CN106632882A - Preparation method of fluorine-containing cation acrylate resin cathode electrophoresis paint - Google Patents

Abstract

The invention discloses a preparation method of cathodic electrophoretic paint containing fluorine-containing cationic acrylate resin. The polyisocyanate cross-linking agent is acidified after reaction, fully mixed with hydrophobic oxide particles for preparation, and finally added with deionized water to disperse to prepare the cathodic electrophoretic coating. The present invention introduces fluorine-modified acrylate monomers into acrylate resin cathodic electrophoretic coatings, utilizes the excellent chemical resistance and low surface energy of fluorine-containing resins, thereby effectively improving the hydrophobicity of the coating film, and the hydrophobic alumina particles have excellent Hydrophobic properties. The addition of this new type of modifier not only greatly improves the hydrophobic performance of the coating, but also improves the key problem that the electrophoretic emulsion is difficult to disperse due to the presence of fluorine-containing resins in the coating, which makes the stable storage and utilization of the electrophoretic paint solution difficult.

Description

Preparation method of fluorine-containing cationic acrylate resin cathodic electrophoretic coating

technical field

The invention relates to a preparation process of a new material, in particular to a preparation method of a fluorine-containing cationic acrylate resin cathodic electrophoretic paint.

Background technique

Electrophoretic coating is a new technology developed in the 1960s. Due to its unique advantages, its application area has rapidly expanded. Electrophoretic coating can be used for everything from car bodies to small badges and eye frames. The technical content of electrophoretic coatings is very high, and its development and production are considered to be the most difficult type of coatings, and the requirements for use and management are higher than ordinary coatings.

The development of electrophoretic coatings has a history of 60 years. Since 1971, the American PPG company developed the first generation of cathodic electrophoretic coatings, and electrophoretic coatings have entered a rapid development track, especially cathodic electrophoretic coatings. Compared with electrophoretic coatings, the corrosion resistance is 3-4 times higher, and the penetration rate is 1.3-1.5 times higher, and the metal surface is not easy to ionize and dissolve during electrodeposition, which solves the problem of workpiece surface corrosion, and has been widely used. Gradually fully replaced the anodic electrophoretic coating, the current cathodic electrophoretic coating presents several schools: the anti-corrosion cationic electrophoretic coating started by the American PPG company; the cationic electrophoretic coating for cars and trucks pioneered by the German Hocehst company; The improved cationic electrophoretic coating represented by Shendong Kansai Paint Co., Ltd., and some leading cathodic electrophoretic coating companies have developed corner anti-rust, weather-resistant and low-temperature curing fourth-generation and fifth-generation cathodic electrophoretic coatings. The sixth and seventh generations have also been researched and developed in the laboratory.

There are many types of cathodic electrophoretic coatings. At present, the most widely used types mainly include: epoxy cathodic electrophoretic coatings based on the adduct of bisphenol A epoxy resin and organic amines, cathodic electrophoretic coatings mainly based on acrylate copolymers, and polyurethane cathodic electrophoretic coatings. coating. Acrylic cathodic electrophoretic coatings are widely used in bottom-surface-in-one electrophoretic coatings because of their excellent gloss retention, weather resistance, UV aging resistance, and high decorative properties.

In recent years, the rapid development of high-performance hardware products, especially lamps, bathroom accessories, metal crafts, and the continuous development and progress of electrophoretic coating technology have put forward higher requirements for the performance of coatings, especially hydrophobicity, weather resistance and decoration. Require. Traditional water-based cathodic electrophoretic coatings have poor hydrophobicity, weather resistance and decoration, and cannot meet the new requirements of high-end hardware products for water-based cathodic electrophoretic coatings. In recent years, the phenomena of superhydrophobicity (contact angle greater than 150°) and self-cleaning in nature have aroused people's research interest. How to develop a water-based cathodic electrophoretic coating film with superhydrophobic properties has become a hot spot in the research and development of resin emulsions for cathodic electrophoretic coatings.

Contents of the invention

The present invention aims at various deficiencies in the prior art, and provides a method for preparing a hydrophobic fluorine-containing cationic acrylate resin cathodic electrophoretic coating.

In order to achieve the above object, the present invention is realized by such technical scheme:

The invention discloses a preparation method of cathodic electrophoretic paint containing fluorine-containing cationic acrylate resin. The polyisocyanate cross-linking agent is acidified after reaction, fully mixed with hydrophobic oxide particles for preparation, and finally added with deionized water to disperse to prepare the cathodic electrophoretic coating.

