A composite anhydride modified UV light curable epoxy acrylate, its preparation method and application

Abstract

The application discloses a kind of composite anhydride modified UV light-cured epoxy acrylate and its preparation method and application;The preparation method comprises the following steps: glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin, part of catalyst, part of polymerization inhibitor are stirred and heated to 75~80 ℃ And keep warm 0.8~1.2h, then subsection temperature rises, and the rest catalyst and the rest polymerization inhibitor are added in batches, finally rise to 115~125 ℃ Reaction 4~5h, obtain composite anhydride modified UV light-cured epoxy acrylate.Preparation method, low price, product cost is low, reaction process does not use any solvent, reduces VOC emission;Epoxy acrylate prepared has higher functionality after film forming, better hardness, adhesion, flexibility, impact resistance and chemical resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of preparation of ultraviolet light-cured epoxy acrylate paint, and particularly relates to a composite anhydride modified UV light-cured epoxy acrylate, a preparation method and application thereof. BACKGROUND

[0002] Ultraviolet light (UV) curing technology refers to a process that under the irradiation of ultraviolet light, a photoinitiator in the system absorbs energy to generate free radicals or cations, and then initiates the grafting, polymerization, crosslinking and other chemical reactions of oligomers and active diluents containing active groups, thereby promoting the rapid solidification of the substrate surface into a film. Unlike existing traditional coatings such as solvent-based, water-based and heat-cured coatings, the advantage of UV curing technology is that the curing speed of the paint film is fast, no solvent is needed, the operation is simple, and the curing process is not easily affected by temperature, environment and other factors. With the gradual change of China's industry to green environmental protection, high efficiency and energy saving, and intelligentization, the industrial application of ultraviolet light curing technology has developed rapidly.

[0003] Epoxy acrylate resin is the most commonly used UV light-curing resin, and bisphenol A epoxy acrylate is the fastest curing speed class in epoxy acrylate oligomers, and is also the most widely used class. Due to the presence of rigid benzene ring structure in the structure, UV curing film brittleness is large, flexibility is poor, and weather resistance, light aging resistance and yellowing resistance are not good. To address these defects, Chinese invention patent CN102295730A discloses a synthetic method of intramolecular toughening epoxy vinyl ester resin, first adopts long-chain saturated dibasic acid and flexible diol reaction to obtain terminal carboxyl long-chain saturated dibasic acid monoester, then reacts with epoxy resin and unsaturated monocarboxylic acid to reduce acid value to below 10mgKOH / g. The method advantage is that flexible molecular chain is introduced on the resin backbone, and then the toughness of the resin is improved. Its shortcoming is that the introduction of dibasic acid monoester can increase the molecular weight and viscosity of the resin, and the consumption is large, and the resin viscosity increases, and storage is unstable, and the film hardness reduces, and the toughening effect is poor. Patent application publication number CN104558522A discloses a method for modifying modified epoxy acrylates. The modified epoxy resin is produced by reacting bisphenol A epoxy resin and 1,2-cyclohexanediol diglycidyl ether. The synthesis method involves adding the two materials and a catalyst to a reaction vessel, stirring and heating to 80-90°C. A mixture of acrylic acid and a polymerization inhibitor is gradually added dropwise over 0.5-1 hour, and then gradually heating the temperature until the acid value drops below 3.0 mgKOH / g to obtain the modified epoxy acrylate. While this patent addresses the issues of high resin viscosity, brittle coatings, and poor flexibility, it actually achieves this goal by physically blending 1,2-cyclohexanediol diglycidyl ether diacrylate into ordinary epoxy acrylate resin, which significantly reduces the hardness of the coating. Therefore, developing a modified epoxy acrylate resin that combines high hardness, high toughness, and good flexibility is a technical problem that urgently needs to be addressed in this field. Summary of the Invention

[0004] In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the object of the present invention is to provide a method for preparing a composite anhydride-modified UV-curable epoxy acrylate, which is inexpensive, has low product cost, does not use any solvents in the reaction process, and reduces VOC emissions. The prepared epoxy acrylate has high hardness, excellent adhesion, flexibility, impact resistance and chemical resistance after curing.

[0005] Another object of the present invention is to provide a composite anhydride-modified UV-curable epoxy acrylate.

