High-stable UV-moisture dual-curing three-protection paint and preparation method thereof

Abstract

The application belongs to the technical field of paint coating, and particularly relates to a high-stability UV and moisture dual-curing three-protection paint and a preparation method thereof, which comprises, based on the total amount of raw materials, 25.5-77.9 wt% of 3,3,5-trimethylcyclohexyl acrylate, 20-54 wt% of polyurethane acrylate with an isocyanate group, 1-8.5 wt% of an auxiliary stable crosslinking agent, 0.1-5 wt% of a dehydrating agent, and 1-7 wt% of a photoinitiator; the weight ratio of the polyurethane acrylate to the 3,3,5-trimethylcyclohexyl acrylate and the auxiliary stable crosslinking agent is 1:(1.10-1.40):(0.05-0.30); and the auxiliary stable crosslinking agent is selected from trimethylolpropane triacrylate and / or trimethylolpropane trimethacrylate. The application has the properties of UV and moisture dual curing, and has high stability and can resist acid and alkali environments.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of paint coating, and particularly relates to a high-stability UV moisture dual-curing three-proof paint and a preparation method thereof. BACKGROUND

[0002] At present, most traditional UV three-proof paints use IBOA (i.e. isobornyl acrylate) as a monomer. Relevant research shows that IBOA itself has considerable sensitization risk. In order to avoid users from causing skin sensitization due to contact with IBOA and meet diversified market demands, it is necessary to develop sustainable and biologically friendly IBOA free UV three-proof systems.

[0003] In the prior art, there is a UV three-proof paint with UV and moisture dual-curing characteristics. Since a circuit board is an uneven surface, most of the surface of the three-proof paint sprayed on the circuit board has been cured after UV irradiation, while the shadow area needs to be cured by a moisture curing process to achieve surface dryness. The UV three-proof paint with UV and moisture dual-curing characteristics can be quickly cured by UV irradiation, and at the same time, in the area where light cannot directly irradiate, it can be cured by moisture. In the first step of the moisture curing process, the isocyanate group -N=C=O in the resin reacts with water molecules in the environment to generate unstable carbamic acid. In the second step, the unstable carbamic acid intermediate immediately decomposes to release carbon dioxide and generate a primary amine and a hydroxyl group. In the third step, the newly generated primary amine has high reactivity and will quickly react with another isocyanate group on the adjacent resin molecule to form a stable urea bond, ultimately leading to the formation of a stable urea bond between resin molecules and the construction of a three-dimensional cross-linked network structure. UV curing provides high hardness and fast surface dryness performance, while moisture curing is relatively slow and from the surface to the inside, which can effectively cure the area (shadow area, thick film deep layer) that cannot be reached by UV light. The two curing methods ensure the uniformity and firmness of the coating, and the formula does not contain components that cause allergic reactions. However, the UV three-proof paint with UV and moisture dual-curing characteristics has poor stability and cannot be applied to acid and alkali environments.

[0004] It should be noted that this part of the present application only provides background technology related to the present application, and does not necessarily constitute prior art or public knowledge. SUMMARY

[0005] The purpose of the present application is to overcome the defects of poor stability and poor acid and alkali resistance of the UV three-proof paint in the prior art, and to provide a high-stability UV moisture dual-curing three-proof paint and a preparation method thereof. On the basis of having UV and moisture dual-curing performance, it has relatively high stability and can resist acid and alkali environments.

[0006] To achieve the above object, in a first aspect, the present application provides a high-stability UV-humidity dual-curing three-protection paint, comprising the following raw material components by weight percentage: 25.5-77.9 wt% of 3,3,5-trimethylcyclohexyl acrylate, 20-54 wt% of polyurethane acrylate with isocyanate groups, 1-8.5 wt% of auxiliary stable crosslinking agent, 0.1-5 wt% of dehydrating agent, and 1-7 wt% of photoinitiator, based on the total amount of raw materials; and the weight ratio of polyurethane acrylate and 3,3,5-trimethylcyclohexyl acrylate, auxiliary stable crosslinking agent is 1:(1.10-1.40):(0.05-0.30); the auxiliary stable crosslinking agent is selected from trimethylolpropane triacrylate and / or trimethylolpropane trimethacrylate.

[0007] Preferably, in the present application, the content of isocyanate groups in the polyurethane acrylate is 10%-18% by mass.

[0008] In some preferred embodiments of the present application, the content of 3,3,5-trimethylcyclohexyl acrylate is 30-75 wt%, and / or the weight ratio of polyurethane acrylate and 3,3,5-trimethylcyclohexyl acrylate, auxiliary stable crosslinking agent is 1:(1.135-1.298):(0.142-0.230).

