Single-component photo-thermal dual-curing epoxy resin three-proofing coating

Abstract

The single-component photo-thermal dual-curing epoxy resin three-proofing coating comprises the following raw materials in parts by mass: 100 parts of acrylic acid / organic silicon dual-modified epoxy resin, 8-25 parts of a diluent, 6-18 parts of an epoxy curing agent and 1-6 parts of a photoinitiator, the diluent is an acrylic acid glycidyl ether compound; the photoinitiator is an epoxy alkyl anthracene ether compound. The three-proofing coating disclosed by the invention has excellent adhesive force on a PCB (Printed Circuit Board), and has the characteristics of photo-initiation rapid curing and high toughness; the problem of molecular migration of the photoinitiator in the coating is avoided, and the weather resistance of the three-proofing coating is obviously improved.

Description

Technical Field

[0001] The invention relates to an epoxy resin coating, in particular to a one-component epoxy resin three-proof coating. Background Art

[0002] Conformal coatings, i.e., moisture-proof, salt spray-proof, and mildew-proof coatings, play a vital role in the modern electronics industry. They are mainly used to coat printed circuit boards (PCBs) with soldered plug-in components to form a protective layer to improve the reliability and service life of electronic products and ensure safety in use. Traditional conformal coatings mainly include acrylic conformal coatings, polyurethane conformal coatings, and silicone conformal coatings, but their adhesion, temperature resistance, weather resistance, and curing speed are poor.

[0003] Light-curing conformal coating is a circuit board surface coating material that is cured by the dual effects of ultraviolet light and moisture. It is widely used in the three-proof protection of electronic circuit boards due to its fast curing, high hardness, strong durability and environmental protection characteristics. However, in actual applications, light-curing conformal coating is not well compatible with the photoinitiator system, which easily causes small molecule migration, resulting in a decrease in the adhesion of the coating on the substrate, and at the same time has a greater impact on the reliability of the coating, which easily leads to a reduction in the life of electronic products. Summary of the invention

[0004] The technical problem to be solved by the present invention is to overcome the above-mentioned defects of the prior art and provide a single-component light-heat dual-curing epoxy resin three-proof coating which can be quickly cured and has strong adhesion.

[0005] The technical solution adopted by the present invention to solve the technical problem is as follows: a one-component light-heat dual-curing epoxy resin three-proof coating, the raw materials of which include, by weight: 100 parts of acrylic acid / organic silicon dual-modified epoxy resin, 8-25 parts of diluent, 6-18 parts of epoxy curing agent, and 1-6 parts of photoinitiator; The acrylic acid / organic silicon double-modified epoxy resin is obtained by reacting an organic alkoxy polysiloxane and an acrylic monomer compound with a multifunctional epoxy resin respectively; The diluent is a glycidyl ether of acrylic acid compound; The photoinitiator is an epoxyalkyl anthracene ether compound, and its chemical structure is: ; Among them, R 1 represents hydrogen, ethyl or chlorine, R 2 represents a C2~C6 alkylene group, R 3 represents hydrogen, methyl or ethyl.

[0006] Preferably, the weight ratio of the organoalkoxy polysiloxane, the acrylic monomer compound and the multifunctional epoxy resin is 15-40:5-35:100.

[0007] More preferably, the multifunctional epoxy resin is a multifunctional glycidylamine resin.

[0008] More preferably, the multifunctional epoxy resin is one or a combination of two or more of bisphenol A glycidyl ether, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether methane, triglycidyl-p-aminophenol, triglycidyl triisocyanate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl xylene diamine, tetraglycidyl-1,3-bisaminomethylcyclohexylamine and their homologues and derivatives.

[0009] More preferably, the active group of the organoalkoxy polysiloxane is: -SiR n (OR ， ) 3-n , where R represents H, Me, Et, Bu, Ph, Pr, C 6 H 4 CH 2 , C 8 H 17 , C 12 H 25 One of the ， It represents one of H, Me, Et, and Bu.

[0010] More preferably, the acrylic monomer is one or a combination of two or more of acrylic acid, methacrylic acid, acrylic anhydride, and acetic acrylic anhydride.

[0011] Preferably, the preparation method of the acrylic acid / silicone dual-modified epoxy resin comprises: (1) A multifunctional epoxy resin and an organic alkoxy polysiloxane undergo a dealcoholization reaction in a solvent under catalytic conditions to obtain a uniform liquid; (2) The obtained uniform liquid is mixed with an acrylic monomer compound, reacted under catalytic conditions, and the solvent is removed to obtain the product.

[0012] More preferably, in the preparation method of acrylic acid / organic silicon dual-modified epoxy resin, the catalyst in step (1) is sodium ethoxide, potassium ethoxide, hydrochloric acid, acetic acid, AlCl 3 、TiCl 3 SnCl 3 、ZrCl 4 , BF 3 、ZnCl 2 One or a combination of two or more.

[0013] More preferably, in the method for preparing acrylic acid / silicone dual-modified epoxy resin, the catalyst in step (2) is one or a combination of two or more of N,N-dimethylaniline, N,N-dimethylbenzylamine, trimethylbenzylammonium chloride, tetraethylammonium bromide, triphenylphosphine, triphenylantimony, and chromium acetylacetonate.