[0006] Another object of the present invention is to provide an application of the above-mentioned composite anhydride-modified UV-curable epoxy acrylate for preparing a coating, wherein the cured coating film has the characteristics of high hardness, excellent flexibility and impact resistance, chemical resistance, heat resistance and fast curing speed.

[0007] The application achieves the objective by the following technical scheme.

[0008] The application provides a preparation method of a composite anhydride modified UV light curable epoxy acrylate, comprising the following steps:

[0009] (1) according to the following formula, the raw materials are weighed by weight parts:

[0010]

[0011] (2) glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin, part of the catalyst, part of the polymerization inhibitor are stirred and heated to 75-80℃ and kept for 0.8-1.2h, then the remaining catalyst and the remaining polymerization inhibitor are added in batches by increasing the temperature in sections, and finally the temperature is increased to 115-125℃ and reacted for 4-5h to obtain the composite anhydride modified UV light curable epoxy acrylate;

[0012] The weight of the part of the catalyst is 55-65% of the total weight of the catalyst; the weight of the part of the polymerization inhibitor is 55-65% of the total weight of the polymerization inhibitor.

[0013] Preferably, the epoxy resin is one of epoxy resins E51, E44, F44, F51, 170, 128, R-828, S-21 and BD-20.

[0014] Preferably, the catalyst is at least one of tetraethylammonium bromide, tetrabutylammonium bromide, N,N dimethyl benzylamine and triphenylphosphine.

[0015] Preferably, the polymerization inhibitor is at least one of p-hydroxyanisole, p-benzoquinone, methylhydroquinone, hydroquinone and 2,5-dimethylhydroquinone.

[0016] Preferably, the step of increasing the temperature in sections and adding the remaining catalyst and the remaining polymerization inhibitor in batches is specifically:

[0017] The temperature is increased by 8-10℃ every 0.8-1.2h; the remaining catalyst and the remaining polymerization inhibitor are added in 4-5 times.

[0018] The application further provides a composite anhydride modified UV light curable epoxy acrylate, comprising, by weight parts:

[0019]

[0020] The application further provides the application of the composite anhydride modified UV light curable epoxy acrylate to the preparation of a coating.

[0021] Preferably, the coating comprises 65-87 parts of the composite anhydride modified UV curable epoxy acrylate, 10-30 parts of an active diluent and 3-5 parts of a photoinitiator.

[0022] Preferably, the reactive diluent is one of tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, hexanediol diacrylate, and triethylene glycol diacrylate.

[0023] Preferably, the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and 1-hydroxycyclohexyl phenyl ketone.

[0024] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0025] (1) The present invention introduces a vinyl-containing carboxyl intermediate generated by compounding glutaric anhydride, maleic anhydride, and phthalic anhydride with hydroxyethyl acrylate, introduces a vinyl-containing monocarboxylic acid intermediate, and simultaneously introduces a rigid benzene ring, thereby increasing the vinyl functionality and rigid benzene ring content of the modified epoxy acrylic resin product, increasing the crosslinking density of its UV-cured coating, and improving the hardness and chemical resistance.

[0026] (2) The present invention combines glutaric anhydride, maleic anhydride and phthalic anhydride and reasonably limits their ratio to combine the rigid structure and the flexible long chain, thereby optimizing and improving the balance between high hardness, high flexibility and high impact resistance of the UV-cured coating.

[0027] (3) The UV-curable epoxy acrylate prepared by the present invention through a one-step method has a simple synthesis process, mild reaction conditions, low industrial operation difficulty, a wide source of raw materials and low prices, and a low resin preparation cost. The coating prepared from the resin can be directly applied to UV curing and has the prospect of large-scale production in industry.

[0028] (4) The composite anhydride-modified UV-curable epoxy acrylate of the present invention can be applied to many fields such as primer and topcoat, plastic paint and printing ink. The coating has a high cross-linking density, high hardness but good flexibility, and excellent chemical resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is the infrared spectrum of the composite anhydride modified UV-curable epoxy acrylate in Example 1 of the present invention.

[0030] Figure 2 This is the H-NMR spectrum of the composite anhydride-modified UV-curable epoxy acrylate in Example 1 of the present invention.

[0031] Figure 3 This is the gel chromatogram of the composite anhydride modified UV-curable epoxy acrylate in Example 1 of the present invention.