As a further improvement, the specific preparation steps described in the present invention are: in the reaction kettle, add solvent and part of the initiator, mix the acrylate mixed monomer and epoxy functional monomer and fluorine-containing acrylate at 70-100°C The monomer mixture and part of the initiator solution are added dropwise into the reactor, and the dripping is completed within 2-4 hours, and the heat preservation reaction is continued for 2-4 hours, and then polyamine is added for ring-opening reaction, and the heat preservation reaction is continued for 2-4 hours, and finally added Stir the organic acid for 20-60 minutes, after cooling down to obtain a cationic fluorine-modified acrylate resin, and then prepare a fully-sealed polyisocyanate crosslinking agent, mix a certain amount of cationic fluorine-modified acrylate resin, fully-sealed polyisocyanate crosslinker Mix evenly with ethylene glycol monobutyl ether, organic acid and hydrophobic oxide particles, acidify at 50-70°C for 2-4 hours, then add a certain amount of deionized water, disperse for 15-30min under high-speed stirring, and control the pH If it is 5.0-6.5, a hydrophobic fluorine-containing cationic acrylate resin cathodic electrophoretic coating can be obtained.

As a further improvement, the preparation method of the fully-blocked polyisocyanate crosslinking agent of the present invention is to add isophorone diisocyanate in the reaction kettle, and slowly add diethylene glycol butyl ether dropwise under stirring conditions. Put it into the reactor, drop it in 1 hour, heat to 70°C, react for 2-4 hours, when the free NCO content is measured to be less than 0.5%, cool down and discharge.

As a further improvement, the fluorine-containing acrylate monomers described in the present invention are hexafluorobutyl methacrylate, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate, tridecafluorooctyl methacrylate, acrylic acid One or more of trifluorooctyl and perfluoroalkylethyl methacrylate.

As a further improvement, the epoxy functional monomer described in the present invention is glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether and glycidyl ether group-terminated allyl alcohol random polyether A mixture of one or more.

As a further improvement, the acrylate mixed monomer described in the present invention includes styrene, methyl methacrylate, ethyl methacrylate, butyl acrylate, isopropyl acrylate, 2-hydroxyethyl acrylate, methyl One or more of 2-hydroxyethyl acrylate and 2-hydroxypropyl methacrylate, and the polyamine is one of diethanolamine, triethanolamine, ethylenediamine, propylenediamine, butylenediamine Or multiple mixtures, the organic acid is one or more of formic acid, acetic acid, lactic acid and sulfamic acid.

As a further improvement, in the cationic fluorine-modified acrylate resin of the present invention, 25-50 parts by weight of acrylate monomers, 10-20 parts by weight of fluorine-containing acrylate monomers, 15-30 parts by weight of epoxy functional monomers parts by weight, 5-10 parts by weight of polyamine, and 0.5-2 parts by weight of initiator.

As a further improvement, the hydrophobic oxide particles in the present invention are hydrophobic alumina, preferably fumed alumina treated with octylsilane.

As a further improvement, the components of the cathodic electrophoretic coating of the present invention are 50-60 parts by weight of cationic fluorine-modified acrylate resin, 20-25 parts by weight of fully blocked polyisocyanate crosslinking agent, and 0.1 parts by weight of hydrophobic oxide particles. -2 parts by weight.

As a further improvement, after the varnish film is formed in the cathodic electrophoretic coating prepared by the present invention, the contact angle between the coating film and water is greater than 150 degrees.

The beneficial effects of the present invention are as follows:

1. The invention provides a hydrophobic cationic acrylate resin cathodic electrophoretic coating and a preparation method thereof. Ordinary acrylic resin cathodic electrophoretic coatings do not have waterproof performance. The present invention introduces fluorine-modified acrylate monomers into acrylate resin cathodic electrophoretic coatings, and utilizes the excellent chemical resistance and low surface energy of fluorine-containing resins to effectively improve the coating film. Hydrophobic properties.

2. The present invention adopts hydrophobic alumina particles as coating modifier. Hydrophobic alumina particles have excellent hydrophobic properties and are inexpensive. The addition of this new type of modifier not only greatly improves the hydrophobic performance of the coating, but also improves the key problem that the electrophoretic emulsion is difficult to disperse due to the presence of fluorine-containing resins in the coating, which makes the stable storage and utilization of the electrophoretic paint solution difficult.