[0009] In some preferred embodiments of the present application, the molecular weight of the polyurethane acrylate is 600-3500 g / mol and its functionality is 0.7-1.2.

[0010] In some preferred embodiments of the present application, the dehydrating agent is selected from p-toluenesulfonyl isocyanate and / or N,N-dicyclohexyl carbodiimide, and the photoinitiator is selected from 1-hydroxy-cyclohexyl-phenyl ketone and / or 2,4,6(trimethylbenzoyl) diphenyl phosphine oxide.

[0011] In some preferred embodiments of the present application, the raw material components of the high-stability UV-humidity dual-curing three-protection paint further comprise a free radical polymerization inhibitor and / or a catalytic humidity curing agent, and when the free radical polymerization inhibitor and the catalytic humidity curing agent are present, the weight ratio of the free radical polymerization inhibitor, the catalytic humidity curing agent, and the polyurethane acrylate is (1-4):(5-25):1000.

[0012] In some preferred embodiments of the present application, the catalytic humidity curing agent is selected from at least one of 、 、 .

[0013] In some preferred embodiments of the present application, the free radical polymerization inhibitor is selected from at least one of 、 、 . R, R1are each independently selected from alkyl groups having 4-10 carbon atoms.

[0014] In some preferred embodiments of the present application, the raw material components of the high-stability UV-humidity dual-curing three-protection paint further comprise: 0.01-0.03wt% of a fluorescent whitening agent, and 0-2wt% of an adhesion promoter, based on the total amount of the raw materials.

[0015] Further preferably, the fluorescent whitening agent is selected from at least one of 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene, 1,4-2(benzoxazolyl-2-yl)naphthalene, 4,4-bis(2-benzoxazolyl)stilbene, and 4.4-bis(2-dimethoxystyryl)diphenyl; and the adhesion promoter is selected from alkyl acrylate phosphate and / or methacryloxy silane.

[0016] In a second aspect, the present application provides a preparation method of a high-stability UV-humidity dual-curing three-protection paint, which is used to prepare the high-stability UV-humidity dual-curing three-protection paint of the first aspect, and the preparation method comprises the following steps:

[0017] S1, mixing a required amount of 3,3,5-trimethylcyclohexyl acrylate, an auxiliary stabilizing crosslinking agent, a polyurethane acrylate, and a dehydrating agent to obtain a first mixed solution;

[0018] S2, introducing a photoinitiator into the first mixed solution to obtain a second mixed solution.

[0019] In some preferred embodiments of the present application, the preparation method further comprises:

[0020] In the second mixing in S2, a free radical polymerization inhibitor and / or a fluorescent whitening agent are further introduced;

[0021] Then, in the obtained second mixed solution, a catalytic humidity curing agent and / or an adhesion promoter are further introduced to perform third mixing.

[0022] In some preferred embodiments of the present application, the conditions of the first mixing comprise: a stirring speed of 1700-2300 rpm, and a stirring time of 100-150 s.

[0023] In some preferred embodiments of the present application, the conditions of the second mixing comprise: a stirring speed of 2000-2500 rpm, a total stirring time of 150-200 s, and a stirring number of 1-3 times.

[0024] In some preferred embodiments of the present application, the conditions of the third mixing comprise: a stirring speed of 1500-2000 rpm, and a stirring time of 100-150 s.

[0025] Advantages:

