High-matting-property high-fullness matte finish resin and preparation method thereof

Abstract

The invention discloses matt finish paint resin with high extinction property and high fullness and a preparation method of the matt finish paint resin. The resin is prepared from the following components in percentage by mass: 15-25% of vegetable oil fatty acid, 15-20% of polyhydric alcohol, 0.1-0.5% of a color reducing agent, 20-30% of polybasic acid and 30-40% of a diluent. Various reaction raw material compositions are screened out through a large number of experiments, reasonable specific reaction steps are formulated, and the resin prepared through alcoholysis and esterification reactions is more complete in reaction and better and faster in comprehensive performance. Especially by introducing 1-10% dimer acid to replace phthalic anhydride and carefully controlling the material ratio, the influence of molecular weight on the fullness of the resin can be reduced under the condition of greatly improving the molecular weight of the alkyd resin, the compatibility of the resin and a curing agent is improved, and the curing effect of the alkyd resin is improved. Therefore, the alkyd resin which still has a good leveling effect under the condition of high molecular weight is obtained, and the matting property is better, so that a coating film with high fullness and high matting property is obtained.

Description

Technical Field

[0001] The invention relates to a high-matting and high-fullness matte topcoat resin and a preparation method thereof. Background Art

[0002] In the past, people liked to use high-gloss paint to decorate walls, furniture, etc., but now with the continuous change of aesthetics and the improvement of living standards, it is found that the high-gloss coating surface has a stimulating effect on people's eyes under the irradiation of the line, so people need a matte finish with soft gloss, no irritation to the eyes and very elegant, and matte paint has become people's first choice. At present, the common matte topcoat alkyd resin on the market has such a drawback that the comprehensive performance of good matting is general, and the matting of good comprehensive performance is poor. This is because, in order to pursue good matting, matting resin usually pursues a large resin molecular weight to enhance the dryness of the resin and thus improve the matte powder orientation effect. However, after the molecular weight becomes larger, the leveling and fullness are poor, and the compatibility with the polyurethane curing agent is poor, and the final surface effect is poor. The molecular weight pursuing the surface effect is usually small, so the sub-powder orientation is poor and the matting is poor.

[0003] Therefore, the development of an alkyd resin with both high matting and high fullness, which is suitable for high-end quick-drying matte topcoat, has important market application prospects. Summary of the invention

[0004] The purpose of the present invention is to develop an alkyd resin with both high matting and high fullness, which is suitable for high-grade quick-drying matte topcoat. Another purpose of the present invention is to provide a method for preparing the paint resin.

[0005] In order to solve the above technical problems, the present invention is implemented by the following technical solutions:

[0006] The high-mattness and high-fullness matte topcoat resin of the invention comprises the following raw materials by mass percentage: 15-25% of vegetable oil fatty acid, 15-20% of polyol, 0.1-0.5% of color reducing agent, 20-30% of polyacid and 30-40% of diluent.

[0007] Wherein, the vegetable oil fatty acid is a vegetable oil fatty acid with an iodine value of 120-140, such as soybean oil fatty acid,

[0008] Wherein, the polyol is propylene glycol, ethylene glycol, neopentyl glycol, diethylene glycol or monopentaerythritol.

[0009] Wherein, the color reducing agent is one of triphenyl phosphite and hypophosphorous acid.

[0010] Wherein, the polyacid is one or more of dimer acid, phthalic acid, benzoic acid or maleic anhydride.

[0011] Wherein, the diluent is one of xylene, trimethylbenzene or n-butyl ester or a mixture of several of them.

[0012] The method for preparing the high-mattness and high-fullness matte topcoat resin of the present invention comprises the following steps:

[0013] 1) Add vegetable oil fatty acid, polyol and part of diluent into a reaction vessel according to mass percentage, and slowly increase the temperature;

[0014] 2) Introduce nitrogen into the reactor to evacuate the air in the reactor;

[0015] 3) Raise the temperature to 220-230°C and keep the temperature for 1-2 hours, then measure the transparency of the resin;

[0016] 4) cooling down and adding polyacid, polyol, part of diluent and color reducing agent;

[0017] 5) Raise the temperature to 190-210°C and keep warm for 2-3 hours;

[0018] 6) Slowly add part of the diluent, continue to keep warm for 2-3 hours, and measure the acid value and viscosity;

[0019] 7) Cool down to 130-140°C, add diluent, and stir for 0.5-1.5 hours;

[0020] 8) Cooling and filtering to obtain a matte topcoat resin with high extinction and high fullness.

