Acrylic acid adhesive resin for high-temperature-resistant non-adhesive-residue metal plate and preparation method of acrylic acid adhesive resin

Abstract

The invention discloses a high-temperature-resistant non-adhesive-residue acrylic acid adhesive for a metal plate and a preparation method of the high-temperature-resistant non-adhesive-residue acrylic acid adhesive. The high-temperature-resistant non-adhesive-residue acrylic acid adhesive is prepared from 5-15% by mass of butyl methacrylate, 5-10% by mass of ethyl acrylate, 5-15% by mass of acrylonitrile, 0-10% by mass of maleic anhydride, 0-10% by mass of glycidyl methacrylate, 0-3% by mass of acrylic acid, 0.1-2% by mass of an initiator and 50-70% by mass of ethyl acetate. The acrylic acid adhesive resin is appropriate in viscosity, still stable in stripping force and excellent in heat resistance after being coated on a PET (polyethylene terephthalate) film, cured and the like, pasted on a stainless steel metal plate and baked for 2 hours at the temperature of 150 DEG C, no adhesive is left after stripping, and a good technical effect is achieved in comprehensive performance.

Description

Technical Field

[0001] The invention relates to an acrylic adhesive resin for a high temperature resistant non-residue adhesive metal plate and a preparation method thereof, belonging to the technical field of polymer resins. Background Art

[0002] In modern industry and manufacturing, the widespread use of metal materials has led to an increasing demand for surface protection. Metals are susceptible to corrosion, scratches, pollution and other damage during storage, transportation and processing, which affects their performance and appearance quality.

[0003] In order to effectively protect the metal surface, protective film technology came into being. As an important adhesive, acrylic adhesive plays a key role in metal protective film.

[0004] Acrylic adhesives have a number of advantages that make them suitable for metal protective film applications. First, they have good bonding properties and can be firmly attached to metal surfaces. Second, they have a certain degree of flexibility and weather resistance, which can adapt to the use of metals in different environmental conditions. In addition, acrylic adhesives excel in chemical stability and can resist corrosion from a variety of chemicals.

[0005] With the continuous advancement of science and technology, the performance requirements for metal protective films are getting higher and higher. For example, higher transparency without affecting the appearance of the metal, better scratch resistance to enhance the protection effect, and easier peeling without residual glue. These demands have promoted the continuous innovation and development of acrylic adhesive technology, prompting R&D personnel to optimize and improve its formula and process to meet the market's diversified and high-performance requirements for metal protective films.

[0006] The present invention develops an acrylic adhesive resin with excellent heat resistance, good peeling force stability and suitable viscosity through a large number of experimental screenings and the selection of acrylic monomers, initiators, synthesis conditions and additives. Summary of the invention

[0007] Purpose of the invention: At present, for the metal plate protective film, the functional groups in the glue react chemically with the metal plate surface and form chemical bonds, causing a sharp increase in peeling force, resulting in residual glue on the metal plate when the metal plate protective film pressure-sensitive adhesive is peeled off. At the same time, the high temperature resistance of the metal plate protective film pressure-sensitive adhesive is not very good, and the peeling force increases a lot after high temperature. Therefore, it is urgent to invent a pressure-sensitive adhesive that can withstand higher temperatures and whose peeling force increases by less than 3 times after high temperature, which has become an urgent problem to be solved.

[0008] Technical solution, in order to achieve the above purpose, the technical solution adopted by the present invention is:

[0009] A high temperature resistant non-residue acrylic adhesive resin for metal plates, which is made from the following raw materials: butyl methacrylate, ethyl acrylate, acrylonitrile, maleic anhydride, glycidyl methacrylate, acrylic acid, initiator, ethyl acetate;

[0010] As a preferred embodiment, the above-mentioned high temperature resistant non-residue adhesive resin for metal plates is made of the following raw materials in percentage by mass:

[0011] 5-15% butyl methacrylate, 5-10% ethyl acrylate, 5-15% acrylonitrile, 0-10% maleic anhydride, 0-10% glycidyl methacrylate, 0-3% acrylic acid, 0.1-2% initiator, 50-70% ethyl acetate;

[0012] As a preferred embodiment, the above-mentioned high-temperature resistant and non-residue acrylic adhesive resin for metal plates is made of the following raw materials in percentage by mass: 10% butyl methacrylate, 8% ethyl acrylate, 12% acrylonitrile, 4% maleic anhydride, 3% glycidyl methacrylate, 2% acrylic acid, 1% initiator, and 60% ethyl acetate.

