阅读说明：本技术 一种高支化度水性饱和聚酯改性丙烯酸树脂及其制备方法和金属用水性光油 (High-branching-degree water-based saturated polyester modified acrylic resin, preparation method thereof and water-based gloss oil for metals ) 是由 钟俊文 朱经纬 黄光燕 于 2021-07-01 设计创作，主要内容包括：本发明公开了一种一种高支化度水性饱和聚酯改性丙烯酸树脂,其特征在于包括以下质量组分：水性聚酯树脂100份、丙烯酸酯单体80～95份、助溶剂6～15份、中和剂1～2份、引发剂0.8～1.2份和适量去离子水,其中：所述水性聚酯树脂由多元醇,与有机酸和/或酐经过高温酯化脱水得到；所述丙烯酸酯单体由硬单体、软单体和含羟基丙烯酸单体组成。本发明避免了油性自由基接枝聚合使用大量溶剂和不易控制的特点,可以简单制得具有高支化度、高交联点的改性树脂,制备得到的产物具有优异的耐化型、耐磨性和耐高温蒸煮性。(The invention discloses a high-branching-degree water-based saturated polyester modified acrylic resin which is characterized by comprising the following components in parts by mass: 100 parts of water-based polyester resin, 80-95 parts of acrylate monomer, 6-15 parts of cosolvent, 1-2 parts of neutralizer, 0.8-1.2 parts of initiator and a proper amount of deionized water, wherein: the waterborne polyester resin is obtained by carrying out high-temperature esterification and dehydration on polyhydric alcohol and organic acid and/or anhydride; the acrylate monomer consists of a hard monomer, a soft monomer and a hydroxyl-containing acrylic monomer. The invention avoids the characteristics of using a large amount of solvent and being difficult to control in the oil free radical graft polymerization, can simply prepare the modified resin with high branching degree and high crosslinking point, and the prepared product has excellent chemical resistance, wear resistance and high-temperature cooking resistance.)

1. The high-branching-degree water-based saturated polyester modified acrylic resin is characterized by comprising the following components in parts by mass: 100 parts of water-based polyester resin, 80-95 parts of acrylate monomer, 6-15 parts of cosolvent, 1-2 parts of neutralizer, 0.8-1.2 parts of initiator and a proper amount of deionized water, wherein:

the waterborne polyester resin is obtained by carrying out high-temperature esterification and dehydration on polyhydric alcohol and organic acid and/or anhydride;

the acrylate monomer consists of a hard monomer, a soft monomer and a hydroxyl-containing acrylic monomer.

2. The acrylic resin modified with the highly branched water-based saturated polyester according to claim 1, wherein: the hard monomer comprises a mixture of at least two of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, styrene, cyclohexyl methacrylate, isobornyl methacrylate.

3. The acrylic resin modified with the highly branched water-based saturated polyester according to claim 1, wherein: the soft monomer comprises at least one or a mixture of n-butyl acrylate, isooctyl acrylate, ethyl acrylate and methyl acrylate laurate.

4. The acrylic resin modified with the highly branched water-based saturated polyester according to claim 1, wherein: the hydroxyl-containing acrylate monomer is one or a mixture of hydroxyethyl methacrylate, hydroxypropyl acrylate and n-butyl acrylate.

5. The acrylic resin modified with the highly branched water-based saturated polyester according to claim 1, wherein: the molar ratio of hydroxyl groups to carboxyl groups in the polyhydric alcohol and the organic acid in the waterborne polyester resin is as follows: 1.2-1.4: 1, wherein the molecular weight of the obtained waterborne polyester resin is 1500-5000.

6. The acrylic resin modified with the highly branched water-based saturated polyester according to claim 5, wherein: the polyhydric alcohol is formed by mixing dihydric alcohol and trihydric alcohol, wherein the dihydric alcohol comprises at least one of ethylene glycol, hexanediol, neopentyl glycol, 2-methyl-1, 3-propylene glycol, ethyl butyl propylene glycol, 2, 2-dimethylolpropionic acid and glyceryl stearate; the triol comprises at least one of trimethylolethane, trimethylolpropane and tris (2-hydroxyethyl) isocyanurate (THEIC).