[0026] The present application, by the above technical scheme, especially in the UV and moisture dual-curable polyurethane acrylate with isocyanate group, adding a specific amount of 3,3,5-trimethylcyclohexyl acrylate, auxiliary stable crosslinking agent, isocyanate reactive groups in the polyurethane acrylate and the chain end of the acrylate group in 3,3,5-trimethylcyclohexyl acrylate, three acrylate groups in the auxiliary stable crosslinking agent react with each other, specifically, the three acrylate groups contained in the auxiliary stable crosslinking agent are like three hands, which can simultaneously grab different molecular chains during curing (while ordinary monofunctional additives can only extend the chain, and difunctional additives can only form linear crosslinking), during the curing process, the double bonds in the acrylate groups open and react with the carbon-carbon double bonds on the chain end of the acrylate groups in the polyurethane acrylate and 3,3,5-trimethylcyclohexyl acrylate to form a covalent bond, which will produce a three-dimensional network structure, improve the crosslinking density and make the structure more compact. This structure not only reduces the free volume between the polymer chains, but also increases the tortuosity of the penetration path, thereby hindering the diffusion of penetrants (water molecules, oxygen, salt ions). These microscopic changes work together to significantly enhance the barrier ability of the three-proofing paint to water vapor, salt mist ions and other penetrants in the macroscopic view, that is, it can quickly build a high crosslinking density, rigid polyacrylate network during the UV curing stage, slow down the migration of isocyanate groups in the polyurethane acrylate and water vapor penetration, thereby supporting the compact skeletal structure during the moisture curing process. The reactivity generated by the reaction of the compact skeletal structure during the moisture curing process will quickly react with another isocyanate group in the adjacent polyurethane acrylate to form a stable urea bond, thereby forming a more stable and compact crosslinking structure, ensuring uniform and complete curing of the entire coating. The weather resistance and wear resistance of the UV three-proofing paint are effectively improved, so that the three-proofing paint has high stability and can resist acid and alkali environments based on the UV and moisture dual-curing performance. The present application also cooperates with the addition of a dehydrating agent to improve the curing efficiency and protective performance. When irradiated by ultraviolet light, the photoinitiator will absorb light energy to form free radicals, which will further initiate the polymerization reaction of the polyurethane acrylate and 3,3,5-trimethylcyclohexyl acrylate, and the auxiliary stable crosslinking agent can form a more stable chemical bond between these molecules to connect them into a stable network structure, thereby improving the strength and hardness of the UV three-proofing paint and enabling it to better resist external environmental erosion and damage.

[0027] The application also controls the suitable weight ratio of the polyurethane acrylate and 3,3,5-trimethylcyclohexyl acrylate, the auxiliary stable crosslinking agent, balances the amount of the auxiliary stable crosslinking agent, can obtain a suitable and closely crosslinked network skeleton structure, improves the deep moisture curing efficiency and curing effect, and improves the three-proofing paint stability and acid and alkali resistance, avoids the case that the amount of the auxiliary stable crosslinking agent is too small to cause insufficient skeleton support, and too much to cause too dense network and excessive hindered moisture diffusion, and thus affects the deep curing efficiency.

[0028] The application develops a high-stability UV moisture dual-curing three-proofing paint with better performance and wider application, so as to promote the upgrading and transformation of the related industry, and improve the overall competitiveness and sustainable development of the industry. The preparation method of the application is simple and convenient to operate, has strong practicability, and the obtained three-proofing paint has no human sensitization risk, and has good moisture-proof, salt mist-proof and mildew-proof effects. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions of the embodiments of the application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the application, and therefore should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.

[0030] Figure 1 The appearance comparison chart of the three-proofing paint obtained in Example 1 before and after the alkali resistance test.

[0031] Figure 2 The appearance comparison chart of the three-proofing paint obtained in Example 1 before and after the acid resistance test.

[0032] Figure 3 The appearance comparison chart of the three-proofing paint obtained in Example 2 before and after the alkali resistance test.

[0033] Figure 4 The appearance comparison chart of the three-proofing paint obtained in Example 2 before and after the acid resistance test.

[0034] Figure 5 The appearance comparison chart of the three-proofing paint obtained in Example 3 before and after the alkali resistance test.

[0035] Figure 6 The appearance comparison chart of the three-proofing paint obtained in Example 3 before and after the acid resistance test.

[0036] Figure 7 The appearance comparison chart of the three-proofing paint obtained in Example 4 before and after the alkali resistance test.

[0037] Figure 8 Appearance comparison chart of the tri-proof paint obtained from Example 4 of the present application before and after acid resistance test.

[0038] Figure 9 Appearance comparison chart of the tri-proof paint obtained from Example 5 of the present application before and after alkali resistance test.

[0039] Figure 10 Appearance comparison chart of the tri-proof paint obtained from Example 5 of the present application before and after acid resistance test.

[0040] Figure 11 Appearance comparison chart of the tri-proof paint obtained from Comparative Example 1 of the present application before and after alkali resistance test.

[0041] Figure 12 Appearance comparison chart of the tri-proof paint obtained from Comparative Example 1 of the present application before and after acid resistance test.

[0042] Figure 13 Appearance comparison chart of the tri-proof paint obtained from Comparative Example 2 of the present application before and after alkali resistance test.

[0043] Figure 14 Appearance comparison chart of the tri-proof paint obtained from Comparative Example 2 of the present application before and after acid resistance test.

[0044] Figure 15 Appearance comparison chart of the tri-proof paint obtained from Comparative Example 3 of the present application before and after alkali resistance test.

[0045] Figure 16 Appearance comparison chart of the tri-proof paint obtained from Comparative Example 3 of the present application before and after acid resistance test.

[0046] Figure 17 Appearance comparison chart of the tri-proof paint obtained from Comparative Example 4 of the present application before and after alkali resistance test.

