Ultraviolet colorable acrylate monomer, ultraviolet colorable uv adhesive and application

Abstract

The present application relates to ultraviolet coloration acrylate monomer, ultraviolet coloration UV adhesive and application, belong to adhesive technical field. Ultraviolet coloration acrylate monomer can absorb 200 nm-385 nm wavelength, realize the efficient preparation of ultraviolet coloration UV glue. Ultraviolet coloration acrylate monomer as free radical polymerization monomer participates in UV glue polymerization, forms the uniform UV glue block or glue film;Can solve the problem such as high proportion of ordinary fluorescent dye additive, easy migration diffusion. In addition, the formed glue film has the function of absorbing 200 nm-385 nm wavelength light, in addition to the functions such as waterproof, dustproof and antifouling, it can also protect the electronic components below the glue film from the damage of ultraviolet.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of adhesives, in particular to ultraviolet color developing acrylate monomer, ultraviolet color developing UV adhesive and application. BACKGROUND

[0002] The ultraviolet color developing UV adhesive usually contains fluorescent dyes, which can emit visible fluorescence under ultraviolet light. The adhesive forms a film during coating, and the fluorescent dyes on the adhesive emit bright fluorescence under the irradiation of ultraviolet light, helping the operator to determine the uniformity and quality of the coating. The currently marketed ultraviolet color developing UV adhesive has two defects: (1) adding inorganic ultraviolet color developing agents such as metal sulfides or rare earth oxides, which have the disadvantages of high price, environmental pollution and interference with the performance of the UV adhesive; (2) adding organic ultraviolet color developing agents such as fluorescent dye molecules, which have the disadvantage of phase separation and fogging after UV adhesive curing.

[0003] Therefore, it has certain research significance to design a benzotriazole and acrylate integrated molecule, and it is of great significance to further study its application in ultraviolet color developing UV adhesive. SUMMARY

[0004] To solve the above technical problems, the present application provides ultraviolet color developing acrylate monomer, ultraviolet color developing UV adhesive and application. The ultraviolet color developing UV adhesive of the present application is suitable for three-proofing UV adhesive rapid detection and other scenes.

[0005] The present application is realized by the following technical solutions:

[0006] The first object of the present application is to provide an ultraviolet color developing acrylate monomer, which is selected from one or more of the following compounds:

[0007] 、 or .

[0008] In an embodiment of the present application, the ultraviolet color developing acrylate monomer has an absorption wavelength of 200 nm-385 nm.

[0009] In an embodiment of the present application, the ultraviolet color developing acrylate monomer has benzotriazole as an optically active core, and realizes dual functions through the following modular modification:

[0010] Anchoring module: introducing a polymerizable double bond (acrylate / allyl ether / siloxane group) at the para position of the benzene ring and the 2nd nitrogen position of benzotriazole respectively or simultaneously, embedding into the UV polymer network through covalent bonding, thereby solving the problem of phase separation of organic ultraviolet color developing agents.

[0011] In one embodiment of the present application, the synthesis method of the ultraviolet color developing acrylate monomer is as follows:

[0012] (1) Constructing optical core: coupling reaction (Suzuki coupling) of halogenated benzotriazole and aryl boronic acid containing phenolic hydroxyl or alcohol hydroxyl or alkyl substitution is carried out to obtain a benzotriazole intermediate which is dihydroxyl aryl functionalized and dialkyl aryl functionalized;

[0013] (2) Functional modification: introducing polymerizable double bond by esterification and etherification to the benzotriazole intermediate obtained in step;

[0014] (3) Cross-linking and curing: copolymerization of the compound obtained in step (2) with acrylate monomer and resin to form a three-dimensional network, complete molecular anchoring, and obtain the ultraviolet color developing acrylate monomer.

[0015] A second object of the present application is to provide the use of the ultraviolet color developing acrylate monomer in preparing the ultraviolet color developing UV adhesive.

