CN115418065A - Surface super-hydrophobic blue-light-proof ultraviolet-proof heat insulation film and preparation method thereof - Google Patents

Surface super-hydrophobic blue-light-proof ultraviolet-proof heat insulation film and preparation method thereof Download PDF

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CN115418065A
CN115418065A CN202211233217.8A CN202211233217A CN115418065A CN 115418065 A CN115418065 A CN 115418065A CN 202211233217 A CN202211233217 A CN 202211233217A CN 115418065 A CN115418065 A CN 115418065A
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stirring
pva
ultraviolet
proof
light
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戚燕俐
严茂引
任玉荣
赵宏顺
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Changzhou University
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2250/00—Layers arrangement
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    • B32B2307/00—Properties of the layers or laminate
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    • B32B2307/00—Properties of the layers or laminate
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    • B32B2307/00—Properties of the layers or laminate
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    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
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    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Abstract

The invention discloses a surface super-hydrophobic blue-light-proof ultraviolet-proof heat-insulating film and a preparation method thereof, wherein the heat-insulating film is prepared from the following raw materials in parts by mass: 100 parts of PVA resin; 1-3 parts of SAN resin; 200-560 parts of deionized water; 30-50 parts of tetrahydrofuran; 0.01-0.1 part of blue light near-infrared absorbent; 0.1-0.2 part of ultraviolet near-infrared light shielding agent; 1-3 parts of a defoaming agent. Through the compound use of the blue light near-infrared absorbent and the ultraviolet light near-infrared absorbent, the film has excellent blue light and ultraviolet shielding effects, and the near-infrared shielding effect can be improved after mutual synergy, so that the synergistic heat insulation effect is realized. Water and tetrahydrofuran are used as media, ultraviolet light and blue light can be effectively shielded, a heat insulation effect is achieved, toxic elements such as nickel, cadmium and lead are not contained, the using amount of filler is small, the cost is low, and the functional film has a super-hydrophobic surface and good light transmittance.

Description

Surface super-hydrophobic blue-light-proof ultraviolet-proof heat insulation film and preparation method thereof
Technical Field
The invention belongs to the technical field of functional optical films, and particularly relates to a surface super-hydrophobic blue-light-proof ultraviolet-proof heat-insulating film and a preparation method thereof.
Background
The wavelength range of the sunlight is only between 200 and 2500nm, and the sunlight comprises ultraviolet light, visible light and near infrared light. The intensity and energy distribution of solar electromagnetic radiation that passes through the atmosphere to the ground also changes. Excessive ultraviolet radiation can cause photochemical changes, which can cause a series of damages to human body functions such as skin, eyes and immune system of human body. In addition, the high-energy visible light band (400-500 nm), blue light, in the visible region also has relatively high energy. After long-term exposure to blue light, the human body functions are also damaged in a series. Near infrared light (700-2500 nm) has thermal effects, accounting for about 52% of the energy in sunlight. After absorbing a large amount of near infrared light, heat accumulation can be caused, a large amount of cooling equipment is used, and energy loss is caused. At present, functional materials with heat insulation effect also form a great social demand. The material with the heat insulation effect effectively reduces indoor heat accumulation, improves indoor comfort and reduces energy loss through modes such as heat insulation, heat radiation and the like.
At present, in order to reduce the harm of ultraviolet light and blue light in solar radiation to human body functions, heat insulation film materials with blue light prevention or ultraviolet light prevention functions appear in succession, a part of films for preventing blue light realize blue light shielding performance through a light refraction principle, and the other part of films realize corresponding functions by coating blue light prevention or ultraviolet light prevention coatings on the surface layers of the films. Most of the heat insulation films are developed based on absorption or reflection of near infrared light, wherein the film absorbing the near infrared light mostly depends on rare earth raw materials such as indium tin oxide, antimony tin oxide, zinc tin oxide, and the like, and the film reflecting the near infrared light often depends on addition of high content of white inorganic particles such as titanium dioxide, zinc oxide, barium titanate, and the like. Therefore, a large amount of blue light prevention, ultraviolet light prevention and heat insulation filler is required to be added into the traditional blue light prevention and ultraviolet light prevention heat insulation film for compounding, and therefore combination of all functions is achieved. After a large amount of filler is added, the cost of the product is increased, and certain influence is brought to the optical performance of the film. The film is difficult to ensure that the film has excellent blue light prevention, ultraviolet light prevention and heat insulation effects and also has good light transmittance.
Disclosure of Invention
The invention aims to overcome the defects, and provides a surface super-hydrophobic blue light-proof ultraviolet-proof heat-insulating film and a preparation method thereof.
In order to realize the purpose, the invention is realized by the following technical scheme:
the surface super-hydrophobic blue-light-proof ultraviolet-proof heat insulation film is prepared from the following raw materials in parts by mass:
Figure BDA0003882410410000021
preferably, the heat insulation film is a multilayer film, the bottom layer is a PVA film compounded with a blue light near-infrared light absorbent, and the upper layer is an SAN layer attached with an ultraviolet light near-infrared light absorbent.
Preferably, the PVA resin is a PVA synthetic resin having a viscosity ranging from 54 to 66mPa · s, a pH ranging from 5 to 7, an alcoholysis degree of 98 to 99mol%, and an ash content of at most 0.4%.
Preferably, the polymer system selected by the invention is water-based PVA, particularly, the selected PVA is high-temperature soluble PVA which can be completely dissolved at the temperature of more than 80 ℃ and can be completely insoluble at the temperature of less than 40 ℃, so that the functional film can be ensured not to be hydrolyzed in the using process, and the using requirement can be met.