[0014] More preferably, in the preparation method of acrylic acid / silicone dual-modified epoxy resin, the solvent is one or a combination of two or more of toluene, xylene, pentane, hexane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, methanol, ethanol, isopropanol, n-butanol, mixed propanol, acetone, methyl butyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone.

[0015] More preferably, in the method for preparing acrylic acid / silicone dual-modified epoxy resin, the reaction conditions in step (1) are: temperature 40° C. to 120° C., and time 2 to 8 hours.

[0016] More preferably, in the method for preparing acrylic acid / silicone dual-modified epoxy resin, the reaction conditions in step (2) are: temperature 40° C. to 120° C., and time 2 to 8 hours.

[0017] Preferably, the acrylic / silicone double-modified epoxy resin is obtained by reacting an organic alkoxy polysiloxane and an acrylic monomer compound with a multifunctional epoxy resin respectively; the weight ratio of the organic alkoxy polysiloxane, the acrylic monomer compound and the multifunctional epoxy resin is 20-30:10-25:100.

[0018] Preferably, the one-component light-heat dual-curing epoxy resin three-proof coating comprises, by weight, 100 parts of acrylic / silicone dual-modified epoxy resin, 10-20 parts of diluent, 8-13 parts of epoxy curing agent, and 2-4 parts of photoinitiator.

[0019] Preferably, the epoxy curing agent is a latent epoxy curing agent.

[0020] Preferably, the diluent is one or a combination of two or more of allyl glycidyl ether, methacrylate glycidyl ether, and 4-hydroxybutyl acrylate glycidyl ether.

[0021] Preferably, the epoxy curing agent is one or a combination of two or more selected from the group consisting of modified aliphatic amines, aromatic diamines, dicyandiamides, imidazoles, organic acid anhydrides, organic hydrazides, Lewis acid-amine complexes and microcapsules.

[0022] Preferably, the raw materials of the one-component light-heat dual-curing epoxy resin three-proof coating also include 8 to 20 parts of a toughening agent (by mass, corresponding to every 100 parts of acrylic acid / silicone dual-modified epoxy resin), and the toughening agent is a liquid rubber toughened epoxy resin.

[0023] More preferably, the raw materials of the one-component photo-thermally dual-curable epoxy resin three-proof coating further include 10-16 parts of a toughening agent (by mass, corresponding to every 100 parts of acrylic / silicone double-modified epoxy resin); the toughening agent is one or a combination of two or more of silicone rubber, polyurethane rubber, carboxyl-terminated liquid nitrile rubber, liquid polysulfide rubber, acrylate rubber, and chloroprene rubber.

[0024] Preferably, the raw materials of the one-component photo-thermally dual-curable epoxy resin three-proof coating further include 0.2-2 parts of an antifoaming agent (by mass, corresponding to every 100 parts of acrylic / silicone double-modified epoxy resin), and the antifoaming agent is a silicone oil-based antifoaming agent.

[0025] More preferably, the raw materials of the one-component photo-thermally dual-curable epoxy resin three-proof coating further include 0.5-1 part of an antifoaming agent (by mass, corresponding to every 100 parts of acrylic / silicone double-modified epoxy resin).

[0026] Preferably, the raw materials of the one-component photo-thermally dual-curable epoxy resin three-proof coating further include 0.2-2 parts of a leveling agent (by mass, corresponding to every 100 parts of acrylic / silicone double-modified epoxy resin), and the leveling agent is a silicone-oxide type epoxy floor leveling agent.

[0027] More preferably, the raw materials of the one-component photo-thermally dual-curable epoxy resin three-proof coating further include 0.5-1 part of a leveling agent (by mass, corresponding to every 100 parts of acrylic / silicone double-modified epoxy resin).

[0028] The present invention has the following beneficial effects: The three-proof coating of the present invention has excellent adhesion to the PCB circuit board, and at the same time has the characteristics of photo-initiated rapid curing and high toughness; it avoids the molecular migration problem of the photo-initiator in the coating and significantly improves the weather resistance of the three-proof coating.

[0029] In addition to the purposes, features, and advantages described above, the present invention has other purposes, features, and advantages. The following will refer to the accompanying drawings and make a further detailed description of the present invention. Description of the Drawings

[0030] The accompanying drawings constituting a part of this application are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings: Figure 1 is the 1 1H-NMR spectrum of the photo-initiator in Example 1 of the present invention; Figure 2 is the 13 13C-NMR spectrum of the photo-initiator in Example 1 of the present invention; Figure 3 It is the ultraviolet absorption spectrum of the photoinitiator of Example 1 of the present invention. DETAILED DESCRIPTION

[0031] In order to make the purpose, scheme and beneficial technology of the present invention clearer, the present invention is further described in detail below in conjunction with the embodiments and drawings. It should be pointed out that the embodiments described in this specification are only for explaining the present invention, not for limiting the present invention.

[0032] For simplicity, only some numerical ranges are explicitly disclosed herein. However, any lower limit can be combined with any upper limit to form an unambiguous range; and any lower limit can be combined with other lower limits to form an unambiguous range, and any upper limit can be combined with any other upper limit to form an unambiguous range. In addition, although not explicitly stated, each point or single value between the range endpoints is included in the range. Thus, each point or single value can be combined with any other point or single value as its own lower limit or upper limit or with other lower limits or upper limits to form an unambiguous range.