[0047] Figure 18 Appearance comparison chart of the tri-proof paint obtained from Comparative Example 4 of the present application before and after acid resistance test.

[0048] Figure 19 Appearance comparison chart of the tri-proof paint obtained from Comparative Example 5 of the present application before and after alkali resistance test.

[0049] Figure 20 Appearance comparison chart of the tri-proof paint obtained from Comparative Example 5 of the present application before and after acid resistance test.

[0050] Figure 21 Appearance comparison chart of the tri-proof paint obtained from Comparative Example 6 of the present application before and after acid resistance test.

[0051] Figure 22Appearance comparison chart of the tri-proof paint obtained from Invention Comparative Example 7 before and after acid resistance test.

[0052] Figure 23 Appearance comparison chart of the tri-proof paint obtained from Invention Comparative Example 8 before and after acid resistance test. DETAILED DESCRIPTION

[0053] In the present application, the orientation words such as "upper", "lower", "left", "right" are generally understood in connection with the orientation shown in the drawings and the actual application, unless otherwise specified.

[0054] In addition, the terms "first", "second", "third", etc. are used only for descriptive purposes and should not be construed as indicating or implying relative importance or an indicated number of technical features. Therefore, the features defined with "first", "second", etc. can explicitly or implicitly include one or more of the features. In the description of the present application, the meaning of "a plurality of" is two or more, unless otherwise specifically limited.

[0055] In the present application, unless otherwise specifically specified and limited, the "on" or "under" of the first feature to the second feature can be that the first and second features are in direct contact, or the first and second features are indirectly in contact through an intermediate medium. Moreover, the "over", "above" and "on" of the first feature to the second feature can be that the first feature is directly above or obliquely above the second feature, or only indicates that the horizontal height of the first feature is higher than that of the second feature. The "under", "below" and "under" of the first feature to the second feature can be that the first feature is directly below or obliquely below the second feature, or only indicates that the horizontal height of the first feature is less than that of the second feature.

[0056] The endpoints of the ranges and any values disclosed herein are not limited to the precise values or points stated. The ranges or values should be interpreted as including values near the recited ones. For numeric ranges, the endpoints of each range, the endpoints of each range and individual point values, and individual point values can be combined with each other to produce one or more new numeric ranges, which should be considered as specifically disclosed herein. Among them, the terms "optional", "optional" mean that it can be included, or not included (or can be, or can not be).

[0057] In a first aspect, the present application provides a high-stability UV-humidity dual-curing three-protection paint, comprising the following raw material components by weight percentage: 25.5-77.9 wt% of 3,3,5-trimethylcyclohexyl acrylate, 20-54 wt% of polyurethane acrylate with isocyanate groups, 1-8.5 wt%, preferably 1-2.5 wt% of auxiliary stable crosslinking agent, 0.1-5 wt% of dehydrating agent, and 1-7 wt% of photoinitiator, wherein the weight ratio of the polyurethane acrylate and the 3,3,5-trimethylcyclohexyl acrylate and the auxiliary stable crosslinking agent is 1:(1.10-1.40):(0.05-0.30), preferably 1:(1.20-1.40):(0.05-0.20), and further preferably 1:(1.25-1.40):(0.05-0.20); and the auxiliary stable crosslinking agent is selected from trimethylolpropane triacrylate and / or trimethylolpropane trimethacrylate.

[0058] Preferably, the content of isocyanate groups in the polyurethane acrylate is 10%-18% by mass. The use of a suitable content of isocyanate groups in the polyurethane acrylate is more conducive to promoting the reaction between the polyurethane acrylate and the 3,3,5-trimethylcyclohexyl acrylate and the auxiliary stable crosslinking agent to form more stable chemical bonds, thereby forming a more stable network structure framework that is more conducive to humidity curing, further improving the strength and hardness of the UV three-protection paint, and also enabling it to better resist the erosion and damage of the external environment.

[0059] The content of isocyanate groups in the present application is measured by back titration.

[0060] In some preferred embodiments of the present application, the content of 3,3,5-trimethylcyclohexyl acrylate is 30-75 wt%.

[0061] Preferably, the weight ratio of the polyurethane acrylate and the 3,3,5-trimethylcyclohexyl acrylate and the auxiliary stable crosslinking agent is 1:(1.135-1.298):(0.142-0.230), and further preferably 1:(1.135-1.160):(0.142-0.230). The use of the preferred ratio of the polyurethane acrylate and the 3,3,5-trimethylcyclohexyl acrylate and the auxiliary stable crosslinking agent is more conducive to improving the protective performance of the UV-humidity dual-curing three-protection paint.