Preferably, the SAN resin is a SAN synthetic resin having a melt flow rate of 12g/10min and a density of 1.21g/cm 3 。
Preferably, the blue light near-infrared light absorber is one or more of transparent yellow pigment, hestery yellow pigment, sun-proof yellow pigment or permanent yellow pigment. Particularly, the blue light near-infrared light absorber is a nanoscale organic yellow pigment which is not easy to agglomerate, and the uniformly dispersed organic yellow pigment is beneficial to transmitting visible light.
Preferably, the ultraviolet light near-infrared light shielding agent is one or two of nano-scale silicon dioxide or titanium dioxide with the surface coated with an organic silicon modifier, and the particle size range is 15-20 nm; the organic silicon modifier is one or more of KH570, KH550 and KH 560; the modification method is not particularly limited, and the modification method can be any conventional method in the field, or can be directly selected from commercially available organic silicon modified nano SiO 2 Or TiO 2 。
Preferably, the defoaming agent is a modified polyether silicon type defoaming agent. The defoaming agent is prepared by introducing a polyether chain on a polysiloxane chain through a condensation technology, can be dispersed in a water-based system, has stable chemical properties and high temperature resistance, and is suitable for a PVA water-based system.
The invention selects the organic pigment as the blue light near-infrared light absorber, and because the groups in the organic molecular structure generate energy absorption behavior when the vibration energy level and the rotation energy level jump. Wherein, in the near infrared spectrum region (780-2500 nm), the low energy electron transition and the frequency doubling absorption of the stretching vibration of the hydrogen-containing atomic group (such as O-H, N-H, C-H) are mainly generated.
The four preferred yellow organic pigments have a molecular structure with a few groups, such as N-H, C-H, C = C. Near-infrared light shielding performance can be achieved in addition to absorption of blue light. This is because in the near infrared band, the yellow organic pigments have few absorption peak positions, and the rest bands are expressed in the form of energy reflection, so that the yellow organic pigments have good near infrared reflection behavior. The chemical composition and content of the yellow organic pigment are adjusted, so that the yellow organic pigment can be realized after compounding, and the added yellow organic pigment is used for improving the near infrared light reflectivity, reducing the heat conduction and having the heat insulation performance. The selected yellow organic pigment is added into the polymer to ensure that the material has certain light transmittance.
The nano titanium dioxide or silicon dioxide mainly plays a role in shielding ultraviolet light, the yellow pigment simultaneously plays a role in shielding blue light and near infrared light, and after the nano titanium dioxide or silicon dioxide and the blue pigment are compounded, the effect of shielding the near infrared light is improved, and the synergistic heat insulation effect is realized.
The invention also provides a preparation method of the surface super-hydrophobic blue-light-proof ultraviolet-proof heat-insulating film, which comprises the following steps:
adding PVA resin into deionized water while stirring until the PVA resin is fully dispersed;
adding a defoaming agent, stirring until the PVA is completely dissolved, adding a blue light near-infrared light absorber, and continuously stirring to obtain a PVA aqueous solution;
pouring the obtained PVA aqueous solution into a flat plate mold, and performing vacuum drying to obtain a PVA film;
mixing and stirring tetrahydrofuran and deionized water, and then adding SAN resin while stirring;
after the SAN resin is completely dissolved, adding an ultraviolet near-infrared light absorbent, and continuously stirring to obtain a SAN solution;
and pouring the SAN solution into a flat plate mould with a PVA film on the bottom layer, standing and ventilating until the solvent is volatilized, thus obtaining the PVA film.
Preferably, the stirring speed of the PVA resin is 150-200 r/min and the temperature is controlled between 20-25 ℃ in the process of dispersing the PVA resin in deionized water; in the dissolving process of the PVA resin, the stirring speed is 150-200 r/min, and the temperature is 85-95 ℃.
Preferably, the vacuum pressure of the vacuum drying is kept between-0.06 and-0.1 MPa, and the temperature is controlled to be 35 to 50 ℃.
Preferably, the volume ratio of tetrahydrofuran and deionized water added into the SAN resin is (3-5): (5-7).
Preferably, the reaction vessel and the flat plate mold used in the preparation method of the invention are both made of stainless steel.
Specifically, the preparation method may include the steps of:
(1) Pouring deionized water into a stainless steel stirring barrel for stirring, wherein the stirring speed is 100-150 r/min, and the temperature is controlled between 20 ℃ and 25 ℃; slowly adding PVA resin into a stirring barrel, adjusting the stirring speed to be 150-200 r/min, and continuously stirring for 10-15 min after the material is added;
(2) After the PVA is fully dispersed in the water, slowly adding a defoaming agent, keeping the stirring speed at 150-200 r/min, heating to 90 ℃ while stirring, and continuously stirring for 60-90 min until the PVA is completely dissolved; after PVA is completely dissolved, slowly adding a blue light near-infrared light absorber, keeping the stirring speed at 150-200 r/min, keeping the temperature at 90 ℃, and continuously stirring for 60-120 min;
(3) Turning off the heat source, cooling the stirred PVA aqueous solution to room temperature, adjusting the stirring speed to be 100-150 r/min, pouring the PVA aqueous solution into a stainless steel flat plate mould, placing the stainless steel flat plate mould into a vacuum drying oven for standing for 12-18 h, keeping the vacuum pressure in the vacuum drying oven to be-0.06-0.1 MPa during standing, controlling the temperature to be 35-50 ℃, and evaporating water to obtain a PVA film;
(4) Pouring tetrahydrofuran and deionized water into a stainless steel stirring barrel according to a certain proportion, stirring at the speed of 100-150 r/min and the temperature of 20-25 ℃, and continuously stirring for 15-30 min; adding SAN resin slowly into a stirring barrel, adjusting the stirring speed to 150-200 r/min, and continuously stirring for 30-60 min after the addition is finished;
(5) After the SAN is completely dissolved, slowly adding the ultraviolet near-infrared absorbent, keeping the stirring speed at 150-200 r/min, and continuously stirring for 10-15 min;
(6) Adjusting the stirring speed to be 100-150 r/min, pouring the stirred SAN solution into a stainless steel flat plate mould with a PVA film on the bottom layer, placing the stainless steel flat plate mould into a fume hood for standing for 6-8 h, controlling the temperature to be 20-25 ℃, and evaporating the solvent to obtain a finished product.