[0033] In the description of this article, it should be noted that, unless otherwise specified, “above” and “below” are inclusive of the number, and the “multiple” in “one or more” means two or more, and the “multiple” in “one or more” means two or more.

[0034] The embodiment of the present invention provides a one-component light-heat dual-curing epoxy resin three-proof coating, which comprises, by weight, 100 parts of acrylic acid / organic silicon dual-modified epoxy resin, 8-25 parts of diluent, 6-18 parts of epoxy curing agent, and 1-6 parts of photoinitiator; The acrylic acid / organic silicon double-modified epoxy resin is obtained by reacting an organic alkoxy polysiloxane and an acrylic monomer compound with a multifunctional epoxy resin respectively; The diluent is a glycidyl ether of acrylic acid compound; The photoinitiator is an epoxyalkyl anthracene ether compound, and its chemical structure is: ; Among them, R 1 represents hydrogen, ethyl or chlorine, R 2 represents a C2~C6 alkylene group, R 3 represents hydrogen, methyl or ethyl.

[0035] Acrylic / silicone double-modified epoxy resin is an epoxy resin with acrylic functional groups and silicone flexible groups introduced into it; the acrylic functional groups help to achieve rapid curing after photoinitiation, and the introduction of silicone flexible groups improves the toughness and hydrophobicity of the coating.

[0036] Using acrylic acid glycidyl ether compounds as raw materials, on the one hand, reduces the viscosity of the resulting coating, making the resulting coating easy to operate during spraying, brushing, etc.; the acrylic acid group further enhances the photocuring activity, and the glycerol ether group ensures the thermal curing properties, making the coating cure faster and having a better curing effect, which together ensure that the three-proof coating has excellent comprehensive performance.

[0037] As the photoinitiator of this system, the epoxy alkyl anthracene ether compound not only has good photocuring activity, but its epoxy active group can also enable the initiator to participate in thermal curing, effectively reducing the phenomenon of small molecule migration and effectively improving the adhesion and weather resistance of the coating.

[0038] When preparing the one-component light-heat dual-curing epoxy resin three-proof coating, all raw materials can be mixed evenly. After application, it can be light-cured for 10 to 60 seconds under 365 nm light conditions, and then baked at 80 to 120°C for 1 to 6 hours to form a dense protective coating.

[0039] The one-component photothermal dual-curing epoxy resin three-proof coating provided by the embodiment of the present invention has the following advantages: the three-proof coating of the embodiment of the present invention has excellent adhesion to the PCB circuit board, and has the characteristics of light-induced rapid curing and high toughness; it avoids the molecular migration problem of the photoinitiator in the coating and significantly improves the weather resistance of the three-proof coating.

[0040] In an embodiment of the present invention, the weight ratio of the organic alkoxy polysiloxane, the acrylic monomer compound and the multifunctional epoxy resin is 15-40:5-35:100.

[0041] In some embodiments of the present invention, the multifunctional epoxy resin is a multifunctional glycidylamine resin.

[0042] In some embodiments of the present invention, the multifunctional epoxy resin is one or a combination of two or more of bisphenol A glycidyl ether, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether methane, triglycidyl-p-aminophenol, triglycidyl triisocyanate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl xylene diamine, tetraglycidyl-1,3-bisaminomethylcyclohexylamine and their homologues and derivatives.

[0043] In some embodiments of the present invention, the active group of the organoalkoxy polysiloxane is: -SiR n (OR ， ) 3-n , where R represents H, Me, Et, Bu, Ph, Pr, C 6 H 4 CH 2 , C8 H 17 , C 12 H 25 One of the ， It represents one of H, Me, Et, and Bu.

[0044] In some embodiments of the present invention, the acrylic monomer is one or a combination of two or more of acrylic acid, methacrylic acid, acrylic anhydride, and acetic acrylic anhydride.

[0045] In an embodiment of the present invention, the preparation method of the acrylic acid / silicone double-modified epoxy resin comprises: (1) A multifunctional epoxy resin and an organic alkoxy polysiloxane undergo a dealcoholization reaction in a solvent under catalytic conditions to obtain a uniform liquid; (2) The obtained uniform liquid is mixed with an acrylic monomer compound, reacted under catalytic conditions, and the solvent is removed to obtain the product.

[0046] In some embodiments of the present invention, in the method for preparing acrylic acid / organic silicon dual-modified epoxy resin, the catalyst in step (1) is sodium ethoxide, potassium ethoxide, hydrochloric acid, acetic acid, AlCl 3 、TiCl 3 SnCl 3 、ZrCl 4 , BF 3 、ZnCl 2 One or a combination of two or more.

[0047] In some embodiments of the present invention, in the method for preparing an acrylic acid / silicone dual-modified epoxy resin, the catalyst in step (2) is one or a combination of two or more of N,N-dimethylaniline, N,N-dimethylbenzylamine, trimethylbenzylammonium chloride, tetraethylammonium bromide, triphenylphosphine, triphenylantimony, and chromium acetylacetonate.