3. The present invention perfectly combines acrylate and epoxy resin. Acrylate makes up for the deficiency that epoxy resin is only suitable for primer because of its excellent weather resistance, good color retention and gloss retention; acrylic acid is used Ester resin as the main resin, and hydrophobic alumina particles as the coating, they both have excellent weather resistance, and have excellent matting effect, excellent performance, long life modifier, and can be widely used in various high-quality hardware products.

detailed description

The invention discloses a cathodic electrophoretic coating with hydrophobic fluorine-containing cationic acrylate resin and a preparation method thereof. The technical scheme of the invention will be further described in detail below in conjunction with specific examples, but the scope of the invention does not Limitation to the following examples.

Example 1

(1) Preparation of cationic fluorine-modified acrylate resin

In a reaction kettle equipped with a mechanical stirring device, a thermometer, a constant pressure dropping funnel and a reflux condenser, 10 parts by weight of butyl acetate as a solvent and 0.2 parts by weight of an initiator azobisisobutyronitrile were added, and acrylic acid Ester mixed monomer (10 parts by weight of methyl methacrylate, 15 parts by weight of butyl acrylate), 15 parts by weight of glycidyl ether group-capped allyl alcohol random polyether and fluorine-containing acrylate monomer perfluoroalkyl ethyl 10 parts by weight of methyl methacrylate and 0.3 parts by weight of initiator azobisisobutyronitrile solution were added dropwise into the reactor, and the dripping was completed within 2 hours, and the reaction was continued for 2 hours. Then add 5 parts by weight of polyamine triethanolamine to carry out ring-opening reaction, continue the heat preservation reaction for 4 hours, finally add organic acid acetic acid and stir for 20 minutes, after cooling down, a cationic fluorine-modified acrylate resin is obtained.

(2) Preparation of fully blocked polyisocyanate crosslinking agent

In a reaction kettle equipped with a stirring device, a constant pressure dropping funnel and a reflux condenser, add 50 parts by weight of isophorone diisocyanate, and slowly add about 75 parts by weight of diethylene glycol butyl ether dropwise under stirring conditions. Into the reaction kettle, dropwise added in 1 hour. Heating to 70°C, reacting for 4 hours, and when the free NCO content is measured to be less than 0.5%, the temperature is lowered and the material is discharged.

(3) Preparation of cathodic electrophoretic emulsion

With the cationic fluorine-modified acrylate resin of 50 weight parts, the fully blocked polyisocyanate crosslinking agent of 20 weight parts and ethylene glycol monobutyl ether 20 weight parts, the acetic acid of quantitative and the hydrophobic aluminum oxide of 0.1 weight part ( Fumed alumina treated with octylsilane), mixed evenly, and acidified at 50°C for 4 hours. Then add 40 parts by weight of deionized water, and disperse for 15-30 minutes under high-speed stirring to obtain a hydrophobic cationic acrylate resin cathodic electrophoretic coating, and control the pH to 5.0.

Use the electrophoretic emulsion prepared in this example to directly carry out cathodic electrophoretic coating, the electrophoresis voltage is 220V, the electrophoresis temperature is 30°C, and the electrophoresis time is 5 minutes. The obtained coating film was baked at 170° C. for 30 minutes. The appearance of the obtained coating film was uniform and smooth, the contact angle between the coating film and water was 150°, and other properties of the coating film met the product standards.

Example 2

(1) Preparation of cationic fluorine-modified acrylate resin

In a reaction kettle equipped with a mechanical stirring device, a thermometer, a constant pressure dropping funnel and a reflux condenser, add 30 parts by weight of butyl acetate as a solvent and 1 part by weight of benzoyl peroxide as an initiator, and acrylate Mixed monomers (20 parts by weight of ethyl methacrylate, 30 parts by weight of isopropyl acrylate), 30 parts by weight of allyl glycidyl ether and 20 parts by weight of fluorine-containing acrylate monomer hexafluorobutyl acrylate and initiator over The solution of 1 weight part of benzoyl oxide was added dropwise into the reaction kettle, and the dripping was completed within 4 hours, and the reaction was continued for 2 hours. Then add 10 parts by weight of polyamine diethanolamine to carry out ring-opening reaction, continue the heat preservation reaction for 2 hours, finally add organic acid lactic acid and stir for 30 minutes, and obtain cationic fluorine-modified acrylate resin after cooling down.