[0021] As a preferred embodiment, the present invention provides a method for preparing a high-mattness and high-fullness matte topcoat resin, comprising the following steps:

[0022] (1) Add vegetable oil fatty acid and monopentaerythritol to a four-necked flask equipped with a stirring device, a thermometer and nitrogen protection, raise the temperature to 220-230° C., and stir for 1 hour;

[0023] (2) then adding neopentyl glycol, dimer acid, phthalic acid, maleic anhydride and refluxing xylene, slowly raising the temperature to about 200° C. and refluxing for esterification for 3 hours;

[0024] (3) Add some reflux xylene and reflux at 200-210°C for 2 hours for mid-control;

[0025] (4) After the reaction is completed, the temperature is cooled to below 140° C. and xylene is added to dilute the mixture to 60% solid content;

[0026] (5) Continue cooling to 70-80° C. and stirring for 30-40 minutes, then filter and package to obtain a high-dust matte topcoat resin.

[0027] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0028] The resin obtained by alcoholysis and esterification reaction of the present invention has a more complete reaction, better and faster comprehensive performance. In particular, by introducing 1-10% of dimer acid to replace phthalic anhydride, the material ratio is carefully controlled, and the influence of the molecular weight on the fullness of the resin can be reduced while the molecular weight of the alkyd resin is greatly increased, and the compatibility of the resin and the curing agent is improved, so that the alkyd resin with good leveling effect under the condition of high molecular weight is obtained, and the matting property is better, so that a coating film with both high fullness and high matting property is obtained.

[0029] The specific reaction mechanism of the present invention is as follows: (1) After introducing 1%-10% dimer acid to replace phthalic anhydride, the dimer acid has a main chain plasticizing effect on the resin, improves the elasticity of the main chain, and thus improves the defect self-repairing performance of the resin during the film forming process, which is actually equivalent to improving the leveling property of the resin, thereby improving the fullness of the resin. (2) The long carbon chain ester bond content of dimer acid is extremely low, and it has excellent solubility and extensibility in conventional solvents (such as xylene), which can reduce the viscosity of the resin, thereby being very beneficial for the resin to penetrate into the pores of matt powder. As is well known, matt powder is a porous and highly adsorbable silica powder. The easier it is for the resin to penetrate into the sub-powder pores, the less likely the matt powder is to sink. In this way, when forming a film, more matt powder is matte on the surface of the paint film, and less matt powder sinks into the paint film, thereby improving the matte property and transparency of the paint film. (3) The introduction of dimer acid also improves the compatibility of the resin with the polyurethane curing agent, thereby improving the fullness and transparency. Since the adduct in the polyurethane curing agent is usually trimethylolpropane or neopentyl glycol, these two substances have a relatively similar structure to the dimer acid contained in the alkyd resin, which is conducive to the compatibility of the two resins. (4) The introduction of too little dimer acid (less than 1%) does not improve the elasticity of the resin much, so the resin does not have the self-repairing function of defects, the leveling is poor, and the improvement effect is poor; the introduction of more than 10% dimer acid will make the resin too soft, reduce the glass transition temperature of the resin too much, and affect the drying property, and then affect the orientation of the matte powder, causing the matte powder to sink below the paint film after the resin film is formed, not only the matte property is deteriorated, but also the transparency of the paint film is affected.

[0030] By combining the raw materials of the present invention, not only can a coating film with high matting and high fullness be obtained, but also the elasticity of the film is improved, thereby improving the wear resistance of the film, thereby obtaining a high-quality matte coating. However, experiments have found that too much dimer acid reduces the glass transition temperature of the resin too much, which will reduce the matting and wear resistance. DETAILED DESCRIPTION

[0031] The present invention is further described in detail below with reference to specific embodiments, but is not intended to limit the present invention.