[0048] In some embodiments of the present invention, in the method for preparing an acrylic / silicone dual-modified epoxy resin, the solvent is one or a combination of two or more of toluene, xylene, pentane, hexane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, methanol, ethanol, isopropanol, n-butanol, mixed propanol, acetone, methyl butyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone.

[0049] In some embodiments of the present invention, in the method for preparing acrylic acid / silicone dual-modified epoxy resin, the reaction conditions in step (1) are: temperature 40° C. to 120° C., and time 2 to 8 hours.

[0050] In some embodiments of the present invention, in the method for preparing acrylic acid / silicone dual-modified epoxy resin, the reaction conditions in step (2) are: temperature 40° C. to 120° C., and time 2 to 8 hours.

[0051] In an embodiment of the present invention, the acrylic / silicone double-modified epoxy resin is obtained by reacting an organic alkoxy polysiloxane and an acrylic monomer compound with a multifunctional epoxy resin respectively; the weight ratio of the organic alkoxy polysiloxane, the acrylic monomer compound and the multifunctional epoxy resin is 20-30:10-25:100.

[0052] In an embodiment of the present invention, the one-component light-heat dual-curing epoxy resin three-proof coating comprises, by weight, 100 parts of acrylic / silicone dual-modified epoxy resin, 10-20 parts of diluent, 8-13 parts of epoxy curing agent, and 2-4 parts of photoinitiator.

[0053] In an embodiment of the present invention, the epoxy curing agent is a latent epoxy curing agent.

[0054] In an embodiment of the present invention, the diluent is one or a combination of two or more of allyl glycidyl ether, methacrylate glycidyl ether, and 4-hydroxybutyl acrylate glycidyl ether.

[0055] In an embodiment of the present invention, the epoxy curing agent is one or a combination of two or more selected from the group consisting of modified aliphatic amines, aromatic diamines, dicyandiamides, imidazoles, organic acid anhydrides, organic hydrazides, Lewis acid-amine complexes and microcapsules.

[0056] 9,10-Dibutoxyl anthracene (DBA) is a widely used photosensitizer, which usually needs to be used in combination with 2,4,5-triarylimidazole dimer (HABI). When DBA is used alone as a photoinitiator, its utilization efficiency of exposure energy is limited, and the photon yield needs to be improved, which will lead to longer exposure time and slower curing. Moreover, this problem is difficult to solve by conventional means such as increasing the addition amount. If the addition amount is too high, the coating quality will be affected.

[0057] The inventors of the present invention have found that the CO bond at the 9,10 position of the 9,10-dialkoxyanthracene photosensitizer will break when exposed, the anthracene ring will dimerize, and a small molecule alkoxy fragment will be released at the same time; this small molecule fragment cannot be well combined with the formed coating, hindering the adhesion of the coating on the substrate, reducing the adhesion, and the coating is easy to peel off. On the basis of the parent structure of the alkoxyanthracene in the present invention, an ethylene oxide functional group is introduced, and the functional group can also undergo ring-opening curing when the coating system of the present invention is cured, thereby greatly reducing the possibility of migration of small molecule fragments after light initiation, thereby significantly improving the adhesion and weather resistance of the coating.

[0058] In an embodiment of the present invention, the raw materials of the one-component light-heat dual-curing epoxy resin three-proof coating also include 8 to 20 parts of a toughening agent (by mass, corresponding to every 100 parts of acrylic acid / silicone dual-modified epoxy resin), and the toughening agent is a liquid rubber toughened epoxy resin.

[0059] In some embodiments of the present invention, the raw materials of the one-component light-heat dual-curing epoxy resin three-proof coating also include 10 to 16 parts of a toughening agent (calculated by mass, corresponding to every 100 parts of acrylic acid / silicone dual-modified epoxy resin); the toughening agent is one or a combination of two or more of silicone rubber, polyurethane rubber, terminal carboxyl liquid nitrile rubber, liquid polysulfide rubber, acrylate rubber, and chloroprene rubber.

[0060] In an embodiment of the present invention, the raw materials of the one-component light-heat dual-curing epoxy resin three-proof coating also include 0.2 to 2 parts of a defoamer (by mass, corresponding to every 100 parts of acrylic acid / silicone dual-modified epoxy resin), and the defoamer is a silicone oil defoamer.

[0061] In some embodiments of the present invention, the raw materials of the one-component light-heat dual-curing epoxy resin three-proof coating also include 0.5 to 1 part of a defoamer (by mass, corresponding to every 100 parts of acrylic acid / silicone dual-modified epoxy resin).

[0062] In an embodiment of the present invention, the raw materials of the one-component light-heat dual-curing epoxy resin three-proof coating also include 0.2 to 2 parts of a leveling agent (by mass, corresponding to every 100 parts of acrylic acid / silicone dual-modified epoxy resin), and the leveling agent is a siloxane-type epoxy floor leveling agent.

[0063] In some embodiments of the present invention, the raw materials of the one-component light-heat dual-curing epoxy resin three-proof coating also include 0.5 to 1 part of a leveling agent (by mass, corresponding to every 100 parts of acrylic acid / silicone dual-modified epoxy resin).

