CN113045994B - High-temperature-resistant ceramic composite membrane of metal substrate and preparation method thereof - Google Patents

Abstract

The invention relates to a high-temperature-resistant ceramic composite film of a metal substrate and a preparation method thereof. The high-temperature-resistant ceramic composite film is characterized in that a high-temperature-resistant printing layer is arranged on the upper side surface of a metal substrate, a high-temperature-resistant organic silicon layer and a ceramic adhesive layer are arranged on the lower side surface of the metal substrate, and the adhesive layer can be kept at a high temperature of more than 500 ℃ for at least 72 hours without foaming and falling, fading of surface patterns and curling and wrinkling of edges. The high temperature resistance of the invention is obviously higher than that of the high temperature resistant film on the market.

Description

High-temperature-resistant ceramic composite membrane of metal substrate and preparation method thereof

Technical Field

The invention relates to the technical field of high-temperature-resistant composite films, in particular to a metal-substrate high-temperature-resistant ceramic composite film and a preparation method thereof.

Background

The high temperature resistant film is widely applied to manufacturing industries which can generate high temperature, such as steel, casting, pharmacy, kiln industry and the like. At present, polyimide is generally used as a film substrate in a high-temperature-resistant label on the market, and the polyimide can only resist 260 ℃ and cannot meet the requirement of higher temperature. In addition, some products using aluminum foil as a substrate have poor temperature resistance of the adhesive layer, so that the adhesive layer is rapidly carbonized and cracked at 500 ℃ to generate bubbles and even fall off. Although a general high-temperature resistant film can be used for a printed label, the high-temperature resistance of the printed layer is generally not considered because the printed layer is far from a heat source. In the kiln industry, where baking is required, the entire product is exposed to the same elevated temperature and the printed layer on the surface of the product rapidly yellows, or even blackens and fades.

The high temperature resistant films on the market at present have the following problems: 1. can not resist the high temperature of more than 500 ℃ for a long time; 2. after high temperature, the viscosity of the adhesion layer is rapidly reduced, and even foaming and falling off are realized; 3. the high temperature resistance of the printed layer is generally poor and yellowing begins above 200 ℃ until it becomes black and faded.

Disclosure of Invention

In order to solve one or more of the above technical problems, the present invention provides a metal-based high temperature resistant ceramic composite film and a method for preparing the same.

The technical scheme for solving the technical problems is as follows: the utility model provides a metal substrate's high temperature resistant ceramic composite film, prints layer, metal substrate, high temperature resistant organosilicon layer and ceramic adhesive layer including high temperature resistant, the both sides of metal substrate coat respectively has high temperature resistant printing layer and high temperature resistant organosilicon layer, be equipped with on the high temperature resistant organosilicon layer ceramic adhesive layer.

The invention has the beneficial effects that: the high-temperature-resistant ceramic composite film is characterized in that a high-temperature-resistant printing layer is arranged on the upper side surface of a metal substrate, a high-temperature-resistant organic silicon layer and a ceramic adhesive layer are arranged on the lower side surface of the metal substrate, and the adhesive layer can be kept at a high temperature of more than 500 ℃ for at least 72 hours without foaming and falling, fading of surface patterns and curling and wrinkling of edges. The high temperature resistance of the invention is obviously higher than that of the high temperature resistant film on the market.

On the basis of the technical scheme, the invention can be further improved as follows.

Further, the components of the high-temperature-resistant printing layer comprise one or more of fluorine-silicon modified acrylic resin and fluorine-silicon modified polyester resin, one or more of cellulose propionate, vinyl acetate and hydroxypropyl methyl cellulose, one or more of titanium dioxide, lithopone, zinc powder and aluminum powder, and zinc stearate.

The beneficial effect of adopting the further scheme is that: organic silicon resin is selected as a high-temperature-resistant printing layer component, so that the high-temperature-resistant effect of the printing layer can be effectively improved.

