 nm, and the test method of the haze and the light transmittance is the same as that of the embodiment 1.
Example 6
The in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film comprises the following steps:
(1) pre-treating;
treating the PET film with oxygen plasma for 5 minutes, immersing the PET film into 1mg/mL poly (diallyldimethylammonium chloride) solution for 20 minutes, and then immersing the PET film into 1mg/mL polymethacrylic acid solution for 20 minutes; wherein the number average molecular weight of the poly (diallyldimethylammonium chloride) is 150000, the number average molecular weight of the polymethacrylic acid is 6500, the thickness of the PET film is 0.1mm, the haze is 2%, and the light transmittance is 95%.
(2) Immersing the membrane obtained in the step (1) into a polyoxyethylene solution for 12min, and then immersing the membrane into an aqueous solution with the pH value of 5 for three times; wherein the concentration of the polyoxyethylene solution is 0.55 wt%, the pH of the solution is 5, the temperature of the solution is 18.5 ℃, the number average molecular weight of the polyoxyethylene is 100000, and the time for each immersion in the aqueous solution is 1 min.
(3) Immersing the membrane obtained in the step (2) into a hydrogen bond donor dispersion liquid for 12min, and then immersing the membrane into an aqueous solution with the pH value of 5 for three times; the hydrogen bond donor dispersion liquid is a mixed liquid of a polyvinylpyrrolidone solution and a polymethacrylic acid solution, the molar ratio of hydrogen bond acceptor polyvinylpyrrolidone to hydrogen bond donor polymethacrylic acid in the mixed liquid is 0.5:1, particles with hydrogen bond donors are dispersed in the mixed liquid, the particles with hydrogen bond donors are particles with the hydrogen bond donors attached to the surfaces, the particles are formed by combining excessive hydrogen bond donors and hydrogen bond acceptors through hydrogen bonding, the concentration of the polyvinylpyrrolidone solution is 0.5 wt%, the pH of the solution is 5, the temperature of the solution is 18.5 ℃, the concentration of the polymethacrylic acid solution is 0.1 wt%, the pH is 5, the temperature is 18.5 ℃, the number average molecular weight of the polyvinylpyrrolidone is 55000, and the number average molecular weight of the polymethacrylic acid is 4000.
(4) Sequentially and alternately repeating the steps (2) and (3) for 10 times to obtain the haze film;
the thickness of the finally prepared haze film is 1-5 microns, the haze is 20-30%, the light transmittance is 90-92%, hydrogen bond compound particles which are in hydrogen bond action with the surface of the film are attached to the surface of the film, the particle size of the hydrogen bond compound particles is 80-200 nm, and the test method of the haze and the light transmittance is the same as that of the embodiment 1.
Example 7
The in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film comprises the following steps:
(1) pre-treating;
treating the PMMA film by using oxygen plasma for 5 minutes, immersing the PMMA film into a 1mg/mL poly (diallyldimethylammonium chloride) solution for 20 minutes, and then immersing the PMMA film into a 1mg/mL polymethacrylic acid solution for 20 minutes; wherein the number average molecular weight of the poly (diallyldimethylammonium chloride) is 120000, the number average molecular weight of the polymethacrylic acid is 6500, the thickness of the PMMA film is 0.1mm, the haze is 2%, and the light transmittance is 93%.
(2) Immersing the membrane obtained in the step (1) into a polyoxyethylene solution for 18min, and then immersing the membrane into an aqueous solution with the pH value of 1 for three times; wherein the concentration of the polyoxyethylene solution was 0.8 wt%, the pH of the solution was 1, the temperature of the solution was 12 ℃, the number average molecular weight of the polyoxyethylene was 350000, and the time per immersion in the aqueous solution was 1 min.