[0064] Example The following examples describe the disclosure of the present invention in more detail, and these examples are intended for illustrative purposes only, as it will be apparent to those skilled in the art that various modifications and variations will be made within the scope of the disclosure of the present invention. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are by weight. Unless otherwise stated, all reagents used in the examples are available through conventional commercial sources or are synthesized according to conventional methods and can be used directly without further processing. Unless otherwise stated, the instruments used in the examples are available through conventional commercial sources.

[0065] Example 1 The single-component light-heat dual-curing epoxy resin three-proof coating of this embodiment includes, by weight, the following raw materials: Acrylic acid / silicone double modified epoxy resin (homemade) 100 parts; Diluent (allyl glycidyl ether) 13 parts; Toughening agent (EP-2000) 10 parts; Epoxy curing agent (dicyandiamide) 8 parts; Photoinitiator (homemade) 3 parts; Defoaming agent (KS-603) 0.8 parts; Leveling agent (BYK-333) 0.8 parts.

[0066] The self-made acrylic / organic silicon double-modified epoxy resin of this embodiment is obtained by reacting an organic alkoxy polysiloxane and an acrylic monomer compound with a multifunctional epoxy resin respectively; the weight ratio of the organic alkoxy polysiloxane, the acrylic monomer compound and the multifunctional epoxy resin is 25:12.5:100; wherein the active group of the organic alkoxy polysiloxane is: -SiMe 2 (OMe); the acrylic monomer compound is acrylic acid; and the multifunctional epoxy resin is bisphenol A glycidyl ether resin.

[0067] The preparation method of acrylic acid / organic silicon double modified epoxy resin in this embodiment is: (1) Add 80g of bisphenol A glycidyl ether resin and 20g of alkoxy polysiloxane into a three-necked flask, dissolve in toluene, and add 1g of AlCl 3 (catalyst), control the temperature at 100°C and distill off the alcoholate, react for 6 hours to obtain a transparent and uniform liquid; (2) Add 10 g of acrylic acid according to the ratio, add 1 g of N,N-dimethylaniline (catalyst) dropwise, control the temperature at 120°C, react for 8 hours, and obtain a transparent and uniform liquid. Remove the solvent by distillation under reduced pressure to obtain an acrylic acid / silicone dual-modified epoxy resin.

[0068] The main chemical reactions involved are as follows: .

[0069] The self-made photoinitiator in this embodiment is an epoxyalkyl anthracene ether compound, 9,10-di-(1,2-epoxy n-heptyloxy) anthracene, and its chemical structure can be expressed as: .

[0070] Figure 1 is the photoinitiator of this embodiment 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl 3 ): δ 8.28 (d, J =10.01 Hz, 4H), 7.49 (d, J = 7.2 Hz, 4H), 4.17 (t, J = 6.59 Hz, 4H), 3.03 – 2.91(m, 2H), 2.77 (t, J = 4.53 Hz, 2H), 2.55 – 2.44 (m, 2H), 2.06 (p, J = 6.86 Hz, 4H), 1.79 – 1.56 (m, 12H).

[0071] Figure 2 is the photoinitiator of this embodiment 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl 3 ): δ 147.5,125.2, 125.1, 122.7, 75.9, 52.3, 47.2, 32.5, 30.6, 26.2, 26.1.

[0072] Figure 3 : is the ultraviolet absorption spectrum of the photoinitiator of this embodiment. From the figure, it can be seen that the photoinitiator has multiple absorption peaks in the ultraviolet region and can be used for photoinitiation.

[0073] The photoinitiator of this embodiment is prepared by a two-step reaction of anthraquinone and bromoolefin compounds, and the preparation method is as follows: ; Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0074] Step 1: Add m-chloroperbenzoic acid (4 mmol, 0.81 g) and replace Ar three times in a 50 mL handle bottle, add 6 ml of anhydrous DCM, stir until the solid is dissolved, then add 7-bromo-1-heptene (2 mmol, 0.35 g) dropwise, react at room temperature for 12 h, and then concentrate and distill the reaction solution to obtain epibromoheptane.

[0075] Step 2: Place anthraquinone (2.0 mmol, 490 mg), sodium dithionite (6.0 mmol, 1040 mg), and methyl trioctyl ammonium chloride (0.2 mmol, 80 mg) in a 20 mL Schlenk tube with a branch tube, and replace the argon three times. Add 3.2 mL of toluene to the reaction system, add 35 wt% NaOH solution (1.8 mmol, 210 mg) dropwise to the reaction system under stirring, and heat to 35 ℃ for 30 min. Then slowly add 35 wt% NaOH solution (18.2 mmol, 2080 mg) dropwise to the reaction system, complete the addition within 10 min, and heat to 45 ℃ for 1 h. Slowly add epoxide bromide (8.0 mmol, 1544 mg) dropwise to the reaction system, heat to 60 ℃ for 12 h. After the reaction was completed, 10 mL of deionized water was added to the reaction system, the reaction solution was transferred to a separatory funnel and extracted with DCM three times, and the organic phase was washed with anhydrous Na 2 SO 4 The mixture was dried and the solvent was distilled off under reduced pressure. The crude product was separated by column chromatography to obtain 9,10-di-(1,2-epoxy-n-heptyloxy)anthracene (615 mg, yield 76%).