7. The acrylic resin modified with the highly branched water-based saturated polyester according to claim 6, wherein: the mass ratio of the dihydric alcohol to the trihydric alcohol is 50: 20-60.

8. The acrylic resin modified with the highly branched water-based saturated polyester according to claim 1, wherein: the organic acid in the water-based polyester resin adopts dibasic acid which comprises the mixture of at least two of isophthalic acid, adipic acid, phthalic acid and sebacic acid.

9. The acrylic resin modified with the highly branched water-based saturated polyester according to claim 1, wherein: the mass ratio of the hard monomer, the soft monomer and the hydroxyl-containing acrylic monomer in the acrylic ester monomer is (80-120): (40-50): (20-40).

10. The acrylic resin modified with the highly branched water-based saturated polyester according to claim 1, wherein: the neutralizing agent is N-methylethanolamine or N, N-dimethylethanolamine.

11. A preparation method of the acrylic resin modified by the high-branching-degree water-based saturated polyester as claimed in any one of claims 1 to 10, which is characterized by comprising the following steps:

step S1, adding polyhydric alcohol and organic acid monomer according to a proportion into a reactor with an oil-water separator, heating to 140 +/-5 ℃ until the solid is completely dissolved, keeping the temperature for reaction for at least 0.5h, continuing to heat to 180 +/-5 ℃ for reaction for at least 1h, and continuing to heat to 230 +/-5 ℃ for reaction;

step S2, sampling and testing the acid value to judge the reaction progress, cooling to 170 +/-5 ℃ when the acid value is less than or equal to 10 and reaches a central control point, adding the trimellitic anhydride and continuing to preserve heat; continuously sampling, testing the acid value, and judging that the reaction end point is reached, cooling to 150 +/-5 ℃, adding a cosolvent for dilution, cooling to 70 +/-5 ℃, adding an acrylate monomer, and cooling to 40 +/-5 ℃ of the end point temperature;

step S3, adding a neutralizing agent and a proper amount of deionized water, and dispersing at a high speed for 10min to obtain a stable dispersion liquid;

and S4, heating the dispersion liquid obtained in the step S3 to 65-80 ℃, adding an initiator, carrying out heat preservation reaction for 3-5 hours, and then adding deionized water to adjust the solid content of the product, so as to obtain the high-branching-degree water-based saturated polyester modified acrylic resin.

12. The water-based gloss oil for metals is characterized by comprising the following components in parts by weight:

100 parts of the polyester-modified acrylic resin according to any one of claims 1 to 10

Ethylene glycol monobutyl ether 15-30 parts

NOVARES TD90D 12-25 parts

Bayhydrol BL 51404-8 parts

CYMEL 30310-22 parts

NACURE 1550.2-0.6 part

BYK-0240.4-1 part

BYK-3780.6-1.5 parts

Polyfluo 4001-3 parts

20-50 parts of deionized water.

Technical Field

The invention belongs to the technical field of polyester modified acrylic resin, and particularly relates to preparation of high-branching-degree water-based saturated polyester modified acrylic resin and application of the high-branching-degree water-based saturated polyester modified acrylic resin in a boiling-resistant water-based finishing paint.

Background

The pop can is a very widely used physical container at present, and the surface gloss oil is required to have good chemical stability and wear resistance in the production, storage and transportation processes. In the production process of certain pop can foods, the contents of the pop can are required to be steamed and sterilized, and the external gloss oil of the pop can is required to have the steaming-resistant characteristic. However, the existing pop can external gloss oil has defects in boiling resistance and wear resistance, especially in high-temperature boiling (such as boiling at 121 ℃).

Chinese patent CN 108587382A discloses water-based gloss oil for metals and a preparation method thereof, and polyester modified water-based acrylic resin mentioned in the boiling-resistant gloss oil cannot be used for preparing modified resin with high branching degree by adopting a solution free radical graft polymerization method.

Chinese patent CN 106749945 a discloses a method for preparing polyester modified waterborne acrylic resin, which is also polymerized by solution free radical grafting, and since linear polyester is used, modified resin with high branching degree cannot be prepared.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides the high-branching-degree water-based saturated polyester modified acrylic resin, the preparation method thereof and the metal water-based gloss oil, which have the characteristics of avoiding using a large amount of solvents and being difficult to control in oily free radical graft polymerization, can simply prepare the modified resin with high branching degree and high crosslinking point, and the prepared product has excellent chemical resistance, wear resistance and high-temperature cooking resistance.