(3) Immersing the membrane obtained in the step (2) into a hydrogen bond donor dispersion liquid for 12min, and then immersing the membrane into an aqueous solution with the pH value of 1 for three times; the hydrogen bond donor dispersion liquid is a mixed liquid of a polyoxyethylene solution and a polyacrylic acid solution, the molar ratio of a hydrogen bond acceptor polyoxyethylene to a hydrogen bond donor polyacrylic acid in the mixed liquid is 0.7:1, hydrogen bond donor particles are dispersed in the mixed liquid, the hydrogen bond donor particles are particles with hydrogen bond donors attached to the surfaces, the hydrogen bond donor particles are formed by bonding excessive hydrogen bond donors and hydrogen bond acceptors through hydrogen bonding, the concentration of the polyoxyethylene solution is 0.4 wt%, the pH of the solution is 1, the temperature of the solution is 12 ℃, the concentration of the polyacrylic acid solution is 0.1 wt%, the pH is 1, the temperature is 12 ℃, the number average molecular weight of polyoxyethylene is 200000, and the number average molecular weight of polyacrylic acid is 50000.
(4) Sequentially and alternately repeating the steps (2) and (3) for 50 times to obtain the haze film;
the thickness of the finally prepared haze film is 8-12 microns, the haze is 40-45%, the light transmittance is 85-88%, hydrogen bond compound particles which are in hydrogen bond action with the surface of the film are attached to the surface of the film, the particle size of the hydrogen bond compound particles is 80-200 nm, and the test method of the haze and the light transmittance is the same as that of the embodiment 1.
Example 8
The in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film comprises the following steps:
(1) pre-treating;
treating the PVC membrane by using oxygen plasma for 5 minutes, immersing the PVC membrane into a 1mg/mL poly (diallyldimethylammonium chloride) solution for 20 minutes, and then immersing the PVC membrane into a 1mg/mL polymethacrylic acid solution for 20 minutes; wherein the number average molecular weight of the poly (diallyldimethylammonium chloride) is 140000, the number average molecular weight of the polymethacrylic acid is 6500, the thickness of the PVC film is 0.1mm, the haze is 8%, and the light transmittance is 83%.
(2) Immersing the membrane obtained in the step (1) into a polyvinylpyrrolidone solution for 5min, and then immersing the membrane into a water solution with the pH value of 4 for three times; wherein the concentration of polyvinylpyrrolidone solution is 0.15 wt%, the pH of the solution is 4, the temperature of the solution is 14 deg.C, the number average molecular weight of polyvinylpyrrolidone is 80000, and the time for soaking in water solution each time is 1 min.
(3) Immersing the membrane obtained in the step (2) into a hydrogen bond donor dispersion liquid for 18min, and then immersing the membrane into a water solution with the pH value of 4 for three times; the hydrogen bond donor dispersion liquid is a mixed liquid of a polyvinylpyrrolidone solution and a polyacrylic acid solution, the molar ratio of hydrogen bond acceptor polyvinylpyrrolidone to hydrogen bond donor polyacrylic acid in the mixed liquid is 0.2:1, particles with hydrogen bond donor are dispersed in the mixed liquid, the particles with hydrogen bond donor are particles with hydrogen bond donor attached to the surface, the particles are formed by combining excessive hydrogen bond donor and hydrogen bond acceptor through hydrogen bond action, the concentration of the polyvinylpyrrolidone solution is 0.24 wt%, the pH of the solution is 4, the temperature of the solution is 14 ℃, the concentration of the polyacrylic acid solution is 0.1 wt%, the pH is 4, the temperature is 14 ℃, the number average molecular weight of polyvinylpyrrolidone is 100000, and the number average molecular weight of polyacrylic acid is 450000.
(4) Sequentially and alternately repeating the steps (2) and (3) for 100 times to obtain the haze film;
the thickness of the finally prepared haze film is 20-30 microns, the haze is 50-60%, the light transmittance is 80-85%, hydrogen bond compound particles which are in hydrogen bond action with the surface of the film are attached to the surface of the film, the particle size of the hydrogen bond compound particles is 100-150 nm, and the test method of the haze and the light transmittance is the same as that of the embodiment 1.
