Epoxy modified water-based acrylic resin for glass baking varnish and preparation method of epoxy modified water-based acrylic resin

Abstract

The invention discloses water-based acrylic resin for epoxy modified glass baking varnish and a preparation method of the water-based acrylic resin. The adhesive is prepared from the following components in percentage by weight: 5-10% of hydroxyethyl methylacrylate, 5-15% of butyl acrylate, 5-10% of lauryl methacrylate, 5-10% of oxazolidine ethyl acrylate, 2-10% of acrylic acid, 1-5% of epoxy resin, 0.1-3% of an initiator, 10-30% of n-butyl alcohol and 5-15% of ethylene glycol butyl ether. The optimal raw material composition and proportion are screened through a large number of experiments, the optimal synthesis process is preferably obtained through a large number of experiments, and the conversion rate reaches up to 99%. The acrylic resin disclosed by the invention has excellent adhesive force and solvent resistance, meanwhile, a coating film has the advantages of high hardness, good flexibility, high gloss and the like, and a very good technical effect is achieved in comprehensive performance.

Description

Technical Field

[0001] The invention relates to an epoxy modified glass baking varnish water-based acrylic resin, in particular to an epoxy modified glass baking varnish water-based acrylic resin with high adhesion, good solvent resistance, high hardness, good flexibility, high gloss and easy popularization and application, and a preparation method thereof, belonging to the technical field of polymer resins. Background Art

[0002] Acrylic resin has the characteristics of good transparency, bright color, corrosion resistance, high hardness and good toughness, and is widely used in coating materials. However, in certain environments, the use of ordinary acrylic resin has certain performance defects, mainly in terms of poor adhesion to the surface of certain materials, solvent resistance and mechanical properties, which affects the development and application of acrylic resin. Summary of the invention

[0003] Purpose of the invention: The purpose of the present invention is to introduce epoxy resin into acrylic resin for modification in view of the shortcomings of the prior art, preferably adjust the optimal acrylic resin monomer and initiator composition, and add special acrylic monomers such as lauryl methacrylate and ethyl acrylate to preferably prepare a water-based acrylic resin with high adhesion, good solvent resistance, good flexibility, high transparency, high hardness and other excellent comprehensive properties.

[0004] Technical solution, in order to achieve the above purpose, the technical solution adopted by the present invention is:

[0005] The invention discloses a water-based acrylic resin for epoxy-modified glass baking paint, which is prepared from the following raw materials: methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, lauryl methacrylate, oxazolidine ethyl acrylate, acrylic acid, epoxy resin, initiator, n-butanol and ethylene glycol butyl ether.

[0006] As a preferred embodiment, the above-mentioned water-based acrylic resin for epoxy-modified glass baking paint is made of the following raw materials in mass percentage: it is made of the following raw materials in mass percentage: 15-25% of methyl methacrylate, 5-10% of hydroxyethyl methacrylate, 5-15% of butyl acrylate, 5-10% of lauryl methacrylate, 5-10% of oxazolidine ethyl acrylate, 2-10% of acrylic acid, 1-5% of epoxy resin, 0.1-3% of initiator, 10-30% of n-butanol and 5-15% of ethylene glycol butyl ether.

[0007] As a preferred embodiment, the above-mentioned epoxy-modified glass baking varnish uses a water-based acrylic resin, and the initiator is tert-butyl peroxide 2-ethylhexanoate.

[0008] As a preferred embodiment, the above-mentioned water-based acrylic resin for epoxy-modified glass baking varnish is epoxy resin 601 produced by Jiangsu Sanmu Chemical Co., Ltd.

[0009] As a preferred embodiment, the water-based acrylic resin for epoxy-modified glass baking varnish described above, wherein the special acrylic ester monomers added to the resin are lauryl methacrylate and oxazolidine ethyl acrylate.

[0010] As a preferred embodiment, the above-mentioned water-based acrylic resin for epoxy-modified glass baking varnish is prepared by using n-butanol and ethylene glycol butyl ether as solvents.

[0011] The method for preparing a water-based acrylic resin for epoxy-modified glass baking varnish of the present invention comprises the following steps:

[0012] (1) Add epoxy resin, n-butanol and ethylene glycol butyl ether mixture into a reaction device and heat to 120-125° C.;

[0013] (2) Methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, lauryl methacrylate, oxazolidine ethyl acrylate, acrylic acid, and initiator are mixed evenly and added to a dropping funnel;

[0014] (3) When the temperature of the reaction device in step (1) reaches 120-125° C., the mixture in step (2) is added dropwise, and the addition is completed over 3.5-4 hours. After the addition is completed, the mixture is kept warm for 1.5-2 hours. Then, the first portion of the initiator is added, and the mixture is kept warm again for 0.5-1 hour. Then, the second portion of the initiator is added, and the mixture is kept warm again for 0.5-1 hour.