Further, the preparation method of the high-temperature-resistant printing layer comprises the steps of dissolving one or more of fluorine-silicon modified acrylic resin and fluorine-silicon modified polyester resin and one or more of cellulose propionate, vinyl cellulose acetate and hydroxypropyl methyl cellulose by using an organic solvent, adding one or more of titanium dioxide, lithopone, zinc powder and aluminum powder and a first auxiliary agent, mixing to prepare a high-temperature-resistant printing coating liquid, coating the high-temperature-resistant printing coating liquid on one side surface of a metal substrate, and drying.

The beneficial effect of adopting the further scheme is that: mix with silicone resin and cellulose and dissolve preparation and print the layer, compare other structures that become the one deck alone with the cellulose, can permeate the dyestuff and print the in situ, the rendition effect is better, and it is higher to print the definition, and the adhesive force of dyestuff is stronger, can delay the time that the printing layer yellowed and blackened, and high temperature resistant time is long, can tolerate 500 ℃ high temperature more than 72 hours at least.

Further, the first auxiliary agent comprises one or more of a dispersing agent, an anti-settling agent and a thickening agent; the titanium dioxide is rutile type titanium dioxide, and the particle size of the titanium dioxide is D90.1-1.5 mu m; the drying temperature is 60-250 ℃, and the drying time is 2-10 minutes.

Further, the high-temperature-resistant organic silicon layer comprises one or more of methyl phenyl silicone resin, fluorine-silicon modified polyester resin and fluorine-silicon modified acrylic resin;

the preparation method of the high-temperature-resistant organic silicon layer comprises the steps of coating organic silicon resin on the other side of the metal substrate and baking for 5-10 minutes at the temperature of 60-250 ℃.

Further, the ceramic adhesive layer comprises one of acrylic pressure-sensitive adhesive, acrylic glue and silicone rubber resin, one or more of methyl phenyl silicone resin, fluorine-silicon modified polyester resin and fluorine-silicon modified acrylic resin, and one or more of alumina, zirconia, silica and silicon carbide.

The beneficial effect of adopting the further scheme is that: compared with the adhesive with a single component, the ceramic adhesive layer has high-temperature resistance and can resist the high temperature of more than 1200 ℃. The ceramic adhesive layer has stronger bonding force with the substrate.

Further, the preparation method of the ceramic adhesive layer comprises the steps of dissolving one of acrylic pressure-sensitive adhesive, acrylic glue and silicone rubber resin and one or more of methyl phenyl silicone resin, fluorine-silicon modified polyester resin and fluorine-silicon modified acrylic resin with an organic solvent, adding one or more of alumina, zirconia, silica and silicon carbide and a second auxiliary agent, mixing to prepare a ceramic coating, and then coating the ceramic coating on the surface of the high-temperature resistant organic silicon layer and drying.

Further, the second auxiliary agent comprises a curing agent and a curing accelerator, the curing agent comprises methyl ethyl ketone peroxide, and the curing accelerator comprises silica sol. The drying temperature is 50-70 ℃, and the drying time is 2-10 minutes; the grain diameter of the alumina, the zirconia, the silicon dioxide and the silicon carbide is D900.1-0.5 μm.

Further, the ceramic adhesive layer comprises a substrate, wherein the substrate covers the ceramic adhesive layer; or/and the metal base is a hard aluminum foil base material, the thickness of the metal base is 25-150 mu m, the thickness of the high-temperature-resistant printing layer is 2-10 mu m, the thickness of the high-temperature-resistant organic silicon layer is 5-25 mu m, and the thickness of the ceramic adhesive layer is 2-10 mu m.

The beneficial effect of adopting the above further scheme is: the hard aluminum foil base material is adopted as the metal base, so that the weight is light, the density is low, and the combination with each layer is good. Generally, if each layer is thick, the high-temperature resistance is good, but the adhesive force is poor, and the proper thickness range can ensure good adhesive force under the condition of good high-temperature resistance.

A preparation method of a metal-based high-temperature-resistant ceramic composite membrane comprises the following steps:

s1, degreasing a metal base material, and then applying corona to two sides to obtain a metal substrate; the adhesion is improved.