[0062] In some preferred embodiments of the present application, the polyurethane acrylate has a molecular weight of 600-3500 g / mol, preferably 1000-5500 g / mol, and a functionality of 0.7-1.2. With this preferred scheme, the polyurethane acrylate has higher reactivity and crosslinking density, forming a more compact three-dimensional network structure, thereby improving the mechanical strength, chemical resistance, heat resistance and other properties of the resin; and the oxygen resistance is smaller, which is more conducive to improving the curing efficiency. If the molecular weight and / or functional group of the polyurethane acrylate is too large, the viscosity will increase sharply, the processability will be poor, and the heat resistance and chemical resistance will decrease. The polyurethane acrylate resin can be obtained by commercial purchase, for example, it can be purchased from Changxing Material Industrial Co., Ltd., Arkema Group (Sartomer); it can also be prepared by existing methods.

[0063] The polyurethane acrylate of the present application is preferably an aliphatic polyurethane acrylate with an isocyanate group, which has excellent weather resistance and is not prone to yellowing. The polyurethane acrylate of the present application can be obtained by commercial purchase or preparation.

[0064] In some preferred embodiments of the present application, the dehydrating agent is selected from p-toluenesulfonyl isocyanate and / or N,N-dicyclohexyl carbodiimide.

[0065] Preferably, the photoinitiator is selected from 1-hydroxy-cyclohexyl-phenyl ketone and / or 2,4,6(trimethylbenzoyl) diphenyl phosphine oxide.

[0066] In some preferred embodiments of the present application, the raw material components of the high-stability UV-humidity dual-curing three-protection paint further include a free radical polymerization inhibitor and / or a catalytic humidity curing agent.

[0067] Preferably, when the free radical polymerization inhibitor and the catalytic humidity curing agent are contained, the weight ratio of the free radical polymerization inhibitor, the catalytic humidity curing agent and the polyurethane acrylate is (1-4):(5-25):1000. With the appropriate ratio of free radical polymerization inhibitor and catalytic humidity curing agent, the humidity curing is more conducive to proceed.

[0068] In some preferred embodiments of the present application, the catalytic humidity curing agent is selected from at least one of (dimorpholinyl diethyl ether), (N,N-dimethyl-p-toluidine).

[0069] In some preferred embodiments of the present application, the free radical polymerization inhibitor is selected from at least one of (2,6-di-tert-butyl-4-methylphenol), (3,5-di-tert-butyl-4-hydroxyphenylpropionic acid C7-C9 mixed ester), (Octamine (CAS: 37338-62-8)), (As C 20 H 27 N) wherein R, R1are each independently selected from an alkyl group having a carbon number of 4-10. The alkyl group having a carbon number of 4-10 can be, for example, C4H9, C8H 17 or other alkyl chains.

[0070] In some embodiments, the free radical polymerization inhibitor is selected from at least one of C 25 H 42 O3(CAS: 125643-61-0), C 33 H 52 O2(CAS 7786-17-6), C 25 H 44 OS2(CAS: 110553-27-0), Octamine (CAS: 37338-62-8), C 20 H 27 N(CAS: 68411-46-1).

[0071] In some preferred embodiments of the present application, the raw material components of the high-stability UV-humidity dual-curing three-protection paint further comprise: 0.01-0.03wt% of a fluorescent whitening agent, and 0-2wt%, preferably 0.5-2wt% of an adhesion promoter, based on the total amount of the raw materials. With this preferred scheme, the adhesion performance of the UV-humidity dual-curing three-protection paint to the substrate is improved, and it is easy to identify.

[0072] Further preferably, the fluorescent whitening agent is selected from at least one of 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene (C 26 H 26 N2O2S), 1,4-2(benzoxazolyl-2-yl)naphthalene (C 24 H 14 O2N2), 4,4-bis(2-benzoxazolyl)stilbene (C 28 H 18 N2O2), 4.4-bis(2-dimethoxystyryl)diphenyl (C 30 H 26 O2).

[0073] Preferably, the adhesion promoter is selected from alkyl acrylate phosphate and / or methacryloyloxysilane.

[0074] In a second aspect, the present application provides a preparation method of a high-stability UV-humidity dual-curing three-protection paint, which is used to prepare the high-stability UV-humidity dual-curing three-protection paint of the first aspect, and the preparation method comprises the following steps:

[0075] S1, a required amount of 3,3,5-trimethylcyclohexyl acrylate, auxiliary stabilizing crosslinking agent, polyurethane acrylate, dehydrating agent are mixed for the first time to obtain a first mixed solution;

[0076] S2, a photoinitiator is introduced into the first mixed solution for secondary mixing to obtain a second mixed solution.