In order to solve the technical problems, the invention adopts the following technical scheme:

a high-branching-degree water-based saturated polyester modified acrylic resin comprises the following components in parts by mass: 100 parts of water-based polyester resin, 80-95 parts of acrylate monomer, 6-15 parts of cosolvent, 1-2 parts of neutralizer, 0.8-1.2 parts of initiator and a proper amount of deionized water, wherein:

the waterborne polyester resin is obtained by carrying out high-temperature esterification and dehydration on polyhydric alcohol and organic acid and/or anhydride;

the acrylate monomer consists of a hard monomer, a soft monomer and a hydroxyl-containing acrylic monomer.

Preferably, the hard monomer comprises a mixture of at least two of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, styrene, cyclohexyl methacrylate, and isobornyl methacrylate.

Preferably, the soft monomer comprises at least one or more of n-butyl acrylate, isooctyl acrylate, ethyl acrylate and methyl acrylate laurate.

Preferably, the hydroxyl-containing acrylate monomer is one or a mixture of hydroxyethyl methacrylate, hydroxypropyl acrylate and n-butyl acrylate.

Preferably, the molar ratio of the hydroxyl group to the carboxyl group in the polyhydric alcohol and the organic acid in the aqueous polyester resin is: 1.2-1.4: 1, wherein the molecular weight of the obtained waterborne polyester resin is 1500-5000.

Preferably, the polyhydric alcohol is formed by mixing dihydric alcohol and trihydric alcohol, and the dihydric alcohol comprises at least one of ethylene glycol, hexanediol, neopentyl glycol, 2-methyl-1, 3-propylene glycol, ethylbutyl propylene glycol, 2, 2-dimethylolpropionic acid and glycerol stearate; the triol comprises at least one of trimethylolethane, trimethylolpropane and tris (2-hydroxyethyl) isocyanurate (THEIC).

Preferably, the mass ratio of the dihydric alcohol to the trihydric alcohol is 50: 20-60.

Preferably, the organic acid in the aqueous polyester resin is a dibasic acid comprising a mixture of at least two of isophthalic acid, adipic acid, phthalic acid and sebacic acid.

Preferably, the mass ratio of the hard monomer to the soft monomer to the hydroxyl-containing acrylic monomer in the acrylic ester monomer is (80-120): (40-50): (20-40).

Preferably, the neutralizing agent is N-methylethanolamine or N, N-dimethylethanolamine.

In addition, the invention also provides a preparation method of the high-branching-degree water-based saturated polyester modified acrylic resin, which comprises the following steps:

step S1, adding polyhydric alcohol and organic acid monomer according to a proportion into a reactor with an oil-water separator, heating to 140 +/-5 ℃ until the solid is completely dissolved, keeping the temperature for reaction for at least 0.5h, continuing to heat to 180 +/-5 ℃ for reaction for at least 1h, and continuing to heat to 230 +/-5 ℃ for reaction; the heating and heat preservation time can be effectively and strictly controlled by distributing the heating, so that alcohol loss and deviation of the molar ratio of the alcohol acid are avoided, and the expected product can be obtained.

Step S2, sampling and testing acid value to judge reaction progress, cooling to 170 +/-5 ℃ after reaching a central control point, adding trimellitic anhydride and continuing heat preservation; continuously sampling, testing acid value and judging that the reaction end point is reached, cooling to 150 +/-5 ℃, adding cosolvent for dilution, cooling to 70 +/-5 ℃, adding acrylate monomer, and cooling to 40 +/-5 ℃.

Step S3, adding a neutralizing agent and a proper amount of deionized water, and dispersing at a high speed for 10min to obtain a stable dispersion liquid;

and S4, heating the dispersion liquid obtained in the step S3 to 65-80 ℃, adding an initiator, carrying out heat preservation reaction for 3-5 hours, and then adding deionized water to adjust the solid content of the product, so as to obtain the high-branching-degree water-based saturated polyester modified acrylic resin.