[0032] Figure 4 Schematic diagram of the synthesis process of composite anhydride modified UV-curable epoxy acrylate in Example 1 of the present invention. DETAILED DESCRIPTION

[0033] The present invention will be further described in detail below with reference to the examples, but the embodiments of the present invention are not limited thereto.

[0034] The comparative example in each embodiment is that the EA resin produced by Beixin Carpoly Chemical Group Co., Ltd. replaces the modified epoxy acrylate of the present invention as the oligomer component of the UV-curing coating, and the other components and proportions are the same as those in the embodiment.

[0035] In the following examples, the properties of UV-curable resins and light-curable coatings were tested according to the following methods: the viscosity of the resin was measured using an NDJ-8 rotational viscometer in accordance with GB / T 21059-2007; the acid value of the resin was measured in accordance with GB / T 6743-2008; the hardness of the coating was measured in accordance with GB / T 6739-2006; the adhesion of the coating was measured in accordance with GB-T 9286-1998; the water resistance of the coating was measured by a room temperature immersion method in accordance with GB / T 5209-1985; the alcohol resistance of the coating was measured in accordance with GB / T 1763-79; the acid / alkali resistance of the coating was measured in accordance with GB / T 9274-2009; the impact resistance of the coating was measured in accordance with GB / T 20624.2-2006; and the flexibility of the coating was measured using a QTY-10A paint film bending tester in accordance with GB / T 1731-1993.

[0036] Example 1

[0037] (1) Preparation of composite anhydride-modified UV-curable epoxy acrylate: The composite anhydride-modified UV-curable epoxy acrylate resin of this embodiment has a raw material formula with a mass percentage composition as shown in Table 1:

[0038]

[0039] Preparation process of composite anhydride modified UV curable epoxy acrylate in this embodiment:

[0040] The above-mentioned glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60%wt of the total catalyst), and p-hydroxyanisole (total amount is 60wt% of the total polymerization inhibitor) are added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser, and the temperature is raised to 75°C and kept warm for 1 hour; then 10wt% of tetraethylammonium bromide and p-hydroxyanisole are added every 1 hour, and the temperature is gradually raised to 83°C, 90°C, 97°C, and 105°C, and finally raised to 120°C and kept warm for 4-5 hours. The acid value is measured to be below the theoretical value of 3.0 mgKOH / g, and the material is cooled and discharged to obtain a composite anhydride-modified UV-curable epoxy acrylate.

[0041] (2) Physical and chemical properties of composite anhydride modified UV-curable epoxy resin: appearance is slightly yellow, transparent and clear; acid value is 2.7 mgKOH / g; viscosity is 124500 mPa·s.

[0042] (3) Preparation of UV curing coating:

[0043] The configuration composition of UV curing coatings in parts by mass is shown in Table 2 below:

[0044]

[0045] Add the above formula into the container and disperse it at a low speed of 600r / min for 10-15min. After the paint is left to stand without bubbles, use a four-sided wet film applicator to apply the film on the wood board, glass board and tinplate respectively. The film thickness is 25±2μm and the power is 600mW / cm 2 , cured under a UV curing machine with a wavelength of 365nm, and the coating performance was tested. The coating performance is shown in the table below. The performance of Example 1 and the same EA resin on the market were compared, and the coating performance was shown in Table 3.

[0046] (4) Table 3:

[0047]

[0048] As can be seen from Table 3, compared with existing products, the composite anhydride-modified UV-curable epoxy acrylate resin obtained in the present invention not only has a lower resin viscosity, but also has a moderate hardness of the cured film, improved adhesion of the paint film, greatly enhanced flexibility and impact resistance, and has excellent chemical resistance.

[0049] Figure 1 This is the infrared spectrum of the composite anhydride modified UV-curable epoxy acrylate in Example 1. As can be seen from the figure, 910 cm -1 The peak of epoxy group at 1719cm -1The peak of ester bond appears at 3467cm -1 The peak attributable to hydroxyl group is enhanced at 1607 cm -1 The characteristic peak of carbon-carbon double bond appeared at 1760 cm, which proved the ring opening of epoxy resin and the successful grafting of carboxyl intermediate with acrylic acid. -1 、1850cm -1 The characteristic peak of the anhydride carbonyl group at shows that the anhydride group also reacted during the process.

