CN101892004B - Ultraviolet-cured heat-resistant coating and preparation and application methods thereof - Google Patents

Abstract

An ultraviolet curing heat-resistant coating and its preparation and application method belong to the technical field of coatings. The composition of the paint is by mass percentage: photosensitive organic resin 20% to 25%, photosensitive monomer 25% to 32%, photoinitiator 2.5% to 3.5%, high temperature resistant resin powder 1% to 2.1%, nano-alumina 0.8% to 2.1%, mica powder 2.5% to 5.5%, talc powder 2.5% to 5.5%, inorganic binder 30% to 37%, silane coupling agent 1.8% to 2.7% and additive 0.2%. The agent is composed of 0.1% each of defoamer and leveling agent. The coating preparation method: adding nano-alumina, mica powder, talc powder, inorganic binder, high temperature resistant resin powder and silane coupling agent to the photosensitive monomer; stirring and dispersing, ultrasonic treatment to obtain slurry; adding to the slurry Photosensitive organic resin, photoinitiator, defoamer, and leveling agent are stirred and mixed, dispersed and ultrasonically treated to obtain a coating. The coating application method: the coating is uniformly coated on the steel plate, and the coating is obtained by ultraviolet irradiation. The invention has the advantages of environmental protection, high efficiency and energy saving.

Description

A kind of ultraviolet curing heat-resistant coating and its preparation and application method

Technical field:

The invention relates to an environment-friendly fast-curing coating used on the surface of steel plates, in particular to an ultraviolet-curing heat-resistant coating and a preparation and application method thereof.

Background technique:

Heat-resistant coatings play an irreplaceable role in many fields such as industrial production and daily life. It cannot be ignored that many links in the preparation, coating and curing of traditional heat-resistant coatings cannot meet the requirements of environmental friendliness, high efficiency, Requirements for low energy consumption, such as the toxicity and high emission of volatile organic compounds in some solvent-based coatings.

At present, the main direction of heat-resistant coating research is green environmental protection and reduction. Chinese patent CN 101024739A discloses a water-based inorganic heat-resistant coating. Its composition (weight percentage) is: kaolin 35-46%, quartz powder 30-35% , ceramic short fiber 4-10%, titanium dioxide 4-8%, iron red 10-15%, the liquid phase is sodium water glass and additives, the additives are 3.5-6.5% of the liquid phase mass, the cured coating is attached Strong force, high hardness and impact strength; the patent CN1751106A applied by DuPont Company of the United States in China relates to a heat-resistant powder coating, the main components of which are polysiloxane resin and low-melting glass particles. The coating can withstand 550 The high temperature above ℃ does not fall off from the substrate. For the above-mentioned environmentally friendly heat-resistant coatings, although the volatile organic compounds in the preparation and coating process of water-based coatings and powder coatings are relatively low, the curing methods of the coatings are both Thermal curing, the coating is cured at a higher temperature in a baking equipment to form a film. This method consumes a lot of energy, and the curing speed of the coating is slow and the production efficiency is low.

Invention content:

The purpose of the present invention is to solve the problems existing in the prior art, to provide a UV-curable heat-resistant coating and its preparation and application method, the coating can be quickly cured on the steel substrate, and the coating can withstand short-term high-temperature heat treatment after curing No cracking, no falling off.

The present invention is an ultraviolet curing heat-resistant coating, and its components are: 20% to 25% of photosensitive organic resin, 25% to 32% of photosensitive monomer, 2.5% to 3.5% of photoinitiator, high temperature resistant resin Powder 1%～2.1%, Nano alumina 0.8%～2.1%, Mica powder 2.5%～5.5%, Talc powder 2.5%～5.5%, Inorganic binder 30%～37%, Silane coupling agent 1.8%～2.7% % and 0.2% of auxiliary agent, said auxiliary agent is made up of each 0.1% of defoamer and leveling agent.