By the method, the invention selects SiO 2 And TiO 2 One or two of them can be used as ultraviolet light and near infrared light shielding agent. Selected SiO 2 And (or) TiO 2 Is nano-scale, and the surface is coated by an organic silicon modifier; on the one hand, ensure SiO 2 And (or) TiO 2 Can be uniformly dispersed in tetrahydrofuran solvent, and on the other hand, can ensure that the resin has certain adhesiveness with SAN resin, thereby firmly adhering to the surface of the material. Tetrahydrofuran and water are mixed to prepare a proper solvent, SAN synthetic resin is promoted to form a micron-sized ellipsoid shape in the solvent in cooperation with SiO 2 And (or) TiO 2 Build a multi-level micro-nano structure and is based on SiO 2 And (or) TiO 2 The organic silicon modifier on the surface enriches hydrophobic chemical components on the surface layer of the micro-nano structure to achieve super-hydrophobic characteristics. The multistage micro-nano structure can further improve the effect of filtering blue light, near infrared light and ultraviolet light, and improve heat insulation and ensure light transmittance.
Compared with the prior art, the invention has the beneficial effects that:
the heat-insulating film disclosed by the invention has excellent blue light and ultraviolet shielding effects by compounding the blue light near-infrared light absorbent and the ultraviolet light near-infrared light shielding agent, and can improve the near-infrared light shielding effect after mutual cooperation, thereby realizing the synergistic heat-insulating effect. Water and tetrahydrofuran are used as media, ultraviolet light and blue light can be effectively shielded, a heat insulation effect is achieved, toxic elements such as nickel, cadmium and lead are not contained, the using amount of filler is small, the cost is low, and the functional film has a super-hydrophobic surface and good light transmittance.
According to the preparation method, the SAN component is attached to the surface of the PVA polymer through the micron-sized ellipsoid, the ultraviolet near-infrared light absorbent is distributed on the surfaces of the base material and the SAN ellipsoid, a micro-nano structure is constructed, the super-hydrophobic surface is obtained, in addition, a part of air with a low heat conductivity coefficient is trapped in the micro-nano structure, the heat insulation effect is favorably further improved, and meanwhile, the light transmittance of the film is ensured.
Drawings
FIG. 1 is a schematic diagram of the hydrophobicity of the surface superhydrophobic blue light-proof anti-ultraviolet heat insulation film and the blue light-proof anti-ultraviolet function;
fig. 2 is an electron microscope image of a micro-nano structure formed on the surface of the super-hydrophobic blue-light-proof ultraviolet-proof heat-insulating film prepared in example 1.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below with reference to the accompanying drawings and specific examples.
Example 1
The embodiment provides a surface super-hydrophobic type blue light-proof ultraviolet-proof heat insulation film.
The raw materials comprise the following components in parts by weight: 100 parts of PVA resin, 2.5 parts of SAN resin, 260 parts of deionized water, 40 parts of tetrahydrofuran, 0.01 part of sun-proof yellow pigment and SiO modified by silane coupling agent 2 0.1, defoaming agent 1.
The preparation method comprises the following steps:
(1) pouring 200 parts of deionized water into a stainless steel stirring barrel for stirring, wherein the stirring speed is 100r/min, and the temperature is controlled at 20 ℃; slowly adding 100 parts of PVA resin into a stirring barrel, adjusting the stirring speed to 150r/min, and continuously stirring for 10min after the material is added;
(2) after the PVA is fully dispersed in the water, slowly adding a defoaming agent, keeping the stirring speed at 150r/min, heating to 90 ℃ while stirring, and continuously stirring for 60min until the PVA is completely dissolved; after PVA is completely dissolved, slowly adding 0.01 part of fast yellow, keeping the stirring speed at 150r/min and the temperature at 90 ℃, and continuously stirring for 90min;
(3) turning off the heat source, cooling the stirred PVA aqueous solution to room temperature, adjusting the stirring speed to be 100r/min, pouring the PVA aqueous solution into a stainless steel flat plate mould, putting the stainless steel flat plate mould into a vacuum drying oven for standing for 12 hours, controlling the vacuum pressure to be between-0.06 and-0.1 MPa during standing, controlling the temperature to be 40 ℃, and evaporating water to obtain a functional PVA film;
(4) pouring 40 parts of tetrahydrofuran and 60 parts of deionized water into a stainless steel stirring barrel, stirring at the speed of 100r/min and the temperature of 20 ℃, and continuously stirring for 15min; slowly adding 2.5 parts of SAN resin into a stirring barrel, adjusting the stirring speed to 150r/min, and continuously stirring for 30min after the addition is finished;
(5) after SAN was completely dissolved, 0 was slowly added1 part of SiO 2 Keeping the stirring speed at 150r/min, and continuously stirring for 10min; (6) adjusting the stirring speed to 100r/min, pouring the stirred SAN solution into a stainless steel flat plate die with the prepared PVA film, placing the stainless steel flat plate die into a fume hood, standing for 6 hours, controlling the temperature to be 20 ℃, and evaporating the solvent to obtain a finished product.
Example 2
The embodiment provides a surface super-hydrophobic type blue light-proof ultraviolet-proof heat insulation film.
The raw materials comprise the following components in parts by weight: 100 parts of PVA resin, 2.5 parts of SAN resin, 360 parts of deionized water, 40 parts of tetrahydrofuran, 0.05 part of transparent yellow pigment and SiO modified by silane coupling agent 2 0.2, defoaming agent 2.