The invention also provides water-based gloss oil for metals, which is characterized by comprising the following components in parts by weight:

100 parts of the polyester modified acrylic resin

Ethylene glycol monobutyl ether 15-30 parts

NOVARES TD90D 12-25 parts

Bayhydrol BL 51404-8 parts

CYMEL 30310-22 parts

NACURE 1550.2-0.6 part

BYK-0240.4-1 part

BYK-3780.6-1.5 parts

Polyfluo 4001-3 parts

20-50 parts of deionized water.

Compared with the prior art, the invention has the following advantages:

(1) the process for modifying acrylic resin by using water-based polyester avoids the characteristics of using a large amount of solvent and being difficult to control in the oil free radical graft polymerization, and can simply prepare modified resin with high branching degree and high crosslinking point.

(2) The waterborne polyester modified acrylic resin enables a paint film to have excellent chemical resistance, wear resistance and high-temperature cooking resistance. Can fully meet the requirements of the pop-top can in the production and application processes.

(3) The water-based polyester modified acrylic resin prepared by the invention does not contain an emulsifier completely, and the environment-friendly property of the coating is improved.

Detailed Description

The invention will be further elucidated with reference to the following specific examples. It is to be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereof which may occur to those skilled in the art upon reading the present specification.

The following are references to the names of substances referred to in this application by acronyms in English and Chinese:

NOVARES TD90D liquid petroleum resin

Bayhydrol BL 5140 blocked isocyanate

CYMEL 303 amino resin

NACURE 155 organic acid catalyst

BYK-024 defoaming agent

BYK-378 leveling agent

Polyfluo400 polyfluoro wax

The polyester has good mechanical strength, hardness, wear resistance, high glossiness and good flexibility, but ester bonds are easy to hydrolyze; the acrylic resin has color retention, chemical resistance and aging resistance, but is insufficient in flexibility. The invention effectively combines two resins to make up the defects of single resin, in particular to polyester modified acrylic resin with high branching degree, which can well meet the application of the canned water-borne gloss oil.

The key point of the invention is that the molar ratio of hydroxyl and carboxyl is controlled, the high-branching self-emulsifying water-based polyester with the number average molecular weight of 1500-5000 is designed and synthesized, the acrylic ester monomer is emulsified to form stable pre-emulsion by depending on the surface activity of the water-based polyester, and then the initiator is dripped into the pre-emulsion to enable the acrylic ester monomer to generate free radical polymerization reaction, and finally the stable high-branching water-based polyester modified acrylic resin is formed. In preparing the composition, the branching degree of the polyester is controlled by controlling the addition amount of the polyhydric alcohol (TMP, THEIC). Compared with the reference, the reference adopts solution free radical polymerization, and the invention adopts emulsion polymerization, thus avoiding the characteristics of using a large amount of solvent and being difficult to control in the oil free radical graft polymerization. The preparation method of the high-branching-degree water-based saturated polyester modified acrylic resin comprises the following steps:

1. adding raw materials of organic binary, polyhydric alcohol and organic acid monomer into a three-neck round-bottom flask provided with an oil-water separator, heating to 140 ℃, keeping the temperature for reaction for 1h after the solid is completely dissolved, continuing to heat to 180 ℃, keeping the temperature for reaction for 2h, continuing to heat to 230 ℃, reacting, sampling, testing the acid value, judging the reaction process, (after a central control point is reached, cooling to 170 ℃, adding trimellitic anhydride, continuing to keep the temperature at 170 ℃) (the steps in brackets correspond to comparative example 1 and examples 1-3), and sampling, testing the acid value, and judging the reaction end point. Cooling to 150 ℃, adding cosolvent for dilution, continuously cooling to 70 ℃, adding acrylate monomer for dilution, and controlling the end point temperature to be 40 ℃.

2. Adding a neutralizing agent and deionized water, and dispersing at a high speed (1000-.

3. Heating the dispersion liquid to 65-80 ℃, dropwise adding an initiator aqueous solution into the dispersion liquid, preserving the heat for 3-5 hours, and then adding deionized water to dilute the mixture until the solid content is about 40% and the pH value is about 7-9.