(2) Preparation of fully blocked polyisocyanate crosslinking agent

In a reaction kettle equipped with a stirring device, a constant pressure dropping funnel and a reflux condenser, add 50 parts by weight of isophorone diisocyanate, and slowly add about 75 parts by weight of diethylene glycol butyl ether dropwise under stirring conditions. Into the reaction kettle, dropwise added in 1 hour. Heating to 70°C, reacting for 2 hours, and when the free NCO content is measured to be less than 0.5%, cool down and discharge.

(3) Preparation of cathodic electrophoretic emulsion

With the cationic fluorine modified acrylate resin of 60 weight parts, the fully blocked polyisocyanate crosslinking agent of 25 weight parts and ethylene glycol monobutyl ether 20 weight parts, the lactic acid of quantitative and the hydrophobicity aluminum oxide of 2 weight parts ( Fumed alumina treated with octylsilane), mixed evenly, and acidified at 70°C for 2 hours. Then add 60 parts by weight of deionized water, and disperse for 15-30 minutes under high-speed stirring to obtain a hydrophobic cationic acrylate resin cathodic electrophoretic coating, and control the pH to 6.5.

Use the electrophoretic emulsion prepared in this example to directly carry out cathodic electrophoretic coating, the electrophoresis voltage is 220V, the electrophoresis temperature is 30°C, and the electrophoresis time is 5 minutes. The obtained coating film was baked at 170°C for 30 minutes. The appearance of the obtained coating film was uniform and flat, the contact angle between the coating film and water was 161°, and other properties of the coating film met the product standards.

Example 3

(1) Preparation of cationic fluorine-modified acrylate resin

In a reaction kettle equipped with a mechanical stirring device, a thermometer, a constant pressure dropping funnel and a reflux condenser, 20 parts by weight of butyl acetate as a solvent and 0.5 parts by weight of an initiator azobisisobutyronitrile were added, and acrylic acid Ester mixed monomer (10 parts by weight of ethyl methacrylate, 20 parts by weight of isopropyl acrylate, 10 parts by weight of 2-hydroxyethyl methacrylate), 20 parts of epoxy functional monomer glycidyl methacrylate and A solution of 20 parts by weight of the fluorine-containing acrylate monomer tridefluorooctyl methacrylate and 0.5 parts by weight of the initiator azobisisobutyronitrile was added dropwise into the reaction kettle, and the solution was completed within 3 hours, and the reaction was continued for 2 hours. Then add 7 parts by weight of polyamine propylenediamine to carry out ring-opening reaction, continue the heat preservation reaction for 4 hours, finally add organic acid formic acid and stir for 60 minutes, after cooling down, a cationic fluorine-modified acrylate resin is obtained.

(2) Preparation of fully blocked polyisocyanate crosslinking agent

In a reaction kettle equipped with a stirring device, a constant pressure dropping funnel and a reflux condenser, add 50 parts by weight of isophorone diisocyanate, and slowly add about 75 parts by weight of diethylene glycol butyl ether dropwise under stirring conditions. Into the reaction kettle, dropwise added in 1 hour. Heat to 70°C, react for 3 hours, and when the free NCO content is measured to be less than 0.5%, cool down and discharge.

(3) Preparation of cathodic electrophoretic emulsion

The cationic fluorine-modified acrylate resin of 55 parts by weight, the fully-blocked polyisocyanate crosslinking agent of 23 parts by weight and 20 parts by weight of ethylene glycol monobutyl ether, quantitative formic acid and the hydrophobic aluminum oxide of 1.5 parts by weight ( Fumed alumina treated with octylsilane), mixed evenly, and acidified at 70°C for 1 hour. Then add 50 parts by weight of deionized water, and disperse for 15-30 minutes under high-speed stirring to obtain a hydrophobic cationic acrylate resin cathodic electrophoretic coating, and control the pH to 5.5.

Use the electrophoretic emulsion prepared in this example to directly carry out cathodic electrophoretic coating, the electrophoresis voltage is 220V, the electrophoresis temperature is 30°C, and the electrophoresis time is 5 minutes. The obtained coating film was baked at 170° C. for 30 minutes. The appearance of the obtained coating film was uniform and flat, the contact angle between the coating film and water was 160°, and other properties of the coating film met the product standards.