S2, coating a high-temperature-resistant printing coating on the metal substrate and drying;

s3, coating a high-temperature-resistant organic silicon layer on the reverse side of the metal substrate coated with the high-temperature-resistant printing layer and drying;

s4, coating a ceramic adhesive layer on the high-temperature-resistant organic silicon layer;

and S5, covering a release film substrate on the ceramic adhesive layer.

The beneficial effects of the invention are: the upper side surface of the metal substrate is provided with a high-temperature-resistant printing layer, the lower side surface of the metal substrate is provided with a high-temperature-resistant organic silicon layer and a ceramic adhesive layer, and the adhesive layer can be kept at a high temperature of more than 500 ℃ for at least 72 hours without foaming and falling, fading of surface patterns and curling and wrinkling of edges. The high temperature resistance of the invention is obviously higher than that of the high temperature resistant film on the market.

Drawings

FIG. 1 is a schematic structural diagram of a high temperature resistant ceramic composite membrane according to the present invention.

In the drawings, the reference numbers indicate the following list of parts:

1. a high temperature resistant print layer; 2. a metal substrate; 3. a high temperature resistant silicone layer; 4. a ceramic adhesive layer; 5. a substrate.

Detailed Description

The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.

As shown in fig. 1, the high temperature resistant ceramic composite film of a metal substrate of this embodiment includes a high temperature resistant printing layer 1, a metal substrate 2, a high temperature resistant organic silicon layer 3 and a ceramic adhesive layer 4, the high temperature resistant printing layer 1 and the high temperature resistant organic silicon layer 3 are respectively coated on two sides of the metal substrate 2, and the ceramic adhesive layer 4 is disposed on the high temperature resistant organic silicon layer 3.

The high-temperature-resistant ceramic composite film also comprises a substrate 5, wherein the substrate 5 covers the ceramic adhesive layer 4; the thickness of the metal substrate 2 is 25-150 μm, the thickness of the high-temperature-resistant printing layer 1 is 2-10 μm, the thickness of the high-temperature-resistant organic silicon layer 3 is 5-25 μm, and the thickness of the ceramic adhesive layer 4 is 2-10 μm. The hard aluminum foil base material is adopted as the metal base, so that the weight is light, the density is low, and the combination with each layer is good. Generally, if each layer is thick, the high-temperature resistance is good, but the adhesive force is poor, and the proper thickness range can ensure good adhesive force under the condition of good high-temperature resistance.

The high-temperature-resistant printing layer 1 comprises one or more of fluorine-silicon modified acrylic resin and fluorine-silicon modified polyester resin, one or more of cellulose propionate, vinyl acetate and hydroxypropyl methyl cellulose, one or more of titanium dioxide, lithopone, zinc powder and aluminum powder, and a leveling agent. The preparation method of the high-temperature resistant printing layer 1 comprises the steps of dissolving one or more of fluorine-silicon modified acrylic resin and fluorine-silicon modified polyester resin and one or more of cellulose propionate, vinyl cellulose acetate and hydroxypropyl methyl cellulose by using an organic solvent, adding one or more of titanium dioxide, lithopone, zinc powder and aluminum powder and a first auxiliary agent, mixing to prepare a high-temperature resistant printing coating liquid, coating the high-temperature resistant printing coating liquid on one side surface of a metal substrate, and drying; the drying temperature is 60-250 ℃, and the drying time is 2-10 minutes. Wherein the first auxiliary agent comprises one or more of a dispersing agent, an anti-settling agent and a thickening agent; the titanium dioxide is rutile type titanium dioxide, and the particle size of the titanium dioxide is D900.1-1.5 mu m. Mix with silicone resin and cellulose and dissolve preparation and print the layer, compare other structures that become the one deck alone with the cellulose, can permeate the dyestuff and print the in situ, the rendition effect is better, and it is higher to print the definition, and the adhesive force of dyestuff is stronger, can delay the time that the printing layer yellowed and blackened, and high temperature resistant time is long, can tolerate 500 ℃ high temperature more than 72 hours at least.