2500；所述流平剂为聚硅氧烷丙烯酸酯

2100。The photosensitive organic resin is bisphenol A type epoxy acrylate; the photosensitive monomer is tripropylene glycol diacrylate; the photoinitiator is 1-hydroxycyclohexyl benzophenone, benzophenone and triethanolamine, its composition is 1:1:0.3 by mass ratio; the high temperature resistant resin powder is N,N-diaminodiphenylmethane type bismaleimide resin powder; the inorganic adhesive The bonding agent is low-temperature glass powder, and its main components are lead oxide, zinc oxide, diboron trioxide, and silicon dioxide; the silane coupling agent is γ-(methacryloyloxy)propyltrimethoxysilane; the The defoamer is polysiloxane acrylate

2500; the leveling agent is polysiloxane acrylate

2100.

In the above-mentioned UV-curable heat-resistant coating, the mica powder has an average particle diameter of 4.9 μm; the talc powder has an average particle diameter of 4.5 μm; the N,N-diaminodiphenylmethane type bismaleimide Amine resin powder, with an average particle size of 5.8 μm;

The preparation method of described ultraviolet curing heat-resistant coating, carries out as follows:

(1) Add nano-alumina, mica powder, talcum powder, inorganic binder, high-temperature-resistant resin powder, and silane coupling agent to the photosensitive monomer, and the mass percentage of the composition of the coating is 0.8% to 2.1% of nano-alumina , mica powder 2.5%~5.5%, talc powder 2.5%~5.5%, inorganic binder 30%~37%, high temperature resistant resin powder 1%~2.1%, silane coupling agent 1.8%~2.7%, photosensitive monomer 25% to 32%; use a high-speed dispersing homogenizer to disperse for 15 minutes, and then treat in an ultrasonic cleaning machine for 5 minutes as a treatment cycle, and process a total of 6 cycles to obtain a pre-dispersed slurry;

(2) Add the obtained above-mentioned slurry into photosensitive organic resin, photoinitiator, defoamer, and leveling agent, and the composition mass percentage of coating is 20%～25% of photosensitive organic resin, 2%～5% of photoinitiator %, 0.1% defoamer, and 0.1% leveling agent, mixed with an electric agitator, and then treated with the above-mentioned high-speed dispersion and ultrasonic cleaning method for 6 cycles to obtain a UV-curable heat-resistant coating.

2500；所述流平剂为聚硅氧烷丙烯酸酯

2100。In the above-mentioned preparation method of UV-curable heat-resistant coating, the inorganic binder is low-temperature glass powder; the high-temperature-resistant resin powder is N,N-diaminodiphenylmethane type bismaleimide resin powder; The silane coupling agent is gamma-(methacryloyloxy)propyltrimethoxysilane; the photosensitive organic resin is bisphenol A type epoxy acrylate. Described photoinitiator is the mixture that 1-hydroxycyclohexyl benzophenone, benzophenone and triethanolamine form, and its composition is by mass ratio 1-hydroxycyclohexyl benzophenone: benzophenone: triethanol is 1 : 1: 0.3, the defoamer is polysiloxane acrylate

2500; the leveling agent is polysiloxane acrylate

2100.

The application method of the UV-curable heat-resistant coating is as follows: uniformly apply the UV-curable heat-resistant coating on the surface-pretreated steel plate with a wire bar applicator, and irradiate with 100-140mW/ ^cm2 of UV light 65-90s to cure the coating to obtain a coating.

Compared with the prior art, the present invention has the advantages and positive effects as follows: it is an environmentally friendly fast-curing coating for the surface of steel plates, and is also suitable for electrical steel plates, home appliance plates, color-coated plates, and anti-fingerprint plates etc. Its preparation and coating process have low volatile organic compound emissions, and the coating can be quickly cured under ultraviolet radiation, which has the characteristics of safety, environmental protection, high efficiency, and energy saving. The coating has good adhesion after curing, and the adhesion is grade 1 before heat treatment; after heat treatment at 300-600°C for 1 hour in a nitrogen atmosphere, the coating remains intact and the surface is smooth and smooth, without cracking, bubbling, etc., heat treatment at 600°C for 1 hour Rear adhesion is grade 2.