[0015] As a preferred embodiment, the above-mentioned epoxy-modified glass baking varnish uses a water-based acrylic resin, and the initiator is tert-butylbenzoyl peroxide.

[0016] As a preferred embodiment, the above-mentioned epoxy-modified glass baking varnish uses a water-based acrylic resin, and the epoxy resin is epoxy resin 601.

[0017] As a preferred embodiment, a method for preparing a water-based acrylic resin for epoxy-modified glass baking varnish is characterized in that, in step (3), when the temperature of the reaction device in step (1) reaches 120-125°C, the mixture of step (2) is added dropwise, and the mixture is added over 4 hours. After the addition, the mixture is kept warm for 2 hours, and then the first initiator is added, and the mixture is kept warm for 1 hour. Then, the second initiator is added, and the mixture is kept warm for 1 hour.

[0018] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0019] The present invention introduces epoxy resin into the acrylic resin system through a large number of experimental screenings, and at the same time preferably adjusts the best acrylic resin monomer, special acrylic monomer and initiator system composition. The epoxy resin selected by the present invention is epoxy resin 601, and the special acrylic monomer is the acrylic resin synthesized from lauryl methacrylate and ethyl acrylate. It not only has the advantages of high adhesion, good solvent resistance, and good flexibility, but also has excellent comprehensive properties such as high transparency and high hardness. In addition, the initiator used is tert-butyl peroxide 2-ethylhexanoate. At a relatively high reaction temperature of 125°C, the resin has a high conversion rate of 99% through a longer dripping time and a method of adding two portions of initiator and then keeping warm again. The acrylic resin prepared by the present invention has the advantages of high adhesion, good solvent resistance, and good flexibility, and also has excellent comprehensive properties such as high transparency and high hardness. DETAILED DESCRIPTION

[0020] Example 1

[0021] 1. A water-based acrylic resin for epoxy-modified glass baking varnish, which is made of the following raw materials in percentage by mass: 20% of methyl methacrylate, 7% of hydroxyethyl methacrylate, 6% of butyl acrylate, 8% of lauryl methacrylate, 9% of oxazolidine ethyl acrylate, 5% of acrylic acid, 3% of epoxy resin, 2% of initiator, 27% of n-butanol and 13% of ethylene glycol butyl ether.

[0022] 2. The method for preparing a water-based acrylic resin for epoxy-modified glass baking varnish of the present invention comprises the following steps:

[0023] (1) Add 30 g of epoxy resin 601 (produced by Jiangsu Sanmu Chemical Co., Ltd., the same below), 130 g of ethylene glycol butyl ether and 270 g of n-butanol into a reaction apparatus, stir and heat to 120-125° C.;

[0024] (2) Mix a certain amount of methyl methacrylate (200 g), hydroxyethyl methacrylate (70 g), butyl acrylate (60 g), lauryl methacrylate (80 g), oxazolidine ethyl acrylate (90 g), acrylic acid (50 g), and tert-butyl peroxy 2-ethylhexanoate (16 g) and add the mixture to a dropping funnel;

[0025] (3) When the temperature of the reaction device in step (1) reaches 120-125° C., the mixed monomer and initiator in step (2) are added dropwise, and the dripping is completed over 4 hours. After the dripping is completed, the temperature is kept warm for 2 hours, and then 2 grams of tert-butyl peroxide 2-ethylhexanoate (TBPO) is added. The temperature is kept warm for 1 hour, and then 2 grams of tert-butyl peroxide 2-ethylhexanoate (TBPO) is added. After the temperature is kept warm for 1 hour, the material is discharged. The final reaction conversion rate can reach 99%, and the resin solid content is 59.5%.

[0026] Comparative Example 1

[0027] A method for preparing water-based acrylic resin for epoxy-modified glass baking varnish comprises the following steps:

[0028] (1) Add 130 g of ethylene glycol butyl ether and 270 g of n-butanol into a reaction apparatus, stir and heat to 120-125° C.;

[0029] (2) Mix a certain amount of methyl methacrylate (200 g), hydroxyethyl methacrylate (70 g), butyl acrylate (90 g), lauryl methacrylate (80 g), oxazolidine ethyl acrylate (90 g), acrylic acid (50 g), and tert-butyl peroxy-2-ethylhexanoate (16 g) and add the mixture to a dropping funnel;

[0030] (3) When the temperature of the reaction device in step (1) reaches 120-125° C., the mixed monomer and initiator in step (2) are added dropwise, and the dripping is completed over 4 hours. After the dripping is completed, the temperature is kept warm for 2 hours, and then 2 grams of tert-butyl peroxide 2-ethylhexanoate (TBPO) is added. The temperature is kept warm for 1 hour, and then 2 grams of tert-butyl peroxide 2-ethylhexanoate (TBPO) is added. After the temperature is kept warm for 1 hour, the material is discharged. The final reaction conversion rate can reach 98%, and the resin solid content is 59%.