[0013] As a preferred embodiment, the high temperature resistant and non-residue adhesive metal plate described above uses an acrylic pressure-sensitive adhesive resin, and the initiator is benzoyl peroxide.

[0014] The method for preparing a high temperature resistant non-residue adhesive acrylic adhesive resin for metal plates of the present invention comprises the following steps:

[0015] (1) butyl methacrylate, ethyl acrylate, acrylonitrile, glycidyl methacrylate, acrylic acid, and half of the initiator are uniformly mixed to obtain a mixed monomer; 15 to 40% of the mixed monomer, all of the maleic anhydride, and part of the ethyl acetate are added to a reaction device, and heated to a certain temperature while stirring;

[0016] (2) Evenly mix the remaining mixed monomers and part of ethyl acetate, and add them together into the dropping funnel;

[0017] (3) When the temperature of the reaction device in step (1) reaches a predetermined value, the mixture in step (2) is added dropwise, and the mixture is kept warm for a period of time after the addition is completed. Then, an initiator is added, and the mixture is kept warm for a period of time again. Then, a second portion of the initiator is added, and the mixture is kept warm for a period of time. After the insulation is completed, the remaining ethyl acetate is added and stirred to obtain the product.

[0018] As a preferred embodiment, the method for preparing a high temperature resistant non-residue adhesive acrylic adhesive resin for metal plates of the present invention comprises the following steps:

[0019] (1) butyl methacrylate, ethyl acrylate, acrylonitrile, glycidyl methacrylate, acrylic acid, and half of the initiator are uniformly mixed, and 15-40% of the mixed monomers, all of the maleic anhydride, and 25% of the total amount of ethyl acetate are added to a reaction device, and the mixture is heated while being stirred and kept at 80-88° C. for 1 hour;

[0020] (2) Evenly mix the remaining mixed monomers and 20% of the total amount of ethyl acetate and add them together into the dropping funnel;

[0021] (3) When the temperature of the reaction apparatus in step (1) is maintained at 80-88° C. for 1 hour, the mixture in step (2) is added dropwise, and the mixture is added dropwise over 2-3 hours. After the addition is completed, the mixture is kept warm for 1-2 hours, and then the first portion of the initiator is added. The mixture is kept warm again for 1-2 hours. Then, the second portion of the initiator is added. The mixture is kept warm for 1-2 hours. After the insulation is completed, the remaining ethyl acetate is added and stirred for 5-10 minutes to obtain the product.

[0022] As a preferred embodiment, in the above-mentioned method for preparing the acrylic pressure-sensitive adhesive resin for high-temperature resistant and non-residue metal plate, the initiator is benzoyl peroxide.

[0023] As a preferred embodiment, the above-mentioned method for preparing a high-temperature resistant and non-residue acrylic adhesive resin for metal plates, in step (3), after the temperature of the reaction device in step (1) is maintained at 80-88°C for 1 hour, the mixture of step (2) is added dropwise, and the dripping is completed within 2 hours. After the dripping is completed, the mixture is kept warm for 1 hour, and then the first portion of initiator is added, and the mixture is kept warm again for 1 hour. Then, the second portion of initiator is added, and the mixture is kept warm for 1.5 hours. After the insulation is completed, the remaining ethyl acetate is added and stirred for 5-10 minutes to obtain the product.

[0024] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0025] The present invention adopts conventional processes through a large number of experimental screenings, and at the same time preferably adjusts the best acrylic monomer, initiator system and additive composition. The present invention selects BPO as the initiator, and at a relatively low reaction temperature of about 80°C, a relatively short dropwise addition time and a method of heat preservation again after adding the initiator make the resin have a higher conversion rate. The relatively low reaction temperature and relatively short dropwise addition time make the resin molecular weight controlled at a relatively high level without affecting the film-forming performance of the resin.

[0026] The invention creatively introduces acrylonitrile and glycidyl methacrylate in a specific ratio, so that the resin has better heat resistance and stable peeling degree, and there is no residual adhesive after peeling. At the same time, after adding a specific amount of maleic anhydride, the resin has good peeling stability on the steel plate after high-temperature baking.