[0050] Figure 2 This is the H-NMR spectrum of the composite anhydride-modified UV-curable epoxy acrylate in Example 1, with a benzene ring proton peak on phthalic anhydride at 7.7-7.8 ppm, benzene ring proton peaks at 7.1 ppm and 6.8 ppm attributed to the epoxy resin, a double bond proton peak at 5.9-6.3 ppm attributed to hydroxyethyl acrylate, a hydroxyl group generated by the esterification reaction of anhydride and hydroxyethyl acrylate at 5.4 ppm, a double bond proton peak of maleic anhydride at 4.8 ppm, and methylene peaks on glutaric anhydride and hydroxyethyl acrylate at 3.7-4.5 ppm. The above results prove that anhydride, hydroxyethyl acrylate and acrylic acid are successfully grafted onto E51.

[0051] Figure 3 This is the gel chromatogram of the composite anhydride modified UV-curable epoxy acrylate in Example 1. The data of the UV-curable epoxy acrylate synthesized in this Example 1 can be obtained: the number average molecular weight (Mn) is 1282 g / mol, and the weight average molecular weight (Mw) is 1321 g / mol.

[0052] Figure 4 The reaction flow chart and molecular structure diagram in Example 1, in which the composite acid anhydride reacts with hydroxyethyl acrylate to generate a carboxyl-containing intermediate, which then undergoes a ring-opening reaction with acrylic acid and epoxy resin E51. There are many types of acid anhydrides, and there are many possible molecular structures generated during the reaction.

[0053] Compared with Comparative Patent 1 (CN102295730A), the resin prepared by the present invention has low viscosity, can balance film hardness and flexibility, and has a low reaction temperature, a simple process, and good storage stability. Compared with Comparative Patent 2 (CN104558522A), the resin prepared by the present invention has uniform components, can reconcile the contradiction between high film hardness and high toughness, and has low resin production costs and a simple process.

[0054] Example 2

[0055] (1) Preparation of composite anhydride-modified UV-curable epoxy acrylate: The composite anhydride-modified UV-curable epoxy acrylate resin of this embodiment has a raw material formula with a mass percentage composition as shown in Table 4:

[0056]

[0057]

[0058] Preparation process of the composite anhydride modified UV-curable epoxy acrylate of the present embodiment:

[0059] The above-mentioned pentanedioic anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (60% wt of the total amount of catalyst), p-hydroxyanisole (60% wt of the total amount of total polymerization inhibitor) were added into a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser tube, and heated to 75°C and kept for 1 h; then 10% wt of tetraethylammonium bromide and p-hydroxyanisole were added every 1 h, and the temperature was gradually increased to 83°C, 90°C, 97°C, 105°C, and finally to 120°C, and then kept for 4-5 h after the reaction, and the acid value was determined to be below 3.0 mgKOH / g, and the temperature was lowered to discharge the material, to obtain the composite anhydride modified UV-curable epoxy acrylate.

[0060] (2) Physicochemical properties of the composite anhydride modified UV-curable epoxy resin: the appearance is slightly yellow transparent and clear; the acid value is 1.8 mgKOH / g; the viscosity is 118350 mPa·s.

[0061] (3) Preparation of UV-curable coating:

[0062] The configuration of the UV-curable coating is as follows in Table 5 in mass parts:

[0063]

[0064] The above-mentioned formula substances were added into a container and dispersed at a low speed of 600 r / min for 10-15 min. After the coating was left to stand without bubbles, a four-sided wet film applicator was used to coat the wood board, glass plate, and tin plate, respectively, and the coating thickness was 25±2 μm, and then cured under a UV curing machine with a power of 600 mW / cm 2 , wavelength 365 nm, and the coating performance was tested. The coating performance is shown in Table 6, which is compared with the performance of the same EA resin on the market and the coating 2 of the present embodiment.