[0076] Example 2 The single-component light-heat dual-curing epoxy resin three-proof coating of this embodiment includes, by weight, the following raw materials: Acrylic acid / silicone double modified epoxy resin (homemade) 100 parts; Diluent (glycidyl methacrylate) 20 parts; Toughening agent (carboxyl-terminated liquid nitrile rubber) 16 parts; Epoxy curing agent (m-phenylenediamine) 13 parts; Photoinitiator (homemade) 3 parts; Defoaming agent (KS-603) 0.5 parts; Leveling agent (BYK-333) 0.5 parts.

[0077] The self-made acrylic / organic silicon double-modified epoxy resin of this embodiment is obtained by reacting an organic alkoxy polysiloxane and an acrylic monomer compound with a multifunctional epoxy resin respectively; the weight ratio of the organic alkoxy polysiloxane, the acrylic monomer compound and the multifunctional epoxy resin is 24.66:19.18:100; wherein the active group of the organic alkoxy polysiloxane is: -SiEt(OMe) 2 ; The acrylic monomer compound is methacrylic acid; and the multifunctional epoxy resin is TDE-85.

[0078] The preparation method of acrylic acid / organic silicon double modified epoxy resin in this embodiment is: (1) Add 73g of TDE-85 and 18g of alkoxy polysiloxane into a three-necked flask, dissolve in xylene, dropwise add 0.8g of sodium ethoxide (catalyst), control the temperature at 90°C and distill to remove the alcoholate, react for 7h, and obtain a transparent and uniform liquid; (2) Add 14 g of methacrylic acid according to the ratio, add 0.5 g of triphenylphosphine (catalyst) dropwise, control the temperature at 100 °C, react for 8 h, and obtain a transparent and uniform liquid. Remove the solvent by distillation under reduced pressure to obtain an acrylic acid / silicone dual-modified epoxy resin.

[0079] The self-made photoinitiator in this embodiment is an epoxyalkyl anthracene ether compound, 9,10-di-(1,2-epoxy-n-octyloxy) anthracene, and its chemical structure can be expressed as: .

[0080] The photoinitiator of this embodiment is prepared by a two-step reaction of anthraquinone and bromoolefin compounds, and the preparation method is as follows: ; Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0081] Step 1: Add m-chloroperbenzoic acid (4 mmol, 0.81 g) and replace Ar three times in a 50 mL handle bottle, add 6 ml of anhydrous DCM, stir until the solid is dissolved, then add 8-bromo-1-octene (2 mmol, 0.38 g) dropwise, react at room temperature for 12 h, and then concentrate and distill the reaction solution to obtain epibromooctane.

[0082] Step 2: Place anthraquinone (2.0 mmol, 490 mg), sodium dithionite (6.0 mmol, 1040 mg), and methyl trioctyl ammonium chloride (0.2 mmol, 80 mg) in a 20 mL Schlenk tube with a branch tube, and replace the argon three times. Add 3.2 mL of toluene to the reaction system, add 35 wt% NaOH solution (1.8 mmol, 210 mg) dropwise to the reaction system under stirring, and heat to 35 ℃ for 30 min. Then slowly add 35 wt% NaOH solution (18.2 mmol, 2080 mg) dropwise to the reaction system, complete the addition within 10 min, and heat to 45 ℃ for 1 h. Slowly add epoxy bromide octane (8 mmol, 1657 mg) dropwise to the reaction system, heat to 60 ℃ for 12 h. After the reaction was completed, 10 mL of deionized water was added to the reaction system, the reaction solution was transferred to a separatory funnel and extracted with DCM three times, and the organic phase was washed with anhydrous Na 2 SO 4 The mixture was dried and the solvent was distilled off under reduced pressure. The crude product was separated by column chromatography to obtain 9,10-di-(1,2-epoxy-n-octyloxy)anthracene (586 mg, yield 63%).

[0083] Example 3 The single-component light-heat dual-curing epoxy resin three-proof coating of this embodiment includes, by weight, the following raw materials: Acrylic acid / silicone double modified epoxy resin (homemade) 100 parts; Diluent (allyl glycidyl ether) 15 parts; Toughening agent (carboxyl-terminated liquid nitrile rubber) 12 parts; Epoxy curing agent (dicyandiamide) 10 parts; Photoinitiator (homemade) 2.5 parts; Defoaming agent (KS-603) 0.625 parts; Leveling agent (BYK-333) 0.625 parts.

[0084] The self-made acrylic / organic silicon double-modified epoxy resin of this embodiment is obtained by reacting an organic alkoxy polysiloxane and an acrylic monomer compound with a multifunctional epoxy resin respectively; the weight ratio of the organic alkoxy polysiloxane, the acrylic monomer compound and the multifunctional epoxy resin is 20:21.67:100; wherein the active group of the organic alkoxy polysiloxane is: -SiMe(OMe) 2 ; The acrylic monomer compound is acrylic acid; and the multifunctional epoxy resin is AG-80 epoxy resin.

[0085] The preparation method of acrylic acid / organic silicon double modified epoxy resin in this embodiment is: (1) Add 60g AG-80 epoxy resin and 12g alkoxy polysiloxane into a three-necked flask, dissolve in toluene, and add 0.4g SnCl 3 (catalyst), control the temperature at 100°C and distill off the alcoholate, react for 6 hours to obtain a transparent and uniform liquid; (2) Add 13 g of acrylic acid according to the ratio, add 1 g of trimethylbenzyl ammonium chloride (catalyst) dropwise, control the temperature at 110°C, react for 8 hours, and obtain a transparent and uniform liquid. Remove the solvent by distillation under reduced pressure to obtain an acrylic acid / silicone dual-modified epoxy resin.