Description of drawings

Figure 1 is the surface morphology (SEM) of the coating of the present invention after heat treatment for 1 h at 300 ° C and 600 ° C in nitrogen atmosphere, where (a) is the surface morphology (SEM) after heat treatment at 300 ° C for 1 h in nitrogen atmosphere, (b) ) is the surface morphology (SEM) after heat treatment at 600 °C for 1 h. It can be seen from the figure that the coating remains intact after heat treatment, and there is no obvious hole on the surface.

Detailed ways

In the following, the UV-curable heat-resistant coating and its preparation and application methods of the present invention will be described in detail in conjunction with the examples.

The bisphenol A type epoxy acrylate mentioned below is carried out by E-51 epoxy resin and acrylic acid under the conditions of using N,N-dimethylaniline as a catalyst and hydroquinone as a polymerization inhibitor. Prepared, the esterification reaction temperature is 110°C; E-51 epoxy resin, acrylic acid, N,N-dimethylaniline, and hydroquinone are all commercially available.

2500、聚硅氧烷丙烯酸酯

2100均为市场购得。The involved tripropylene glycol diacrylate, 1-hydroxycyclohexyl benzophenone, benzophenone, triethanolamine, N, N-diaminodiphenylmethane type bismaleimide resin powder, nano-alumina, Mica powder, talc powder, low-temperature glass powder, γ-(methacryloyloxy)propyltrimethoxysilane, polysiloxane acrylate

2500, polysiloxane acrylate

2100 are purchased from the market.

Example 1

2500；所述流平剂为聚硅氧烷丙烯酸酯

2100。上述材料N，N-二氨基二苯甲烷型双马来酰亚胺树脂粉末，平均粒径为5.8μm；云母粉，平均粒径为4.9μm；滑石粉，平均粒径为4.5μm。UV-curable heat-resistant coating, its composition by mass percentage is: 24.1% of photosensitive organic resin, 30.2% of photosensitive monomer, 3.1% of photoinitiator, 1.1% of high temperature resistant resin powder, 1.1% of nano-alumina, 2.7% of mica powder, 2.7% of talcum powder, 32.7% of inorganic binder, 2.1% of silane coupling agent and 0.2% of auxiliary agent, and said auxiliary agent is composed of 0.1% of defoamer and leveling agent respectively. The photosensitive organic resin is bisphenol A epoxy acrylate; the photosensitive monomer is tripropylene glycol diacrylate; the photoinitiator is 1-hydroxycyclohexyl benzophenone, benzophenone and The mixture of triethanolamine is composed of 1-hydroxycyclohexyl benzophenone by mass ratio: benzophenone: triethanolamine is composed of 1: 1: 0.3; the high temperature resistant resin powder is N, N-diamino di Benzene type bismaleimide resin powder; the inorganic binder is a low-temperature glass powder, and its main components are lead oxide, zinc oxide, diboron trioxide, silicon dioxide; the silane coupling agent is γ -(methacryloyloxy)propyltrimethoxysilane; the defoamer is polysiloxane acrylate

2500; the leveling agent is polysiloxane acrylate

2100. The above-mentioned N,N-diaminodiphenylmethane type bismaleimide resin powder has an average particle size of 5.8 μm; mica powder has an average particle size of 4.9 μm; talc powder has an average particle size of 4.5 μm.

Its preparation method of ultraviolet curing heat-resistant coating is as follows:

Add nano-alumina, mica powder, talc powder, inorganic binder, high-temperature-resistant resin powder, and silane coupling agent to the photosensitive monomer, and the mass percentage according to the composition of the coating is: nano-alumina 1.1%, mica powder 2.7% , 2.7% talcum powder, 32.7% inorganic binder, 1.1% high temperature resistant resin powder, 2.1% silane coupling agent, 30.2% photosensitive monomer, disperse with a high-speed dispersing homogenizer for 15 minutes, and then process it in an ultrasonic cleaner for 5 minutes One treatment cycle, a total of 6 cycles were processed to obtain the pre-dispersed slurry.