The high-temperature-resistant organic silicon layer 3 in this embodiment includes one or more of methyl phenyl silicone resin, fluorosilicone modified polyester resin, and fluorosilicone modified acrylic resin; the preparation method of the high temperature resistant organic silicon layer 3 comprises coating organic silicon resin on the other side of the metal substrate 2 and baking at 60-250 ℃ for 5-10 minutes.

The ceramic adhesive layer 4 in this embodiment includes one of acrylic pressure-sensitive adhesive, acrylic glue, and silicone resin, one or more of methyl phenyl silicone resin, fluorosilicone modified polyester resin, and fluorosilicone modified acrylic resin, and one or more of alumina, zirconia, silica, and silicon carbide. The preparation method of the ceramic adhesive layer 4 comprises the steps of dissolving one of acrylic pressure-sensitive adhesive, acrylic glue and silicone rubber resin and one or more of methyl phenyl silicone resin, fluorine-silicon modified polyester resin and fluorine-silicon modified acrylic resin with an organic solvent, adding one or more of alumina, zirconia, silica and silicon carbide and a second auxiliary agent, mixing to prepare a ceramic coating, coating the ceramic coating on the surface of the high-temperature-resistant organic silicon layer 3, and drying at the temperature of 50-70 ℃ for 2-10 minutes. The grain diameter of the ceramic fillers of alumina, zirconia, silica and silicon carbide is D900.1-0.5 μm, the second auxiliary agent comprises a curing agent and a curing accelerator, the curing agent comprises methyl ethyl ketone peroxide, and the curing accelerator comprises silica sol. Methyl ethyl ketone is dissolved, and the curing accelerator comprises silica sol. Compared with the adhesive with a single component, the ceramic adhesive layer has high-temperature resistance and can resist high temperature of more than 1200 ℃. The ceramic adhesive layer has stronger bonding force with the substrate.

A preparation method of a metal-based high-temperature-resistant ceramic composite membrane comprises the following steps:

s1, degreasing a metal base material, and then performing corona treatment on two sides of the metal base material to obtain a metal substrate 2;

s2, coating a layer of high-temperature-resistant printing coating on the metal substrate 2 and drying;

s3, coating a high-temperature-resistant organic silicon layer 3 on the reverse side of the metal substrate 2 coated with the high-temperature-resistant printing layer 1 and drying;

s4, coating a ceramic adhesive layer 4 on the high-temperature-resistant organic silicon layer 3;

and S5, covering a release film substrate 5 on the ceramic adhesive layer 4.

The high temperature resistant ceramic composite membrane of this embodiment sets up one deck high temperature resistant printing layer 1 at the side of going up of metal substrate 2, and the downside of metal substrate 2 is provided with high temperature resistant organosilicon layer 3, ceramic gluing layer 4, can keep not bubbling of 72 hours gluing layer at least under the high temperature more than 500 ℃ and drop, the surface pattern does not fade, the edge does not curl and corrugates. The high temperature resistance of the invention is obviously higher than that of the high temperature resistant film on the market.

The following experiments were conducted on the high temperature resistant printing layer, the metal substrate, the high temperature resistant silicone layer, and the ceramic adhesive layer with different composition, ratio, thickness, and other parameters, respectively, and the comparison was conducted as follows. Now 27 sets of comparative experiments were performed, corresponding to examples 1-27, respectively.

In examples 1-27, the formulations in parts by weight of the high temperature print resistant layers are shown in Table 1:

TABLE 1 high-temp. resistance printing layer formula table

The preparation process of the high temperature resistant printing layer in the embodiment 1 to 27 includes mixing the organic solvent according to the proportion, then weighing the corresponding organic silicon resin and the corresponding cellulose respectively, adding the organic silicon resin and the corresponding cellulose into the mixed solvent, fully dissolving the organic silicon resin and the corresponding cellulose into the mixed solvent to obtain a mixed solution 1, then weighing the titanium dioxide, the lithopone and the zinc powder according to the formula, adding the titanium dioxide, the lithopone and the zinc powder into the solution 1, fully stirring and dispersing the titanium dioxide, the lithopone and the zinc powder, then adding the corresponding auxiliary agent, and continuously stirring the mixture to obtain the high temperature resistant printing coating.