[0065] (4) Table 6:

[0066]

[0067]

[0068] Example 3

[0069] (1) Preparation of composite anhydride-modified UV-curable epoxy acrylate: The composite anhydride-modified UV-curable epoxy acrylate resin of this embodiment has a raw material formula with a mass percentage composition as shown in Table 7:

[0070]

[0071] Preparation process of composite anhydride modified UV curable epoxy acrylate in this embodiment:

[0072] The above-mentioned glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60%wt of the total catalyst), and p-hydroxyanisole (total amount is 60wt% of the total polymerization inhibitor) are added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser, and the temperature is raised to 75°C and kept warm for 1 hour; then 10wt% of tetraethylammonium bromide and p-hydroxyanisole are added every 1 hour, and the temperature is gradually raised to 83°C, 90°C, 97°C, and 105°C, and finally raised to 120°C and kept warm for 4-5 hours. The acid value is measured to be below the theoretical value of 3.0 mgKOH / g, and the material is cooled and discharged to obtain a composite anhydride-modified UV-curable epoxy acrylate.

[0073] (2) Physical and chemical properties of composite anhydride modified UV-curable epoxy resin: appearance is slightly yellow, transparent and clear; acid value is 1.5 mgKOH / g; viscosity is 115600 mPa·s.

[0074] (3) Preparation of UV curing coating:

[0075] The configuration composition of UV curing coatings in parts by mass is shown in Table 8 below:

[0076]

[0077] Add the above formula into the container and disperse it at a low speed of 600r / min for 10-15min. After the paint is left to stand without bubbles, use a four-sided wet film applicator to apply the film on the wood board, glass board and tinplate respectively. The film thickness is 25±2μm and the power is 600mW / cm 2 , cured under a UV curing machine with a wavelength of 365nm, and the coating performance was tested. The coating performance is shown in the table below. The performance of Example 3 and the same EA resin on the market were compared, and the coating performance was shown in Table 9.

[0078] (4) Table 9:

[0079]

[0080] Example 4

[0081] (1) Preparation of composite anhydride-modified UV-curable epoxy acrylate: The composite anhydride-modified UV-curable epoxy acrylate resin of this embodiment has a raw material formula with a mass percentage composition as shown in Table 10:

[0082]

[0083] Preparation process of composite anhydride modified UV curable epoxy acrylate in this embodiment:

[0084] The above-mentioned glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60%wt of the total catalyst), and p-hydroxyanisole (total amount is 60wt% of the total polymerization inhibitor) are added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser, and the temperature is raised to 75°C and kept warm for 1 hour; then 10wt% of tetraethylammonium bromide and p-hydroxyanisole are added every 1 hour, and the temperature is gradually raised to 83°C, 90°C, 97°C, and 105°C, and finally raised to 120°C and kept warm for 4-5 hours. The acid value is measured to be below the theoretical value of 3.0 mgKOH / g, and the material is cooled and discharged to obtain a composite anhydride-modified UV-curable epoxy acrylate.

[0085] (2) Physical and chemical properties of composite anhydride modified UV-curable epoxy resin: appearance is slightly yellow, transparent and clear; acid value is 2.5 mgKOH / g; viscosity is 143150 mPa·s.

[0086] (3) Preparation of UV curing coating:

[0087] The configuration composition of UV curing coatings in parts by mass is shown in Table 11 below:

[0088]

[0089] Add the above formula into the container and disperse it at a low speed of 600r / min for 10-15min. After the paint is left to stand without bubbles, use a four-sided wet film applicator to apply the film on the wood board, glass board and tinplate respectively. The film thickness is 25±2μm and the power is 600mW / cm 2 , cured under a UV curing machine with a wavelength of 365nm, and the coating performance was tested. The coating performance is shown in the table below. The performance of Example 4 and the same EA resin on the market were compared, and the coating performance was shown in Table 12.

[0090] (4) Table 12:

[0091]

[0092] Example 5

[0093] (1) Preparation of composite anhydride-modified UV-curable epoxy acrylate: The composite anhydride-modified UV-curable epoxy acrylate resin of this embodiment has a raw material formula with a mass percentage composition as shown in Table 13:

[0094]

[0095] Preparation process of composite anhydride modified UV curable epoxy acrylate in this embodiment:

[0096] The above-mentioned glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60%wt of the total catalyst), and p-hydroxyanisole (total amount is 60wt% of the total polymerization inhibitor) are added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser, and the temperature is raised to 75°C and kept warm for 1 hour; then 10wt% of tetraethylammonium bromide and p-hydroxyanisole are added every 1 hour, and the temperature is gradually raised to 83°C, 90°C, 97°C, and 105°C, and finally raised to 120°C and kept warm for 4-5 hours. The acid value is measured to be below the theoretical value of 3.0 mgKOH / g, and the material is cooled and discharged to obtain a composite anhydride-modified UV-curable epoxy acrylate.