The preparation method comprises the following steps:
(1) pouring 300 parts of deionized water into a stainless steel stirring barrel for stirring, wherein the stirring speed is 100r/min, and the temperature is controlled at 25 ℃; slowly adding 100 parts of PVA resin into a stirring barrel, adjusting the stirring speed to 200r/min, and continuously stirring for 15min after the material is added;
(2) after the PVA is fully dispersed in the water, slowly adding a defoaming agent, keeping the stirring speed at 200r/min, heating to 90 ℃ while stirring, and continuously stirring for 90min until the PVA is completely dissolved; after PVA is completely dissolved, slowly adding 0.05 part of transparent yellow, keeping the stirring speed at 200r/min and the temperature at 90 ℃, and continuously stirring for 120min;
(3) closing the heat source, cooling the stirred PVA aqueous solution to room temperature, adjusting the stirring speed to 150r/min, pouring the PVA aqueous solution into a stainless steel flat plate mould, placing the stainless steel flat plate mould into a vacuum drying oven for standing for 18 hours, keeping the vacuum pressure between-0.06 and-0.1 MPa during standing, controlling the temperature to be 45 ℃, and evaporating water to obtain a functional PVA film;
(4) pouring 40 parts of tetrahydrofuran and 60 parts of deionized water into a stainless steel stirring barrel, stirring at the speed of 150r/min and at the temperature of 25 ℃, and continuously stirring for 15min; slowly adding 2.5 parts of SAN resin into a stirring barrel, adjusting the stirring speed to 200r/min, and continuously stirring for 30min after the addition is finished;
(5) after SAN is dissolved, 0.2 part of SiO is slowly added 2 Keeping the stirring speed at 200r/min, and continuously stirring15min；
(6) Adjusting the stirring speed to 150r/min, pouring the stirred SAN solution into a stainless steel flat plate mold with the prepared PVA film, placing the stainless steel flat plate mold into a fume hood for standing for 8 hours, controlling the temperature to be 25 ℃, and evaporating the solvent to obtain a finished product.
Example 3
The embodiment provides a surface super-hydrophobic type blue light-proof ultraviolet-proof heat insulation film.
The raw materials comprise the following components in parts by weight: 100 parts of PVA resin, 3 parts of SAN resin, 550 parts of deionized water, 50 parts of tetrahydrofuran, 0.06 part of Hersteryellow pigment and modified TiO of silane coupling agent 2 0.1, defoamer 1.
The preparation method comprises the following steps:
(1) pouring 500 parts of deionized water into a stainless steel stirring barrel for stirring, wherein the stirring speed is 150r/min, and the temperature is controlled at 25 ℃; slowly adding 100 parts of PVA resin into a stirring barrel, adjusting the stirring speed to 200r/min, and continuously stirring for 15min after the material is added;
(2) after the PVA is fully dispersed in the water, slowly adding a defoaming agent, keeping the stirring speed at 200r/min, heating to 90 ℃ while stirring, and continuously stirring for 90min until the PVA is completely dissolved; after PVA is completely dissolved, slowly adding 0.06 part of hesteryellow, keeping the stirring speed at 200r/min and the temperature at 90 ℃, and continuously stirring for 90min;
(3) turning off the heat source, cooling the stirred PVA aqueous solution to room temperature, adjusting the stirring speed to be 150r/min, pouring the PVA aqueous solution into a stainless steel flat plate mould, putting the stainless steel flat plate mould into a vacuum drying oven for standing for 18 hours, controlling the vacuum pressure to be between-0.06 and-0.1 MPa during standing, controlling the temperature to be 45 ℃, and evaporating water to obtain a functional PVA film;
(4) pouring 50 parts of tetrahydrofuran and 50 parts of deionized water into a stainless steel stirring barrel, stirring at the speed of 150r/min and at the temperature of 25 ℃, and continuously stirring for 15min; slowly adding 3 parts of SAN resin into a stirring barrel, adjusting the stirring speed to 200r/min, and continuously stirring for 30min after the addition is finished;
(5) after SAN is dissolved, 0.1 part of TiO is slowly added 2 Keeping the stirring speed at 200r/min, and continuously stirring for 15min;
(6) adjusting the stirring speed to 150r/min, pouring the stirred SAN solution into a stainless steel flat plate mold with the prepared PVA film, placing the stainless steel flat plate mold into a fume hood for standing for 8 hours, controlling the temperature to be 25 ℃, and evaporating the solvent to obtain a finished product.
Example 4
The embodiment provides a surface super-hydrophobic type blue light-proof ultraviolet-proof heat insulation film.
The raw materials comprise the following components in parts by weight: 100 parts of PVA resin, 2.5 parts of SAN resin, 460 parts of deionized water, 40 parts of tetrahydrofuran, 0.01 part of permanent yellow pigment, 0.02 part of sun-proof yellow pigment and modified TiO of silane coupling agent 2 0.1 modification of SiO with silane coupling agent 2 0.1 and an antifoaming agent 2.