The following are compared by way of specific examples:

example 1

Putting 45.5g of neopentyl glycol, 20.7g of trimethylolpropane, 86.2g of isophthalic acid, 25.2g of adipic acid and 16.3g of 2-methyl-1, 3-propanediol into a reaction bottle; heating to 140 ℃ and preserving the temperature for 1 hour; heating the materials to 180 ℃ for reaction for 2 hours, and keeping the temperature for 2 hours; heating to 230 +/-3 ℃ within 3h, preserving the heat for 3h, and starting sampling to test until the acid value is less than or equal to 10; cooling to 170 ℃, adding 6.0g of trimellitic anhydride, keeping the temperature for 1h, starting sampling to test the acid value, and taking the acid value of 25 as a reaction end point; cooling to 150 ℃, adding 19.3g of ethylene glycol monobutyl ether and diluting; the temperature is continuously reduced to 70 ℃. Then, 40g of methyl methacrylate, 50g of styrene, 20g of butyl methacrylate, 40g of n-butyl acrylate, 10g of isooctyl acrylate and 20g of hydroxyethyl methacrylate were added thereto, and the mixture was stirred for 30 minutes. 2.8g of N, N-dimethylethanolamine was added and stirred for 20 min. Controlling the temperature of the system at 40 ℃, adding 738.2g of deionized water, and dispersing at a high speed of 1200rpm/min for 10 min. Standing for defoaming for 1 h. A pre-emulsion with a solids content of 38% is obtained.

Heating the pre-emulsion to 75 ℃, starting to dropwise add 35g of initiator aqueous solution with the mass concentration of 5.7%, finishing dropping within 1 hour, keeping the temperature for 4 hours, adding 44.8g of deionized water, stirring for 10 minutes, and filtering to obtain the high-branching-degree water-based polyester modified acrylic resin with the solid content of 35%.

Example 2

Putting 54.8g of neopentyl glycol, 52.8g of tris (2-hydroxyethyl) isocyanurate (THEIC), 35.2g of isophthalic acid and 50.9g of adipic acid into a reaction bottle; heating to 140 ℃ and preserving the temperature for 1 hour; heating the materials to 180 ℃ for reaction for 2 hours, and keeping the temperature for 2 hours; heating to 230 +/-3 ℃ within 3h, preserving the heat for 3h, and starting sampling to test until the acid value is less than or equal to 10; cooling to 170 ℃, adding 6.3g of trimellitic anhydride, preserving heat for 1h, starting sampling to test the acid value, and taking the acid value of 25 as a reaction end point; cooling to 150 ℃, adding 19.3g of ethylene glycol monobutyl ether and diluting; the temperature is continuously reduced to 70 ℃. Then, 30g of methyl methacrylate, 40g of styrene, 40g of butyl methacrylate, 40g of n-butyl acrylate, 10g of lauryl methacrylate and 20g of hydroxypropyl acrylate were added thereto, and the mixture was stirred for 30 minutes. 2.9g of N, N-dimethylethanolamine was added and stirred for 20 min. Controlling the temperature of the system at 40 ℃, adding 747.4g of deionized water, and dispersing at a high speed of 1200rpm/min for 10 min. Standing for defoaming for 1 h. A pre-emulsion with a solids content of 38% is obtained.

Heating the pre-emulsion to 75 ℃, starting to dropwise add 35g of initiator aqueous solution with the mass concentration of 5.7%, finishing dropping within 1 hour, keeping the temperature for 4 hours, adding 46.2g of deionized water, stirring for 10 minutes, and filtering to obtain the high-branching-degree water-based polyester modified acrylic resin with the solid content of 35%.

Example 3

Putting 56.7g of neopentyl glycol, 28.7g of trimethylolpropane, 43.1g of isophthalic acid and 47.9g of adipic acid into a reaction bottle; heating to 140 ℃ and preserving the temperature for 1 hour; heating the materials to 180 ℃ for reaction for 2 hours, and keeping the temperature for 2 hours; heating to 230 +/-3 ℃ within 3h, preserving the heat for 3h, and starting sampling to test until the acid value is less than or equal to 10; cooling to 170 ℃, adding 13.6g of trimellitic anhydride, preserving heat for 1h, starting sampling to test the acid value, and taking the acid value as 45 as a reaction end point; cooling to 150 ℃, adding 20g of ethylene glycol monobutyl ether and diluting; the temperature is continuously reduced to 70 ℃. Then, 50g of methyl methacrylate, 15g of styrene, 20g of butyl methacrylate, 25 g of cyclohexyl methacrylate, 40g of n-butyl acrylate, 10g of isooctyl acrylate and 20g of hydroxypropyl acrylate were added thereto, and the mixture was stirred for 30 minutes. 5.3g of N-methylethanolamine was added thereto, and the mixture was stirred for 20 min. The temperature of the system is controlled to be 40 ℃, 741.3g of deionized water is added, and high-speed dispersion is carried out for 10min at 1200 rpm/min. Standing for defoaming for 1 h. A pre-emulsion with a solids content of 38% is obtained.