[0097] (2) Physical and chemical properties of composite anhydride modified UV-curable epoxy resin: appearance is slightly yellow, transparent and clear; acid value is 2.7 mgKOH / g; viscosity is 138550 mPa·s.

[0098] (3) Preparation of UV curing coating:

[0099] The configuration composition of UV curing coatings in parts by mass is shown in Table 14 below:

[0100]

[0101] Add the above formula into the container and disperse it at a low speed of 600r / min for 10-15min. After the paint is left to stand without bubbles, use a four-sided wet film applicator to apply the film on the wood board, glass board and tinplate respectively. The film thickness is 25±2μm and the power is 600mW / cm 2 , cured under a UV curing machine with a wavelength of 365nm, and the coating performance was tested. The coating performance is shown in the table below. The performance of Example 5 and the same EA resin on the market were compared, and the coating performance was shown in Table 15.

[0102] (4) Table 15:

[0103]

[0104]

[0105] Example 6

[0106] (1) Preparation of composite anhydride-modified UV-curable epoxy acrylate: The composite anhydride-modified UV-curable epoxy acrylate resin of this embodiment has a raw material formula with a mass percentage composition as shown in Table 16:

[0107]

[0108] Preparation process of composite anhydride modified UV curable epoxy acrylate in this embodiment:

[0109] The above-mentioned glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60%wt of the total catalyst), and p-hydroxyanisole (total amount is 60wt% of the total polymerization inhibitor) are added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser, and the temperature is raised to 75°C and kept warm for 1 hour; then 10wt% of tetraethylammonium bromide and p-hydroxyanisole are added every 1 hour, and the temperature is gradually raised to 83°C, 90°C, 97°C, and 105°C, and finally raised to 120°C and kept warm for 4-5 hours. The acid value is measured to be below the theoretical value of 3.0 mgKOH / g, and the material is cooled and discharged to obtain a composite anhydride-modified UV-curable epoxy acrylate.

[0110] (2) Physical and chemical properties of composite anhydride modified UV-curable epoxy resin: appearance is slightly yellow, transparent and clear; acid value is 1.9 mgKOH / g; viscosity is 134800 mPa·s.

[0111] (3) Preparation of UV curing coating:

[0112] The configuration composition of UV curing coatings in parts by mass is shown in Table 17 below:

[0113]

[0114]

[0115] Add the above formula into the container and disperse it at a low speed of 600r / min for 10-15min. After the paint is left to stand without bubbles, use a four-sided wet film applicator to apply the film on the wood board, glass board and tinplate respectively. The film thickness is 25±2μm and the power is 600mW / cm 2 , cured under a UV curing machine with a wavelength of 365nm, and the coating performance was tested. The coating performance is shown in the table below. The performance of Example 6 and the same EA resin on the market were compared. The coating performance is shown in Table 18.

[0116] (4) Table 18:

[0117]

[0118] Example 7

[0119] (1) Preparation of composite anhydride-modified UV-curable epoxy acrylate: A composite anhydride-modified UV-curable epoxy acrylate resin, the raw material formula mass percentage composition is shown in Table 19:

[0120]

[0121]

[0122] Preparation process of composite anhydride modified UV curable epoxy acrylate in this embodiment:

[0123] The above-mentioned glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60%wt of the total catalyst), and p-hydroxyanisole (total amount is 60wt% of the total polymerization inhibitor) are added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser, and the temperature is raised to 75°C and kept warm for 1 hour; then 10wt% of tetraethylammonium bromide and p-hydroxyanisole are added every 1 hour, and the temperature is gradually raised to 83°C, 90°C, 97°C, and 105°C, and finally raised to 120°C and kept warm for 4-5 hours. The acid value is measured to be below the theoretical value of 3.0 mgKOH / g, and the material is cooled and discharged to obtain a composite anhydride-modified UV-curable epoxy acrylate.