Example 9
The in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film comprises the following steps:
(1) pre-treating;
treating the PC film by using oxygen plasma for 5 minutes, immersing the PC film into a 1mg/mL poly (diallyldimethylammonium chloride) solution for 20 minutes, and then immersing the PC film into a 1mg/mL polymethacrylic acid solution for 20 minutes; wherein the number average molecular weight of the poly (diallyldimethylammonium chloride) is 200000, the number average molecular weight of the polymethacrylic acid is 6500, the thickness of the PC film is 0.1mm, the haze is 3%, and the light transmittance is 88%.
(2) Immersing the membrane obtained in the step (1) into a polyoxyethylene solution for 4min, and then immersing the membrane into an aqueous solution with the pH value of 1 for three times; wherein the concentration of the polyoxyethylene solution is 1 wt%, the pH of the solution is 1, the temperature of the solution is 27 ℃, the number average molecular weight of the polyoxyethylene is 100000, and the time for each immersion in the aqueous solution is 1 min.
(3) Immersing the membrane obtained in the step (2) into a hydrogen bond donor dispersion liquid for 20min, and then immersing the membrane into an aqueous solution with the pH value of 1 for three times; the hydrogen bond donor dispersion liquid is a mixed liquid of a polyvinylpyrrolidone solution and a polymethacrylic acid solution, the molar ratio of a hydrogen bond acceptor polyvinylpyrrolidone to the hydrogen bond donor polymethacrylic acid in the mixed liquid is 0.1:1, particles with the hydrogen bond donor are dispersed in the mixed liquid, the particles with the hydrogen bond donor are particles with the hydrogen bond donor attached to the surface, the particles are formed by combining excessive hydrogen bond donors and hydrogen bond acceptors through hydrogen bonding, the concentration of the polyvinylpyrrolidone solution is 1 wt%, the pH of the solution is 1, the temperature of the solution is 27 ℃, the concentration of the polymethacrylic acid solution is 0.1 wt%, the pH is 1, the temperature is 27 ℃, the number average molecular weight of the polyvinylpyrrolidone is 100000, and the number average molecular weight of the polymethacrylic acid is 5000.
(4) Sequentially and alternately repeating the steps (2) and (3) for 20 times to obtain the haze film;
the thickness of the finally prepared haze film is 10-15 microns, the haze is 87-89%, the light transmittance is 85-87%, hydrogen bond compound particles which are in hydrogen bond action with the surface of the film are attached to the surface of the film, the particle size of the hydrogen bond compound particles is 80-200 nm, and the test method of the haze and the light transmittance is the same as that of the example 1.
Example 10
The in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film comprises the following steps:
(1) pre-treating;
treating the PC film by using oxygen plasma for 5 minutes, immersing the PC film into a 1mg/mL poly (diallyldimethylammonium chloride) solution for 20 minutes, and then immersing the PC film into a 1mg/mL polymethacrylic acid solution for 20 minutes; wherein the number average molecular weight of the poly (diallyldimethylammonium chloride) is 200000, the number average molecular weight of the polymethacrylic acid is 6500, the thickness of the PC film is 0.1mm, the haze is 0%, and the light transmittance is 89%;
then the obtained membrane is immersed in a polyoxyethylene solution for 4min and then is immersed in an aqueous solution with the pH value of 1 for three times; wherein the concentration of the polyoxyethylene solution is 1 wt%, the pH of the solution is 1, the temperature of the solution is 27 ℃, the number average molecular weight of the polyoxyethylene is 100000, and the time for each immersion in the aqueous solution is 1 min.
(2) Immersing the membrane obtained in the step (1) into a hydrogen bond donor dispersion liquid for 20min, and then immersing the membrane into an aqueous solution with the pH value of 1 for three times; the hydrogen bond donor dispersion liquid is a mixed liquid of a polyvinylpyrrolidone solution and a polymethacrylic acid solution, the molar ratio of a hydrogen bond acceptor polyvinylpyrrolidone to the hydrogen bond donor polymethacrylic acid in the mixed liquid is 0.1:1, particles with the hydrogen bond donor are dispersed in the mixed liquid, the particles with the hydrogen bond donor are particles with the hydrogen bond donor attached to the surface, the particles are formed by combining excessive hydrogen bond donors and hydrogen bond acceptors through hydrogen bonding, the concentration of the polyvinylpyrrolidone solution is 1 wt%, the pH of the solution is 1, the temperature of the solution is 27 ℃, the concentration of the polymethacrylic acid solution is 0.1 wt%, the pH is 1, the temperature is 27 ℃, the number average molecular weight of the polyvinylpyrrolidone is 100000, and the number average molecular weight of the polymethacrylic acid is 5000.