The preparation method comprises the following steps:
(1) pouring 400 parts of deionized water into a stainless steel stirring barrel for stirring, wherein the stirring speed is 100r/min, and the temperature is controlled at 20 ℃; slowly adding 100 parts of PVA resin into a stirring barrel, adjusting the stirring speed to 150r/min, and continuously stirring for 10min after the material is added;
(2) after the PVA is fully dispersed in the water, slowly adding a defoaming agent, keeping the stirring speed at 150r/min, heating to 90 ℃ while stirring, and continuously stirring for 60min until the PVA is completely dissolved; after PVA is completely dissolved, slowly adding 0.01 part of permanent yellow and 0.02 part of sun-proof yellow, keeping the stirring speed at 150r/min, keeping the temperature at 90 ℃, and continuously stirring for 90min;
(3) turning off the heat source, cooling the stirred PVA aqueous solution to room temperature, adjusting the stirring speed to be 100r/min, pouring the PVA aqueous solution into a stainless steel flat plate mould, putting the stainless steel flat plate mould into a vacuum drying oven for standing for 16 hours, controlling the vacuum pressure to be between-0.06 and-0.1 MPa during standing, controlling the temperature to be 50 ℃, and evaporating water to obtain a functional PVA film;
(4) pouring 40 parts of tetrahydrofuran and 60 parts of deionized water into a stainless steel stirring barrel, stirring at the speed of 150r/min and at the temperature of 25 ℃, and continuously stirring for 15min; slowly adding 2.5 parts of SAN resin into a stirring barrel, adjusting the stirring speed to 200r/min, and continuously stirring for 30min after the addition is finished;
(5) after SAN is dissolved, 0.1 part of SiO is slowly added 2 And 0.1 part of TiO 2 Keeping the stirring speed at 150r/min, and continuously stirring for 15min;
(6) adjusting the stirring speed to 100r/min, pouring the stirred SAN solution into a stainless steel flat plate mould with the prepared PVA film, placing the stainless steel flat plate mould into a fume hood for standing for 6 hours, controlling the temperature to be 20 ℃, and evaporating the solvent to obtain a finished product.
Example 5
The embodiment provides a surface super-hydrophobic type blue light-proof ultraviolet-proof heat insulation film.
The raw materials comprise the following components in parts by weight: 100 parts of PVA resin, 2.5 parts of SAN resin, 360 parts of deionized water, 40 parts of tetrahydrofuran, 0.07 part of sun-proof yellow pigment and SiO modified by silane coupling agent 2 0.1 modification of TiO with silane coupling agent 2 0.1 and an antifoaming agent 3.
The preparation method comprises the following steps:
(1) pouring 300 parts of deionized water into a stainless steel stirring barrel for stirring, wherein the stirring speed is 100r/min, and the temperature is controlled at 20 ℃; slowly adding 100 parts of PVA resin into a stirring barrel, adjusting the stirring speed to 200r/min, and continuously stirring for 15min after the material is added;
(2) after the PVA is fully dispersed in the water, slowly adding a defoaming agent, keeping the stirring speed at 200r/min, heating to 90 ℃ while stirring, and continuously stirring for 90min until the PVA is completely dissolved; after PVA is completely dissolved, slowly adding 0.07 part of fast yellow, keeping the stirring speed at 200r/min and the temperature at 90 ℃, and continuously stirring for 120min;
(3) closing the heat source, cooling the stirred PVA aqueous solution to room temperature, adjusting the stirring speed to be 100r/min, pouring the PVA aqueous solution into a stainless steel flat plate mould, putting the stainless steel flat plate mould into a vacuum drying oven for standing for 14 hours, keeping the vacuum pressure between-0.06 and-0.1 MPa during standing, controlling the temperature to be 50 ℃, and evaporating water to obtain a functional PVA film;
(4) pouring 40 parts of tetrahydrofuran and 60 parts of deionized water into a stainless steel stirring barrel, stirring at the speed of 100r/min and at the temperature of 20 ℃, and continuously stirring for 10min; slowly adding 2.5 parts of SAN resin into a stirring barrel, adjusting the stirring speed to 200r/min, and continuously stirring for 20min after the addition is finished;
(5) after SAN dissolved, 0.1 part of S was slowly addediO 2 And 0.1 part of TiO 2 Keeping the stirring speed at 100r/min, and continuously stirring for 15min;
(6) adjusting the stirring speed to 100r/min, pouring the stirred SAN solution into a stainless steel flat plate mould with the prepared PVA film, placing the stainless steel flat plate mould into a fume hood for standing for 8 hours, controlling the temperature to be 25 ℃, and evaporating the solvent to obtain a finished product.
Example 6
The embodiment provides a surface superhydrophobic type blue light-proof ultraviolet-proof heat insulation film.
The raw materials comprise the following components in parts by weight: 100 parts of PVA resin, 1 part of SAN resin, 270 parts of deionized water, 30 parts of tetrahydrofuran, 0.03 part of sun-proof yellow pigment and 0.03 part of silane coupling agent modified SiO 2 0.1, defoaming agent 1.
The preparation method comprises the following steps:
(1) pouring 200 parts of deionized water into a stainless steel stirring barrel for stirring, wherein the stirring speed is 100r/min, and the temperature is controlled at 20 ℃; slowly adding 100 parts of PVA resin into a stirring barrel, adjusting the stirring speed to 150r/min, and continuously stirring for 10min after the material is added;
(2) after the PVA is fully dispersed in the water, slowly adding a defoaming agent, keeping the stirring speed at 150r/min, heating to 90 ℃ while stirring, and continuously stirring for 60min until the PVA is completely dissolved; after PVA is completely dissolved, slowly adding 0.03 part of fast yellow, keeping the stirring speed at 150r/min and the temperature at 90 ℃, and continuously stirring for 90min;
(3) turning off the heat source, cooling the stirred PVA aqueous solution to room temperature, adjusting the stirring speed to be 100r/min, pouring the PVA aqueous solution into a stainless steel flat plate mould, putting the stainless steel flat plate mould into a vacuum drying oven for standing for 12 hours, controlling the vacuum pressure to be between-0.06 and-0.1 MPa during standing, controlling the temperature to be 40 ℃, and evaporating water to obtain a functional PVA film;
(4) pouring 30 parts of tetrahydrofuran and 70 parts of deionized water into a stainless steel stirring barrel, stirring at the speed of 100r/min and at the temperature of 20 ℃, and continuously stirring for 10min; slowly adding 1 part of SAN resin into a stirring barrel, adjusting the stirring speed to 150r/min, and continuously stirring for 20min after the addition is finished;
(5) after SAN is dissolved, 0.1 part of SiO is slowly added 2 Keeping the stirring speed at 150r/min, and continuously stirring for 15min;
(6) adjusting the stirring speed to 100r/min, pouring the stirred SAN solution into a stainless steel flat plate mould with the prepared PVA film, placing the stainless steel flat plate mould into a fume hood for standing for 6 hours, controlling the temperature to be 25 ℃, and evaporating the solvent to obtain a finished product.
