Mirror silver resin with excellent thermal insulation performance and preparation method thereof

Abstract

The present invention belongs to the field of thermal insulation resin technology, and in particular to a mirror silver resin with excellent thermal insulation performance and a preparation method thereof. The present invention adds boron-containing phenolic resin and aluminum oxide / copper MOF composite material to the raw materials of the prior art basis, and the mirror silver resin prepared has excellent thermal insulation, heat resistance and corrosion resistance and can reach a higher mirror degree. The boron-containing phenolic resin added by the present invention can significantly improve the heat resistance of the mirror silver resin and improve the hardness and strength of the resin, and the composite use of aluminum oxide / copper MOF composite material and epoxy resin can significantly improve the corrosion resistance of the mirror silver resin, and aluminum oxide / copper MOF composite material can effectively reflect and scatter solar radiation when shared with silver paste, and the gap in the aluminum oxide / copper MOF composite material can also reduce the transfer of heat to achieve the effect of thermal insulation.

Description

Technical Field

[0001] The invention belongs to the technical field of thermal insulation resins, and particularly relates to a mirror silver resin with excellent thermal insulation performance and a preparation method thereof. Background Art

[0002] Mirror silver ink is a solvent-based ink with special effects. Printed on the reverse side of transparent materials, it creates a mirrored effect on the front side, enhancing the product's visual appeal and aesthetics while also extending the lifespan of the coated material. Mirror silver resin, the primary resin component of mirror silver ink, typically appears transparent or translucent, with a fine and uniform texture, creating a smooth mirrored finish. Generally speaking, the need for a good mirror effect in mirror silver inks results in a relatively low resin content, which in turn results in low adhesion.

[0003] Patent CN105669906B discloses an alcohol-washing-resistant, high-temperature-resistant mirror silver resin and its preparation method. A method for preparing an alcohol-washing-resistant, high-temperature-resistant mirror silver resin comprises the following steps: 1) preparing a cellulose acetate butyrate macromonomer; 2) copolymerizing the cellulose acetate butyrate macromonomer, an acrylate monomer, and a functional acrylate monomer to obtain an alcohol-washing-resistant, high-temperature-resistant mirror silver resin. The alcohol-washing-resistant, high-temperature-resistant mirror silver resin of the present invention has a good silver powder arrangement effect, good alcohol wiping resistance (can reach more than 100 times), excellent mechanical properties, and good comprehensive performance. However, the prior art has a technical problem of not being able to improve the heat resistance and heat preservation of the mirror silver resin by adding suitable additives. Summary of the Invention

[0004] The object of the present invention is to provide a mirror silver resin with excellent thermal insulation performance and a preparation method thereof, so as to solve the technical problem in the prior art that no suitable additives are added to improve the heat resistance and thermal insulation of the mirror silver resin.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A mirror silver resin with excellent thermal insulation performance is prepared from the following components in parts by weight: 20-30 parts of cellulose, 60-80 parts of solvent, 1-3 parts of a first initiator, 1-5 parts of an aluminum oxide / copper-MOF composite material, 30-40 parts of an epoxy resin, 10-20 parts of a boron-containing phenolic resin, 50-60 parts of an acrylic monomer, and 1-3 parts of a second initiator.

[0007] A method for preparing a mirror silver resin with excellent thermal insulation performance comprises the following steps:

[0008] S1. Add cellulose and solvent into a reactor, heat to 50-60°C, add the first initiator, and heat to 85-90°C for 1-3 hours;

[0009] S2, adding the alumina / copper-MOF composite material to the epoxy resin and the boron-containing phenolic resin to prepare a thermal insulation additive;

[0010] S3. After the reaction is completed, a heat-insulating agent, an acrylic acid monomer, and a second initiator are added dropwise to the reactor under nitrogen protection for 3 to 4 hours;

[0011] S4. After the dropwise addition is completed, the reaction is carried out at 75-80° C. for 2-4 hours to obtain a mirror silver resin with excellent thermal insulation performance.

[0012] The preparation method of the aluminum oxide / copper-MOF composite material comprises the following steps:

[0013] S11, adding nano-alumina and terephthalic acid to dimethylformamide, and ultrasonicating for 10 to 15 minutes;

[0014] S12, after the ultrasonic treatment, add copper sulfate dimethylformamide solution and stir at 80-90°C for 12-16 hours;

[0015] S13, after filtering and washing, drying at 80-100° C. for 2-4 h, and grinding to obtain an aluminum oxide / copper-MOF composite material.