The preparation process of the high-temperature-resistant printing layer comprises the following steps: and coating the high-temperature-resistant coating on the upper surface of the metal substrate by using a silk-screen printing machine or a gravure printing machine, drying by using an air-blast drying oven, and placing at room temperature. And (5) confirming the hardening of the film layer by adopting a friction test.

In examples 1-27, the thickness of the high temperature print layer is shown in Table 2:

TABLE 2 high-temp. RESISTANT PRINTING LAYER THICKNESS METER

In examples 1-27, the metal substrate thicknesses are shown in Table 3:

TABLE 3 Metal substrate thickness Table

Examples	1-9	10-18	19-27
				Hard aluminum foil thickness/mum	25	100	150

In examples 1-27, the silicone coating formulations are shown in Table 4:

TABLE 4 high temperature resistant organosilicon layer formulation table

Examples	1-9	10-18	19-27
				Methyl phenyl silicone resin	50	0	0
Fluorine-silicon modified resin	0	50	0
				Fluorine-silicon modified acrylic resin	0	0	50
Solvent(s)	50	50	50
				Baking conditions	120 ℃ for 5 minutes	10 minutes at 60 DEG C	5 minutes at 150 DEG C
Thickness of high temperature resistant silicone layer	2μm	6μm	10μm

In the above examples 1 to 27, the preparation process of the high temperature resistant silicone layer was: coating the other side of the substrate with silicone resin with certain solid content by using a gravure coater or screen printing, baking for 5-10 minutes at 60-250 ℃,

in examples 1-27, the ceramic bond layer formulations are shown in Table 5:

TABLE 5 ceramic adhesive layer recipe table

Examples	1-9	10-18	19-27
				Acrylic pressure-sensitive adhesive	50	0	0
Acrylic glue	0	50	0
				Silicone rubber adhesive	0	0	50
Solvent(s)	50	50	50
				Methyl phenyl silicone resin	50	0	0
Fluorosilicone modified polyester resin	0	25	0
				Fluorine-silicon modified acrylic resin	0	25	50
Alumina oxide	50	25	15
				Zirconium oxide	0	15	15
Silicon dioxide	0	10	10
				Silicon carbide	0	0	10
Curing agent	0.025	0.025	0.025
				Curing accelerator	0.001	0.001	0.001
Baking conditions	120 ℃ for 5 minutes	10 minutes at 60 DEG C	5 minutes at 150 DEG C
				Thickness of adhesive layer	2μm	5μm	1μm

In the above examples 1 to 27, the preparation process of the ceramic adhesive layer was as follows: dissolving one of acrylic pressure-sensitive adhesive, acrylic glue and silicone rubber resin, namely methyl phenyl silicone resin, fluorine-silicon modified polyester resin and fluorine-silicon modified acrylic resin by using an organic solvent, adding a certain amount of alumina, zirconia, silica, silicon carbide and an auxiliary agent, mixing to prepare a ceramic coating, coating the ceramic coating on the surface of the high-temperature resistant organic silicon layer by using a silk-screen printing machine or a gravure printing machine, drying for 2-10 minutes at the drying condition of 50-70 ℃, and covering 70g of glassine paper on the ceramic coating.

The high temperature resistant labels obtained in examples 1 to 27 were cut to a printable label size of 40mm x 100 mm.

Test example:

the following tests were carried out using the 40mm by 100mm size labels cut from examples 1 to 27 above and the control:

printing test: the carbon ribbon is a black ribbon originally arranged in the zebra, and the printing concentration is 10%.

And (3) high temperature resistance test: the labels of examples 1-27 were applied to a steel plate and baked in a 500 ℃ tube oven for 72 hours.

With respect to the printed pattern after baking, the pattern clearly does not fade as a, the pattern dye has faded but still clearly visible as B, and the pattern is not visible or faded and disappears as C.

Regarding the appearance after baking, there was no significant change or slight yellowing as A, slight wrinkling at the edge as B, severe edge wrinkling or coating peeling or blistering in the middle of the label as C.