Example 7
The embodiment provides a surface super-hydrophobic type blue light-proof ultraviolet-proof heat insulation film.
The raw materials comprise the following components in parts by weight: 100 parts of PVA resin, 2.5 parts of SAN resin, 560 parts of deionized water, 40 parts of tetrahydrofuran, 0.06 part of Herster yellow pigment and modified TiO of silane coupling agent 2 0.05 and defoaming agent 1.
The preparation method comprises the following steps:
(1) pouring 500 parts of deionized water into a stainless steel stirring barrel for stirring, wherein the stirring speed is 150r/min, and the temperature is controlled at 25 ℃; slowly adding 100 parts of PVA resin into a stirring barrel, adjusting the stirring speed to 200r/min, and continuously stirring for 15min after the material is added;
(2) after the PVA is fully dispersed in the water, slowly adding a defoaming agent, keeping the stirring speed at 200r/min, heating to 90 ℃ while stirring, and continuously stirring for 90min until the PVA is completely dissolved; after PVA is completely dissolved, slowly adding 0.06 part of hesteryellow, keeping the stirring speed at 200r/min and the temperature at 90 ℃, and continuously stirring for 90min;
(3) closing the heat source, cooling the stirred PVA aqueous solution to room temperature, adjusting the stirring speed to 150r/min, pouring the PVA aqueous solution into a stainless steel flat plate mould, placing the stainless steel flat plate mould into a vacuum drying oven for standing for 18 hours, keeping the vacuum pressure between-0.06 and-0.1 MPa during standing, controlling the temperature to be 45 ℃, and evaporating water to obtain a functional PVA film;
(4) pouring 40 parts of tetrahydrofuran and 60 parts of deionized water into a stainless steel stirring barrel, stirring at the speed of 100r/min and at the temperature of 25 ℃, and continuously stirring for 15min; slowly adding 2.5 parts of SAN resin into a stirring barrel, adjusting the stirring speed to 200r/min, and continuously stirring for 30min after the addition is finished;
(5) after SAN is dissolved, 0.5 part of TiO is slowly added 2 Maintaining the stirring speedContinuously stirring for 15min at the speed of 200 r/min;
(6) adjusting the stirring speed to 150r/min, pouring the stirred SAN solution into a stainless steel flat plate mold with the prepared PVA film, placing the stainless steel flat plate mold into a fume hood for standing for 8 hours, controlling the temperature to be 25 ℃, and evaporating the solvent to obtain a finished product.
Comparative example 1
The present embodiment provides a PVA-based thermal insulation film.
The raw materials comprise the following components in parts by weight: 100 parts of PVA resin, 200 parts of deionized water and 1 part of defoaming agent.
The preparation method comprises the following steps:
(1) pouring deionized water into a stainless steel stirring barrel for stirring, wherein the stirring speed is 100r/min, and the temperature is controlled at 25 ℃; slowly adding 100 parts of PVA resin into a stirring barrel, adjusting the stirring speed to 150r/min, and continuously stirring for 10min after the material is added;
(2) after the PVA is fully dispersed in the water, slowly adding the defoaming agent, keeping the stirring speed at 150r/min, heating to 90 ℃ while stirring, and continuously stirring for 60min until the PVA is completely dissolved;
(3) and (3) turning off the heat source, cooling the stirred PVA aqueous solution to room temperature, adjusting the stirring speed to be 100r/min, pouring the PVA aqueous solution into a stainless steel flat plate mould, placing the stainless steel flat plate mould into a vacuum drying oven for standing for 12 hours, controlling the vacuum pressure to be between-0.06 and-0.1 MPa during standing, controlling the temperature to be 50 ℃, and evaporating water to obtain a finished product.
Comparative example 2
The present embodiment provides a PVA-based thermal insulation film.
The raw materials comprise the following components in parts by weight: 100 parts of PVA resin, 2.5 parts of SAN resin, 260 parts of deionized water, 40 parts of tetrahydrofuran and 1 part of defoaming agent.
The preparation method comprises the following steps:
(1) pouring 200 parts of deionized water into a stainless steel stirring barrel for stirring, wherein the stirring speed is 100r/min, and the temperature is controlled at 20 ℃; slowly adding 100 parts of PVA resin into a stirring barrel, adjusting the stirring speed to 150r/min, and continuously stirring for 10min after the material is added;
(2) after the PVA is fully dispersed in the water, slowly adding a defoaming agent, keeping the stirring speed at 150r/min, heating to 90 ℃ while stirring, and continuously stirring for 60min until the PVA is completely dissolved;
(3) turning off the heat source, cooling the stirred PVA aqueous solution to room temperature, adjusting the stirring speed to be 100r/min, pouring the PVA aqueous solution into a stainless steel flat plate mould, putting the stainless steel flat plate mould into a vacuum drying oven for standing for 12 hours, controlling the vacuum pressure to be between-0.06 and-0.1 MPa during standing, controlling the temperature to be 50 ℃, and evaporating water to obtain a functional PVA film;
(4) pouring 40 parts of tetrahydrofuran and 60 parts of deionized water into a stainless steel stirring barrel, stirring at the speed of 100r/min and at the temperature of 25 ℃, and continuously stirring for 15min; slowly adding 2.5 parts of SAN resin into a stirring barrel, adjusting the stirring speed to 150r/min, and continuously stirring for 30min after the addition is finished;
(5) after SAN is dissolved, adjusting the stirring speed to be 100r/min, pouring the stirred SAN solution into a stainless steel flat plate mould with the prepared PVA film, placing the stainless steel flat plate mould into a fume hood for standing for 6 hours, controlling the temperature to be 25 ℃, and evaporating the solvent to obtain a finished product.