[0032] Example 1

[0033] A method for preparing a matte topcoat resin with high extinction and high fullness comprises the following steps:

[0034] (1) In a 1000 mL four-necked flask equipped with a stirring device, a thermometer and nitrogen protection, 220 g of soybean oil fatty acid, 150 g of monopentaerythritol, 20 g of xylene and 1 g of a color reducing agent (triphenyl phosphite) were added in sequence, the temperature was raised to 210-220° C., and the temperature was kept for 2 hours;

[0035] (2) Pass nitrogen protection, cool to 180°C, and slowly add 50 g of diethylene glycol, 40 g of neopentyl glycol, 230 g of phthalic acid, 16 g of dimer acid, 2 g of maleic anhydride and 50 g of xylene;

[0036] (3) Slowly raise the temperature until liquid is discharged, turn off the nitrogen, control the distillation head temperature ≤ 105°C, and keep it at 150-190°C for 4 hours;

[0037] (4) After the insulation is completed, the temperature is continued to be controlled at 190-200°C for 4 hours of reflux esterification. After dilution, the resin: xylene = 10:5.7, the acid value is ≤9, and the viscosity is 70-80 seconds / 25°C format tube.

[0038] (5) After the reaction is completed, the temperature is lowered to 140-150°C, 200 g of xylene is added for dilution, and then the mixture is stirred for 30-40 minutes and filtered and packaged.

[0039] Example 2

[0040] A method for preparing a matte topcoat resin with high extinction and high fullness comprises the following steps:

[0041] (1) In a 1000 mL four-necked flask equipped with a stirring device, a thermometer and nitrogen protection, 185 g of soybean oil fatty acid, 130 g of monopentaerythritol, 20 g of xylene and 1 g of a color reducing agent (triphenyl phosphite) were added in sequence, the temperature was raised to 210-220° C., and the temperature was kept for 2 hours;

[0042] (2) Pass nitrogen protection, cool to 180°C, and slowly add 50 g of neopentyl glycol, 35 g of dimer acid, 200 g of phthalic acid, 2 g of maleic anhydride and 50 g of xylene;

[0043] (3) Slowly raise the temperature until liquid is discharged, turn off the nitrogen, control the distillation head temperature ≤ 105°C, and keep it at 150-190°C for 4 hours;

[0044] (4) After the insulation is completed, the temperature is continued to be controlled at 190-200°C for 4 hours of reflux esterification. After dilution, the resin: xylene = 10:5.7, the acid value is ≤10, and the viscosity is 60-80 seconds / 25°C format tube.

[0045] (5) After the reaction is completed, the temperature is lowered to 140-150°C, 320 g of xylene is added for dilution, and then the mixture is stirred for 30-40 minutes and filtered and packaged.

[0046] Example 3

[0047] A method for preparing a matte topcoat resin with high extinction and high fullness comprises the following steps:

[0048] (1) In a 1000 mL four-necked flask equipped with a stirring device, a thermometer and nitrogen protection, 160 g of soybean oil fatty acid, 140 g of monopentaerythritol, 80 g of dimer acid, 20 g of xylene and 1 g of a color reducing agent (triphenyl phosphite) were added in sequence, the temperature was raised to 210-220° C., and the temperature was kept for 2 hours;

[0049] (2) Cool to 180°C under nitrogen protection, and slowly add 70 g of ethylene glycol, 190 g of phthalic acid, 4 g of maleic anhydride and 50 g of xylene;

[0050] (3) Slowly raise the temperature until liquid is discharged, turn off the nitrogen, control the distillation head temperature ≤ 105°C, and keep it at 150-190°C for 5 hours;

[0051] (4) After the insulation is completed, the temperature is continued to be controlled at 190-200°C for 4 hours of reflux esterification. After dilution, the acid value is ≤13 and the viscosity is 60-80 seconds / 25°C format tube.

[0052] (5) After the reaction is completed, the temperature is lowered to 140-150°C, 220 g of xylene is added for dilution, and then the mixture is stirred for 30-40 minutes and filtered and packaged.

