CN111849264A

CN111849264A - Glass spraying protective film and preparation method and application thereof

Info

Publication number: CN111849264A
Application number: CN202010789161.9A
Authority: CN
Inventors: 童帅; 刘伟; 韩劲东; 崔玉朋
Original assignee: CSG Holding Co Ltd; Tianjin CSG Energy Conservation Glass Co Ltd
Current assignee: CSG Holding Co Ltd; Tianjin CSG Energy Conservation Glass Co Ltd
Priority date: 2020-08-07
Filing date: 2020-08-07
Publication date: 2020-10-30

Abstract

The invention discloses a glass spraying protective film and a preparation method and application thereof, wherein the protective film comprises the following components in percentage by mass: 8 to 18 percent of PVA powder, 50 to 80 percent of water, 7 to 12 percent of starch, 2 to 16 percent of isopropanol, 1 to 15.5 percent of carboxymethyl cellulose, 0.2 to 0.6 percent of titanium oxide and 0.05 to 0.2 percent of lanthanum chloride. The adhesion force of the glass spraying protective film provided by the invention is between that of a PVC film and that of a PE film, so that the glass spraying protective film does not fall off or is difficult to remove.

Description

Glass spraying protective film and preparation method and application thereof

Technical Field

The invention relates to the technical field of glass protective film manufacturing, in particular to a glass spray coating protective film and a preparation method and application thereof.

Background

At present in the glass production installation, the glass factory sends finished glass to door and window factory or curtain factory, and follow-up construction unit can install glass on door and window or curtain cell cube to on installing the building site with the glass that has installed, and arrange by the building site, continue to carry out subsequent construction. In a series of subsequent processing processes, the conditions of glass scratch, crush damage, rubbing damage and the like are inevitable, and quality defects are caused to the glass. In order to solve the above problems, the demand for a protection film for a hollow glass has arisen. After the hollow glass is processed, a layer of protective film is pasted on the surface of the glass, and then the edge part is cut. The purpose of cutting is to reserve a position for subsequent installation of the section bar and to avoid the protective film from being pressed by the section bar. And when the subsequent construction is completely finished, the front part of the protective film is torn off, so that the glass is put into final customers for use.

The existing hollow glass protective film mostly adopts an electrostatic film (PVC film), but the adhesion between the film and the glass is not firm, and the protective film is easy to fall off in the subsequent processing and transportation process. If a polyethylene film (PE film) is used, the film is difficult to remove if the film is applied for a long time, which adversely affects the final mounting and use.

Disclosure of Invention

The invention aims to provide a glass spraying protective film and a preparation method and application thereof, and aims to solve the problems that the electrostatic film and glass are not firmly adhered and are easy to fall off in the existing glass protective film, and the polyethylene film is difficult to remove after being adhered for too long time.

The embodiment of the invention provides a glass spraying protective film, which comprises the following components in percentage by mass: 8 to 18 percent of PVA powder, 50 to 80 percent of water, 7 to 12 percent of starch, 2 to 16 percent of isopropanol, 1 to 15.5 percent of carboxymethyl cellulose, 0.2 to 0.6 percent of titanium oxide and 0.05 to 0.2 percent of lanthanum chloride

Further, the method comprises the following steps of: 10 to 15 percent of PVA powder, 50 to 70 percent of water, 7 to 12 percent of starch, 3 to 15 percent of isopropanol, 1.5 to 14.5 percent of carboxymethyl cellulose, 0.3 to 0.5 percent of titanium oxide and 0.05 to 0.2 percent of lanthanum chloride.

Further, the method comprises the following steps of: 10 to 15 percent of PVA powder, 50 to 70 percent of water, 8 to 11 percent of starch, 3 to 13 percent of isopropanol, 1.5 to 13.5 percent of carboxymethyl cellulose, 0.3 to 0.5 percent of titanium oxide and 0.05 to 0.15 percent of lanthanum chloride.