(3) Immersing the obtained membrane into a polyoxyethylene solution for 4min, and then immersing the membrane into a water solution with the pH value of 1 for three times; wherein the concentration of the polyoxyethylene solution is 1 wt%, the pH of the solution is 1, the temperature of the solution is 27 ℃, the number average molecular weight of the polyoxyethylene is 100000, and the time for each immersion in the aqueous solution is 1 min.
(4) Sequentially and alternately repeating the steps (2) and (3) for 2 times to obtain the haze film;
the thickness of the finally prepared haze film is 100-150 nm, the haze is 10-15%, the light transmittance is 85-88%, hydrogen bond compound particles which are in hydrogen bond action with the surface of the film are attached to the surface of the film, the particle size of the hydrogen bond compound particles is 10-80 nm, and the testing method of the haze and the light transmittance is the same as that of the embodiment 1.
Example 11
The in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film comprises the following steps:
(1) pre-treating;
treating the silicon-based membrane by using oxygen plasma for 5 minutes, immersing the membrane into 1mg/mL poly (diallyldimethylammonium chloride) solution for 20 minutes, and then immersing the membrane into 1mg/mL polymethacrylic acid solution for 20 minutes; wherein the number average molecular weight of poly (diallyldimethylammonium chloride) is 200000, the number average molecular weight of polymethacrylic acid is 6500, and the thickness of the silicon-based film is 1 mm.
(2) Immersing the membrane obtained in the step (1) into a polyvinylpyrrolidone solution for 16min, and immersing the membrane into a water solution with the pH value of 4 for three times; wherein the concentration of polyvinylpyrrolidone solution is 0.6 wt%, the pH of the solution is 4, the temperature of the solution is 18 deg.C, the number average molecular weight of polyvinylpyrrolidone is 50000, and the time for soaking in the aqueous solution is 1 min.
(3) Immersing the membrane obtained in the step (2) into a hydrogen bond donor dispersion liquid for 10min, and then immersing the membrane into a water solution with the pH value of 4 for three times; the hydrogen bond donor dispersion liquid is a mixed liquid of a polyvinylpyrrolidone solution and a polyacrylic acid solution, the molar ratio of hydrogen bond acceptor polyvinylpyrrolidone to hydrogen bond donor polyacrylic acid in the mixed liquid is 0.6:1, particles with hydrogen bond donor are dispersed in the mixed liquid, the particles with hydrogen bond donor are particles with hydrogen bond donor attached to the surface, the excessive hydrogen bond donor and hydrogen bond acceptor are combined through hydrogen bond action, the concentration of the polyvinylpyrrolidone solution is 0.2 wt%, the pH of the solution is 4, the temperature of the solution is 18 ℃, the concentration of the polyacrylic acid solution is 0.1 wt%, the pH is 4, the temperature is 18 ℃, the number average molecular weight of polyvinylpyrrolidone is 80000, and the number average molecular weight of polyacrylic acid is 400000.
(4) Sequentially and alternately repeating the steps (2) and (3) for 40 times to obtain a particle film;
the thickness of the finally prepared particle film is 3-6 mu m, hydrogen bond compound particles which have hydrogen bond action with the surface of the film are attached to the surface of the particle film, and the particle size of the hydrogen bond compound particles is 80-250 nm.