[0016] A third object of the present application is to provide an ultraviolet color developing UV adhesive, which comprises the following components in parts by weight:

[0017] 35-65 parts of polyurethane carbon-carbon double bond-containing acrylate resin, 0.0001-0.03 parts of the ultraviolet color developing acrylate monomer, 20-45 parts of active hydroxyl-containing functional monomer, 5-15 parts of functional monomer, 3-10 parts of fumed silica, and 0.5-3 parts of photoinitiator. The fumed silica is used to adjust the thixotropy of the UV adhesive.

[0018] In one embodiment of the present application, the active hydroxyl-containing functional monomer is selected from one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate.

[0019] In one embodiment of the present application, the functional monomer is selected from one or more of acrylic acid, methacrylic acid, N-hydroxymethyl acrylamide, glycidyl acrylate, and N,N-dimethyl acrylamide.

[0020] In one embodiment of the present application, the polyurethane carbon-carbon double bond-containing acrylate resin is obtained by the following steps:

[0021] The first monomer, the second monomer, and the third monomer are mixed and heated in a solvent under a nitrogen atmosphere; an initiator is added for reaction, and after cooling, an intermediate product is obtained; a catalyst and isocyanate are further added to the intermediate product for reaction to obtain the polyurethane carbon-carbon double bond-containing acrylate resin; and the solvent is ethyl acetate.

[0022] Specifically, the polyurethane carbon-carbon double bond-containing acrylate resin is obtained by the following steps:

[0023] S1, under a nitrogen atmosphere, 30-85 parts by weight of the first monomer, 5-15 parts by weight of the second monomer, 6-25 parts by weight of the third monomer are mixed and heated to 60-70°C to obtain a mixture;

[0024] S2: 0.02-0.5 parts by weight of an initiator is added to the mixture obtained in S1, and reacted at 76-90°C for 2-8 hours, and then cooled to 40-60°C to obtain an intermediate product;

[0025] S3: 0.01-0.5 parts by weight of a catalyst and 5-30 parts by weight of isocyanate are added to the intermediate product obtained in S2, and reacted for 2-6 hours to obtain the polyurethane carbon-carbon double bond-containing acrylic resin;

[0026] The first monomer is selected from one or more of methyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and morpholine acrylate;

[0027] The second monomer is selected from one or more of acrylic acid, methacrylic acid, N-hydroxymethyl acrylamide, glycidyl acrylate, and N,N-dimethyl acrylamide;

[0028] The third monomer is selected from one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate.

[0029] The photoinitiator is selected from one or more of benzil dimethyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide.

[0030] The catalyst is selected from one or more of dioctyltin laurate, dibutyltin dilaurate, bismuth chloride, and bismuth oxide.

[0031] The isocyanate is selected from isocyanate acrylate.

[0032] In an embodiment of the present application, the photoinitiator is selected from one or more of benzil dimethyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide.

[0033] A fourth object of the present application is to provide a preparation method of the ultraviolet developing UV adhesive, comprising the following steps:

[0034] The polyurethane carbon-carbon double bond-containing acrylic resin, the active hydroxyl functional monomer, the functional monomer, the fumed silica, the ultraviolet developing acrylate monomer, and the photoinitiator are stirred and dispersed to obtain the ultraviolet developing UV adhesive.

[0035] The fifth object of the present application is to provide the application of the UV color developing UV adhesive in PCB, FPC soft board or anti-counterfeiting identification.

[0036] The above technical solution of the present application has the following advantages compared with the prior art:

[0037] The present application provides a UV color developing acrylate monomer, a UV color developing UV adhesive and application. The UV color developing acrylate monomer capable of absorbing 200 nm-385 nm wavelength can realize efficient preparation of the UV color developing UV adhesive, and the UV color developing acrylate monomer as a free radical polymerization monomer participates in UV adhesive polymerization to form a uniform UV adhesive block or adhesive film; and the problems such as high addition ratio of ordinary fluorescent dye additives and easy migration and diffusion can be solved.