[0031] Comparative Example 2

[0032] A method for preparing water-based acrylic resin for epoxy-modified glass baking varnish comprises the following steps:

[0033] (1) Add 30 g of epoxy resin 601, 130 g of ethylene glycol butyl ether and 270 g of n-butanol into a reaction apparatus, stir and heat to 120-125° C.;

[0034] (2) Mix a certain amount of methyl methacrylate (240 g), hydroxyethyl methacrylate (70 g), butyl acrylate (100 g), oxazolidine ethyl acrylate (90 g), acrylic acid (50 g), and tert-butyl peroxy 2-ethylhexanoate (16 g) and add the mixture to a dropping funnel;

[0035] (3) When the temperature of the reaction device in step (1) reaches 120-125° C., the mixed monomer and initiator in step (2) are added dropwise, and the dripping is completed over 4 hours. After the dripping is completed, the temperature is kept warm for 2 hours, and then 2 grams of tert-butyl peroxide 2-ethylhexanoate (TBPO) is added. The temperature is kept warm for 1 hour, and then 2 grams of tert-butyl peroxide 2-ethylhexanoate (TBPO) is added. After the temperature is kept warm for 1 hour, the material is discharged. The final reaction conversion rate can reach 98%, and the resin solid content is 58.9%.

[0036] Comparative Example 3

[0037] A method for preparing water-based acrylic resin for epoxy-modified glass baking varnish comprises the following steps:

[0038] (1) Add 30 g of epoxy resin 601, 130 g of ethylene glycol butyl ether and 270 g of n-butanol into a reaction apparatus, stir and heat to 120-125° C.;

[0039] (2) Mix a certain amount of methyl methacrylate (250 g), hydroxyethyl methacrylate (70 g), butyl acrylate (100 g), lauryl methacrylate (80 g), acrylic acid (50 g), and tert-butyl peroxy-2-ethylhexanoate (16 g) and add the mixture to a dropping funnel;

[0040] (3) When the temperature of the reaction device in step (1) reaches 120-125° C., the mixed monomer and initiator in step (2) are added dropwise, and the dripping is completed over 4 hours. After the dripping is completed, the temperature is kept warm for 2 hours, and then 2 grams of tert-butyl peroxide 2-ethylhexanoate (TBPO) is added. The temperature is kept warm for 1 hour, and then 2 grams of tert-butyl peroxide 2-ethylhexanoate (TBPO) is added. After keeping warm for 1 hour, the material is discharged. The final reaction conversion rate can reach 98%, and the resin solid content is 58.8%.

[0041] Comparative Example 4

[0042] A method for preparing water-based acrylic resin for epoxy-modified glass baking varnish comprises the following steps:

[0043] (1) Add 30 g of epoxy resin 601, 130 g of ethylene glycol butyl ether and 270 g of n-butanol into a reaction apparatus, stir and heat to 120-125° C.;

[0044] (2) Mix a certain amount of methyl methacrylate (200 g), hydroxyethyl methacrylate (70 g), butyl acrylate (60 g), lauryl methacrylate (80 g), oxazolidine ethyl acrylate (90 g), acrylic acid (50 g), and tert-butyl peroxy 2-ethylhexanoate (16 g) and add the mixture to a dropping funnel;

[0045] (3) When the temperature of the reaction device in step (1) reaches 120-125°C, the mixed monomer and initiator in step (2) are added dropwise, and the dripping is completed over 4 hours. After the dripping is completed, the temperature is kept for 2 hours, and then 2 grams of benzoyl peroxide (BPO) are added, and the temperature is kept for 1 hour. Then, 2 grams of benzoyl peroxide (BPO) are added, and the temperature is kept for 1 hour. The material is discharged after the final reaction conversion rate is only 92%, and the resin solid content is 55.2%.

[0046] Application Example 1

[0047] 1. The acrylic resins prepared in Example 1 and Comparative Examples 1, 2, 3 and 4 were prepared into baking varnish according to the formula in Table 1.

[0048] Table 1 Acrylic resin water-based glass paint formula composition

[0049]

[0050]

[0051] Add 20% diluted spray, bake at 170℃ for 20 minutes.