Comparative example 3
The present embodiment provides a PVA-based thermal insulation film.
The raw materials comprise the following components in parts by weight: 100 parts of PVA resin, 1 part of SAN resin, 370 parts of deionized water, 30 parts of tetrahydrofuran and SiO modified by silane coupling agent 2 0.1 modification of TiO with silane coupling agent 2 0.1 and an antifoaming agent 3.
The preparation method comprises the following steps:
(1) pouring 300 parts of deionized water into a stainless steel stirring barrel for stirring, wherein the stirring speed is 100r/min, and the temperature is controlled at 20 ℃; slowly adding 100 parts of PVA resin into a stirring barrel, adjusting the stirring speed to 150r/min, and continuously stirring for 10min after the material is added;
(2) after the PVA is fully dispersed in the water, slowly adding the defoaming agent, keeping the stirring speed at 150r/min, heating to 90 ℃ while stirring, and continuously stirring for 60min until the PVA is completely dissolved;
(3) turning off the heat source, cooling the stirred PVA aqueous solution to room temperature, adjusting the stirring speed to be 100r/min, pouring the PVA aqueous solution into a stainless steel flat plate mould, putting the stainless steel flat plate mould into a vacuum drying oven for standing for 12 hours, controlling the vacuum pressure to be between-0.06 and-0.1 MPa during standing, controlling the temperature to be 40 ℃, and evaporating water to obtain a functional PVA film;
(4) pouring 30 parts of tetrahydrofuran and 70 parts of deionized water into a stainless steel stirring barrel, stirring at the speed of 100r/min and at the temperature of 25 ℃, and continuously stirring for 15min; slowly adding 1 part of SAN resin into a stirring barrel, adjusting the stirring speed to 150r/min, and continuously stirring for 30min after the addition is finished;
(5) after SAN is dissolved, 0.1 part of SiO is slowly added 2 And 0.1 part of TiO 2 Keeping the stirring speed at 150r/min, and continuously stirring for 15min;
(6) adjusting the stirring speed to 100r/min, pouring the stirred SAN solution into a stainless steel flat plate mould with the prepared PVA film, placing the stainless steel flat plate mould into a fume hood for standing for 6 hours, controlling the temperature to be 25 ℃, and evaporating the solvent to obtain a finished product.
Comparative example 4
The present embodiment provides a PVA-based thermal insulation film.
The raw materials comprise the following components in parts by weight: 100 parts of PVA resin, 3 parts of SAN resin, 450 parts of deionized water, 50 parts of tetrahydrofuran, 0.01 part of permanent yellow pigment, 0.02 part of sun-proof yellow pigment and 2 parts of defoaming agent.
The preparation method comprises the following steps:
(1) pouring 400 parts of deionized water into a stainless steel stirring barrel for stirring, wherein the stirring speed is 100r/min, and the temperature is controlled at 20 ℃; slowly adding 100 parts of PVA resin into a stirring barrel, adjusting the stirring speed to 200r/min, and continuously stirring for 10min after the material is added;
(2) after the PVA is fully dispersed in the water, slowly adding a defoaming agent, keeping the stirring speed at 200r/min, heating to 90 ℃ while stirring, and continuously stirring for 60min until the PVA is completely dissolved; after PVA is completely dissolved, slowly adding 0.01 part of permanent yellow and 0.02 part of sun-proof yellow, keeping the stirring speed at 200r/min and the temperature at 90 ℃, and continuously stirring for 90min;
(3) turning off the heat source, cooling the stirred PVA aqueous solution to room temperature, adjusting the stirring speed to be 100r/min, pouring the PVA aqueous solution into a stainless steel flat plate mould, putting the stainless steel flat plate mould into a vacuum drying oven for standing for 16 hours, controlling the vacuum pressure to be between-0.06 and-0.1 MPa during standing, controlling the temperature to be 45 ℃, and evaporating water to obtain a functional PVA film;
(4) pouring 50 parts of tetrahydrofuran and 50 parts of deionized water into a stainless steel stirring barrel, stirring at the speed of 100r/min and at the temperature of 25 ℃, and continuously stirring for 15min; slowly adding 3 parts of SAN resin into a stirring barrel, adjusting the stirring speed to 150r/min, and continuously stirring for 30min after the addition is finished;
(5) after SAN is completely dissolved, adjusting the stirring speed to be 100r/min, pouring the stirred SAN solution into a stainless steel flat plate mold with the prepared PVA film, placing the stainless steel flat plate mold into a fume hood for standing for 6 hours, controlling the temperature to be 25 ℃, and evaporating the solvent to obtain a finished product.
The films prepared in the above examples and comparative examples were tested by the following methods.
(1) The transmission rate testing and calculating method comprises the following steps: the transmittance of the film in ultraviolet, visible and near infrared bands was measured using an ultraviolet-visible-near infrared spectrophotometer (UVPC, UV-3600i plus, shimadzu). Wherein, the calculation formula of the transmittance is as follows:
Figure BDA0003882410410000161
wherein T represents the average transmittance (%), T (. Lamda.) represents the transmittance (%) of the sample at a wavelength of lambda, and lambda 1 And λ 2 Respectively representing the upper and lower wavelength (nm) values. Sunlight reaching the earth can be divided into ultraviolet light, visible light and near infrared light, wherein the ultraviolet band (T) is UV ) 280-400nm, and occupies 5% of visible light energy; visible light band (T) VIS ) 400-800nm, which occupies 43% of visible light energy; near infrared band (T) NIR ) 800-2500nm, and occupies 52% of visible light energy; blue light band (T) B ) Is 400-500nm.
The optical properties of each film obtained by the test and calculation are shown in table 1.