The embodiment of the invention also provides a preparation method of the glass spray coating protective film, which comprises the following steps:

adding deionized water into a reaction kettle according to a formula, and electrifying and heating to keep the temperature at 92-100 ℃;

adding PVA powder, starch, titanium oxide and lanthanum chloride into a reaction kettle according to a formula ratio, and stirring for dissolving;

after the PVA powder is dissolved, adding carboxymethyl cellulose into the reaction kettle, continuously stirring, and stopping heating after the materials are fully reacted and dissolved to obtain mixture liquid;

and when the temperature in the mixture liquid is reduced to 30-40 ℃, adding isopropanol, continuing stirring for 3-10 minutes, stopping stirring, and sieving to obtain the base liquid of the glass spray coating protective film.

Furthermore, the mesh number of the screen is 30-50 meshes.

Furthermore, the titanium oxide and the lanthanum chloride are fine powder with the granularity of more than 80 meshes.

Further, adding carboxymethyl cellulose into the reaction kettle, continuously stirring, and reacting for 90-120 min after the materials are fully reacted and dissolved.

Further, the reaction kettle is a tube array type heat exchange reaction kettle.

Furthermore, the stirring speed is 120 r/min-140 r/min.

The embodiment of the invention also provides an application of the glass spray coating protective film, which is to spray the base solution of the glass spray coating protective film on the surface of glass and then dry the glass to form a film.

The embodiment of the invention provides a glass spraying protective film and a preparation method and application thereof, wherein the protective film comprises the following components in percentage by mass: 8 to 18 percent of PVA powder, 50 to 80 percent of water, 7 to 12 percent of starch, 2 to 16 percent of isopropanol, 1 to 15.5 percent of carboxymethyl cellulose, 0.2 to 0.6 percent of titanium oxide and 0.05 to 0.2 percent of lanthanum chloride. The adhesion force of the glass spraying protective film provided by the embodiment of the invention is between that of a PVC film and that of a PE film, so that the glass spraying protective film does not fall off or is difficult to remove.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

Fig. 1 is a schematic flow chart of a method for preparing a glass spray coating protective film according to an embodiment of the present invention;

FIG. 2 is a graph showing the relationship between the concentration of PVA in the formulation and the tensile strength after film formation according to an embodiment of the present invention;

FIG. 3 is a graph showing the relationship between the reaction time and the tensile strength after film formation in the formulation provided in the example of the present invention;

FIG. 4 is a graph showing the relationship between the reaction temperature and the tensile strength after film formation in the formulation provided in the example of the present invention;

FIG. 5 is a detailed view of a protective film structure provided in accordance with an embodiment of the present invention;

FIG. 6 is a spectrum of a protective film provided by an embodiment of the present invention;

fig. 7 is a DSC diagram of a protective film provided in an embodiment of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.

It is also to be understood that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the specification of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

It should be further understood that the term "and/or" as used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.

The embodiment of the invention provides a glass spraying protective film, which comprises the following components in percentage by mass: 8 to 18 percent of PVA powder, 50 to 80 percent of water, 7 to 12 percent of starch, 2 to 16 percent of isopropanol, 1 to 15.5 percent of carboxymethyl cellulose, 0.2 to 0.6 percent of titanium oxide and 0.05 to 0.2 percent of lanthanum chloride.

According to the mass percentage adopted in the embodiment, a slow-drying type spraying liquid, a quick-drying type spraying liquid and a quick-drying viscous type spraying liquid (the spraying liquid is a protective film base liquid) can be formed, and different types of spraying liquids can be selected according to different spraying requirements.

The spraying liquid prepared by the formula is sprayed on the surface of glass, and a protective film can be formed after the spraying liquid is dried for a short time. The adhesion force of the protective film is between that of the PVC film and that of the PE film, so that the protective film cannot fall off during use, and the protective film cannot be removed difficultly. Meanwhile, the protective film is a degradable film and can be decomposed under natural illumination. The main active ingredient of the formula is PVA powder (polyvinyl alcohol), water is a hydrolysis carrier, isopropanol and carboxymethyl cellulose are used for adjusting the viscosity degree of liquid, titanium oxide and lanthanum chloride are degradation agents, and starch can be used for adjusting the fluidity of the solution to prevent the solution from flowing and is inconvenient to operate.