[0038] In addition, the formed adhesive film has the function of absorbing 200 nm-385 nm wavelength light, and in addition to the functions of waterproof, dustproof and antifouling, it can also protect the electronic components below the adhesive film from damage by ultraviolet rays. BRIEF DESCRIPTION OF DRAWINGS

[0039] In order to make the content of the present application more easily understood, the present application will be further described in detail below according to specific embodiments of the present application and in conjunction with the drawings, in which:

[0040] Figure 1 is the UV and fluorescence emission spectrum of 4-(4,7-diphenyl-2H-benzo[d][1,2,3]triazol-2-yl)butyl acrylate (14) in the present application;

[0041] Figure 2 is the UV and fluorescence emission spectrum of 4-(4,7-bis(4-tert-butylphenyl)-2H-benzo[d][1,2,3]triazol-2-yl)butyl acrylate (15) in the present application;

[0042] Figure 3 is the UV and fluorescence emission spectrum of (2-(4-(acryloyloxy)butyl)-2H-benzo[d][1,2,3]triazole-4,7-diyl)bis(4,1-phenylene)diacrylate (16) in the present application;

[0043] Figure 4 is the presentation diagram of the UV color developing UV adhesive prepared in Example 10 of the present application under weak ultraviolet light;

[0044] Figure 5 is the presentation diagram of the UV color developing UV adhesive prepared in Example 10 of the present application after curing (A) and after weak ultraviolet light irradiation (B);

[0045] Figure 6is the presentation diagram of the UV adhesive with ultraviolet color prepared by Example 12 of the present application under weak ultraviolet light;

[0046] Figure 7 is the presentation diagram of the UV adhesive with ultraviolet color prepared by Example 12 of the present application after curing and weak ultraviolet light irradiation;

[0047] Figure 8 is the presentation diagram of the UV adhesive with ultraviolet color prepared by Example 13 of the present application under weak ultraviolet light;

[0048] Figure 9 is the presentation diagram of the UV adhesive with ultraviolet color prepared by Example 13 of the present application after curing (A) and weak ultraviolet light irradiation (B). DETAILED DESCRIPTION

[0049] The present application will be further described in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present application and implement it. However, the embodiments are not intended to limit the present application.

[0050] The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, etc. used are commercially available unless otherwise specified.

[0051] Example 1

[0052]

[0053] 4-chloro-1-butanol (1) (5.428 g, 50 mmol) was dissolved in diethyl ether (50 mL), two drops of concentrated hydrochloric acid were added, and stirring and cooling were performed at 0°C. Then 3,4-dihydro-2H-pyran (6.3 mL) was added, and stirring was continued at room temperature overnight. After the reaction was completed, neutralization was performed with sodium bicarbonate, and extraction was performed with diethyl ether. The organic layer was washed with water and saturated brine in sequence, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 8.460 g of colorless oil: 4-chloro-1-(2-tetrahydropyranyloxy)butane (2) (yield 88%), which was directly used in the next reaction without further purification.

[0054] Example 2

[0055]

[0056] To a solution of 4,7-dibromo-benzotriazole (3) (27.692 g, 100 mmol) and potassium carbonate (13.8 g) in DMF (200 mL) was added 4-chloro-l-(2-tetrahydropyranyloxy)butane (2) (21.195 g, 110 mmol) and heated to reflux for 12 h. After cooling, the reaction was partitioned between water and chloroform. The organic layer was concentrated and purified by preparative thin layer chromatography (eluent: chloroform / methanol 98:2). After elution and evaporation of the solvent, compound 4,7-dibromo-2-(4-((tetrahydro-2H-pyran-2-yl)oxy)butyl)-2H- benzo[d][l,2,3]triazole (4) (19.491 g, 45% yield) was obtained.

[0057] The hydrogen spectrum of 4,7-dibromo-2-(4-((tetrahydro-2H-pyran-2-yl)oxy)butyl)-2H- benzo[d][l,2,3]triazole (4) is 1 H NMR (400 MHz, CDCl3 ) δ 7.52 (s, 2H), 4.80 (t, J = 7.2 Hz,2H), 4.50 (dd, J = 8.6, 1.6 Hz, 1H), 3.60 – 3.70 (m, 4H), 2.21 – 2.32 (m,2H), 1.63 – 1.83 (m, 8H).