[0016] Preferably, the cellulose in S1 is cellulose acetate butyrate, and the solvent is any one of n-propanol, butyl acetate, and diethylene glycol monobutyl ether.

[0017] Preferably, the first initiator in S1 is any one of azobisisobutyronitrile, benzoyl peroxide, and dicumyl peroxide.

[0018] Preferably, the epoxy resin in S2 is bisphenol A epoxy resin, and the model is any one of E44, E51, and E55.

[0019] Preferably, the alumina / copper-MOF composite material in S2 is a composite material in which a copper-organic framework is anchored on the surface of nano-alumina, and the boron-containing phenolic resin model is TY03.

[0020] Preferably, the acrylic monomer in S3 is one or more combinations of acrylic acid, methyl methacrylate, hydroxyethyl methacrylate, cyclohexyl methacrylate, and isooctyl acrylate.

[0021] Preferably, the second initiator in S3 is any one of azobisisobutyronitrile, benzoyl peroxide, and dicumyl peroxide.

[0022] Preferably, the mass ratio of nano-alumina, terephthalic acid and dimethylformamide in S11 is 1:1.5 to 1.6:100.

[0023] Preferably, the concentration of copper sulfate in the S12 is 0.1 mol / L, and the mass ratio of copper sulfate to dimethylformamide is 1:2.

[0024] Preferably, the centrifugal filtration in S13 is followed by washing with deionized water for multiple times.

[0025] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0026] 1. The mirror silver resin prepared by the present invention by adding boron-containing phenolic resin and aluminum oxide / copper-MOF composite material to the raw materials based on the existing technology has excellent thermal insulation, heat resistance and corrosion resistance and can achieve a high mirror degree.

[0027] 2. The addition of boron-containing phenolic resin in the present invention can significantly improve the heat resistance of the mirror silver resin and increase the hardness and strength of the resin.

[0028] 3. The aluminum oxide / copper-MOF composite material and epoxy resin added in the present invention can significantly improve the corrosion resistance of the mirror silver resin. When the aluminum oxide / copper-MOF composite material is used together with the silver paste, it can effectively reflect and scatter solar radiation. The voids in the aluminum oxide / copper-MOF composite material can also reduce heat transfer to achieve a thermal insulation effect. DETAILED DESCRIPTION

[0029] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0030] Example 1. A mirror silver resin with excellent thermal insulation performance in this embodiment is prepared from the following ingredients in parts by weight: 20 parts of cellulose, 60 parts of solvent, 1 part of a first initiator, 3 parts of an aluminum oxide / copper-MOF composite material, 30 parts of an epoxy resin, 10 parts of a boron-containing phenolic resin, 60 parts of an acrylic monomer, and 3 parts of a second initiator.

[0031] The cellulose is cellulose acetate butyrate, the solvent is n-propanol, the first initiator is benzoyl peroxide, the epoxy resin model is E55, the boron-containing phenolic resin model is TY03, the composition of the acrylic monomer is 25 parts of acrylic acid, 15 parts of methyl methacrylate, 15 parts of hydroxyethyl methacrylate, and 5 parts of cyclohexyl methacrylate, and the second initiator is azobisisobutyronitrile.

[0032] The method for preparing the mirror silver resin with excellent thermal insulation performance of this embodiment comprises the following steps:

[0033] S1. Add the above-mentioned cellulose and solvent into a reactor, heat to 60°C, add benzoyl peroxide, and heat to 90°C for 1 hour;

[0034] S2, adding the above-mentioned number of parts of the aluminum oxide / copper-MOF composite material to the epoxy resin and the boron-containing phenolic resin to prepare a thermal insulation additive;

[0035] S3. After the reaction is completed, a heat-insulating agent, an acrylic acid monomer, and a second initiator are added dropwise to the reactor under nitrogen protection for 4 hours;

[0036] S4. After the dropwise addition is completed, the mixture is reacted at 80° C. for 2 h to obtain a mirror silver resin with excellent thermal insulation performance.