[0027] The acrylic adhesive resin of the invention has suitable viscosity and has excellent properties such as stable peeling force after high-temperature baking, good heat resistance, and no residual adhesive after peeling. DETAILED DESCRIPTION

[0028] Example 1

[0029] 1. A high temperature resistant non-residue acrylic adhesive resin for metal plates, which is made of the following raw materials in percentage by weight:

[0030] 10% butyl methacrylate, 8% ethyl acrylate, 12% acrylonitrile, 4% maleic anhydride, 3% glycidyl methacrylate, 2% acrylic acid, 1% initiator (benzoyl peroxide), 60% ethyl acetate.

[0031] 2. The method for preparing a high temperature resistant non-residue adhesive acrylic adhesive resin for metal plates of the present invention comprises the following steps:

[0032] (1) Add 90 g of ethyl acetate, 18 g of butyl methacrylate, 14.4 g of ethyl acrylate, 21.6 g of acrylonitrile, 24 g of maleic anhydride, 5.4 g of glycidyl methacrylate, 3.6 g of acrylic acid, and 0.9 g of benzoyl peroxide into a reaction apparatus, stir and heat to 80-88° C., and keep warm for 1 hour;

[0033] (2) 72 g of ethyl acetate, 42 g of butyl methacrylate, 33.6 g of ethyl acrylate, 50.4 g of acrylonitrile, 12.6 g of glycidyl methacrylate, 8.4 g of acrylic acid, and 2.1 g of benzoyl peroxide were mixed uniformly and added to a dropping funnel;

[0034] (3) When the temperature of the reaction device in step (1) reaches 80-88° C. and is maintained at that temperature for 1 hour, the mixed monomer and initiator in step (2) are added dropwise, and the dropping is completed over 2 hours. After the dropping is completed, the mixture is kept warm for 1 hour. After the heat preservation is completed, 20 grams of ethyl acetate and 1.5 grams of benzoyl peroxide are added, and the mixture is kept warm for another 1 hour. After the heat preservation is completed, 20 grams of ethyl acetate and 1.5 grams of benzoyl peroxide are added again, and the mixture is kept warm for another 1.5 hours. After the heat preservation is completed, 158 grams of ethyl acetate is added and stirred for 10 minutes to obtain a final resin with a solid content of 39.2% and a viscosity of 5600 mPa·s.

[0035] Example 2

[0036] 1. A high temperature resistant non-residue acrylic adhesive resin for metal plates, which is made of the following raw materials in percentage by weight:

[0037] 16% butyl methacrylate, 8% ethyl acrylate, 6% acrylonitrile, 4% maleic anhydride, 3% glycidyl methacrylate, 2% acrylic acid, 1% initiator, 60% ethyl acetate.

[0038] 2. A method for preparing a high temperature resistant non-residue adhesive acrylic adhesive resin for metal plates, comprising the following steps:

[0039] (1) Add 90 g of ethyl acetate, 28.8 g of butyl methacrylate, 14.4 g of ethyl acrylate, 10.8 g of acrylonitrile, 24 g of maleic anhydride, 5.4 g of glycidyl methacrylate, 3.6 g of acrylic acid, and 0.9 g of benzoyl peroxide into a reaction apparatus, stir and heat to 80-88° C., and keep warm for 1 hour;

[0040] (2) 72 g of ethyl acetate, 67.2 g of butyl methacrylate, 33.6 g of ethyl acrylate, 25.2 g of acrylonitrile, 12.6 g of glycidyl methacrylate, 8.4 g of acrylic acid, and 2.1 g of benzoyl peroxide were mixed uniformly and added to a dropping funnel;

[0041] (3) When the temperature of the reaction device in step (1) reaches 80-88° C. and is maintained at that temperature for 1 hour, the mixed monomer and initiator in step (2) are added dropwise, and the dropping is completed over 2 hours. After the dropping is completed, the mixture is kept warm for 1 hour. After the heat preservation is completed, 20 grams of ethyl acetate and 1.5 grams of benzoyl peroxide are added, and the mixture is kept warm for another 1 hour. After the heat preservation is completed, 20 grams of ethyl acetate and 1.5 grams of benzoyl peroxide are added again, and the mixture is kept warm for another 1.5 hours. After the heat preservation is completed, 158 grams of ethyl acetate are added and stirred for 10 minutes to obtain a final resin with a solid content of 39.5% and a viscosity of 5100 mPa·s.