[0058] Example 3

[0059]

[0060] To a solution of 4,7-dibromo-2-(4-((tetrahydro-2H-pyran-2-yl)oxy)butyl)-2H- benzo[d][l,2,3]triazole (4) (50 mmol, 21.657 g), potassium carbonate (150 mmol, 20.752 g), tetrakis(triphenylphosphine)palladium (3.0 mmol, 12.450 g), p-methylphenylboronic acid (5) (150 mmol, 20.394 g) in a Schlenk tube, after purging with nitrogen, 1,4-dioxane and water (200 mL, volume ratio 5:1) were added, and the mixture was heated and stirred at 120 °C for 6 h. After the reaction was completed, ethyl acetate and saturated ammonium chloride solution were added, and the organic phase was extracted. Anhydrous sodium sulfate was added to remove water, filtered, and concentrated to obtain 2-(4-((tetrahydro-2H-pyran-2-yl)oxy)butyl)-4,7-di-p-tolyl-2H- benzo[d][l,2,3]triazole (6), which was directly used in the next step.

[0061] The obtained 2-(4-((tetrahydro-2H-pyran-2-yl)oxy)butyl)-4,7-di-p-tolyl-2H- benzo[d][1,2,3]triazole (6) was dissolved in methanol 200 mL, p-toluenesulfonic acid (10.332 g, 60 mmol) was added, stirred at room temperature for 12 h, concentrated and column chromatography to obtain 4-(4,7-di-p-tolyl-2H-benzo[d][1,2,3]triazol-2-yl)butan-1 -ol (7) (12,064 g, two-step reaction yield 65%).

[0062] The hydrogen spectrum of the obtained intermediate 4-(4,7-di-p-tolyl-2H-benzo[d][1,2,3]triazol-2-yl)butan-1 -ol (7) is 1 H NMR (400 MHz, CDC13) δ 8.01 (d, J = 8.2 Hz, 4H), 7.65 (s, 2H), 7.58 (d, J = 8.2 Hz, 4H), 4.88 (t, J = 7.2 Hz, 2H), 3.69 (t, J = 6.8 Hz, 2H), 2.25 - 2.35 (m, 2H), 2.15 (s, 6H), 1.65 - 1.75 (m, 2H).

[0063] Example 4

[0064]

[0065] Take 4,7-dibromo-2-(4-((tetrahydro-2H-pyran-2-yl)oxy)butyl)-2H-benzo[d][1,2,3]triazole (4) (50 mmol, 21.657 g), potassium carbonate (150 mmol, 20.752 g), tetrakis(triphenylphosphine)palladium (3.0 mmol, 12.450 g), p-tert-butylphenylboronic acid (8) (150 mmol, 26.706 g), add to the Schlenk tube, after nitrogen replacement, add a mixed solvent of 1,4-dioxane and water (200 mL, volume ratio 5:1 ), stir and heat at 120 degrees Celsius for 6 h, after the reaction is completed, add ethyl acetate and saturated ammonium chloride solution to extract the organic phase, add anhydrous sodium sulfate to remove water, filter and concentrate to obtain 4,7-bis[4-(tert-butyl)phenyl]-2-[4-((tetrahydro-2H-pyran-2-yl)oxy)butyl]-2H-benzo[d][1,2,3]triazole (9), which is directly used for the next step reaction.

[0066] The obtained 4,7-bis[4-(tert-butyl)phenyl]-2-[4-((tetrahydro-2H-pyran-2- yl)oxy)butyl]-2H-benzo[d][1,2,3]triazole (9) was dissolved in methanol 200 mL, p-toluenesulfonic acid (10.332 g, 60 mmol) was added, stirred at room temperature for 12 h, concentrated and column chromatography to obtain the product 4-(4,7-bis(4-tert-butylphenyl)-2H- benzo[d][1,2,3]triazol-2-yl)butan-1 -ol (10) (15.492 g, 68% yield for two steps).

[0067] The hydrogen spectrum of the product 4-(4,7-bis(4-tert-butylphenyl)-2H- benzo[d][1,2,3]triazol-2-yl)butan-1 -ol (10) is 1 H NMR (400 MHz, CDC13) δ 7.99 (d, J = 8.5 Hz, 4H), 7.62 (s, 2H), 7.55 (d, J = 8.5 Hz, 4H), 4.86 (t, J = 7.1 Hz, 2H), 3.71 (t, J = 6.3 Hz, 2H), 2.21 - 2.32 (m, 2H), 1.63 - 1.73 (m, 2H), 1.41 (s, 18H).