Example 12
The in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film comprises the following steps:
(1) pre-treating;
and (3) immersing the silicon-based membrane into the piranha washing liquid for 60min, and washing the silicon-based membrane to be neutral by using deionized water, wherein the thickness of the silicon-based membrane is 1mm, and the piranha washing liquid is a mixed solution of sulfuric acid and hydrogen peroxide in a volume ratio of 9: 3.
(2) Immersing the membrane obtained in the step (1) into a polyoxyethylene solution for 20min, and then immersing the membrane into an aqueous solution with the pH value of 5 for three times; wherein the concentration of the polyoxyethylene solution is 0.5 wt%, the pH of the solution is 5, the temperature of the solution is 27 ℃, the number average molecular weight of the polyoxyethylene is 100000, and the time for each immersion in the aqueous solution is 1 min.
(3) Immersing the membrane obtained in the step (2) into a hydrogen bond donor dispersion liquid for 20min, and then immersing the membrane into an aqueous solution with the pH value of 5 for three times; the hydrogen bond donor dispersion liquid is a mixed liquid of a polyvinylpyrrolidone solution and a polymethacrylic acid solution, the molar ratio of a hydrogen bond acceptor polyvinylpyrrolidone to the hydrogen bond donor polymethacrylic acid in the mixed liquid is 0.8:1, particles with the hydrogen bond donor are dispersed in the mixed liquid, the particles with the hydrogen bond donor are particles with the hydrogen bond donor attached to the surface, the particles are formed by combining excessive hydrogen bond donors and hydrogen bond acceptors through hydrogen bonding, the concentration of the polyvinylpyrrolidone solution is 0.1 wt%, the pH of the solution is 5, the temperature of the solution is 27 ℃, the concentration of the polymethacrylic acid solution is 0.1 wt%, the pH of the solution is 5, the temperature of the solution is 27 ℃, the number average molecular weight of the polyvinylpyrrolidone is 10000, and the number average molecular weight of the polymethacrylic acid is.
(4) Sequentially and alternately repeating the steps (2) and (3) for 25 times to obtain the haze film;
the thickness of the finally prepared particle film is 2-5 mu m, hydrogen bond compound particles which have hydrogen bond action with the surface of the film are attached to the surface of the particle film, and the particle size of the hydrogen bond compound particles is 10-50 nm.
Example 13
The in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film comprises the following steps:
(1) pre-treating;
and (2) immersing the quartz membrane into the piranha washing liquid for 45min, and washing the quartz membrane to be neutral by using deionized water, wherein the thickness of the quartz membrane is 1mm, the haze is 0%, the light transmittance is 93%, and the piranha washing liquid is a mixed solution of sulfuric acid and hydrogen peroxide in a volume ratio of 7: 3.
(2) Immersing the membrane obtained in the step (1) into a polyvinylpyrrolidone solution for 10min, and then immersing the membrane into a water solution with the pH value of 2 for three times; wherein the concentration of the polyvinylpyrrolidone solution is 1 wt%, the pH of the solution is 2, the temperature of the solution is 20 ℃, the number average molecular weight of the polyvinylpyrrolidone is 40000, and the time for soaking in the aqueous solution is 1min each time.
(3) Immersing the membrane obtained in the step (2) into a hydrogen bond donor dispersion liquid for 15min, and then immersing the membrane into a water solution with the pH value of 2 for three times; the hydrogen bond donor dispersion liquid is a mixed liquid of a polyvinylpyrrolidone solution and a polyacrylic acid solution, the molar ratio of hydrogen bond acceptor polyvinylpyrrolidone to hydrogen bond donor polyacrylic acid in the mixed liquid is 0.2:1, particles with hydrogen bond donor are dispersed in the mixed liquid, the particles with hydrogen bond donor are particles with hydrogen bond donor attached to the surface, the excessive hydrogen bond donor and hydrogen bond acceptor are combined through hydrogen bond action, the concentration of the polyvinylpyrrolidone solution is 1 wt%, the pH of the solution is 2, the temperature of the solution is 10 ℃, the concentration of the polyacrylic acid solution is 0.1 wt%, the pH is 2, the temperature is 20 ℃, the number average molecular weight of polyvinylpyrrolidone is 40000, and the number average molecular weight of polyacrylic acid is 450000.