[0052] 2. Paint film detection

[0053] The baking varnish prepared from the acrylic resin of the above Example 1, Comparative Examples 1, 2, 3 and 4 was tested as follows:

[0054] Among them, the hardness (pencil scratch) is measured according to "GB / T6739-1996 Coating Pencil Hardness Determination Method"; the impact (recoil) is measured according to "GBT1732-93 Paint Film Impact Resistance Determination Method"; the adhesion (circle method) is measured according to "GB / T1720-79 (89) Paint Film Adhesion Determination Method"; the specific varnish test results are shown in Table 2 and Table 3:

[0055] Table 2 Mechanical properties and contact angle test results of paint films

[0056]

[0057] The above experimental results show that the present invention screens out various reaction raw material compositions through a large number of experiments, especially through the compatibility of epoxy resin 601, lauryl methacrylate and ethyl acrylate, and the water-based acrylic resin for epoxy-modified glass baking paint prepared not only has the advantages of high adhesion, good solvent resistance, good flexibility, etc., but also has excellent comprehensive properties such as high transparency and high hardness. It can overcome the shortcomings of the existing technology and achieve good unexpected technical effects.

[0058] 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 water-based acrylic resin for epoxy-modified glass baking varnish, characterized in that: It is made from the following raw materials: methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, lauryl methacrylate, oxazolidine ethyl acrylate, acrylic acid, epoxy resin, initiator, n-butanol and ethylene glycol butyl ether.

2. The water-based acrylic resin for epoxy-modified glass baking varnish according to claim 1, characterized in that: The invention is prepared from the following raw materials in percentage by mass: 15-25% of methyl methacrylate, 5-10% of hydroxyethyl methacrylate, 5-15% of butyl acrylate, 5-10% of lauryl methacrylate, 5-10% of oxazolidine ethyl acrylate, 2-10% of acrylic acid, 1-5% of epoxy resin, 0.1-3% of initiator, 10-30% of n-butanol and 5-15% of ethylene glycol butyl ether.

3. The water-based acrylic resin for epoxy-modified glass baking varnish according to claim 1, characterized in that: The invention is prepared from the following raw materials in percentage by mass: 20% of methyl methacrylate, 7% of hydroxyethyl methacrylate, 6% of butyl acrylate, 8% of lauryl methacrylate, 9% of oxazolidine ethyl acrylate, 5% of acrylic acid, 3% of epoxy resin, 2% of initiator, 27% of n-butanol and 13% of ethylene glycol butyl ether.

4. The water-based acrylic resin for epoxy-modified glass baking varnish according to claim 1, characterized in that: The initiator is tert-butyl peroxy 2-ethylhexanoate.

5. The water-based acrylic resin for epoxy-modified glass baking varnish according to any one of claims 1 to 4, characterized in that: The epoxy resin is epoxy resin 601 produced by Jiangsu Sanmu Chemical Co., Ltd.

6. The water-based acrylic resin for epoxy-modified glass baking varnish according to any one of claims 1 to 4, characterized in that: The solvents of the resin are n-butanol and ethylene glycol butyl ether.

7. The method for preparing a water-based acrylic resin for epoxy-modified glass baking varnish according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) Add epoxy resin, n-butanol and ethylene glycol butyl ether mixture into a reaction device and heat to 110-130° C.; (2) Methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, lauryl methacrylate, oxazolidine ethyl acrylate, acrylic acid, and initiator are mixed evenly and added to a dropping funnel; (3) When the temperature of the reaction device in step (1) reaches 110-130° C., start to dropwise add the mixture in step (2), keep the temperature for a period of time after the dropwise addition is completed, then add the first portion of the initiator, keep the temperature for a period of time again, then add the second portion of the initiator, and keep the temperature for a period of time again, to obtain the product.

8. The method for preparing a water-based acrylic resin for epoxy-modified glass baking varnish according to claim 7, characterized in that: The following steps are involved: (1) Add epoxy resin, n-butanol and ethylene glycol butyl ether mixture into a reaction device and heat to 120-130° C.; (2) Methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, lauryl methacrylate, oxazolidine ethyl acrylate, acrylic acid, and initiator are mixed evenly and added to a dropping funnel; (3) When the temperature of the reaction device in step (1) reaches 120-130° C., the mixture in step (2) is added dropwise, and the addition is completed within 1-4 hours. After the addition is completed, the mixture is kept warm for 0.5-2 hours. Then, the first portion of the initiator is added, and the mixture is kept warm again for 0.5-1.5 hours. Then, the second portion of the initiator is added, and the mixture is kept warm again for 0.5-1.5 hours.

9. The method for preparing a water-based acrylic resin for epoxy-modified glass baking varnish according to claim 8, characterized in that: In step (3), when the temperature of the reaction device in step (1) reaches 120-125° C., the mixture of step (2) is added dropwise, and the mixture is added dropwise over 4 hours. After the addition is completed, the mixture is kept warm for 2 hours, 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 again for 1 hour.

10. Use of the water-based acrylic resin for epoxy-modified glass baking varnish according to any one of claims 1 to 6 in preparing glass baking varnish coating films.

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