[0086] The self-made photoinitiator in this embodiment is an epoxyalkyl anthracene ether compound, 9,10-di(1,2-2-(bromomethyl)-3-ethyloxirane)oxy)anthracene, and its chemical structure can be expressed as follows: .

[0087] The photoinitiator of this embodiment is prepared by a two-step reaction of anthraquinone and bromoolefin compounds, and the preparation method is as follows: ; Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0088] Step 1: Add m-chloroperbenzoic acid (4 mmol, 0.81 g) and replace Ar three times in a 50 mL handle bottle, add 6 ml of anhydrous DCM, stir until the solid is dissolved, then add 1-bromo-2-pentene (2 mmol, 0.30 g) dropwise, react at room temperature for 12 h, and then concentrate and distill the reaction solution to obtain 2-(bromomethyl)-3-ethyl oxirane.

[0089] Step 2: Place anthraquinone (2.0 mmol, 490 mg), sodium dithionite (6.0 mmol, 1040 mg), and methyltrioctylammonium chloride (0.2 mmol, 80 mg) into a 20 mL Schlenk tube with a side arm, and displace argon three times. Add 3.2 mL of toluene to the reaction system. While stirring, slowly drip 35 wt% NaOH solution (1.8 mmol, 210 mg) into the reaction system, and heat the reaction system to 35 °C and react for 30 min. Then slowly drip 35 wt% NaOH solution (18.2 mmol, 2080 mg) into the reaction system, complete the dripping within 10 min, heat the reaction system to 45 °C and react for 1 h. Slowly drip 2-(bromomethyl)-3-ethyloxirane (8 mmol, 1296 mg) into the reaction system, heat the reaction system to 60 °C and react for 12 h. After the reaction is completed, add 10 mL of deionized water to the reaction system, transfer the reaction solution to a separatory funnel, extract it three times with DCM, and dry the organic phase with anhydrous Na 2 SO 4 dry, and remove the solvent by distillation under reduced pressure. The crude product was separated by column chromatography to obtain 9,10-bis(1,2-2-(bromomethyl)-3-ethyloxirane)oxy)anthracene (573 mg, yield 76%).

[0090] Comparative Example 1 The coating raw materials of this comparative example are basically the same as those of Example 1, except that instead of preparing the acrylic / silicone double-modified epoxy resin, the raw materials of the acrylic / silicone double-modified epoxy resin - polydimethylsiloxane, acrylic acid, and bisphenol A glycidyl ether resin are directly used as the coating raw materials in their original proportions.

[0091] Comparative Example 2 The coating raw materials of this comparative example are basically the same as those of Example 1, except that instead of using the acrylic / silicone double-modified epoxy resin, the bisphenol A glycidyl ether resin in Example 1 is used instead.

[0092] Comparative Example 3 The coating raw materials of this comparative example are basically the same as those of Example 1, except that instead of using the self-made photoinitiator, a traditional 1173 photoinitiator is used instead.

[0093] Detection and Analysis Perform performance tests on the coatings of each example and comparative example, as well as the same type of three-proof coating products on the market. The detection methods are as follows: Appearance: visual inspection; Viscosity: GB / T 2794-2013; Volume resistivity: GB1410-2006; Dielectric strength: GB / T1408.1-2016; Hardness: GB / T 2411-2008; Tensile strength: GB / T 1040-2018; Adhesion test: GB / T9286-1998; Environmental resistance test: IPC-TM-650.

[0094] The curing method of the coating during the test is: after application, use a 365nm medium pressure mercury lamp with 1000~2000mj / cm 2 Expose to light for 60 s and record the surface drying time, then bake at 100 °C for 2 h.

[0095] The test results are shown in Table 1.

[0096] Table 1 Performance test results of coatings in various embodiments and comparative examples, as well as commercially available products ;

[0097] It can be seen from the experimental data in Table 1 that the one-component light-heat dual-curing epoxy resin three-proof coating prepared by the present invention has the characteristics of rapid surface drying, and the adhesion has achieved level 0. At the same time, compared with existing similar products, its UV resistance, oil resistance, and solvent resistance have been significantly improved. The coating of the embodiment of the present invention forms an epoxy three-dimensional network structure after thermal curing, which improves the strength of the coating and makes it have better mechanical properties and weather resistance. After the epoxy resin structure was changed relative to the method of the present invention, Comparative Examples 1 and 2 failed to cure; after the photoinitiator was replaced relative to the method of the present invention, the weather resistance of the resulting coating decreased.

Claims

1. A one-component light-heat dual-curing epoxy resin three-proof coating, characterized in that: The raw materials include, by mass: 100 parts of acrylic acid / organic silicon double-modified epoxy resin, 8-25 parts of diluent, 6-18 parts of epoxy curing agent, and 1-6 parts of photoinitiator; The acrylic acid / organic silicon double-modified epoxy resin is obtained by reacting an organic alkoxy polysiloxane and an acrylic monomer compound with a multifunctional epoxy resin respectively; The diluent is a glycidyl ether of acrylic acid compound; The photoinitiator is an epoxyalkyl anthracene ether compound, and its chemical structure is: ； Among them, R 1 represents hydrogen, ethyl or chlorine, R 2 represents a C2~C6 alkylene group, R 3 represents hydrogen, methyl or ethyl.