[0077] In some preferred embodiments of the present application, the preparation method further comprises:

[0078] In the secondary mixing in S2, a free radical polymerization inhibitor and / or a fluorescent whitening agent are also introduced;

[0079] After that, in the obtained second mixed solution, a catalytic moisture curing agent and / or an adhesion promoter are continuously introduced for tertiary mixing.

[0080] The present application adopts the above specific mixing steps, compared with the way of mixing all raw materials together, can make the reaction more complete, which is beneficial to improve the stability of the UV three-proof paint.

[0081] In some preferred embodiments of the present application, the conditions of the first mixing include: the stirring speed is 1700-2300 rpm, and the stirring time is 100-150 s.

[0082] In some preferred embodiments of the present application, the conditions of the secondary mixing include: the stirring speed is 2000-2500 rpm, and the total stirring time is 150-200 s. The stirring of the secondary mixing can be multiple times, for example, the stirring times are 1-3 times, and the total stirring time meets the above range.

[0083] In some preferred embodiments of the present application, the conditions of the tertiary mixing include: the stirring speed is 1500-2000 rpm, and the stirring time is 100-150 s.

[0084] The above mixing conditions of the present application can make the component mixing more uniform, which is more beneficial to improve the curing efficiency of the UV moisture dual-curing three-proof paint.

[0085] The following detailed description of the embodiments of the present application is exemplary and is only used to explain the present application, and cannot be understood as a limitation of the present application.

[0086] Example 1

[0087] A three-proof paint, the raw material formula of which is shown in Table 1. Among them, the molecular weight of the polyurethane acrylate is 1000-3500 g / mol and its functionality is 0.8-1.2, the content of isocyanate group is 15% by mass, which is purchased from Changxing Material Industrial Co., Ltd., the model number is 6133N-15 (see the product manual of the company).

[0088] The weight ratio of polyurethane acrylate and 3,3,5-trimethylcyclohexyl acrylate, auxiliary stabilizing crosslinking agent (trimethylolpropane triacrylate) is 1:1.291:0.05. The weight ratio of free radical polymerization inhibitor, catalytic moisture curing agent and polyurethane acrylate is 1.25:7.5:1000.

[0089] Table 1

[0090]

[0091] The preparation process is as follows:

[0092] 1. TMCHA and polyurethane acrylate, trimethylolpropane triacrylate, p-toluenesulfonyl isocyanate are mixed once under the mixer (mixing speed 2000 rpm, 100 s).

[0093] 2. The photoinitiator 184, BHT, UV-OB are added to the mixture obtained in step 1, and mixed twice under the mixer (mixing speed 2000 rpm, total mixing time 150 s).

[0094] 3. DMDEE is added to the mixture obtained in step 2, and mixed once under the mixer (mixing speed 2000 rpm, 150 s).

[0095] Example 2

[0096] The method of Example 1 is referred to, except that the amount of polyurethane acrylate and auxiliary stabilizing crosslinking agent is adjusted so that the weight ratio of polyurethane acrylate and auxiliary stabilizing crosslinking agent is 1:0.25, and the total content of polyurethane acrylate and auxiliary stabilizing crosslinking agent remains unchanged.

[0097] Example 3

[0098] The method of Example 1 is referred to, except that the amount of polyurethane acrylate and 3,3,5-trimethylcyclohexyl acrylate is adjusted so that the weight ratio of polyurethane acrylate and 3,3,5-trimethylcyclohexyl acrylate is 1:1.17.

[0099] Example 4

[0100] The method of Example 1 is referred to, except that the molecular weight of polyurethane acrylate is 600-1300 g / mol and its functionality is 1-2, and the content of isocyanate groups is 10% by mass, which is purchased from Changxing Material Industrial Co., Ltd. and the model number is 6133N-10.

[0101] Example 5

[0102] The method of Example 1 was followed except that the dehydrating agent was N,N-dicyclohexyl carbodiimide and the amount was unchanged.

[0103] Comparative Example 1

[0104] The method of Example 1 was followed except that 3,3,5-trimethylcyclohexyl acrylate was replaced by isobornyl acrylate and the amount was unchanged.

[0105] Comparative Example 2

[0106] The method of Example 1 was followed except that the auxiliary stabilizing crosslinker was not added and the amount was unchanged.

[0107] Comparative Example 3

[0108] The method of Example 1 was followed except that the amounts of polyurethane acrylate and 3,3,5-trimethylcyclohexyl acrylate were adjusted so that the weight ratio of polyurethane acrylate to 3,3,5-trimethylcyclohexyl acrylate was 1:1.42, but the total amount of the two was unchanged.