Add photosensitive organic resin, photoinitiator, defoamer, leveling agent in the above-mentioned slurry that obtains, by coating composition mass percent, be photosensitive organic resin 24.1%, photoinitiator 3.1%, defoamer 0.1%, flow rate Leveling agent 0.1%; mix with an electric stirrer, and then use the above-mentioned high-speed dispersion and ultrasonic cleaning method for 6 cycles to obtain a UV-curable heat-resistant coating.

2500；所述流平剂为聚硅氧烷丙烯酸酯

2100。In the above-mentioned ultraviolet curing heat-resistant coating, the inorganic binder is low-temperature glass powder; the high-temperature-resistant resin powder is N, N-diaminodiphenylmethane type bismaleimide resin powder; the silane The coupling agent is gamma-(methacryloyloxy)propyltrimethoxysilane; the photosensitive organic resin is bisphenol A type epoxy acrylate. Described photoinitiator is the mixture that 1-hydroxycyclohexyl benzophenone, benzophenone and triethanolamine form, and its composition is by mass ratio 1-hydroxycyclohexyl benzophenone: benzophenone: triethanol is 1 : 1: 0.3, the defoamer is polysiloxane acrylate

2500; the leveling agent is polysiloxane acrylate

2100.

The application method of UV curing heat-resistant coating is as follows:

Use a wire bar film applicator to evenly coat the UV-curable heat-resistant coating on the surface-pretreated steel plate, and irradiate the coating with 130mW/cm ² of UV light for 85s to cure the coating to obtain a coating and evaluate its properties. carry out testing. Coating adhesion test shall be carried out according to GB/T 9286-1998 "Paints and varnishes-paint film cross-cut test", and the evaluation of coating corrosion resistance shall refer to GB/T1771-1991 "Neutral salt spray resistance of paints and varnishes After 24 hours of salt water spray, check the corrosion area. If the corrosion area is ≤60%, it is qualified, otherwise it is unqualified. The obtained coating has good adhesion and corrosion resistance before heat treatment. After heat treatment, the adhesion of the coating decreases slightly, which is grade 2, and the corrosion resistance is qualified.

The composition material, preparation method and application method of all the other examples and comparative examples are basically the same as those of Example 1, the difference being the curing light intensity and curing time in the percentage of each composition material and application method, as shown in Table 1, the obtained The coating performance test results are shown in Table 2.

Table 1 Mass percentage of coating material components and curing light intensity and curing time in application

Table 2 coating performance test results

In the above examples, the coating adhesion test is carried out according to GB/T 9286-1998 "Paints and varnishes-paint film cross-cut test", and the corrosion resistance evaluation of coatings refers to GB/T 1771-1991 "Paints and varnishes. Neutral salt spray performance measurement" is carried out, and the corrosion area is checked after 24 hours of salt spray. If the corrosion area is less than or equal to 60%, it is qualified (○), otherwise it is unqualified (×).

It can be seen from Table 2 that the adhesion and corrosion resistance of the coatings in Examples 2 to 7 before heat treatment are good. After the heat treatment, the adhesion of the coatings in Examples 2 to 7 decreased slightly, which was grade 2. In Comparative Example 1, due to the weak curing light intensity and the short curing time used in Comparative Example 2, the degree of cross-linking and curing of the coating is not high, so the adhesion and corrosion resistance of the coating before and after heat treatment are poor.