The adhesion of the coating after baking was evaluated using a rub resistance test, with a weight loss of <1% being a, a weight loss of 1-2% being B, and a weight loss of >2% being C.

Adhesion test on the labels after baking: evaluation was performed by the disk peel test with a mass >99% for a,99% for B and <98% for C.

The evaluation results are shown in table 6:

TABLE 6 Experimental results Table

As can be seen from Table 6, the high temperature-resistant printed layers using the formulations of examples 1-27 can be maintained at a high temperature of 500 ℃ or higher for at least 72 hours, and the printed patterns are clear, fadeless or slightly faded, have no significant change in appearance or slightly yellow, and have good high temperature resistance. The ceramic adhesive layers prepared according to the formulations of examples 1 to 27 have good adhesion, and the quality of the ceramic adhesive layers is still at least more than 98% after the disk peeling test at a high temperature of more than 500 ℃ for 72 hours. And although the ceramic adhesive layer has the embodiment with the weight loss of more than 2%, the embodiment with the weight loss of more than 2% still meets the requirement of certain real conditions (such as baking at 200-300 ℃ for 50 hours) due to the relatively harsh test conditions (baking at 500 ℃ for 72 hours) of each embodiment, and has better adhesive force compared with the existing composite film. Therefore, the refractory ceramic composite films obtained by the formulations of examples 1-27 and the experimental conditions can keep the fastness for a long time, have good pattern definition, have good adhesive force of the adhesive layer, are not easy to fall off by bubbles and the like compared with the existing composite films.

According to tables 1, 2 and 6, the pattern definition is superior to that of the other embodiments in examples 1, 7 to 10, 16 to 19, and 25 to 27, that is, the first group and the seventh to ninth groups. According to the parameter conditions of the examples, the parameter formulas are mutually cooperated, and the pattern definition can be better obtained by using the parameters of the examples compared with other examples.

From tables 1, 2 and 6, it can be seen that the coating adhesion of the first three groups of embodiments, i.e., embodiment 1/10/19, embodiment 2/11/20 and embodiment 3/12/21, is substantially better than that of the other groups of embodiments. It can be seen that the print coating formulations and preparation parameters using the first three sets of examples are superior to those of the other sets of examples. According to the parameter conditions of the examples, the parameter formulas are mutually cooperated, and the adhesion of the high-temperature-resistant printing coating obtained by adopting the parameters of the examples is better than that of the high-temperature-resistant printing coating obtained by other examples.

From tables 3 to 6, the adhesion of examples 1 to 9 and examples 19 to 27 is superior to that of examples 10 to 18, and it can be seen that the high temperature resistant silicone layer, the ceramic adhesive layer formulation and the preparation parameters of examples 1 to 9 and examples 19 to 27 are superior to those of examples 10 to 18. Carry out the experiment under high temperature environment, the adhesion on ceramic gluing layer is except selecting the proportion etc. with silicone resin and is relevant, because the silicone resin that this embodiment selected all adopts through the screening, generally can both satisfy the demand, so ceramic gluing layer adhesion mainly can receive the condition influence of toasting, adopts the low temperature to toast for a long time and does not do benefit to the adhesion on gluing layer. The ceramic adhesive layer is baked for 5min at the temperature of 120-150 ℃, so that the loss of the adhesive force of the ceramic adhesive layer can be reduced.

Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.

In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood according to specific situations by those of ordinary skill in the art.

In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature "under," "beneath," and "under" a second feature may be directly under or obliquely under the second feature, or may simply mean that the first feature is at a lesser elevation than the second feature.