The protective film prepared by the formula in the embodiment has the degradable characteristic, and the specific degradation principle is as follows:

in the reaction system of the formula, PVA molecules and titanium oxide react under the irradiation of ultraviolet rays. Titanium oxide is excited under the action of ultraviolet light to generate electron-hole pairs, dissolved oxygen, water molecules and the like adsorbed on the surface of titanium oxide react with the electron-hole pairs to generate OH^-And O^2-Will react with the PVA molecules. The reaction that occurs with the PVA molecule is: the methylene or the hydrogen on the hydroxyl on the PVA main chain is captured by the generated hydroxyl radical, so that a carbon-oxygen double bond and a carbon-carbon double bond are formed, the carbon-carbon double bond is damaged by oxygen along with the extension of the ultraviolet irradiation time, and the purpose of final degradation is achieved.

In a specific embodiment, the protective film comprises, by mass percent: 10 to 15 percent of PVA powder, 50 to 70 percent of water, 7 to 12 percent of starch, 3 to 15 percent of isopropanol, 1.5 to 14.5 percent of carboxymethyl cellulose, 0.3 to 0.5 percent of titanium oxide and 0.05 to 0.2 percent of lanthanum chloride.

In this embodiment, the base solution of the protective film prepared according to the mass percentage used in this embodiment has a better effect after film formation. Compared with the formula, the base liquid of the protective film prepared by the formula is dried more quickly, and the film forming speed is higher.

In a further embodiment, the protective film comprises, in mass percent: 10 to 15 percent of PVA powder, 50 to 70 percent of water, 8 to 11 percent of starch, 3 to 13 percent of isopropanol, 1.5 to 13.5 percent of carboxymethyl cellulose, 0.3 to 0.5 percent of titanium oxide and 0.05 to 0.2 percent of lanthanum chloride.

In this embodiment, the protective film base liquid prepared by the mass percentage used in this embodiment has a better coverage effect and a better protective effect than the protective film base liquid prepared by the above two mass ratios.

As shown in fig. 1, an embodiment of the present invention further provides a method for preparing the glass spray coating protective film, which includes:

s101, adding deionized water into a reaction kettle according to a formula, and electrifying and heating to keep the temperature at 92-100 ℃;

s102, adding PVA powder, starch, titanium oxide and lanthanum chloride into a reaction kettle according to a formula ratio, and stirring for dissolving;

s103, after the PVA powder is dissolved, adding carboxymethyl cellulose into the reaction kettle, continuing stirring, and stopping heating after the materials are fully reacted and dissolved to obtain mixture liquid;

and S104, when the temperature in the mixture liquid is reduced to 30-40 ℃, adding isopropanol, continuing stirring for 3-10 minutes, stopping stirring, and sieving to obtain the base liquid of the glass spray coating protective film.

In this embodiment, in the preparation process of the protective film base solution, deionized water (i.e. pure water with impurities in the form of ions removed) is added into the reaction kettle according to the formula of the base solution, and then the reaction kettle is heated to keep the temperature inside the reaction kettle constant, so that the formula can react. The deionized water is added, so that impurities in water can be reduced, interference is reduced, and the preparation of the formula is more accurate. When heating, the temperature is generally selected to be kept at 92-100 ℃, and the constant temperature of 96 ℃ is adopted in the embodiment to achieve the best heating effect.

According to the mass percentage of the formula, PVA powder, starch, titanium oxide and lanthanum chloride are added into a reaction kettle, wherein the PVA powder is an effective component of a main body of the formula, the starch can be used for adjusting the fluidity of the solution, and the titanium chloride and the lanthanum chloride are degradation agents of the solution. The components are added into a reaction kettle and fully stirred and dissolved, and the specific process is as follows: adding the above formula components into a reaction kettle, opening a stirring rod of the reaction kettle, and fully stirring at 96 ℃ to dissolve the formula components.

After the PVA powder in the reaction kettle is dissolved, adding the carboxymethyl cellulose, and continuing stirring until all materials in the reaction kettle form a mixture liquid. Specifically, adding carboxymethyl cellulose into the reaction kettle, continuously stirring, and reacting for 90-120 min after the materials are fully reacted and dissolved. After obtaining the mixture liquid, the heating was stopped and the stirring bar continued to stir.