[0124] (2) Physical and chemical properties of composite anhydride modified UV-curable epoxy resin: appearance is water white, transparent and clear; acid value is 2.1 mgKOH / g; viscosity is 103850 mPa·s.

[0125] (3) Preparation of UV curing coating:

[0126] The configuration composition of UV curing coatings in parts by mass is shown in Table 20 below:

[0127]

[0128] Add the above formula into the container and disperse it at a low speed of 600r / min for 10-15min. After the paint is left to stand without bubbles, use a four-sided wet film applicator to apply the film on the wood board, glass board and tinplate respectively. The film thickness is 25±2μm and the power is 600mW / cm 2 , cured under a UV curing machine with a wavelength of 365nm, and the coating performance was tested. The coating performance is shown in the table below. The performance of Example 7 and the same EA resin on the market were compared, and the coating performance was shown in Table 21.

[0129] (4) Table 21:

[0130]

[0131]

[0132] Example 8

[0133] (1) Preparation of composite anhydride-modified UV-curable epoxy acrylate: The composite anhydride-modified UV-curable epoxy acrylate resin of this embodiment has a raw material formula with a mass percentage composition as shown in Table 22:

[0134]

[0135] Preparation process of composite anhydride modified UV curable epoxy acrylate in this embodiment:

[0136] The above-mentioned glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60%wt of the total catalyst), and p-hydroxyanisole (total amount is 60wt% of the total polymerization inhibitor) are added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser, and the temperature is raised to 75°C and kept warm for 1 hour; then 10wt% of tetraethylammonium bromide and p-hydroxyanisole are added every 1 hour, and the temperature is gradually raised to 83°C, 90°C, 97°C, and 105°C, and finally raised to 120°C and kept warm for 4-5 hours. The acid value is measured to be below the theoretical value of 3.0 mgKOH / g, and the material is cooled and discharged to obtain a composite anhydride-modified UV-curable epoxy acrylate.

[0137] (2) Physical and chemical properties of composite anhydride modified UV-curable epoxy resin: appearance is water white, transparent and clear; acid value is 1.6 mgKOH / g; viscosity is 101450 mPa·s.

[0138] (3) Preparation of UV curing coating:

[0139] The configuration composition of UV curing coatings in parts by mass is shown in Table 23:

[0140]

[0141] Add the above formula into the container and disperse it at a low speed of 600r / min for 10-15min. After the paint is left to stand without bubbles, use a four-sided wet film applicator to apply the film on the wood board, glass board and tinplate respectively. The film thickness is 25±2μm and the power is 600mW / cm 2 , cured under a UV curing machine with a wavelength of 365nm, and the coating performance was tested. The coating performance is shown in the table below. The performance of Example 8 and the same EA resin on the market were compared. The coating performance is shown in Table 24.

[0142] (4) Table 24:

[0143]

[0144] Example 9

[0145] (1) Preparation of composite anhydride-modified UV-curable epoxy acrylate: The composite anhydride-modified UV-curable epoxy acrylate resin of this embodiment has a raw material formula with a mass percentage composition as shown in Table 25:

[0146]

[0147] Preparation process of composite anhydride modified UV curable epoxy acrylate in this embodiment:

[0148] The above-mentioned glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60%wt of the total catalyst), and p-hydroxyanisole (total amount is 60wt% of the total polymerization inhibitor) are added to a four-necked flask equipped with a stirring paddle, a thermometer, and a condenser, and the temperature is raised to 75°C and kept warm for 1 hour; then 10wt% of tetraethylammonium bromide and p-hydroxyanisole are added every 1 hour, and the temperature is gradually raised to 83°C, 90°C, 97°C, and 105°C, and finally raised to 120°C and kept warm for 4-5 hours. The acid value is measured to be below the theoretical value of 3.0 mgKOH / g, and the material is cooled and discharged to obtain a composite anhydride-modified UV-curable epoxy acrylate.

[0149] (2) Physical and chemical properties of composite anhydride modified UV-curable epoxy resin: appearance is water white, transparent and clear; acid value is 2.0 mgKOH / g; viscosity is 97650 mPa·s.