TABLE 1 comparison of optical Properties of PVA-based thermal insulation films
Figure BDA0003882410410000171
(2) The heat insulation performance test method comprises the following steps: and testing the heat insulation performance of the sample by adopting a self-made heat insulation device. The heat insulation device is prepared from a foam box, the top of the heat insulation device is covered by glass to prevent external air flow from influencing internal temperature change, and a thermocouple type digital display thermometer is arranged inside the heat insulation device. During the test, the sample was placed on top of the thermal insulation unit and an infrared lamp with a power of 250W was placed 50cm from the vertical height of the sample. After the infrared lamp is turned on, the thermometer records the internal temperature change every 2min, and continuously records for 60min.
The heat insulating properties of each film obtained by the test are shown in table 2.
TABLE 2 comparison of thermal insulation Properties of PVA-based thermal insulation films
Scheme(s) Internal temperature/DEG C of the device after 60min of radiation Insulation effect (compared to glass samples)/° c
Glass sample 61 0
Example 1 57 4
Example 2 50 11
Example 3 50 11
Example 4 54 7
Example 5 51 10
Example 6 55 6
Example 7 51 10
Comparative example 1 61 0
Comparative example 2 59 2
Comparative example 3 58 3
Comparative example 4 56 4
(3) Contact angle test method: a2. Mu.L drop of deionized water was placed on the surface of the sample to be tested, and a timer was started after the drop of deionized water contacted the sample surface and an instantaneous static water contact angle of 30s was recorded. Each sample was measured 5 times at different locations and the average of the five measurements was taken as the final water contact angle value.
The hydrophobic properties of each film obtained by the test are shown in Table 3.
Scheme(s) Water contact Angle/°
Example 1 150
Example 2 158
Example 3 151
Example 4 157
Example 5 157
Example 6 152
Example 7 160
Comparative example 1 54
Comparative example 2 120
Comparative example 3 158
Comparative example 4 122
FIG. 1 is a schematic diagram of the hydrophobic and blue light and ultraviolet resistant of the surface superhydrophobic blue light and ultraviolet resistant heat insulation film of the invention; fig. 2 is an electron microscope image of a micro-nano structure formed on the surface of the super-hydrophobic blue-light-proof ultraviolet-proof heat-insulating film prepared in embodiment 1 of the present invention, wherein SAN forms a micro-scale ellipsoid, and an ultraviolet near-infrared light absorber forms a nano-scale aggregate distributed on the surfaces of the PVA substrate and the SAN ellipsoid.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and technical principles of the described embodiments, and such modifications and variations should also be considered as within the scope of the present invention.

Claims (10)

1. The surface super-hydrophobic blue-light-proof ultraviolet-proof heat insulation film is characterized by being prepared from the following raw materials in parts by mass:
Figure FDA0003882410400000011
2. the surface superhydrophobic blue-light-proof ultraviolet-proof heat insulation film according to claim 1, wherein the heat insulation film is a multilayer film, the bottom layer is a PVA film compounded with a blue-light near-infrared light absorbent, and the upper layer is an SAN layer attached with the ultraviolet-light near-infrared light absorbent.
3. The surface superhydrophobic blue-light-proof ultraviolet-proof heat insulation film according to claim 1 or 2, wherein the blue-light near-infrared light absorber is one or more of transparent yellow pigment, hestery yellow pigment, sun-proof yellow pigment or permanent yellow pigment.
4. The surface superhydrophobic blue light-proof ultraviolet-proof heat insulation film according to claim 1 or 2, wherein the ultraviolet light near infrared light shielding agent is one or both of nano-scale silicon dioxide or titanium dioxide coated with a silicone modifier on the surface.
5. The surface superhydrophobic blue light-proof ultraviolet-proof heat insulation film according to claim 4, wherein the organic silicon modifier is one or more of KH570, KH550 and KH 560.
6. The surface superhydrophobic blue light prevention and ultraviolet protection heat insulation film according to claim 1, wherein the defoaming agent is a modified polyether silicon defoaming agent.
7. The preparation method of the surface superhydrophobic blue light-proof ultraviolet-proof heat insulation film according to any one of claims 1 to 6, characterized by comprising the following steps:
adding PVA resin into deionized water while stirring until the PVA resin is fully dispersed;
adding a defoaming agent, stirring until the PVA is completely dissolved, adding a blue light near-infrared light absorber, and continuously stirring to obtain a PVA aqueous solution;
pouring the obtained PVA aqueous solution into a flat plate mold, and performing vacuum drying to obtain a PVA film;
mixing and stirring tetrahydrofuran and deionized water, and then adding SAN resin while stirring;
after the SAN resin is completely dissolved, adding an ultraviolet near-infrared light absorbent, and continuously stirring to obtain a SAN solution;
and pouring the SAN solution into a flat plate mould with a PVA film on the bottom layer, standing and ventilating until the solvent is volatilized, thus obtaining the PVA film.
8. The preparation method of the surface superhydrophobic blue light-proof ultraviolet-proof heat insulation film according to claim 7, wherein in the process of dispersing the PVA resin in deionized water, the stirring speed is 150-200 r/min, and the temperature is controlled between 20 ℃ and 25 ℃; in the dissolving process of the PVA resin, the stirring speed is 150-200 r/min, and the temperature is 85-95 ℃.
9. The method for preparing the surface superhydrophobic blue light-proof ultraviolet-proof heat insulation film according to claim 7, wherein the vacuum pressure of the vacuum drying is kept between-0.06 and-0.1 MPa, and the temperature is controlled to be 35 to 50 ℃.
10. The preparation method of the surface superhydrophobic blue light and ultraviolet prevention heat insulation film according to claim 7, wherein the volume ratio of tetrahydrofuran and deionized water added with SAN resin is (3-5): (5-7).
CN202211233217.8A 2022-10-10 2022-10-10 Surface super-hydrophobic blue-light-proof ultraviolet-proof heat insulation film and preparation method thereof Pending CN115418065A (en)

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