WO2016000537A1 - Amino baking varnish composition having self-cleaning function and preparation method therefor - Google Patents

Abstract

An amino baking varnish composition having a self-cleaning function, comprising the following raw materials in parts by weight: 7.0-12.0 of a hyperbranched polyester polyol resin, 25.0-30.0 of a hydroxyacrylic resin, 25.0-30.0 of a terminated isocyanate resin, 5.0-10.0 of an amino resin, 0.5-1.0 of an anti-graffiti resin, 2.0-3.0 of coating aids, and 15.0-35.0 of a diluent. A preparation method therefor comprises adding the various components into a reactor in sequence and stirring same. The composition has a long-lasting self-cleaning function.

Description

Amino baking paint composition with self-cleaning function and preparation method thereof Technical field

The invention relates to the technical field of coatings and preparation methods thereof. More specifically, it relates to an amino baking varnish composition having a self-cleaning function and a method of preparing the same.

Background technique

The amino baking varnish is mainly composed of a hydroxy-containing acrylic resin or an alkyd resin or an amino resin, and is packaged in a single component at a normal temperature. At a relatively high temperature (above 140 ° C), a chemical reaction occurs between the components to form a chemical reaction. It has a three-dimensional network structure, high hardness, excellent adhesion, high gloss, good gloss and color retention, and is widely used in the coating of shells for automobiles, ships and airplanes.

With the development of the automobile manufacturing industry, people are increasingly demanding the coating of automotive parts, especially in terms of environmental protection and certain special functions. Automobile aluminum alloy wheels are inevitably stained with dust, oil and brakes during driving. Conventional hub varnishes have poor stain resistance, especially when it is hard to clean the brakes. In addition, winter in northern China At the time of the season, the car body, the windshield and the rearview mirror are easy to form a layer of frost, which affects the appearance of the car and the safety of driving.

According to the principle of "self-cleaning of lotus leaf", the coating forms a nano-structure similar to the roughness of the lotus leaf on the surface of the coating during the dry film formation process. The uneven nano coating can make the dust particles adhere to the surface of the coating. Suspended state, the contact angle of water and coating surface is greatly increased, and the accumulation or adsorption of pollution The particles break away from the surface of the coating under the scouring of wind and rain for self-cleaning purposes.

In the prior art, a silicone self-cleaning agent is generally added to achieve a certain self-cleaning purpose, but a low surface energy silicone auxiliaries easily migrate to the surface of the paint film, and the auxiliaries are lost over time. The cleaning function will be reduced.

Therefore, there is a need to provide an amino baking varnish having a long-lasting self-cleaning function and a method of preparing the same.

Summary of the invention

The first technical problem to be solved by the present invention is to provide an amino baking paint composition having a self-cleaning function, which utilizes a plurality of terminal hydroxyl functional groups in a nano-scale hyperbranched polyester resin to achieve a high cross-linking density of a paint film. And an amino baking varnish with long-lasting self-cleaning function prepared by anti-graffiti resin which is involved in the cross-linking reaction of paint film.

A second technical problem to be solved by the present invention is to provide a method for preparing an amino baking varnish composition having a self-cleaning function, which is simple in preparation process and suitable for industrial production.

In order to solve the above first technical problem, the present invention adopts the following technical solutions:

An amino baking varnish composition having a self-cleaning function, comprising the following raw materials by weight:

The above materials are all commercially available.

Preferably, the hyperbranched polyester polyol resin has a hydroxyl value of 240 to 320 mg KOH/g, a viscosity of 20 to 100 cPs, and 25 ° C, based on the solid resin.

Preferably, the blocked isocyanate resin has a deblocking temperature of 110 to 150 °C.

Preferably, the anti-graffiti resin contains a hydroxyl group, and the anti-graffiti resin has a hydroxyl value of 30 to 60 mg KOH/g in terms of a pure solid portion.

Preferably, the coating aid is selected from the group consisting of ultraviolet absorbers, light stabilizers, leveling agents, coupling agents, drier, toughening agents, emulsifiers, thickeners, pigment dispersants, defoamers, and anti-foaming agents. One or more of a skinning agent, a matting agent, an anti-fungal agent, or an antistatic agent. More preferably, the coating aid comprises 0.5 to 1.0 part of a UV absorber, 0.5 to 1.0 part of a light stabilizer, 0.5 to 1.0 part of a leveling agent, and 0.5 to 1.0 part of a coupling agent.