Heating the pre-emulsion to 75 ℃, starting to dropwise add 35g of initiator aqueous solution with the mass concentration of 5.7%, finishing dropping within 1 hour, keeping the temperature for 4 hours, adding 45.3g of deionized water, stirring for 10min, and filtering to obtain the high-branching-degree water-based polyester modified acrylic resin with the solid content of 35%.

Example 4

Putting 44.7g of neopentyl glycol, 59.6g of tris (2-hydroxyethyl) isocyanurate (THEIC), 10.6g of 2, 2-dimethylolpropionic acid, 42.6g of isophthalic acid and 42.6g of adipic acid into a reaction bottle; heating to 140 ℃ and preserving the temperature for 1 hour; heating the materials to 180 ℃ for reaction for 2 hours, and keeping the temperature for 2 hours; heating to 230 +/-3 ℃ within 3h, preserving the temperature for 3h, starting sampling to test the acid value, and taking the acid value as 25 as the reaction end point; cooling to 150 ℃, adding 20g of ethylene glycol monobutyl ether and diluting; the temperature is continuously reduced to 70 ℃. Then, 30g of methyl methacrylate, 40g of styrene, 15g of butyl methacrylate, 25 g of cyclohexyl methacrylate, 40g of n-butyl acrylate, 10g of lauryl methacrylate and 20g of hydroxyethyl methacrylate were added thereto and stirred for 30 min. 6.0g of N-methylethanolamine was added thereto, and the mixture was stirred for 20 min. Controlling the temperature of the system at 40 ℃, adding 747.4g of deionized water, and dispersing at a high speed of 1200rpm/min for 10 min. Standing for defoaming for 1 h. A pre-emulsion with a solids content of 38% is obtained.

Heating the pre-emulsion to 75 ℃, starting to dropwise add 35g of initiator aqueous solution with the mass concentration of 5.7%, finishing dropping within 1 hour, keeping the temperature for 4 hours, adding 46.2g of deionized water, stirring for 10 minutes, and filtering to obtain the high-branching-degree water-based polyester modified acrylic resin with the solid content of 35%.

Comparative example 1

Putting 45.5g of neopentyl glycol, 20.7g of trimethylolpropane, 86.2g of isophthalic acid, 25.2g of adipic acid and 16.3g of 2-methyl-1, 3-propanediol into a reaction bottle; heating to 140 ℃ and preserving the temperature for 1 hour; heating the materials to 180 ℃ for reaction for 2 hours, and keeping the temperature for 2 hours; heating to 230 +/-3 ℃ within 3h, preserving the heat for 3h, and starting sampling to test until the acid value is less than or equal to 10; cooling to 170 ℃, adding 6.0g of trimellitic anhydride, keeping the temperature for 1h, starting sampling to test the acid value, and taking the acid value of 25 as a reaction end point; cooling to 150 ℃, adding 116g of ethylene glycol monobutyl ether for dilution; and continuously cooling to 70 ℃, adding 2.8g of N, N-dimethylethanolamine, stirring for 20min, continuously cooling, controlling the system temperature to be 40 ℃, adding 207g of deionized water, and dispersing at a high speed of 1200rpm/min for 10 min. Standing for defoaming for 1 h. Obtaining the water-based polyester with the solid content of 35 percent.