[0042] Example 3 Comparative Example

[0043] 1. A high temperature resistant non-residue acrylic adhesive resin for metal plates, which is made of the following raw materials in percentage by weight:

[0044] 14% butyl methacrylate, 8% ethyl acrylate, 12% acrylonitrile, 3% glycidyl methacrylate, 2% acrylic acid, 1% initiator, 60% ethyl acetate.

[0045] 2. A method for preparing a high temperature resistant non-residue adhesive acrylic adhesive resin for metal plates, comprising the following steps:

[0046] (1) Add 90 g of ethyl acetate, 25.2 g of butyl methacrylate, 14.4 g of ethyl acrylate, 21.6 g of acrylonitrile, 5.4 g of glycidyl methacrylate, 3.6 g of acrylic acid, and 0.9 g of benzoyl peroxide to a reaction apparatus, stir and heat to 80-88° C., and keep warm for 1 hour;

[0047] (2) 72 g of ethyl acetate, 58.8 g of butyl methacrylate, 33.6 g of ethyl acrylate, 50.4 g of acrylonitrile, 12.6 g of glycidyl methacrylate, 8.4 g of acrylic acid, and 2.1 g of benzoyl peroxide were mixed uniformly and added to a dropping funnel;

[0048] (3) When the temperature of the reaction device in step (1) reaches 80-88°C and is maintained at that temperature for 1 hour, the mixed monomer and initiator in step (2) are added dropwise, and the dropping is completed for 2 hours. After the dropping is completed, the mixture is kept warm for 1 hour. After the heat preservation is completed, 20 grams of ethyl acetate and 1.5 grams of benzoyl peroxide are added, and the mixture is kept warm for another 1 hour. After the heat preservation is completed, 20 grams of ethyl acetate and 1.5 grams of benzoyl peroxide are added again, and the mixture is kept warm for another 1.5 hours. After the heat preservation is completed, 158 grams of ethyl acetate are added and stirred for 10 minutes to obtain a final resin with a solid content of 39.3% and a viscosity of 4600 mPa·s.

[0049] Example 4 Performance Test

[0050] The acrylic adhesive resin prepared in Example 1, Example 2 and Example 3 was mixed evenly with the curing agent 651P in a mass ratio of 10:2, and then directly coated on a substrate (50 μm PET film, adhesive thickness 20 μm) using a small coating machine. After coating, it was directly placed in a 90°C oven for baking for 6 to 8 minutes, and the release paper was rewound to obtain a finished film roll, which was then placed in a 55°C oven for maturation for 2 days.

[0051] After the above-mentioned matured film product is left for 24 hours (to remove internal stress), it is pasted to the stainless steel plate. After it is pressed with a pressure of 2 kg by a molding machine, the performance of the sample is tested at room temperature. Samples are made according to the previous steps, and the pasted stainless steel plates are placed in a 150°C oven for high temperature baking for 2 hours. After 2 hours, they are taken out and placed at room temperature for performance testing.

[0052] The resin solid content is measured according to GB / T 2793-1995, the resin viscosity is measured according to GB / T 2794-1995, and the 180° peel strength is measured according to GB / T 2792-1998. The test results are shown in the following table:

[0053]

[0054] The above data show that the present invention has better comprehensive performance and excellent heat resistance. By comparing Examples 1 and 2, it can be found that when the amount of acrylonitrile increases, the peel strength of the resin will be improved, but the viscosity of the resin will also increase, and the residual adhesive will be improved from slight residual adhesive to no residual adhesive after peeling. The increase of acrylonitrile will increase the viscosity of the resin, increase the elastic modulus of the resin system, increase the cohesion of the resin, increase the peel strength, and there will be no residual adhesive after peeling. At the same time, the resin also has better heat resistance and better heat resistance stability.

[0055] By comparing Examples 1 and 3, it can be found that when maleic anhydride is absent, the peeling force of the resin on the steel plate after high-temperature baking increases significantly, indicating that the reduction of maleic anhydride will reduce the heat resistance of the resin and the heat resistance stability is poor. In summary, Example 1 of the present invention is a preferred solution.