2. The one-component light-heat dual-curing epoxy resin three-proof coating according to claim 1, characterized in that: The weight ratio of the organic alkoxy polysiloxane, the acrylic monomer compound and the multifunctional epoxy resin is 15-40:5-35:100; the multifunctional epoxy resin is a multifunctional glycidylamine resin.

3. The one-component light-heat dual-curing epoxy resin three-proof coating according to claim 2, characterized in that: The multifunctional epoxy resin is one or a combination of two or more of bisphenol A glycidyl ether, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether methane, triglycidyl-p-aminophenol, triglycidyl triisocyanate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl xylene diamine, tetraglycidyl-1,3-bisaminomethylcyclohexylamine and homologues and derivatives thereof; The active group of the organoalkoxy polysiloxane is: -SiR n (OR ， ) 3-n , where R represents H, Me, Et, Bu, Ph, Pr, C6H4CH2, C8H 17 , C 12 H 25 One of the ， It represents one of H, Me, Et, and Bu; The acrylic monomer is one or a combination of two or more of acrylic acid, methacrylic acid, acrylic anhydride, and acetic acrylic anhydride.

4. The one-component light-heat dual-curing epoxy resin three-proof coating according to any one of claims 1 to 3, characterized in that: The acrylic acid / organic silicon double-modified epoxy resin is obtained by reacting an organic alkoxy polysiloxane and an acrylic monomer compound with a multifunctional epoxy resin respectively; the weight ratio of the organic alkoxy polysiloxane, the acrylic monomer compound and the multifunctional epoxy resin is 20-30:10-25:100; The preparation method of the acrylic acid / organic silicon double-modified epoxy resin comprises: (1) A multifunctional epoxy resin and an organic alkoxy polysiloxane undergo a dealcoholization reaction in a solvent under catalytic conditions to obtain a uniform liquid; (2) The obtained uniform liquid is mixed with an acrylic monomer compound, reacted under catalytic conditions, and the solvent is removed to obtain the product.

5. The one-component light-heat dual-curing epoxy resin three-proof coating according to claim 4, characterized in that: The catalyst in step (1) is one or a combination of two or more of sodium ethoxide, potassium ethoxide, hydrochloric acid, acetic acid, AlCl3, TiCl3, SnCl3, ZrCl4, BF3, and ZnCl2; The catalyst in step (2) is one or a combination of two or more of N,N-dimethylaniline, N,N-dimethylbenzylamine, trimethylbenzylammonium chloride, tetraethylammonium bromide, triphenylphosphine, triphenylantimony, and chromium acetylacetonate; The solvent is one or a combination of two or more of toluene, xylene, pentane, hexane, octane, cyclohexane, cyclohexanone, toluene-cyclohexanone, methanol, ethanol, isopropanol, n-butanol, mixed propanol, acetone, methyl butyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; The reaction conditions in step (1) are: temperature 40°C to 120°C, time 2 to 8 hours; The reaction conditions in step (2) are: temperature 40°C to 120°C, time 2 to 8 hours.

6. The one-component light-heat dual-curing epoxy resin three-proof coating according to any one of claims 1 to 3, characterized in that: The raw materials include, by mass: 100 parts of acrylic acid / organic silicon double-modified epoxy resin, 10-20 parts of diluent, 8-13 parts of epoxy curing agent, and 2-4 parts of photoinitiator; The epoxy curing agent is a latent epoxy curing agent.

7. The one-component light-heat dual-curing epoxy resin three-proof coating according to any one of claims 1 to 3, characterized in that: The diluent is one or a combination of two or more of allyl glycidyl ether, methacrylate glycidyl ether, and 4-hydroxybutyl acrylate glycidyl ether; The epoxy curing agent is one or a combination of two or more selected from the group consisting of modified aliphatic amines, aromatic diamines, dicyandiamides, imidazoles, organic acid anhydrides, organic hydrazides, Lewis acid-amine complexes and microcapsules.

8. The one-component light-heat dual-curing epoxy resin three-proof coating according to any one of claims 1 to 3, characterized in that: The raw materials also include 8 to 20 parts of a toughening agent, which is a liquid rubber toughened epoxy resin; the raw materials also include 0.2 to 2 parts of a defoaming agent, which is a silicone oil defoaming agent; the raw materials also include 0.2 to 2 parts of a leveling agent, which is a siloxane-type epoxy floor leveling agent.

9. The one-component light-heat dual-curing epoxy resin three-proof coating according to claim 8, characterized in that: The raw materials also include 10 to 16 parts of a toughening agent; the toughening agent is one or a combination of two or more of silicone rubber, polyurethane rubber, carboxyl-terminated liquid nitrile rubber, liquid polysulfide rubber, acrylate rubber, and chloroprene rubber; the raw materials also include 0.5 to 1 part of a defoaming agent; the raw materials also include 0.5 to 1 part of a leveling agent.

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