And after the heating is stopped, reducing the temperature, when the temperature is reduced to 30-40 ℃, adding isopropanol into the mixture liquid to adjust the viscosity of the liquid, continuing stirring for 3-10 minutes, closing the stirring rod to stop stirring, and sieving the finally obtained liquid to obtain the base liquid of the glass spraying protective film. Specifically, the optimal implementation scheme is as follows: after the temperature was lowered to 35 ℃, isopropyl alcohol was added to the mixture liquid, stirring was continued for 5 minutes, and then the obtained liquid was sieved to obtain the base liquid.

In one embodiment, the mesh number of the screen is 30-50 meshes. The mesh number refers to the number of holes per inch of the screen, and in this embodiment, the mesh number of the screen is 30-50 meshes, specifically 40 meshes, so as to filter out redundant solid impurities.

In one embodiment, the titanium oxide and the lanthanum chloride are both selected from fine powders with a particle size of more than 80 meshes. In the present example, the mesh number indicates the particle diameter of particles that can pass through the screen, and the higher the mesh number, the smaller the particle diameter. Titanium oxide and lanthanum chloride with the particle size of more than 80 meshes are adopted, so that the particle size is small, and the full reaction with other materials is facilitated.

In one embodiment, the reaction kettle is a tubular heat exchange reaction kettle. In this embodiment, the reaction kettle adopts a tube type heat exchange reaction kettle, and the technical parameters are as follows: the volume is 71L, the heat exchange area of the jacket is 0.34 square meter, the speed reducer uses BLD 0.8-1 type, and the specification of a discharge valve DN 70. Correspondingly, the reaction kettle can also adopt an enamel reaction kettle or a stainless steel reaction kettle.

In one embodiment, the stirring speed is 120r/min to 140 r/min. The stirring speed in the reaction kettle is 120 r/min-140 r/min, and specifically can be 130 r/min. The stirring speed of 130r/min is adopted, so that the materials in the reaction kettle can react more quickly, and the materials can not damage the molecules in the materials due to the excessively high stirring speed while fully reacting.

The base liquid of the glass spray coating protective film provided by the embodiment of the invention can be divided into slow-drying type mass percentage base liquid, quick-drying type mass percentage base liquid and quick-drying viscous type mass percentage base liquid according to different mass percentages. The required viscosity of the base fluid can be prepared according to different spraying equipment, and the specific quantitative index can be expressed by using the tensile strength after film forming. Referring to fig. 2, a graph of tensile strength and elongation at break at the same PVA concentration is shown, and it can be seen that when the tensile strength after the base solution film forming is in the range of 10% to 15% tensile strength, the film can satisfy the operation requirement of 2 cleaning operations after film forming, and the strength is also greater than the strength of the film with the thickness of 0.1mm of the PVC film.

Further, the reaction time of the material in the reaction vessel at the same PVA concentration also has a relationship with the tensile strength. As shown in fig. 3, when the reaction time is less than 60min, the change of the tensile strength after the prepared base solution is sprayed and formed into a film is large, and the change of the elongation at break is also large. In this case, the reaction time starts to approach the steady state after more than 60min, so the reaction time is set within the range of 90-120 min in this embodiment, so as to ensure that the materials in the reaction kettle can fully react, and obtain a relatively steady product (i.e., the base solution).

Further, the reaction temperature and the tensile strength are related to each other at the same PVA concentration and the same reaction time. As shown in fig. 4, when the temperature in the reaction kettle is too low, the tensile strength and elongation at break of the protective film formed by spraying the prepared base solution are also low, at a temperature of 50 ℃, the tensile strength is less than 16%, and the elongation at break is less than 150%, and when the reaction temperature reaches 70 ℃, the elongation at break is even more than 190%, the tensile strength is even more than 24%, and the span is large; when the temperature reaches over 96 ℃, better tensile strength can be obtained, and the risk of overlarge internal pressure caused by boiling of water in the reaction kettle is avoided.

Referring to fig. 5, the situation after the base liquid is sprayed to form a film is shown, under an electron microscope, the protective film exists in a continuous sheet shape on the glass surface, and no crack exists, so that the protective film formed by spraying has a stable shape and good protective performance after being formed into a film. Meanwhile, the protective film exists in a continuous sheet shape, so that the protective film is more convenient and quicker when the protective film needs to be removed, and the situation of residue when the protective film is removed can not occur.