Example 4

(1) Preparation of cationic fluorine-modified acrylate resin

In a reaction kettle equipped with a mechanical stirring device, a thermometer, a constant pressure dropping funnel and a reflux condenser, 20 parts by weight of butyl acetate as a solvent and 1 part by weight of an initiator azobisisobutyronitrile were added, and acrylic acid Ester mixed monomer (10 parts by weight of methyl methacrylate, 20 parts by weight of butyl acrylate, 5 parts by weight of 2-hydroxyethyl acrylate), 25 parts of epoxy functional monomer glycidyl acrylate and fluorine-containing acrylate mono 10 parts by weight of bulk hexafluorobutyl methacrylate and 1 part by weight of initiator azobisisobutyronitrile solution were added dropwise into the reaction kettle, the dripping was completed within 2 hours, and the heat preservation reaction was continued for 2 hours. Then add 8 parts by weight of polyamine ethylenediamine to carry out ring-opening reaction, continue the heat preservation reaction for 2 hours, finally add organic acid sulfamic acid and stir for 40 minutes, after cooling down, a cationic fluorine-modified acrylate resin is obtained.

(2) Preparation of fully blocked polyisocyanate crosslinking agent

In a reaction kettle equipped with a stirring device, a constant pressure dropping funnel and a reflux condenser, add 50 parts by weight of isophorone diisocyanate, and slowly add about 75 parts by weight of diethylene glycol butyl ether dropwise under stirring conditions. Into the reaction kettle, dropwise added in 1 hour. Heating to 70°C, reacting for 4 hours, and when the free NCO content is measured to be less than 0.5%, the temperature is lowered and the material is discharged.

(3) Preparation of cathodic electrophoretic emulsion

50 parts by weight of cationic fluorine-modified acrylate resin, 20 parts by weight of fully blocked polyisocyanate crosslinking agent and 20 parts by weight of ethylene glycol monobutyl ether, quantitative sulfamic acid and 1 part by weight of hydrophobic oxidation Aluminum (fumed alumina treated with octylsilane), mixed evenly, acidified at 50°C for 2 hours. Then add 40 parts by weight of deionized water, and disperse for 15-30 minutes under high-speed stirring to obtain a hydrophobic cationic acrylate resin cathodic electrophoretic coating, and control the pH to 6.0.

Use the electrophoretic emulsion prepared in this example to directly carry out cathodic electrophoretic coating, the electrophoresis voltage is 220V, the electrophoresis temperature is 30°C, and the electrophoresis time is 5 minutes. The obtained coating film was baked at 170° C. for 30 minutes. The appearance of the obtained coating film was uniform and flat, the contact angle between the coating film and water was 156°, and other properties of the coating film met the product standards.

Example 5

(1) Preparation of cationic fluorine-modified acrylate resin

In a reaction kettle equipped with a mechanical stirring device, a thermometer, a constant pressure dropping funnel and a reflux condenser, 20 parts by weight of butyl acetate as a solvent and 0.5 parts by weight of an initiator azobisisobutyronitrile were added, and acrylic acid Ester mixed monomer (20 parts by weight of ethyl methacrylate, 30 parts by weight of isopropyl acrylate), epoxy functional monomer glycidyl ether group-terminated allyl alcohol random polyether 15 parts by weight and fluorine-containing acrylate monomer 30 parts by weight of dodecafluoroheptyl methacrylate and 1 part by weight of initiator azobisisobutyronitrile solution were added dropwise into the reaction kettle, the dripping was completed within 4 hours, and the reaction was continued for 2 hours. Then add 5 parts by weight of the polyamine butanediamine to carry out the ring-opening reaction, continue the heat preservation reaction for 2 hours, finally add the organic acid acetic acid and stir for 30 minutes, and obtain the cationic fluorine-modified acrylate resin after cooling down.

(2) Preparation of fully blocked polyisocyanate crosslinking agent

In a reaction kettle equipped with a stirring device, a constant pressure dropping funnel and a reflux condenser, add 50 parts by weight of isophorone diisocyanate, and slowly add about 75 parts by weight of diethylene glycol butyl ether dropwise under stirring conditions. Into the reaction kettle, dropwise added in 1 hour. Heating to 70°C, reacting for 2 hours, and when the free NCO content is measured to be less than 0.5%, cool down and discharge.