[0068] Example 5

[0069]

[0070] Take 4,7-dibromo-2-(4-((tetrahydro-2H-pyran-2-yl)oxy)butyl)-2H- benzo[d][1,2,3]triazole (4) (50 mmol, 21.657 g), potassium carbonate (150 mmol, 20.752 g), tetrakis(triphenylphosphine)palladium (3.0 mmol, 12.450 g), p- hydroxyphenylboronic acid (11) (150 mmol, 20.690 g), add to the Schlenk tube, after nitrogen replacement, add a mixed solvent of 1,4-dioxane and water (200 mL, volume ratio 5:1 ), stir and heat at 120 degrees Celsius for 6 h, after the reaction is completed, add ethyl acetate and saturated ammonium chloride solution, extract the organic phase, add anhydrous sodium sulfate to remove water, filter and concentrate to obtain 4,4'-(2-(4-((tetrahydro-2H-pyran-2- yl)oxy)butyl)-2H-benzo[d][1,2,3]triazole-4,7-diyl)diphenol (12), which is directly used for the next step reaction.

[0071] The obtained 4,4'-(2-(4-((tetrahydro-2H-pyran-2-yl)oxy)butyl)-2H- benzo[d][1,2,3]triazole-4,7-diyl)diphenol (12) was dissolved in methanol 200 mL, p-toluenesulfonic acid (10.332 g, 60 mmol) was added, stirred at room temperature for 12 h, concentrated and column chromatography to obtain the product 4,4'-(2-(4-hydroxybutyl)-2H- benzo[d][1,2,3]triazole-4,7-diyl)diphenol (13) (15.492 g, 68% yield for two steps).

[0072] The hydrogen spectrum of the product 4,4'-(2-(4-hydroxybutyl)-2H- benzo[d][1,2,3]triazole-4,7-diyl)diphenol (13) is 1 H NMR (400 MHz, CDC13) δ 9.20 (s, 2H), 8.01 (d, J = 6.8 Hz, 4H), 7.42 (s, 2H), 7.35 (d, J = 6.8 Hz, 4H), 4.82 (t, J = 7.0 Hz, 2H), 3.75 (t, J = 6.3 Hz, 2H), 2.55 (s, 1H), 2.19 - 2.29 (m, 2H), 1.60 - 1.70 (m, 2H).

[0073] Example 6

[0074]

[0075] Take 4-(4,7-bis(4-methylphenyl)-2H-benzo[d][1,2,3]triazol-2-yl)butan-1 -ol (7) (10 mmol, 3.715 g), dichloromethane (50 mL), triethylamine (12 mmol, 1.214 g), acryloyl chloride (12 mmol, 1.086 g), add to a round-bottom flask, reflux and stir under nitrogen protection for 6 h, after the reaction is completed, add ethyl acetate and saturated ammonium chloride solution to extract the organic phase, add anhydrous sodium sulfate to remove water, filter and separate by column to obtain 4-(4,7-di-p-tolyl-2H- benzo[d][1,2,3]triazol-2-yl)butyl acrylate (14) 3.447 g, separation yield 81%. The UV and fluorescence emission spectrum of the product 4-(4,7-di-p-tolyl-2H- benzo[d][1,2,3]triazol-2-yl)butyl acrylate is shown in Figure 1

[0076] ​The hydrogen spectrum of the product obtained, 4-(4,7-diphenyl-2H- benzo[d][1,2,3]triazol-2-yl)butyl acrylate (13), is as follows 1 H NMR (400 MHz, CDC13) δ 8.00 (d, J = 8.2 Hz, 4H), 7.56 (s, 2H), 7.53 (d, J = 8.2 Hz, 4H), 6.30 (dd, J = 17.2, 1.4 Hz, 1H), 6.04 (dd, J = 17.2, 10.6 Hz, 1H), 5.70 (dd, J = 10.6, 1.4 Hz, 1H), 4.70 (t, J = 7.2 Hz, 2H), 4.13 (t, J = 6.6 Hz, 2H), 2.15-2.20 (m, 2H), 2.12 (s, 6H), 1.60 - 1.81 (m, 2H).