[0056] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A high temperature resistant and non-residue acrylic adhesive resin for metal plates, characterized in that: It is made from the following raw materials: butyl methacrylate, ethyl acrylate, acrylonitrile, maleic anhydride, glycidyl methacrylate, acrylic acid, initiator and ethyl acetate.

2. The high temperature resistant non-residue acrylic adhesive resin for metal plates according to claim 1, characterized in that: The invention is prepared from the following raw materials in percentage by mass: 5-15% of butyl methacrylate, 5-10% of ethyl acrylate, 5-15% of acrylonitrile, 0-10% of maleic anhydride, 0-10% of glycidyl methacrylate, 0-3% of acrylic acid, 0.1-2% of initiator and 50-70% of ethyl acetate.

3. The high temperature resistant non-residue acrylic adhesive resin for metal plates according to claim 1, characterized in that: The invention is prepared from the following raw materials in percentage by mass: 10% of butyl methacrylate, 8% of ethyl acrylate, 12% of acrylonitrile, 4% of maleic anhydride, 3% of glycidyl methacrylate, 2% of acrylic acid, 1% of initiator and 60% of ethyl acetate.

4. The high temperature resistant non-residue acrylic adhesive resin for metal plates according to any one of claims 1 to 3, characterized in that: The initiator is benzoyl peroxide.

5. The method for preparing a high temperature resistant non-residue adhesive acrylic adhesive resin for metal plates according to any one of claims 1 to 4, characterized in that: The following steps are involved: (1) butyl methacrylate, ethyl acrylate, acrylonitrile, glycidyl methacrylate, acrylic acid, and half of the initiator are uniformly mixed to obtain a mixed monomer; 15 to 40% of the mixed monomer, all of the maleic anhydride, and part of the ethyl acetate are added to a reaction device, and heated to a certain temperature while stirring; (2) Evenly mix the remaining mixed monomers and part of ethyl acetate, and add them together into the dropping funnel; (3) When the temperature of the reaction device in step (1) reaches a predetermined value, the mixture in step (2) is added dropwise, and the mixture is kept warm for a period of time after the addition is completed. Then, an initiator is added, and the mixture is kept warm for a period of time again. Then, a second portion of the initiator is added, and the mixture is kept warm for a period of time. After the insulation is completed, the remaining ethyl acetate is added and stirred to obtain the product.

6. The method for preparing a high temperature resistant non-residue adhesive acrylic adhesive resin for metal plates according to claim 5, characterized in that: The following steps are involved: (1) butyl methacrylate, ethyl acrylate, acrylonitrile, glycidyl methacrylate, acrylic acid, and half of the initiator are uniformly mixed to obtain a mixed monomer; 15-40% of the mixed monomer, all maleic anhydride, and 25% of the total amount of ethyl acetate are added to a reaction device, and the mixture is heated while being stirred, and the temperature is controlled at 80-90° C. and kept warm for 1-2 hours; (2) Evenly mix the remaining mixed monomers and 20% of the total amount of ethyl acetate and add them together into the dropping funnel; (3) When the temperature of the reaction apparatus in step (1) is maintained at 80-90° C. for 1-2 hours, the mixture in step (2) is added dropwise, and the mixture is added dropwise over 2-4 hours. After the addition is completed, the mixture is kept warm for 1-2 hours, and then the first portion of the initiator is added. The mixture is kept warm again for 1-2 hours. Then, the second portion of the initiator is added. The mixture is kept warm for 1-2 hours. After the insulation is completed, the remaining ethyl acetate is added and stirred for 5-10 minutes to obtain the product.

7. The method for preparing a high temperature resistant non-residue adhesive acrylic adhesive resin for metal plates according to claim 5 or 6, characterized in that: The initiator is benzoyl peroxide.

8. The method for preparing a high temperature resistant non-residue adhesive acrylic adhesive resin for metal plates according to claim 5 or 6, characterized in that: In step (3), after the temperature of the reaction device in step (1) is maintained at 80-88° C. for 1 hour, the mixture of step (2) is added dropwise, and the dropping is completed within 2 hours. After the dropping is completed, the mixture is kept warm for 1 hour, and then the first portion of the initiator is added, and the mixture is kept warm again for 1 hour. Then, the second portion of the initiator is added, and the mixture is kept warm for 1.5 hours. After the insulation is completed, the remaining ethyl acetate is added and stirred for 5-10 minutes to obtain the product.

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