The film forming method comprises the steps of spraying the base liquid on the surface of glass, and drying to form the protective film. For this purpose, the infrared absorption wavelength range of the film can be determined by studying the spectrum of the protective film. And then, the temperature of the heat source is reversely deduced through the Wien displacement law, so that the high-efficiency drying film-forming effect is obtained. As shown in FIG. 6, since the absorption peak of the protective film is estimated to be 2300 to 2500 nm, 2.9X 10 is obtained by using the Wien's displacement law λ mT^-3m, T1160 k 886 ℃. Therefore, the carbon medium wave radiant tube with the temperature of the heating source main body being 850-900 ℃ is used.

TABLE 1

As shown in fig. 7, it can be concluded from the DSC diagram of the protective film that the thermal properties of the protective films of the different formulations vary with increasing PVA content (DSC diagram with reference number 1 for the protective films prepared in mass percent as described in example 1 of table 1, DSC diagram with reference number 2 for the protective films prepared in mass percent as described in example 2 of table 1, and DSC diagram with reference number 3 for the protective films prepared in mass percent as described in example 3 of table 1). Because the PVA powder has certain acidity after being hydrolyzed, the thermal property of the film is reduced along with the increase of acidity caused by further dissolving the PVA powder in water, and the influence of the addition of other materials on the thermal property of the film is little.

DSC, or DSC thermal analysis, also known as differential scanning calorimetry, measures the relationship between the power difference input to a test sample (i.e., sample) and a reference and the temperature at a programmed temperature. It determines various thermodynamic and kinetic parameters, such as specific heat capacity, heat of reaction, heat of transformation, phase diagram, reaction rate, crystallization rate, polymer crystallinity, sample purity, etc., with the rate of heat absorption or release of the sample, i.e., the heat flow rate dH/dt (in millijoules/second) as the ordinate and the temperature T or time T as the abscissa. The method has the advantages of wide application temperature range (-175-725 ℃), high resolution and small sample consumption. It is suitable for analyzing inorganic matter, organic compound and medicine.

The embodiments are described in a progressive manner in the specification, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

It is further noted that, in the present specification, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

Claims

1. The glass spraying protective film is characterized by comprising the following components in percentage by mass: 8 to 18 percent of PVA powder, 50 to 80 percent of water, 7 to 12 percent of starch, 2 to 16 percent of isopropanol, 1 to 15.5 percent of carboxymethyl cellulose, 0.2 to 0.6 percent of titanium oxide and 0.05 to 0.2 percent of lanthanum chloride.

2. The glass spray coating protective film according to claim 1, comprising, in mass percent: 10 to 15 percent of PVA powder, 50 to 70 percent of water, 7 to 12 percent of starch, 3 to 15 percent of isopropanol, 1.5 to 14.5 percent of carboxymethyl cellulose, 0.3 to 0.5 percent of titanium oxide and 0.05 to 0.2 percent of lanthanum chloride.

3. The glass spray coating protective film according to claim 2, comprising, in mass percent: 10 to 15 percent of PVA powder, 50 to 70 percent of water, 8 to 11 percent of starch, 3 to 13 percent of isopropanol, 1.5 to 13.5 percent of carboxymethyl cellulose, 0.3 to 0.5 percent of titanium oxide and 0.05 to 0.15 percent of lanthanum chloride.

4. A method for producing a glass spray coating protective film according to any one of claims 1 to 3, comprising:

5. The method for preparing a glass spray coating protective film according to claim 4, wherein the mesh number of the screen is 30-50 meshes.

6. The method for preparing a glass spray coating protective film according to claim 4, wherein the titanium oxide and the lanthanum chloride are both fine powders of 80 mesh or more.

7. The method for preparing the glass spray coating protective film according to claim 4, wherein the carboxymethyl cellulose is added into the reaction kettle, and the stirring is continued, and the reaction time for fully reacting and dissolving the material is 90-120 min.

8. The method for preparing a glass spray coating protective film according to claim 4, wherein the reaction kettle is a tubular heat exchange reaction kettle.

9. The method for preparing a sprayed glass protective film according to claim 4, wherein the stirring speed is 120 to 140 r/min.

10. The use of the glass spray coating protective film according to any one of claims 1 to 3, wherein the base liquid of the glass spray coating protective film is sprayed on the surface of glass, and then dried to form a film.