[0053] Example 4

[0054] A method for preparing a topcoat resin comprises the following steps:

[0055] (1) In a 1000 mL four-necked flask equipped with a stirring device, a thermometer and nitrogen protection, 230 g of soybean oil fatty acid, 150 g of monopentaerythritol, 20 g of xylene and 1 g of a color reducing agent were added in sequence, the temperature was raised to 210-220° C., and the temperature was kept for 2 hours;

[0056] (2) Pass nitrogen protection, cool to 180°C, and slowly add 50 g of diethylene glycol, 40 g of neopentyl glycol, 230 g of phthalic acid, 2 g of maleic anhydride and 50 g of xylene;

[0057] (3) Slowly raise the temperature until liquid is discharged, turn off the nitrogen, control the distillation head temperature ≤ 105°C, and keep it at 150-190°C for 4 hours;

[0058] (4) After the insulation is completed, the temperature is continued to be controlled at 190-200°C for 4 hours of reflux esterification. After dilution, the resin: xylene = 10:5.7, the acid value is ≤9, and the viscosity is 50-60 seconds / 25°C format tube.

[0059] (5) After the reaction is completed, the temperature is lowered to 140-150°C, 200 g of xylene is added for dilution, and then the mixture is stirred for 30-40 minutes and filtered and packaged.

[0060] Example 5 Testing of paint film properties

[0061] 1. According to the national standard, the resins obtained in Examples 1-4 were made into paints according to the following matte topcoat formula and tested in parallel.

[0062] Quick-drying matte topcoat ratio:

[0063] Component A: Resin: 70 parts, CAC (ethylene glycol ethyl ether acetate): 3 parts, butyl ester: 12 parts, xylene: 8 parts, 6900-20-X (polyamide anti-settling agent): 0.5 parts, wax dispersion: 0.5 parts, 907 (photoinitiator): 5 parts, EFKA4010 (dispersant): 0.2 parts, BYK-052 (defoaming agent): 0.2 parts, BYK323

[0064] (leveling agent): 0.2 parts, BYK-410 (thixotropic agent): 0.05 parts, T-12 (organic tin catalyst): 0.1 parts.

[0065] Component B: 750D curing agent: 50 parts.

[0066] 2. The specific measurement results of various properties of the matte topcoat of Examples 1 to 4 are shown in Table 1.

[0067] Table 1 Performance test results

[0068]

[0070] The above performance test results show that the matte topcoat prepared by the present invention has the advantages of easy polishing, good matte powder dispersion effect, excellent adhesion, good leveling, good heat resistance, etc. compared with conventional commercially available matte topcoat products. In addition, by comparison, it can be found that the matte topcoat prepared in Example 2 of the present invention has the best matte property, the best fullness and the best hardness at the same time, and has achieved a good technical effect.

[0071] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. The present invention may be subject to various changes and improvements without departing from the spirit and scope of the present invention. These changes and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A high-mattness and high-fullness matte topcoat resin, characterized in that: The invention is prepared from the following raw materials in the following mass percentages: 15-25% of vegetable oil fatty acid, 15-20% of polyol, 0.1-0.5% of color reducing agent, 20-30% of polyacid and 30-40% of diluent.

2. The high-mattness and high-fullness matte topcoat resin according to claim 1, characterized in that: The vegetable oil fatty acid is a vegetable oil fatty acid with an iodine value of 120-140.

3. The high-mattness and high-fullness matte topcoat resin according to claim 1, characterized in that: The polyol is propylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol or monopentaerythritol.

4. The high-mattness and high-fullness matte topcoat resin according to claim 1, characterized in that: The color reducing agent is one of triphenyl phosphite and hypophosphorous acid.

5. The high-mattness and high-fullness matte topcoat resin according to claim 1, characterized in that: Among them, The polyacid is one or more of dimer acid, phthalic acid, benzoic acid or maleic anhydride.

6. The high-mattness and high-fullness matte topcoat resin according to claim 1, characterized in that: The diluent is one of xylene, trimethylbenzene or n-butyl ester or a mixture of the two or more.