[0109] Comparative Example 4

[0110] The method of Example 1 was followed except that the amount of the auxiliary stabilizing crosslinker was adjusted so that the weight ratio of polyurethane acrylate to the auxiliary stabilizing crosslinker was 1:0.40.

[0111] Comparative Example 5

[0112] The method of Example 1 was followed except that the dehydrating agent was not added.

[0113] Comparative Example 6

[0114] The method of Example 1 was followed except that the auxiliary stabilizing crosslinker was replaced by tris(2-hydroxyethyl) isocyanuric acid triacrylate (THEICTA) and the amount was unchanged.

[0115] Comparative Example 7

[0116] The method of Example 1 was followed except that the auxiliary stabilizing crosslinker was replaced by pentaerythritol triacrylate (PET3A) and the amount was unchanged.

[0117] Comparative Example 8

[0118] The method of Example 1 was followed except that the polyurethane acrylate was replaced by a polyurethane acrylate containing no isocyanate groups, which was purchased from Changxing Material Industrial Co., Ltd. and the model was 61329.

[0119] Test Example

[0120] The tri-proof paints obtained in the above examples and comparative examples were subjected to performance tests, and the results are shown in Table 2. The appearance of the acid and alkali resistance test samples of Examples 1-5 was photographed, respectively, as Figure 1 、 Figure 2 、 Figure 3 、 Figure 4 、 Figure 5 、 Figure 6 、 Figure 7 、 Figure 8 、 Figure 9 、 Figure 10 The appearance of the acid and alkali resistance test samples of Comparative Examples 1-5 was photographed, respectively, as Figure 11 、 Figure 12 、 Figure 13 、 Figure 14 、 Figure 15 、 Figure 16 、 Figure 17 、 Figure 18 、 Figure 19 、 Figure 20 The appearance of the acid resistance test samples of Comparative Examples 6-8 was photographed, respectively, as Figure 21 、 Figure 22 、 Figure 23 .

[0121] Among them, the adhesion grade was tested according to GB / T 9286-2021, and the water vapor transmission amount was obtained according to GB / T 1037-2021.

[0122] The acid and alkali resistance test is obtained according to GB / T1981.2-2009, the test solution: 5wt% hydrochloric acid aqueous solution for acid resistance test, 5wt% sodium hydroxide aqueous solution for alkali resistance test, test time: 168 h, test temperature: at room temperature of 22-24℃. Among them, the acid and alkali resistance is divided into qualified and unqualified according to the appearance, qualified refers to the evenly distributed three-proof paint film without the phenomenon of blistering, sticking, white spot, cracking, wrinkling, and the metal substrate under the three-proof paint film without obvious corrosion phenomenon; unqualified refers to at least one of the following conditions: the evenly distributed three-proof paint film appears blistering, sticking, white spot, cracking, peeling or wrinkling phenomenon, or the metal substrate under the three-proof paint film appears obvious corrosion phenomenon visible to the naked eye. Among them, it can be seen from the corresponding drawings of the comparative examples that the metal substrate under the three-proof paint film in comparative example 1 has obvious corrosion phenomenon visible to the naked eye, which is unqualified, the metal substrate under the three-proof paint film in comparative example 2 has obvious peeling phenomenon, which is unqualified, the three-proof paint film in comparative example 3 has edge peeling and surface sticking phenomenon, which is unqualified, the three-proof paint film in comparative example 4 has edge peeling phenomenon, which is unqualified, the three-proof paint film in comparative example 5 has bulge at the edge and peeling (black spot) phenomenon, which is unqualified; the three-proof paint material in comparative example 6 and comparative example 7 after replacing the crosslinking agent is not easy to spread evenly and flatly on the substrate, both have shrinkage and wrinkling phenomenon, and both are unqualified; the polyurethane acrylic resin in comparative example 8 does not contain isocyanate groups, the three-proof paint prepared by the polyurethane acrylic resin without isocyanate groups has no moisture curing function, and has soft texture and poor barrier performance (poor water permeation data), in the acid resistance test, the three-proof paint is very easy to deform after touching other test pieces, which is unqualified.

[0123] Table 2

[0124]

[0125] From the above results, it can be seen that, compared with the comparative examples, the embodiment scheme of the present application has higher stability and can resist acid and alkali environment on the basis of having UV and moisture dual curing performance.

[0126] Further, according to examples 1 and 2-5, the preferred scheme of the present application is more conducive to improving stability and acid and alkali resistance.

[0127] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical scheme of the present application, including combining various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application, and all fall within the protection scope of the present application.