In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (6)

1. The high-temperature-resistant ceramic composite film of the metal substrate is characterized by comprising a high-temperature-resistant printing layer, the metal substrate, a high-temperature-resistant organic silicon layer and a ceramic adhesive layer, wherein the high-temperature-resistant printing layer and the high-temperature-resistant organic silicon layer are coated on two sides of the metal substrate respectively, and the ceramic adhesive layer is arranged on the high-temperature-resistant organic silicon layer;

the ceramic adhesive layer comprises one of acrylic acid pressure-sensitive adhesive, acrylic glue and silicon rubber resin, one or more of methyl phenyl silicon resin, fluorine-silicon modified polyester resin and fluorine-silicon modified acrylic resin, and one or more of alumina, zirconia, silicon dioxide and silicon carbide; the preparation method of the ceramic adhesive layer comprises the steps of dissolving one of acrylic pressure-sensitive adhesive, acrylic adhesive and silicone rubber resin, one or more of methyl phenyl silicone resin, fluorine-silicon modified polyester resin and fluorine-silicon modified acrylic resin with an organic solvent, adding one or more of alumina, zirconia, silica and silicon carbide and a second auxiliary agent, mixing to prepare a ceramic coating, coating the ceramic coating on the surface of a high-temperature-resistant organic silicon layer, and baking for 5min at 120-150 ℃;

the components of the high-temperature-resistant printing layer comprise one or more of fluorine-silicon modified acrylic resin and fluorine-silicon modified polyester resin, one or more of cellulose propionate, vinyl acetate and hydroxypropyl methyl cellulose, one or more of titanium dioxide, lithopone, zinc powder and aluminum powder, and zinc stearate; the preparation method of the high-temperature-resistant printing layer comprises the steps of dissolving one or more of fluorine-silicon modified acrylic resin and fluorine-silicon modified polyester resin and one or more of cellulose propionate, vinyl acetate and hydroxypropyl methyl cellulose by using an organic solvent, adding one or more of titanium dioxide, lithopone, zinc powder and aluminum powder and a first auxiliary agent, mixing to prepare a high-temperature-resistant printing coating liquid, coating the high-temperature-resistant printing coating liquid on one side surface of a metal substrate, and drying.

2. The metal-based refractory ceramic composite film according to claim 1, wherein the first auxiliary agent comprises one or more of a dispersant, an anti-settling agent, and a thickener; the titanium dioxide is rutile type titanium dioxide, and the particle size of the titanium dioxide is D90.1-1.5 mu m; the drying temperature is 60-250 ℃, and the drying time is 2-10 minutes.

3. The metal-based refractory ceramic composite film according to claim 1 or 2, wherein the refractory silicone layer comprises one or more of a methyl phenyl silicone resin, a fluorosilicone-modified polyester resin, and a fluorosilicone-modified acrylic resin;

the preparation method of the high-temperature-resistant organic silicon layer comprises the steps of coating organic silicon resin on the other side of the metal substrate and baking for 5-10 minutes at the temperature of 60-250 ℃.

4. The metal-based refractory ceramic composite film according to claim 1 or 2, wherein the second auxiliary agent comprises a curing agent and a curing accelerator, the curing agent comprises methyl ethyl ketone peroxide, and the curing accelerator comprises silica sol; the drying temperature is 50-70 ℃, and the drying time is 2-10 minutes; the particle sizes of the alumina, the zirconia, the silica and the silicon carbide are D90.1-0.5 mu m.

5. The metal-based refractory ceramic composite film according to claim 1 or 2, further comprising a substrate covering the ceramic adhesive layer; or/and the metal base is a hard aluminum foil base material, the thickness of the metal base is 25-150 mu m, the thickness of the high-temperature-resistant printing layer is 2-10 mu m, the thickness of the high-temperature-resistant organic silicon layer is 5-25 mu m, and the thickness of the ceramic adhesive layer is 2-10 mu m.

6. A method for preparing the metal-based refractory ceramic composite membrane according to any one of claims 1 to 5, comprising the steps of:

s1, degreasing a metal base material, and then applying corona to two sides to obtain a metal substrate;

s2, coating a high-temperature-resistant printing coating on the metal substrate and drying;

s3, coating a high-temperature-resistant organic silicon layer on the reverse side of the metal substrate coated with the high-temperature-resistant printing layer and drying;

s4, coating a ceramic adhesive layer on the high-temperature-resistant organic silicon layer;

and S5, covering a release film substrate on the ceramic adhesive layer.

Images