7. The method for preparing the high-mattness and high-fullness matte topcoat resin according to any one of claims 1 to 6, characterized in that: The following steps are involved: 1) Add vegetable oil fatty acid, polyol and part of diluent into a reaction vessel according to mass percentage, and slowly increase the temperature; 2) Introduce nitrogen into the reactor to evacuate the air in the reactor; 3) Raise the temperature to 220-230°C and keep the temperature for 1-2 hours, then measure the transparency of the resin; 4) cooling down and adding polyacid, polyol, part of diluent and color reducing agent; 5) Raise the temperature to 190-210°C and keep warm for 2-3 hours; 6) Slowly add part of the diluent, continue to keep warm for 2-3 hours, and measure the acid value and viscosity; 7) Cool down to 130-140°C, add diluent, and stir for 0.5-1.5 hours; 8) Cooling and filtering to obtain a matte topcoat resin with high extinction and high fullness.

8. A method for preparing a high-mattness and high-fullness matte topcoat resin, characterized in that: The following steps are involved: (1) Add vegetable oil fatty acid and monopentaerythritol to a four-necked flask equipped with a stirring device, a thermometer and nitrogen protection, raise the temperature to 220-230° C., and stir for 1 hour; (2) then adding neopentyl glycol, dimer acid, phthalic acid, benzoic acid and refluxing xylene, slowly raising the temperature to about 200° C. and refluxing for esterification for 3 hours; (3) Add some reflux xylene and reflux at 200-210°C for 2 hours for mid-control; (4) After the reaction is completed, the temperature is cooled to below 140° C. and xylene is added to dilute the mixture to 60% solid content; (5) Continue cooling to 70-80° C. and stirring for 30-40 minutes, then filter and package to obtain a high-dust matte topcoat resin.

9. A method for preparing a high-mattness and high-fullness matte topcoat resin, characterized in that: The following steps are involved: (1) In a 1000 mL four-necked flask equipped with a stirring device, a thermometer and nitrogen protection, 220 g of soybean oil fatty acid, 150 g of monopentaerythritol, 20 g of xylene and 1 g of triphenyl phosphite were added in sequence, the temperature was raised to 210-220° C., and the temperature was kept for 2 hours; (2) Pass nitrogen protection, cool to 180°C, and slowly add 50 g of diethylene glycol, 40 g of neopentyl glycol, 230 g of phthalic acid, 16 g of dimer acid, 2 g of maleic anhydride and 50 g of xylene; (3) Slowly raise the temperature until liquid is discharged, turn off the nitrogen, control the distillation head temperature ≤ 105°C, and keep it at 150-190°C for 4 hours; (4) After the insulation is finished, the temperature is continued to be controlled at 190-200°C for reflux esterification for 4 hours and the control is measured. After the resin: xylene is diluted at 10:5.7, the acid value is ≤9, and the viscosity is 70-80 seconds / 25°C format tube; (5) After the reaction is completed, the temperature is lowered to 140-150°C, 200 g of xylene is added for dilution, and then the mixture is stirred for 30-40 minutes and filtered and packaged.

10. A method for preparing a high-mattness and high-fullness matte topcoat resin, characterized in that: The following steps are involved: (1) In a 1000 mL four-necked flask equipped with a stirring device, a thermometer and nitrogen protection, 185 g of soybean oil fatty acid, 130 g of monopentaerythritol, 20 g of xylene and 1 g of triphenyl phosphite were added in sequence, the temperature was raised to 210-220° C., and the temperature was kept for 2 hours; (2) Pass nitrogen protection, cool to 180°C, and slowly add 50 g of neopentyl glycol, 35 g of dimer acid, 200 g of phthalic acid, 2 g of maleic anhydride and 50 g of xylene; (3) Slowly raise the temperature until liquid is discharged, turn off the nitrogen, control the distillation head temperature ≤ 105°C, and keep it at 150-190°C for 4 hours; (4) After the insulation is finished, the temperature is continued to be controlled at 190-200°C for 4 hours of reflux esterification and the control is measured. After the resin: xylene is diluted at 10:5.7, the acid value is ≤10, and the viscosity is 60-80 seconds / 25°C format tube; (5) After the reaction is completed, the temperature is lowered to 140-150°C, 320 g of xylene is added for dilution, and then the mixture is stirred for 30-40 minutes and filtered and packaged.

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