[0037] The preparation method of the aluminum oxide / copper-MOF composite material comprises the following steps:

[0038] S11, adding 1 part of nano-alumina and 1.5 parts of terephthalic acid to 100 parts of dimethylformamide, and ultrasonicating for 15 minutes;

[0039] S12, after the ultrasonic treatment, add 50 parts of 0.1 mol / L copper sulfate dimethylformamide solution and stir at 90°C for 12 hours;

[0040] S13, centrifugally filtering, washing with deionized water, drying at 100° C. for 2 h, and grinding to obtain an alumina / copper-MOF composite material.

[0041] Example 2. A mirror silver resin with excellent thermal insulation performance in this example is prepared from the following ingredients in parts by weight: 25 parts of cellulose, 75 parts of solvent, 2 parts of a first initiator, 4 parts of an alumina / copper-MOF composite material, 30 parts of an epoxy resin, 15 parts of a boron-containing phenolic resin, 55 parts of an acrylic monomer, and 2 parts of a second initiator.

[0042] The cellulose is cellulose acetate butyrate, the solvent is n-propanol, the first initiator is benzoyl peroxide, the epoxy resin model is E55, the boron-containing phenolic resin model is TY03, the components of the acrylic monomer are 20 parts of acrylic acid, 15 parts of methyl methacrylate, 10 parts of cyclohexyl methacrylate, and 10 parts of isooctyl acrylate, and the second initiator is benzoyl peroxide.

[0043] The preparation method of the aluminum oxide / copper-MOF composite material is the same as that in Example 1.

[0044] The preparation method of the above-mentioned mirror silver resin with excellent thermal insulation performance is the same as that of Example 1.

[0045] Example 3. A mirror silver resin with excellent thermal insulation performance in this example is prepared from the following ingredients in parts by weight: 30 parts of cellulose, 70 parts of solvent, 3 parts of a first initiator, 5 parts of an alumina / copper-MOF composite material, 40 parts of an epoxy resin, 10 parts of a boron-containing phenolic resin, 50 parts of an acrylic monomer, and 1 part of a second initiator.

[0046] The cellulose is cellulose acetate butyrate, the solvent is butyl acetate, the first initiator is benzoyl peroxide, the epoxy resin model is E44, the boron-containing phenolic resin model is TY03, the components of the acrylic monomer are 20 parts of acrylic acid, 15 parts of methyl methacrylate, and 15 parts of hydroxyethyl methacrylate, and the second initiator is benzoyl peroxide.

[0047] The preparation method of the aluminum oxide / copper-MOF composite material is the same as that in Example 1.

[0048] The preparation method of the above-mentioned mirror silver resin with excellent thermal insulation performance is the same as that of Example 1.

[0049] Example 4. A mirror silver resin with excellent thermal insulation performance in this example is prepared from the following ingredients in parts by weight: 20 parts of cellulose, 80 parts of solvent, 1 part of a first initiator, 3 parts of an alumina / copper-MOF composite material, 30 parts of an epoxy resin, 15 parts of a boron-containing phenolic resin, 55 parts of an acrylic monomer, and 3 parts of a second initiator.

[0050] The cellulose is nitrocellulose, the solvent is diethylene glycol monobutyl ether, the first initiator is dicumyl peroxide, the epoxy resin model is E51, the boron-containing phenolic resin model is TY03, the composition of the acrylic monomer is 20 parts of acrylic acid, 15 parts of methyl methacrylate, 15 parts of hydroxyethyl methacrylate, and 5 parts of isooctyl acrylate, and the second initiator is dicumyl peroxide.

[0051] The preparation method of the aluminum oxide / copper-MOF composite material is the same as that in Example 1.

[0052] The preparation method of the above-mentioned mirror silver resin with excellent thermal insulation performance is the same as that of Example 1.

[0053] Example 5. A mirror silver resin with excellent thermal insulation performance in this example is prepared from the following ingredients in parts by weight: 20 parts of cellulose, 60 parts of solvent, 3 parts of a first initiator, 3 parts of an alumina / copper-MOF composite material, 30 parts of an epoxy resin, 15 parts of a boron-containing phenolic resin, 55 parts of an acrylic monomer, and 1 part of a second initiator.

[0054] The cellulose is cellulose acetate butyrate, the solvent is diethylene glycol monobutyl ether, the first initiator is benzoyl peroxide, the epoxy resin model is E55, the boron-containing phenolic resin model is TY03, the composition of the acrylic monomer is 15 parts of acrylic acid, 15 parts of methyl methacrylate, 15 parts of hydroxyethyl methacrylate, and 10 parts of cyclohexyl methacrylate, and the second initiator is azobisisobutyronitrile.