(3) Preparation of cathodic electrophoretic emulsion

With the cationic fluorine modified acrylate resin of 60 weight parts, the fully blocked polyisocyanate cross-linking agent of 25 weight parts and 20 weight parts of ethylene glycol monobutyl ether, the hydrophobic aluminum oxide of quantitative acetic acid and 0.5 weight part ( Fumed alumina treated with octylsilane), mixed evenly, and acidified at 70°C for 1 hour. Then add 60 parts by weight of deionized water, and disperse for 15-30 minutes under high-speed stirring to obtain a hydrophobic cationic acrylate resin cathodic electrophoretic coating, and control the pH to 5.5.

Use the electrophoretic emulsion prepared in this example to directly carry out cathodic electrophoretic coating, the electrophoresis voltage is 220V, the electrophoresis temperature is 30°C, and the electrophoresis time is 5 minutes. The obtained coating film was baked at 170°C for 30 minutes. The appearance of the obtained coating film was uniform and smooth, the contact angle between the coating film and water was 154°, and other properties of the coating film met the product standards.

Example 6

(1) Preparation of cationic fluorine-modified acrylate resin

In a reaction kettle equipped with a mechanical stirring device, a thermometer, a constant pressure dropping funnel and a reflux condenser, 10 parts by weight of butyl acetate as a solvent and 0.5 parts by weight of an initiator azobisisobutyronitrile were added, and acrylic acid Ester mixed monomer (10 parts by weight of methyl methacrylate, 20 parts by weight of butyl acrylate, 10 parts by weight of 2-hydroxyethyl acrylate), epoxy functional monomer glycidyl ether group-terminated allyl alcohol random polymer 15 parts by weight of ether, 10 parts by weight of trifluorooctyl acrylate monomer and 0.5 parts by weight of initiator azobisisobutyronitrile solution are added dropwise into the reaction kettle, and the dripping is completed within 2 hours, and the heat preservation reaction is continued for 2 Hour. Then add 5 parts by weight of polyamine triethanolamine to carry out ring-opening reaction, continue the heat preservation reaction for 4 hours, finally add organic acid acetic acid and stir for 30 minutes, after cooling down, a cationic fluorine-modified acrylate resin is obtained.

(2) Preparation of fully blocked polyisocyanate crosslinking agent

In a reaction kettle equipped with a stirring device, a constant pressure dropping funnel and a reflux condenser, add 50 parts by weight of isophorone diisocyanate, and slowly add about 75 parts by weight of diethylene glycol butyl ether dropwise under stirring conditions. Into the reaction kettle, dropwise added in 1 hour. Heating to 70°C, reacting for 4 hours, and when the free NCO content is measured to be less than 0.5%, the temperature is lowered and the material is discharged.

(3) Preparation of cathodic electrophoretic emulsion

With the cationic fluorine modified acrylate resin of 50 weight parts, the fully blocked polyisocyanate cross-linking agent of 20 weight parts and 20 weight parts of ethylene glycol monobutyl ether, the hydrophobicity aluminum oxide of quantitative acetic acid and 1.5 weight parts ( Fumed alumina treated with octylsilane), mixed evenly, and acidified at 50°C for 2 hours. Then add 40 parts by weight of deionized water, and disperse for 15-30 minutes under high-speed stirring to obtain a hydrophobic cationic acrylate resin cathodic electrophoretic coating, and control the pH to 5.5.

Use the electrophoretic emulsion prepared in this example to directly carry out cathodic electrophoretic coating, the electrophoresis voltage is 220V, the electrophoresis temperature is 30°C, and the electrophoresis time is 5 minutes. The obtained coating film was baked at 170°C for 30 minutes. The appearance of the obtained coating film was uniform and flat, the contact angle between the coating film and water was 161°, and other properties of the coating film met the product standards.

Finally, it should also be noted that the above examples are only specific implementation examples of the present invention. Apparently, the present invention is not limited to the above examples, and many variations are possible. All deformations that can be directly derived or associated by those skilled in the art from the content disclosed in the present invention should be considered as the protection scope of the present invention.