Claims (7)

1. A UV-curable heat-resistant coating, characterized in that the composition of the coating is by mass percentage: 20% to 25% of photosensitive organic resin, 25% to 32% of photosensitive monomer, and 2.5% to 3.5% of photoinitiator , high temperature resistant resin powder 1% ~ 2.1%, nano-alumina 0.8% ~ 2.1%, mica powder 2.5% ~ 5.5%, talc powder 2.5% ~ 5.5%, inorganic binder 30% ~ 37%, silane coupling agent 1.8% to 2.7% and 0.2% of auxiliary agent, said auxiliary agent is composed of 0.1% each of defoamer and leveling agent, said photosensitive organic resin is bisphenol A type epoxy acrylate; said photosensitive monomer is three Propylene glycol diacrylate; Described photoinitiator is the mixture that 1-hydroxycyclohexyl benzophenone, benzophenone and triethanolamine form, and its composition is by mass ratio 1-hydroxycyclohexyl benzophenone: benzophenone : triethanolamine is 1:1:0.3; the high temperature resistant resin powder is N,N-diaminodiphenylmethane type bismaleimide resin powder; the inorganic binder is low temperature glass powder. 2. The UV-curable heat-resistant coating according to claim 1, characterized in that the silane coupling agent is γ-(methacryloyloxy)propyl trimethoxysilane; the defoamer is polysilicon oxyalkane acrylate

The leveling agent is polysiloxane acrylate

3. The UV-curable heat-resistant coating according to claim 1, characterized in that the mica powder has an average particle size of 4.9 μm; the talc powder has an average particle size of 4.5 μm. 4. The UV-curable heat-resistant coating according to claim 1, characterized in that the N,N-diaminodiphenylmethane type bismaleimide resin powder has an average particle diameter of 5.8 μm. 5. a preparation method of ultraviolet curing heat-resistant coating as claimed in claim 1, is characterized in that carrying out as follows: (1) Add nano-alumina, mica powder, talcum powder, inorganic binder, high-temperature-resistant resin powder, and silane coupling agent to the photosensitive monomer, and the mass percentage of the composition of the coating is 0.8% to 2.1% of nano-alumina , mica powder 2.5%~5.5%, talc powder 2.5%~5.5%, inorganic binder 30%~37%, high temperature resistant resin powder 1%~2.1%, silane coupling agent 1.8%~2.7%, photosensitive monomer 25% to 32%; use a high-speed dispersing homogenizer to disperse for 15 minutes, and then treat in an ultrasonic cleaning machine for 5 minutes as a treatment cycle, and process a total of 6 cycles to obtain a pre-dispersed slurry; (2) Add photosensitive organic resin, photoinitiator, defoamer, and leveling agent to the above slurry obtained, and the composition mass percentage of the coating is 20% to 25% of photosensitive organic resin and 2.5% to 3.5% of photoinitiator. %, 0.1% defoamer, 0.1% leveling agent; mixed with an electric agitator, and then processed by the above-mentioned high-speed dispersion and ultrasonic cleaning method for 6 cycles to obtain a UV-curable heat-resistant coating. 6. the preparation method of ultraviolet curing heat-resistant coating according to claim 5 is characterized in that described inorganic binder is low-temperature glass powder; Described high-temperature-resistant resin powder is N, N-diaminodiphenylmethane Type bismaleimide resin powder; The silane coupling agent is γ-(methacryloyloxy)propyltrimethoxysilane; The photosensitive organic resin is bisphenol A type epoxy acrylate, so Described photoinitiator is the mixture that 1-hydroxycyclohexyl benzophenone, benzophenone and triethanolamine form, and its composition is by mass ratio 1-hydroxycyclohexyl benzophenone: benzophenone: triethanolamine is 1: 1:0.3, the defoamer is polysiloxane acrylate The leveling agent is polysiloxane acrylate

7. An application method of the UV-curable heat-resistant coating as claimed in claim 1, characterized in that the UV-curable heat-resistant coating is evenly coated on the surface-pretreated steel plate by using a wire bar applicator , with 100-140mW/cm ² of ultraviolet light, irradiating for 65-90s to cure the coating and obtain a coating.

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