[0055] The preparation method of the aluminum oxide / copper-MOF composite material is the same as that in Example 1.

[0056] The preparation method of the above-mentioned mirror silver resin with excellent thermal insulation performance is the same as that of Example 1.

[0057] Comparative Example 1: The difference between this comparative example and Example 1 is that the amount of boron-containing phenolic resin is changed to 50 parts.

[0058] Comparative Example 2: The difference between this comparative example and Example 1 is that the amount of the aluminum oxide / copper-MOF composite material is changed to 20 parts.

[0059] Comparative Example 3: This comparative example differs from Example 1 in that the boron-containing phenolic resin and the aluminum oxide / copper-MOF composite material are not added.

[0060] Test Case

[0061] Preparation of mirror silver ink: 20 parts of the resin prepared in this embodiment and the comparative example were added with 60 parts of ethyl acetate diluent, and then 40 parts of aluminum silver paste, 2 parts of S402 leveling agent, 2 parts of K450 anti-settling agent, 1 part of HR-8424 defoaming agent and 9 parts of GS-8880 curing agent were added at a stirring speed of 200 rpm to prepare a mirror silver ink.

[0062] Spray coating: spray the above-mentioned mirror silver ink on a transparent ABS plate (75 mm × 150 mm) and cure and dry at 80°C for 0.5 to 1 hour.

[0063] According to GB / T 1721-2008 “Varnishes, oils and thinners, determination of appearance and transparency”, the physical properties of the prepared resin samples such as color, appearance, uniformity, transparency, and fluidity were observed.

[0064] Corrosion resistance test

[0065] According to GB / T 1771-2007 "Determination of resistance of paints and varnishes to neutral salt spray", the test coating thickness is 90-120μm, and the salt spray damage resistance evaluation standard is unilateral spread of rust >2mm or blistering of the coating.

[0066] Impact resistance test

[0067] The impact resistance test of the coating film was carried out in accordance with the standard GB / T 1732-1993 "Determination of impact resistance of paint films", and the test coating film thickness was 20 to 30 μm.

[0068] Hardness test

[0069] The coating hardness was tested in accordance with GB / T6739-2006 “Paints and varnishes - Determination of film hardness by pencil method”, using a Zhonghua brand pencil.

[0070] Coating gloss test

[0071] According to GB / T1743-1979 "Determination of gloss of paint films", use a gloss meter to test the gloss of the coating film.

[0072] Adhesion test

[0073] According to GB / T1720-1979 "Determination of adhesion of paint and varnish films", the coating thickness is 20 to 30 μm, and the adhesion test experiment is carried out after the coating film is dried and cured for 24 hours.

[0074] Insulation test

[0075] Make a paper box measuring 50mm x 100mm x 70mm. Insulate the outside of the box with a 10cm thick foam board. Fix a 500W iodine-tungsten lamp 30cm above the top of the box to simulate sunlight for heating. Place the sample on top of the box so that the heat source directly illuminates the sample. Insert a mercury thermometer from the side of the box and place it in the center to test the insulation temperature of the coating. Before turning on the power, record the temperature inside the box. After turning on the power, start timing and reading from the beginning of the irradiation. Record the temperature inside the box every 5 minutes and calculate the temperature difference after 1 hour.

[0076] The test results are shown in Table 1 below:

[0077]

[0078]

[0079] As can be seen from the data in Table 1, the resins prepared in Examples 1 to 5 have a transparent appearance and a bluish luster, and the glossiness of the coating films ranges from 80% to 82%, indicating that the prepared resins have good stability and the mirror silver ink prepared from the resins has a good mirror effect. The corrosion resistance is between 33 and 35 days, indicating that the prepared resins have excellent corrosion resistance. The impact resistance is 50 kg×cm, the pencil hardness is 4H, and the adhesion is level 0, indicating that the prepared resins have excellent mechanical properties and strong substrate adhesion. The temperature difference in the box after 1 hour is between 17 and 18°C, indicating that the prepared resins have excellent thermal insulation properties. It further illustrates that the mirror silver resin prepared by the present invention has high stability, the prepared mirror silver ink has excellent mirror effect, excellent corrosion resistance, thermal insulation, mechanical properties, and strong substrate adhesion.