Preferably, the diluent is selected from one or more of an ester solvent, a ketone solvent, an alcohol solvent or an alcohol ether solvent;

Preferably, the ester solvent is one or more selected from the group consisting of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate or amyl acetate;

Preferably, the ketone solvent is selected from one or more of acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone or methyl isobutyl ketone;

Preferably, the alcohol solvent is selected from one or more of methanol, ethanol or butanol;

Preferably, the alcohol ether solvent is selected from the group consisting of ethylene glycol-diethyl ether, ethylene glycol-butyl ether, diethylene glycol-B One or several of the ethers.

In order to solve the above second technical problem, the present invention adopts the following technical solutions:

A method for preparing an amino baking varnish composition having a self-cleaning function, comprising the following preparation steps:

(1) 15.0 parts to 20.0 parts of diluent is added to the stirred reactor, and then added 7.0 parts to 12.0 parts of hyperbranched polyester polyol resin and stirring is continued for 8-15min;

(2) sequentially adding 5.0 parts to 10.0 parts of amino resin, 25.0 parts to 30.0 parts of hydroxy acrylic resin, 25.0 parts to 30.0 parts of blocked isocyanate resin, 0.5 parts to 1.0 part of anti-graffiti resin, and the like in the reactor of the step (1). 2.0 parts to 3.0 parts of paint auxiliaries, stirring for 20 to 40 minutes, and filtering to obtain an amino baking varnish with self-cleaning function.

Preferably, the stirring speed in the step (1) is: 200 to 250 r/min; and the stirring speed in the step (2) is 300 to 350 r/min.

The beneficial effects of the present invention are as follows:

The self-cleaning amino baking varnish of the invention utilizes a plurality of terminal hydroxyl functional groups in the nano-scale hyperbranched polyester resin to achieve a high cross-linking density of the paint film, and the high cross-linking density of the paint film and the low surface energy can effectively reduce the water. The adhesion and infiltration of dust, oil, brakes and bird droppings on the surface of the paint film reduces the frequency of vehicle cleaning to a certain extent. The anti-graffiti resin which participates in the cross-linking reaction of the paint film makes the self-cleaning amino baking varnish of the invention have a long-lasting self-cleaning function.

detailed description

The invention will now be further described with reference to the embodiments.

Hyperbranched polyester polyol resin: BBHA D5025 (CyGLAZ BB500) or BB D5025, all purchased from Singapore Lishi Technology Co., Ltd.;

Hydroxy acrylic resin: SETALUX 1215BA-68 was purchased from Nuplex Resin (Suzhou) Co., Ltd., or DESMOPHEN A870BA was purchased from BAYER;

Blocked isocyanate resin: BL 3175 was purchased from BAYER; BLR 8086, purchased from Deqian (Shanghai) Chemical Co., Ltd.;

Amino resin: CYMEL 1158 was purchased from CYTEC, or Luwipal 072 was purchased from BASF;

Anti-Graffiti Resin: TEGO Protect 5001 or TEGO Protect 5000 are both purchased by Homemade Degussa (China) Investment Co., Ltd.;

Coating additives:

Leveling agent BYK-331, BYK-358N or OTSN;

UV absorbers: TINUVIN-1130, TINUVIN-400, CHISOKB5228;

Light stabilizer: TINUVIN-292, TINUVIN-123, CHISOKB523;

Photo coupling agent: DC 6040 or KBM 403.

Example 1

Table 1 Example 1 raw material parts by weight

Add 12 parts of butyl acetate, 9 parts of propylene glycol methyl ether acetate and 10.6 parts of cyclohexanone to the stirred tank, slowly add 11.6 parts of BBHA D5025 at 200r/min stirring speed, stir for 10min, then slowly add 10.0. CYMEL 1158, 25.4 parts of SETALUX 1215BA-68, 25.9 parts of BL 3175, 0.6 parts of Protect 5001, 0.3 parts of BYK-331, 0.7 parts of TINUVIN-400, 0.3 parts of TINUVIN-292 and 0.8 parts of DC 6040, after the completion of the feeding, the stirring speed is increased to 350r/min, and the stirring is continued for 30 minutes, and then filtered and discharged to obtain an amino baking varnish having a self-cleaning function.

Performance test of the amino baking varnish with self-cleaning function prepared in Example 1

The prepared amino baking varnish with self-cleaning function is diluted to 24 to 26 seconds (coating-4 viscosity cup, 25 ° C) and sprayed on aluminum plate. (Iwata 101 spray gun, spraying pressure 0.4 MPa, control dry film thickness 25 ～30μm), leveling 6~8min, and finally baking at 140°C×30min, which is a self-cleaning amino baking paint coating.