The reactant addition levels for each example are shown in table 1 below:

table 1: the addition amount of reactants in each example and comparative example

The high-branching-degree waterborne polyester modified acrylic resin obtained in the above examples and comparative examples is compounded according to the following table 2 to prepare the cooking-resistant waterborne finishing paint, which is detailed in the following table 2:

table 2: ingredient list of boiling-resistant water-based finishing paint

	Example 1	Example 2	Example 3	Example 4	Comparative example 1
						Deionized water	18	18	18	18	18
Ethylene glycol monobutyl ether	10	10	10	10	10
						High-branching-degree water-based polyester modified acrylic resin	50	50	50	50	50
NOVARES TD90D	10	12	8	8	0
						Bayhydrol BL 5140	3	3	3	3	3
CYMEL 303	7	9	7	9	7
						NACURE 155	0.2	0.2	0.2	0.2	0.2
BYK-024	0.3	0.3	0.3	0.3	0.3
						BYK-378	0.5	0.5	0.5	0.5	0.5
Polyfluo400	1	1	1	1	1

Note: all values in table 1 are parts by mass.

The following performance tests were performed on the aqueous gloss oil for metals prepared in examples 1 to 4 and comparative example 1:

(1) the aqueous gloss oil for metals prepared in examples 1-4 and comparative example 1 is respectively and uniformly coated on an A4 aluminum plate with the surface subjected to cleaning treatment, the thickness of the aluminum plate is 3 micrometers, the aluminum plate is baked in an oven at 205 ℃ for 2min, and then a test sample is taken out and naturally cooled.

(2) Detecting performance index of water-based gloss oil for metal on aluminum material

Solvent resistance: a1 kg iron hammer is wrapped by gauze, a test sample plate with a certain thickness is wiped after being dipped in butanone, and the number of times of wiping is recorded once after wiping until the substrate is exposed.

High temperature cooking resistance: adding water into a pressure cooker, putting a test sample plate to be detected into the pressure cooker, covering the pressure cooker, powering on a power supply to start heating, starting to record when the temperature reaches 121 ℃, turning off the power supply after cooking for 60min, opening the pressure cooker cover to take out the test sample plate after the pressure is relieved, and checking whether a paint film of the test sample plate turns white and falls off.

Hardness: the hardness of the paint film was determined using a pencil of known hardness, with the pencil hardness being such that the paint film was not scratched.

Adhesion force: preparing a test sample plate according to a general method for detecting the coating, vertically crossing the test sample plate by using a lattice scriber to scribe hundreds of lattices on the test sample plate, and then adhering the test sample plate by using a 3M adhesive tape. The 0 grade is optimal and does not fall off completely; grade 5 is worst, and the shedding area is more than 65%.

Abrasion resistance: a Taber test method is adopted, the rotating speed of a rotating disc is 60 r/min, a pressurizing arm bears 1kg of load, a hard rubber friction wheel embedded with carborundum abrasive materials is used for wearing the surface of a paint film, and the number of turns required for the paint film to be worn out and exposed out of a substrate is recorded.

(3) And (3) detection results: see table 3.

Table 3: performance index of paint film plate made of boiling-resistant water-based finishing paint of examples 1-4 and comparative example 1

	Solvent resistance	Resistance to high temperature cooking	Hardness of	Adhesion force	Wear resistance
						Example 1	>300	No blushing and no falling off	3H	Level 0	400
Example 2	>300	No blushing and no falling off	3H	Level 0	450
						Example 3	>300	No blushing and no falling off	3H	Level 0	400
Example 4	>300	No blushing and no falling off	3H	Level 0	500
						Comparative example 1	100	Severe blushing and partial loss	3H	Stage 2	108

The test results of the examples 1 to 4 in the table show that the water-based gloss oil for metals provided by the invention can be well coated on the aluminum material, and has good hardness, solvent resistance, high-temperature boiling resistance and wear resistance.

The technical innovation points of the invention are as follows:

1. high-branching-degree water-based saturated polyester modified acrylic acid, namely, replacing a surfactant with high-hydroxyl-value water-based polyester, dispersing an acrylic acid monomer in water to form a stable pre-emulsion, and carrying out free radical polymerization by taking water as a solvent to prepare the emulsifier-free high-branching-degree water-based saturated polyester modified acrylic acid;

2. the high-temperature cooking resistant and wear resistant tin water-soluble varnish is prepared by fully combining the high mechanical strength, good wear resistance, high glossiness and good flexibility of polyester and the color retention, chemical resistance and aging resistance of acrylic resin.