(4) Sequentially and alternately repeating the steps (2) and (3) for 80 times to obtain the haze film;
the thickness of the finally prepared haze film is 15-17 mu m, and the haze is 97-98% and the light transmittance is 84-85% according to the test of GB/T2410-2008. The surface of the film is adhered with hydrogen bond compound particles which have hydrogen bond action with the surface of the film, the particle size of the hydrogen bond compound particles is 500-600 nm, and the haze and the light transmittance test method are the same as those in the embodiment 1.
Example 14
The in-situ growth and haze control method of hydrogen bond composite particles on the surface of a film comprises the following steps:
(1) pre-treating;
treating the PET film with oxygen plasma for 5 minutes, immersing the PET film into 1mg/mL poly (diallyldimethylammonium chloride) solution for 20 minutes, and then immersing the PET film into 1mg/mL polymethacrylic acid solution for 20 minutes; wherein the number average molecular weight of the poly (diallyldimethylammonium chloride) is 150000, the number average molecular weight of the polymethacrylic acid is 6500, the thickness of the PET film is 0.1mm, the haze is 2%, and the light transmittance is 95%.
(2) Immersing the membrane obtained in the step (1) into a polyoxyethylene solution for 15min, and then immersing the membrane into an aqueous solution with the pH value of 2 for three times; wherein the concentration of the polyoxyethylene solution is 1 wt%, the pH of the solution is 2, the temperature of the solution is 15 ℃, the number average molecular weight of the polyoxyethylene is 600000, and the time for each immersion in the aqueous solution is 1 min.
(3) Immersing the membrane obtained in the step (2) into a hydrogen bond donor dispersion liquid for 15min, and then immersing the membrane into a water solution with the pH value of 2 for three times; the hydrogen bond donor dispersion liquid is a mixed liquid of polyoxyethylene and polyacrylic acid solution, the molar ratio of hydrogen bond acceptor polyoxyethylene to hydrogen bond donor polyacrylic acid in the mixed liquid is 0.2:1, hydrogen bond donor particles are dispersed in the mixed liquid, the hydrogen bond donor particles are particles with hydrogen bond donors attached to the surfaces, the hydrogen bond donor particles are formed by bonding excessive hydrogen bond donors and hydrogen bond acceptors through hydrogen bonding, the concentration of the polyoxyethylene solution is 1 wt%, the pH of the solution is 2, the temperature of the solution is 15 ℃, the concentration of the polymethacrylic acid solution is 0.1 wt%, the pH is 2, the temperature is 15 ℃, the number average molecular weight of the polyoxyethylene is 600000, and the number average molecular weight of the polyacrylic acid is 450000.
(4) Repeating the steps (2) and (3) for 40 times in turn to obtain the haze film;
the thickness of the finally prepared haze film is 10-12 microns, the haze is 93-94%, the light transmittance is 91-93%, hydrogen bond compound particles which are in hydrogen bond action with the surface of the film are attached to the surface of the film, the particle size of the hydrogen bond compound particles is 200-500 nm, and the test method of the haze and the light transmittance is the same as that of the example 1.