[0150] (3) Preparation of UV curing coating:

[0151] The configuration composition of UV curing coatings in parts by mass is shown in Table 26:

[0152]

[0153] Add the above formula into the container and disperse it at a low speed of 600r / min for 10-15min. After the paint is left to stand without bubbles, use a four-sided wet film applicator to apply the film on the wood board, glass board and tinplate respectively. The film thickness is 25±2μm and the power is 600mW / cm 2 , cured under a UV curing machine with a wavelength of 365nm, and the coating performance was tested. The coating performance is shown in the table below. The performance of Example 9 and the same EA resin on the market were compared, and the coating performance was shown in Table 27.

[0154] (4) Table 27:

[0155]

[0156] In the above embodiments, the epoxy resin can be one of epoxy resins E51, E44, F44, F51, 170, 128, R-828, S-21, and BD-20.

[0157] In the above embodiments, the catalyst can be at least one of tetraethylammonium bromide, tetrabutylammonium bromide, N,N-dimethylbenzylamine, and triphenylphosphine.

[0158] In the above embodiments, the polymerization inhibitor can be at least one of p-hydroxyanisole, p-benzoquinone, methylhydroquinone, hydroquinone, and 2,5-dimethylhydroquinone.

[0159] In the above embodiments, the reactive diluent can be one of dipropylene glycol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, hexanediol diacrylate, and triethylene glycol diacrylate.

[0160] In the above embodiments, the photoinitiator can be at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 1-hydroxycyclohexyl phenyl ketone.

[0161] The above embodiments are preferred embodiments of the present application, but the embodiments of the present application are not limited to the above embodiments, and any changes, modifications, substitutions, combinations, simplifications, and the like, which do not depart from the spirit and principles of the present application, are equivalent replacement modes and are included in the scope of the present application.

Claims

1. A method for preparing a composite anhydride-modified UV-curable epoxy acrylate, characterized in that: The following steps are involved: (1) Weigh the raw materials according to the following formula by weight: (2) Glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin, part of the catalyst, and part of the polymerization inhibitor are stirred and heated to 75° C. to 80° C. and kept warm for 0.8 to 1.2 hours, then the temperature is raised in stages, the remaining catalyst and the remaining polymerization inhibitor are added in batches, and the temperature is finally raised to 115 to 125° C. and reacted for 4 to 5 hours to obtain a composite anhydride-modified UV-curable epoxy acrylate; The weight of the partial catalyst is 55% to 65% of the total weight of the catalyst; the weight of the partial polymerization inhibitor is 55% to 65% of the total weight of the polymerization inhibitor.

2. The method for preparing composite anhydride-modified UV-curable epoxy acrylate according to claim 1, wherein: The epoxy resin is one of epoxy resins E51, E44, F44, F51, 170, 128, R-828, S-21, and BD-20.

3. The method for preparing composite anhydride-modified UV-curable epoxy acrylate according to claim 1, wherein: The catalyst is at least one of tetraethylammonium bromide, tetrabutylammonium bromide, N,N-dimethylbenzylamine and triphenylphosphine.

4. The method for preparing composite anhydride-modified UV-curable epoxy acrylate according to claim 1, wherein: The polymerization inhibitor is at least one of p-hydroxyanisole, p-benzoquinone, methylhydroquinone, hydroquinone, and 2,5-dimethylhydroquinone.

5. The method for preparing composite anhydride modified UV-curable epoxy acrylate according to claim 1, wherein: The stepwise heating and batchwise addition of the remaining catalyst and the remaining polymerization inhibitor are specifically as follows: Raise the temperature by 8-10°C every 0.8-1.2 hours; add the remaining catalyst and remaining inhibitor in 4-5 batches.

6. A composite anhydride modified UV-curable epoxy acrylate, characterized in that: In parts by weight, comprising:

7. The use of the composite anhydride modified UV-curable epoxy acrylate according to claim 6, characterized in that: Used to prepare coatings.

8. The use according to claim 7, characterized in that The coating comprises, by weight, 65 to 87 parts of composite anhydride-modified UV-curable epoxy acrylate, 10 to 30 parts of reactive diluent, and 3 to 5 parts of photoinitiator.

9. The use according to claim 8, characterized in that The active diluent is one of tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, hexanediol diacrylate and triethylene glycol diacrylate.

10. The use according to claim 8, characterized in that The photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and 1-hydroxycyclohexyl phenyl ketone.

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