Claims

1. A high-stable UV moisture dual-curing three-antireflection coating, characterized by, comprising the following raw material components: 25.5-77.9 wt% of 3,3,5-trimethylcyclohexyl acrylate, 20-54 wt% of polyurethane acrylate with isocyanate groups, 1-8.5 wt% of auxiliary stable crosslinking agent, 0.1-5 wt% of dehydrating agent, 1-7 wt% of photoinitiator, based on the total amount of raw materials; and the weight ratio of the polyurethane acrylate and 3,3,5-trimethylcyclohexyl acrylate, auxiliary stable crosslinking agent is 1:(1.10-1.40):(0.05-0.30); the auxiliary stable crosslinking agent is selected from trimethylolpropane triacrylate and / or trimethylolpropane trimethacrylate.

2. The high-stable UV moisture dual-curable paint according to claim 1, characterized in that, The content of 3,3,5-trimethylcyclohexyl acrylate is 30-75 wt%, and / or the weight ratio of the polyurethane acrylate and 3,3,5-trimethylcyclohexyl acrylate, auxiliary stable crosslinking agent is 1:(1.135-1.298):(0.142-0.230).

3. The high-stable UV moisture dual-curable paint according to claim 1, characterized in that, The content of isocyanate groups in the polyurethane acrylate is 10%-18% by mass; and / or, The molecular weight of the polyurethane acrylate is 600-3500 g / mol and its functionality is 0.7-1.

2.

4. The high-stable UV moisture dual-curable paint according to claim 1, wherein The dehydrating agent is selected from p-toluenesulfonyl isocyanate and / or N,N-dicyclohexyl carbodiimide, and the photoinitiator is selected from 1-hydroxy-cyclohexyl-phenyl ketone and / or 2,4,6(trimethylbenzoyl) diphenyl phosphine oxide.

5. The high-stable UV moisture dual-curable paint according to claim 1, wherein The raw material components of the high-stability UV-humidity dual-curing three-protection paint further comprise a free radical polymerization inhibitor and / or a catalytic humidity curing agent, and when the free radical polymerization inhibitor and the catalytic humidity curing agent are present, the weight ratio of the free radical polymerization inhibitor, the catalytic humidity curing agent and the polyurethane acrylate is (1-4):(5-25):1000.

6. The high-stable UV moisture dual-curable paint according to claim 5, wherein The catalytic moisture curing agent is selected from and / or ; The free radical polymerization inhibitor is selected from at least one of , , , wherein R, R1are each independently selected from an alkyl group having a carbon number of 4-10.

7. The high-stable UV moisture dual-curable paint according to claim 1, wherein The raw material components of the high-stability UV-humidity dual-curing three-protection paint further comprise: 0.01-0.03 wt% of a fluorescent whitening agent and 0-2 wt% of an adhesion promoter, based on the total amount of raw materials; wherein the fluorescent whitening agent is selected from at least one of 2,5-bis(5-tert-butyl-2-benzoxazolyl) thiophene, 1,4-2(benzoxazolyl-2-yl) naphthalene, 4,4-bis(2-benzoxazolyl) stilbene, 4.4-bis(2-dimethoxy styryl) biphenyl; and the adhesion promoter is selected from alkyl acrylate phosphate and / or methacryloyloxy silane.

8. A method for preparing a high-stable UV-moisture dual-curing three-antireflection coating, characterized in that, It is used for preparing the high-stability UV-humidity dual-curing three-protection paint as claimed in any one of claims 1-7, and its preparation method comprises the following steps: S1, mixing the required amount of 3,3,5-trimethylcyclohexyl acrylate, auxiliary stable crosslinking agent, polyurethane acrylate and dehydrating agent once to obtain a first mixed solution; S2, introducing the photoinitiator into the first mixed solution for secondary mixing to obtain a second mixed solution.

9. The preparation method of the high-stability UV moisture dual-curing conformal coating according to claim 8, characterized in that, The preparation method further comprises: In the secondary mixing in S2, a free radical polymerization inhibitor and / or a fluorescent whitening agent are also introduced; Then, in the obtained second mixed solution, a catalytic humidity curing agent and / or an adhesion promoter are continuously introduced for tertiary mixing.

10. The preparation method of the high-stability UV moisture dual-curing conformal coating according to claim 9, characterized in that, The conditions of the first mixing include: stirring speed of 1700-2300 rpm, and stirring time of 100-150 s; The conditions of the second mixing include: stirring speed of 2000-2500 rpm, and total stirring time of 150-200 s; The conditions of the third mixing include: stirring speed of 1500-2000 rpm, and stirring time of 100-150 s.

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