Claims (7)
1. The in-situ growth and haze control method of the hydrogen bond compound particles on the surface of the film is characterized by comprising the following steps: pretreating a base film, introducing a hydrogen bond donor on the surface of the base film, then sequentially and alternately depositing a hydrogen bond acceptor and particles with the hydrogen bond donor, or pretreating the base film, introducing the hydrogen bond acceptor on the surface of the base film, then sequentially and alternately depositing particles with the hydrogen bond donor and the hydrogen bond acceptor, wherein the particles with the hydrogen bond donor are particles with the hydrogen bond donor attached to the surface, which are formed by combining excessive hydrogen bond donors and hydrogen bond acceptors through hydrogen bond action, the particles with the hydrogen bond donor on the surface of the base film grow in situ along with the increase of the alternating times, and the haze control is realized by controlling the in situ growth of the particles, so that the haze;
the hydrogen bond donor dispersion liquid is a mixed liquid of a hydrogen bond acceptor solution and a hydrogen bond donor solution, and the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor in the mixed liquid is 0.1-0.8: 1;
the hydrogen bond acceptor is polyvinylpyrrolidone or polyethylene oxide; the hydrogen bond donor is polyacrylic acid and/or polymethacrylic acid; the solvent of the hydrogen bond acceptor solution and the hydrogen bond donor solution is water or ethanol; the concentration of the hydrogen bond acceptor solution is 0.1-1 wt%, the pH of the solution is 1-5, and the temperature of the solution is 10-27 ℃;
the number average molecular weight of the polyvinylpyrrolidone is 10000-100000, the number average molecular weight of the polyoxyethylene is 100000-600000, the number average molecular weight of the polyacrylic acid is 8000-450000, and the number average molecular weight of the polymethacrylic acid is 4000-6500;
the concentration of the hydrogen bond donor solution is 0.1 wt%, the pH value is 1-5, and the temperature is 10-27 ℃.
2. The in-situ growth and haze control method of hydrogen bond composite particles on the film surface according to claim 1, characterized by comprising the following specific steps:
(1) pretreating a base film to introduce a hydrogen bond donor on the surface of the base film;
(2) immersing the basement membrane into a hydrogen bond receptor solution for 4-20 min, and then eluting the basement membrane;
(3) immersing the eluted basement membrane into hydrogen bond donor dispersion liquid for 4-20 min, and then eluting the basement membrane;
(4) sequentially and alternately repeating the steps (2) and (3) to obtain the haze film;
the hydrogen bond donor dispersion liquid is provided with hydrogen bond donor particles, and the step of eluting the basement membrane is to immerse the basement membrane into an aqueous solution with the pH value of 1-5 for 1min and repeat the above steps for more than three times; the hydrogen bond donor dispersion liquid, the hydrogen bond acceptor solution and the aqueous solution have the same pH.
3. The method for in-situ growth and haze control of hydrogen bond complex particles on film surface according to claim 2, wherein in step (1), the base film is quartz film or silicon-based film, and the pretreatment is oxidation treatment or plasma treatment.
4. The method for in-situ growth and haze control of hydrogen bonding compound particles on the surface of a film according to claim 2, wherein in the step (1), the base film is a PET film, a PMMA film, a PVC film or a PC film, and the pretreatment is a plasma treatment.
5. The in-situ growth and haze control method of the hydrogen bond complex particles on the film surface according to claim 3, wherein the oxidation treatment is that the base film is soaked in the piranha washing solution for 30-60 min and then washed to be neutral by deionized water.
6. The method for in-situ growth of hydrogen bond composite particles on the surface of a film and controlling the haze according to claim 3 or 4, wherein the plasma treatment process comprises: treating the base film with oxygen plasma for 5 minutes, immersing in 1mg/mL poly (diallyldimethylammonium chloride) solution for 20 minutes, and then immersing in 1mg/mL polymethacrylic acid solution for 20 minutes; wherein the number average molecular weight of the poly (diallyldimethylammonium chloride) is 100000-200000, and the number average molecular weight of the poly (methacrylic acid) is 6500.
7. The in-situ growth and haze control method of film surface hydrogen bond complex particles according to claim 1, wherein the haze of the haze film is 0-98%, the light transmittance of the haze film is 80-93%, hydrogen bond complex particles which are in hydrogen bond interaction with the film surface are attached to the surface of the haze film, and the particle size of the hydrogen bond complex particles is 10 nm-1 μm.
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| CN103449735A (en) * | 2013-08-26 | 2013-12-18 | 北京工业大学 | Nanometer calcium silicate hydrate super-hydrophilicity thin film as well as preparation method and applications of thin film |
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| CN103449735A (en) * | 2013-08-26 | 2013-12-18 | 北京工业大学 | Nanometer calcium silicate hydrate super-hydrophilicity thin film as well as preparation method and applications of thin film |
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