The test method for the performance is shown in Table 2: The surface tension test mixture was purchased from Japan Wako Pure Chemical Industries Co., Ltd. The specific test is to use a cotton swab dipped in syrup to scratch the surface of the paint film, leaving scratches, scratches within 3 seconds without shrinkage, which means that the surface tension can reach the surface tension level represented by the number marked on the bottle. The larger the number, the higher the surface tension.

Table 2 performance testing methods

Comparative Example 1 was to replace the anti-graffiti resin of Example 1 with a mass such as a commercially available silicone additive, and the amount of other materials was unchanged.

Comparative Example 2 is a commercially available SiO ₂ nanoparticle and the like, and the amount of other materials of the anti-graffiti resin of Example 1 is unchanged. The baking properties of Example 1 and Comparative Examples 1, 2 are shown in Table 3.

Table 3 Performance of the baking varnish of Example 1 and Comparative Example

As can be seen from Table 3, the amino baking varnish having the self-cleaning function prepared in Example 1 was excellent in performance, and its surface tension was less than 22.6, which was smaller than the comparative example, and thus had good anti-graffiness. And its anti-graffiti nature does not reduce the anti-graffiti effect with the influence of sunshine, surface scratches and other factors, and has self-cleaning and long-lasting effect. In contrast, the water-resistance and anti-graffiti effect of the paint film of Comparative Example 1 was poor. The SiO ₂ nanoparticles added in Comparative Example 2 only filled the paint film, but reduced the physical and chemical properties of the paint film, and did not achieve the ideal anti-graffiti effect.

Aging tester simulation: The samples prepared in Example 1 and Comparative Examples 1, 2 were placed in an aging tester for about 750 hours, and then taken out, and the graffiti resistance was measured. The results are shown in Table 4.

Table 4 Performance of the baking varnish of Example 1 and Comparative Example after aging resistance test

Example 2

Example 1 was repeated except that the parts by weight of Example 2 were as shown in Table 3. Among them The hyperbranched polyester polyol resin has a hydroxyl value of 240 mg KOH/g as a solid resin and a viscosity of 20 cPs at 25 ° C; the deblocking temperature of the blocked isocyanate resin is 110 ° C; the hydroxyl value of the anti-graffiti resin It was 30 mg KOH/g in terms of pure solids.

Table 5 Example 2 raw material parts by weight

Example 3

The weight fraction of the raw materials of Example 3 is shown in Table 4. Wherein the hyperbranched polyester polyol resin has a hydroxyl value of 320 mg KOH/g as a solid resin, a viscosity of 100 cPs, 25 ° C; a deblocking temperature of the blocked isocyanate resin is 140 ° C; The hydroxyl value was 30 mg KOH/g in terms of pure solids.

Table 6 Example 3 raw material parts by weight

raw material Number of copies Hyperbranched polyester polyol resin BBHA D5025 12 copies Hydroxy acrylic resin SETALUX 1215BA-68 28 copies Blocked isocyanate resin BL 3175 26 copies Amino resin CYMEL 1158 8 servings Anti-graffiti resin TEGO Protect 5001 0.8 parts 1:1 mixing of pigment dispersant and defoamer 2.5 servings 1:1 blend of ethanol and diethylene glycol-diethyl ether 18 servings

(1) adding the diluent to the stirred reactor, and then adding the hyperbranched polyester polyol resin to continue stirring for 15 min; stirring speed is 200r / min;

(2) In the reactor of the step (1), an amino resin, a hydroxy acrylic resin, a blocked isocyanate resin, an anti-graffiti resin and a coating aid are sequentially added, and the mixture is further stirred at a stirring speed of 300 r/min for 40 minutes. Amino baking varnish with self-cleaning function is obtained.

Example 4

The weight fraction of the starting material of Example 4 is shown in Table 5.

Table 7 Example 4 raw material parts by weight

(1) adding the diluent to the stirred reactor, and then adding the hyperbranched polyester polyol resin to continue stirring for 8 min; stirring speed is 250r / min;

(2) In the reactor of the step (1), an amino resin, a hydroxy acrylic resin, a blocked isocyanate resin, an anti-graffiti resin and a coating aid are sequentially added, and the mixture is further stirred at a stirring speed of 350 r/min for 20 minutes. Amino baking varnish with self-cleaning function is obtained.

Example 5, 6

The same as Example 1, except that the hydroxyl value of the hyperbranched polyester polyol resin was 230 mg KOH/g and 330 mg KOH/g, respectively, based on the solid resin.

Examples 7, 8

The same as in Example 1, except that the anti-graffiti resin has a hydroxyl value of 25 mg KOH/g and 65 mg KOH/g, respectively, in terms of pure solid parts.