[0077] Example 7

[0078]

[0079] To a round bottom flask was added 4-(4,7-bis(4-tert-butylphenyl)-2H- benzo[d][1,2,3]triazol-2-yl)butan-1 -ol (10) (10 mmol, 4.556 g), dichloromethane (50 mL), triethylamine (12 mmol, 1.214 g), acryloyl chloride (12 mmol, 1.086 g), stirred and heated under reflux for 6 h under nitrogen protection. After the reaction was completed, ethyl acetate and saturated ammonium chloride solution were added to extract the organic phase, anhydrous sodium sulfate was added to remove water, filtered, and separated by column to obtain 4-(4,7-bis(4-tert-butylphenyl)-2H- benzo[d][1,2,3]triazol-2-yl)butyl acrylate (15) 4.230 g, separation yield 83%. The UV and fluorescence emission spectrum of 4-(4,7-bis(4-tert-butylphenyl)-2H- benzo[d][1,2,3]triazol-2-yl)butyl acrylate is shown in Figure 2

[0080] The hydrogen spectrum of the product obtained, 4-(4,7-diphenyl-2H- benzo[d][1,2,3]triazol-2-yl)butyl acrylate (13), is as follows 1 ​H NMR (400 MHz, CDCl3 ) δ 7.99 (d, J = 8.4 Hz, 4H), 7.55(s, 2H), 7.51 (d, J = 8.4 Hz, 4H), 6.34 (dd, J = 17.3, 1.4 Hz, 1H), 6.04 (dd,J = 17.3, 10.4 Hz, 1H), 5.70 (dd, J = 10.4, 1.4 Hz, 1H), 4.75 (t, J = 7.1 Hz,2H), 4.15 (t, J = 6.4 Hz, 2H), 2.16-2.21 (m, 2H), 1.62 – 1.82 (m, 2H), 1.36(s, 18H)。

[0081] Example 8

[0082]

[0083] To a round bottom flask was added 4,4'-(2-(4-hydroxybutyl)-2H-benzo[d][1,2,3]triazole-4,7-diyl)diphenol (13) (10 mmol, 3.754 g), dichloromethane (50 mL), triethylamine (35 mmol, 3.541 g), acryloyl chloride (35 mmol, 3.168 g), and heated to reflux under nitrogen for 6 h. The reaction was extracted with ethyl acetate and saturated ammonium chloride solution after completion of the reaction. The organic phase was obtained, anhydrous sodium sulfate was added to remove water, filtered, and separated by column to obtain (2-(4-(acryloyloxy)butyl)-2H-benzo[d][1,2,3]triazole-4,7-diyl) bis(4,1- phenylene)diacrylate (16) 4.017 g, separation yield 75%. The UV and fluorescence emission spectra of (2-(4-(acryloyloxy)butyl)-2H-benzo[d][1,2,3]triazole-4,7-diyl) bis(4,1- phenylene)diacrylate are shown in FIG. 1. Figure 3

[0084] The hydrogen spectrum of the obtained product (2-(4-(acryloyloxy)butyl)-2H-benzo[d][1,2,3]triazole-4,7-diyl) bis(4,1-phenylene)diacrylate (16) is shown in FIG. 2. 1 ​H NMR (400 MHz, CDCl3 ) δ 8.11 (d, J =6.8 Hz, 4H), 7.50 (s, 2H), 7.32 (d, J = 6.8 Hz, 4H), 6.38-6.65 (m, 3H),6.42 (dd, J = 16.8, 10.8 Hz, 2H), 6.05 (dd, J = 17.0, 10.4 Hz, 1H), 5.37-5.65(m, 3H), 4.72 (t, J = 7.2 Hz, 2H), 4.18 (t, J = 6.6 Hz, 2H), 2.15-2.22 (m,2H), 1.60 – 1.80 (m, 2H)。