Claims (10)

1. A preparation method for cathodic electrophoretic paint containing fluorine-containing cationic acrylate resin is characterized in that, first prepare cationic fluorine-modified acrylate resin and fully enclosed polyisocyanate crosslinking agent, and cationic fluorine-modified acrylate resin and fully-encapsulated polyisocyanate cross-linking agent The blocked polyisocyanate crosslinking agent is acidified after reaction, fully mixed with hydrophobic oxide particles for preparation, and finally added with deionized water to disperse to prepare the cathodic electrophoretic coating. 2. the preparation method of cathodic electrophoretic coating of fluorine-containing cationic acrylate resin according to claim 1 is characterized in that, described concrete preparation step is: in reactor, add solvent and part initiator, at 70-100 Add the mixture of acrylate mixed monomer, epoxy functional monomer and fluorine-containing acrylate monomer and part of the initiator solution into the reaction kettle dropwise at ℃, finish dropping within 2-4 hours, and continue to keep warm for 2-4 hours , then add polyamine to carry out ring-opening reaction, continue heat preservation reaction for 2-4h, finally add organic acid and stir for 20-60 minutes, after cooling down, obtain cationic fluorine-modified acrylate resin, and then prepare fully blocked polyisocyanate crosslinking agent, A certain amount of cationic fluorine-modified acrylate resin, fully blocked polyisocyanate crosslinking agent, ethylene glycol monobutyl ether, organic acid and hydrophobic oxide particles are mixed uniformly, acidified at 50-70°C for 2-4 hours, and then Add a certain amount of deionized water, stir at a high speed, disperse for 15-30 minutes, control the pH to 5.0-6.5, and obtain a cathodic electrophoretic coating with fluorine-containing cationic acrylate resin. 3. the preparation method of fluorine-containing cationic acrylate resin cathodic electrophoretic coating according to claim 2, is characterized in that, the preparation method of described fully enclosed polyisocyanate cross-linking agent is in reactor, adds isophor For ketone diisocyanate, slowly add diethylene glycol butyl ether dropwise to the reaction kettle under stirring conditions, and finish adding dropwise in 1 hour, heat to 70°C, react for 2-4 hours, and measure the free NCO content when it is less than 0.5% , cooling and discharging. 4. according to the preparation method of the cathodic electrophoretic paint of fluorine-containing cationic acrylate resin described in claim 2 or 3, it is characterized in that, described fluorine-containing acrylate monomer is hexafluorobutyl methacrylate, hexafluorobutyl acrylate One or more of esters, dodecafluoroheptyl methacrylate, trifluorooctyl methacrylate, trifluorooctyl acrylate and perfluoroalkylethyl methacrylate. 5. the preparation method of fluorine-containing cationic acrylate resin cathodic electrophoretic coating according to claim 4 is characterized in that, described epoxy functional monomer is glycidyl methacrylate, glycidyl acrylate, allyl A mixture of one or more of glycidyl ether and glycidyl ether-terminated allyl alcohol random polyether. 6. the preparation method of fluorine-containing cationic acrylate resin cathodic electrophoretic coating according to claim 4, is characterized in that, described acrylate mixed monomer comprises styrene, methyl methacrylate, ethyl methacrylate , butyl acrylate, isopropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, the polyamine It is a mixture of one or more of diethanolamine, triethanolamine, ethylenediamine, propylenediamine and butylenediamine, and the organic acid is one or more of formic acid, acetic acid, lactic acid and sulfamic acid. 7. according to the preparation method of claim 2 or 3 or 5 or 6 described fluorine-containing cationic acrylate resin cathodic electrophoretic coatings, it is characterized in that, in cationic fluorine-modified acrylate resin, acrylate monomer 25-50 weight 10-20 parts by weight of fluorine-containing acrylate monomer, 15-30 parts by weight of epoxy functional monomer, 5-10 parts by weight of polyamine, and 0.5-2 parts by weight of initiator. 8. according to the preparation method of claim 2 or 3 or 5 or 6 described fluorine-containing cationic acrylate resin cathodic electrophoretic coatings, it is characterized in that, described hydrophobic oxide particle is hydrophobic alumina, is preferably octyl Silane treated fumed alumina. 9. the preparation method of fluorine-containing cationic acrylate resin cathodic electrophoretic paint according to claim 8 is characterized in that, each component of described cathodic electrophoretic paint is cationic fluorine-modified acrylate resin 50-60 weight part, all 20-25 parts by weight of blocked polyisocyanate crosslinking agent, and 0.1-2 parts by weight of hydrophobic oxide particles. 10. the preparation method of fluorine-containing cationic acrylate resin cathodic electrophoretic coating according to claim 8 is characterized in that, after the varnish film-forming of prepared cathodic electrophoretic coating, the contact angle of coating film and water is greater than 150 degree.