The surface tension of the amino baking varnish of Examples 2-8 is shown in Table 6. The anti-graffiti performance of the amino baking varnish of Examples 2-8 was not weakened by the influence of sunlight, surface scratches and the like, and the self-cleaning long-lasting effect was obtained.

Table 8 Surface tension of the amino baking paint of Examples 2-8

Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Surface Tension <22.6 <22.6 <22.6 22.6 24.0 24.0 26.8

Example 9

The same as in the fourth embodiment, the only difference is that the order of the addition of the step (2) is the sequential addition of a hydroxy acrylic resin, an amino resin, a blocked isocyanate resin, an anti-graffiti resin and a coating aid, and the stirring speed is: 350 r / After stirring at min, the reaction system agglomerated after 10 minutes, and the stirring speed was increased to 400 r/min, and it was still unable to disperse.

Example 10

The same as in the fourth embodiment, the only difference is that the feeding sequence of the step (2) is to sequentially add an anti-graffiti resin, an amino resin, a hydroxy acrylic resin, a blocked isocyanate resin and a coating auxiliary agent, and continue the stirring speed: 350r/ After stirring under the conditions of min, the reaction system agglomerated after 5 minutes and could not be dispersed.

Example 11

The same as Example 1, except that the materials used in Example 11 are shown in Table 7. The test results of the amino baking varnish prepared in Example 11 were similar to those in Example 1.

Table 9 Example 11 raw material parts by weight

It is apparent that the above-described embodiments of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations or modifications of the various forms may be made by those skilled in the art in light of the above description. It is not possible to exhaust all implementations here. Obvious changes or variations that come within the scope of the invention are still within the scope of the invention.

Claims (9)

An amino baking varnish composition having a self-cleaning function, comprising the following raw materials by weight:

The amino baking varnish composition with self-cleaning function according to claim 1, wherein the hyperbranched polyester polyol resin has a hydroxyl value of 240 to 320 mg KOH/g and a viscosity of 20 to 100 cPs as a solid resin. , 25 ° C. The amino baking varnish composition having a self-cleaning function according to claim 1, wherein the blocked isocyanate resin has a deblocking temperature of 110 to 150 °C. The amino baking varnish composition having a self-cleaning function according to claim 1, wherein the anti-graffiti resin contains a hydroxyl group, and the anti-graffiti resin has a hydroxyl value of from 30 to 60 mg KOH/g in terms of a pure solid portion. The amino baking paint composition with self-cleaning function according to claim 1, wherein the coating auxiliary agent is selected from the group consisting of an ultraviolet absorber, a light stabilizer, a leveling agent, a coupling agent, a drier, and a toughening agent. One or more of a emulsifier, an emulsifier, a thickener, a pigment dispersant, an antifoaming agent, an anti-skinning agent, a matting agent, an antifungal agent, or an antistatic agent. The amino baking paint composition with self-cleaning function according to claim 5, wherein the coating aid comprises 0.5 to 1.0 part of an ultraviolet absorber, 0.3 to 1.0 part of a light stabilizer, and 0.3 to 1.0 part of a stream. A leveling agent and 0.5 to 1.0 part of a coupling agent. The amino baking paint composition with self-cleaning function according to claim 1, wherein the diluent is selected from one or more of an ester solvent, a ketone solvent, an alcohol solvent or an alcohol ether solvent. ; Preferably, the ester solvent is one or more selected from the group consisting of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate or amyl acetate; Preferably, the ketone solvent is selected from one or more of acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone or methyl isobutyl ketone; Preferably, the alcohol solvent is selected from one or more of methanol, ethanol or butanol; Preferably, the alcohol ether solvent is one or more selected from the group consisting of ethylene glycol-diethyl ether, ethylene glycol-butyl ether, and diethylene glycol-diethyl ether. A method for preparing an amino baking varnish composition having a self-cleaning function according to any of claims 1-7, which comprises the following preparation steps: (1) adding 15.0 parts to 20.0 parts of diluent into the reactor, stirring; then adding 7.0 to 12.0 parts of hyperbranched polyester polyol resin and stirring for 8-15min; (2) sequentially adding 5.0 parts to 10.0 parts of amino resin, 25.0 parts to 30.0 parts of hydroxy acrylic resin, 25.0 parts to 30.0 parts of blocked isocyanate resin, 0.5 parts to 1.0 part of anti-graffiti resin, and 2.0 parts to 3.0 parts to the reactor. The coating additive is stirred for 20 to 40 minutes and then filtered to obtain an amino baking varnish with self-cleaning function. The method for preparing an amino baking varnish composition with self-cleaning function according to claim 8, wherein the stirring speed in the step (1) is 200 to 250 r/min; and the stirring speed in the step (2) is: 300 ~ 350r / min.