[0085] Example 9

[0086] The present example provides a UV adhesive with ultraviolet color development, which comprises the following components by weight:

[0087] Polyurethane carbon-carbon double bond-containing acrylic resin 50 parts, hydroxyethyl acrylate 35 parts, N,N-dimethyl acrylamide 10 parts, fumed silica 5 parts, ultraviolet color development acrylate monomer (compound 14 prepared in Example 6) 0.3 parts, 184 photoinitiator (1-hydroxycyclohexyl phenyl ketone) 0.5 parts, photoinitiator TPO (2,4,6-trimethylbenzoyl-diphenyl phosphine oxide) 0.5 parts.

[0088] The preparation method of the UV adhesive of the present example is as follows:

[0089] (1) Preparation of polyurethane carbon-carbon double bond-containing acrylic resin (refer to Chinese patent CN120310441B):

[0090] 40 parts of isooctyl acrylate, 30 parts of butyl acrylate, 15 parts of methyl methacrylate, 10 parts of hydroxyethyl acrylate, 5 parts of N,N-dimethyl acrylamide and 100 parts of ethyl acetate are uniformly mixed, under a nitrogen atmosphere, the temperature is raised to 66°C under stirring, 0.02 parts of initiator azobisisobutyronitrile is added, and the temperature is kept for 2 hours, then 0.01 parts of initiator is added, the temperature is raised to 80°C, and the temperature is kept for 2 hours, and then the temperature is lowered to 40°C.

[0091] To the above treated reaction solution, 0.02 parts of dibutyltin dilaurate is added, the nitrogen gas is stopped, and 12.15 parts of isocyanate acrylate ethyl ester and 12.15 parts of ethyl acetate mixed solution are added dropwise into the reaction solution under stirring for half an hour, the temperature is kept for 6 hours, the temperature is lowered to discharge the material, and polyurethane carbon-carbon double bond-containing acrylic resin is obtained.

[0092] (2) Take 50 parts of the polyurethane carbon-carbon double bond-containing acrylic resin obtained in step (1), 35 parts of hydroxyethyl acrylate, 10 parts of N,N-dimethyl acrylamide, 5 parts of fumed silica, 0.3 parts of the UV colorable acrylate monomer, 0.5 parts of 184 photoinitiator, 0.5 parts of photoinitiator TPO, and disperse for 3 hours by double planetary stirring to obtain a UV adhesive with UV coloration.

[0093] Example 10

[0094] This example provides a UV adhesive with UV coloration. Similar to Example 9, the only difference is that the UV colorable acrylate monomer (monomer compound 14 obtained in Example 6) is 0.1 parts.

[0095] The preparation method is similar to that of Example 9.

[0096] Example 11

[0097] This example provides a UV adhesive with UV coloration. Similar to Example 9, the only difference is that the UV colorable acrylate monomer (monomer compound 14 obtained in Example 6) is 0.05 parts.

[0098] The preparation method is similar to that of Example 9.

[0099] Example 12

[0100] This example provides a UV adhesive with UV coloration. Similar to Example 9, the only difference is that the UV colorable acrylate monomer (monomer compound 15 obtained in Example 7) is 0.05 parts.

[0101] The preparation method is similar to that of Example 9.

[0102] Example 13

[0103] This example provides a UV adhesive with UV coloration. Similar to Example 9, the only difference is that the UV colorable acrylate monomer (monomer compound 16 obtained in Example 8) is 0.05 parts.

[0104] The preparation method is similar to that of Example 9.

[0105] Test Example

[0106] (1) The UV adhesive with UV coloration prepared in Example 10 is strongly blue under UV light, and the results are shown in Figure 4 . Figure 4 The UV adhesive with UV coloration prepared in Example 10 is weakly UV (365 nm, light intensity is 5 mW / cm 2The uncured UV glue liquid can show color, and the colored monomers are uniformly distributed; after strong ultraviolet-induced free radical polymerization and curing, the glue block can also absorb ultraviolet light to show color. It is shown that the UV glue adhesive with ultraviolet color can absorb ultraviolet light to show blue color before and after polymerization.