[0080] As can be seen from the data in Table 1, the amount of boron-containing phenolic resin added to Comparative Example 1 is greater than the scope specified in the present invention, resulting in a decrease in stability, a decrease in coating gloss, and a decrease in thermal insulation and mechanical properties of the obtained resin compared to the resin obtained in the embodiment. The amount of aluminum oxide / copper-MOF composite material added to Comparative Example 2 is greater than the scope specified in the present invention, resulting in a decrease in stability, a decrease in coating gloss, and a decrease in thermal insulation and mechanical properties of the obtained resin. Comparative Example 3 does not add boron-containing phenolic resin and aluminum oxide / copper-MOF composite material, and its stability and glossiness are unaffected, but its mechanical, thermal insulation and corrosion resistance properties are significantly reduced, indicating that the compounding of boron-containing phenolic resin and aluminum oxide / copper-MOF composite material can improve the mechanical, corrosion resistance and thermal insulation properties of mirror silver resin.

[0081] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

[0082] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to specific embodiments. Obviously, many modifications and variations are possible based on the contents of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. Mirror silver resin with excellent heat preservation performance, characterized in that: The invention is prepared from the following ingredients in parts by weight: 20-30 parts of cellulose, 60-80 parts of solvent, 1-3 parts of a first initiator, 1-5 parts of an alumina / copper-MOF composite material, 30-40 parts of an epoxy resin, 10-20 parts of a boron-containing phenolic resin, 50-60 parts of an acrylic monomer, and 1-3 parts of a second initiator; the cellulose is any one of cellulose acetate butyrate and nitrocellulose, and the alumina / copper-MOF composite material is a composite material in which a copper-organic framework is anchored on the surface of nano-alumina; The preparation method of the aluminum oxide / copper-MOF composite material comprises the following steps: S11, adding nano-alumina and terephthalic acid to dimethylformamide, and ultrasonicating for 10-15 minutes; S12. After the ultrasonic treatment, add copper sulfate in dimethylformamide solution and stir at 80-90°C for 12-16 hours; S13, after filtering and washing, drying at 80-100° C. for 2-4 h, and grinding to obtain an alumina / copper-MOF composite material.

2. The mirror silver resin with excellent heat preservation performance according to claim 1, characterized in that: The solvent is any one of n-propanol, butyl acetate, and diethylene glycol monobutyl ether; the first initiator is any one of azobisisobutyronitrile, benzoyl peroxide, and dicumyl peroxide; and the epoxy resin is bisphenol A epoxy resin, any one of model E44, E51, and E55.

3. The mirror silver resin with excellent heat preservation performance according to claim 1, characterized in that: The acrylic monomer is one or more combinations of acrylic acid, methyl methacrylate, hydroxyethyl methacrylate, cyclohexyl methacrylate, and isooctyl acrylate; the second initiator is any one of azobisisobutyronitrile, benzoyl peroxide, and dicumyl peroxide.

4. The mirror silver resin with excellent heat preservation performance according to claim 1, characterized in that: The boron-containing phenolic resin model is TY03.

5. The mirror silver resin with excellent heat-insulating performance according to claim 1, characterized in that: The mass ratio of nano-alumina, terephthalic acid and dimethylformamide in S11 is 1:1.5-1.6:100, the concentration of copper sulfate in S12 is 0.1 mol / L, and the mass ratio of copper sulfate to dimethylformamide is 1:2, and S13 is centrifuged and filtered before washing with deionized water for multiple times.

6. The method for preparing the mirror silver resin with excellent thermal insulation performance according to any one of claims 1 to 5, characterized in that: The steps include: S1. Add cellulose and solvent into a reactor, heat to 50-60°C, add the first initiator, and heat to 85-90°C for 1-3 hours; S2, adding the alumina / copper-MOF composite material to the epoxy resin and the boron-containing phenolic resin to prepare a thermal insulation additive; S3. After the reaction is completed, a heat-insulating agent, an acrylic acid monomer, and a second initiator are added dropwise to the reactor under nitrogen protection for 3 to 4 hours; S4. After the dropwise addition is completed, the reaction is carried out at 75-80°C for 2-4 hours to obtain a mirror silver resin with excellent thermal insulation performance.

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