[0107] (2) The UV glue adhesive with ultraviolet color prepared in Example 10 was cured under a 365 nm UV lamp (18 W 365 nm wavelength LED lamp, light intensity was 100 mW / cm2, and curing time was 10 seconds) to obtain a glue block (2 g). Figure 5 After curing, the entire glue block showed uniform and very obvious blue light under UV lamp irradiation.

[0108] (3) 2 g of the above glue block was taken into a 100 mL round-bottom flask and soaked in 20 mL of ethyl acetate for 72 h. The ethyl acetate leaching experiment showed that there was no residual ultraviolet-colored monomer, indicating that the ultraviolet-colored acrylate monomer (monomer compound 14) fully participated in the polymerization during the UV polymerization. Through the molecular architecture based on "optical core-anchor chain" and the free radical acrylate polymerization initiated by photoinitiator, the preparation of UV glue for easy ultraviolet detection was realized.

[0109] The UV glue adhesive with ultraviolet color prepared in Example 12 was tested according to the above method, and the appearance under weak ultraviolet light is shown in Figure 6 , and the appearance after curing and weak ultraviolet irradiation is shown in Figure 7 .

[0110] The UV glue adhesive with ultraviolet color prepared in Example 13 was tested according to the above method, and the appearance under weak ultraviolet light is shown in Figure 8 , and the appearance after curing and weak ultraviolet irradiation is shown in Figure 9 .

[0111] Obviously, the above examples are only examples for clearly illustrating, and are not intended to limit the embodiments. For those skilled in the art, other different forms of changes or variations can be made on the basis of the above description. Here, it is not necessary and impossible to enumerate all the embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A UV-developing acrylate monomer, characterized in that, The ultraviolet-emitting acrylate monomers are selected from the following compounds: 。 2. The UV-emitting acrylate monomer according to claim 1, characterized in that, The absorption wavelength of the ultraviolet color-developing acrylate monomer is 200 nm-385 nm.

3. The use of the UV-emitting acrylate monomers according to claim 1 in the preparation of UV-emitting adhesives.

4. A UV-developing adhesive, characterized in that, The UV-developing adhesive comprises the following components in parts by weight: The product contains 35-65 parts of polyurethane carbon-carbon double bond acrylic resin, 0.0001-0.03 parts of UV-emitting acrylate monomer as described in claim 1 or 2, 20-45 parts of functional monomer containing active hydroxyl groups, 5-15 parts of functional monomer, 3-10 parts of fumed silica, and 0.5-3 parts of photoinitiator. The active hydroxyl functional monomer is selected from one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate; The functional monomer is selected from one or more of acrylic acid, methacrylic acid, N-hydroxymethylacrylamide, glycidyl acrylate and N,N-dimethylacrylamide.

5. The UV-developing adhesive according to claim 4, characterized in that, The polyurethane-carbon double bond-containing acrylic resin is obtained through the following steps: Under a nitrogen atmosphere, the first monomer, the second monomer, and the third monomer are mixed in a solvent and heated; an initiator is added to react, and after cooling, an intermediate product is obtained; then a catalyst and isocyanate are added to the intermediate product to react and obtain the polyurethane carbon-carbon double bond-containing acrylic resin. The first monomer is selected from one or more of methyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and morpholine acrylate; The second monomer is selected from one or more of acrylic acid, methacrylic acid, N-hydroxymethylacrylamide, glycidyl acrylate and N,N-dimethylacrylamide; The third monomer is selected from one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate.

6. The UV-developing adhesive according to claim 4, characterized in that, The photoinitiator is selected from one or more of benzoyl dimethyl ether, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

7. A method for preparing the ultraviolet-based color-developing UV adhesive according to any one of claims 4-6, characterized in that, Includes the following steps: An acrylic resin containing polyurethane carbon-carbon double bonds, a functional monomer containing active hydroxyl groups, a functional monomer, fumed silica, a UV-emitting acrylate monomer, and a photoinitiator are stirred and dispersed to obtain a UV-emitting adhesive.

8. The application of the ultraviolet color-developing UV adhesive according to any one of claims 4-6 in PCBs, FPC flexible boards or anti-counterfeiting labels.

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