Ultraviolet curing adhesive

Abstract

The invention discloses an ultraviolet light curing adhesive, and relates to the technical field of adhesives, and the ultraviolet light curing adhesive comprises the following components in parts by weight: 30-45 parts of Atlac 430 epoxy bisphenol A vinyl resin, 10-15 parts of amino-terminated hyperbranched polyimide, 1-3 parts of 1, 4-diamino-2, 3-dicyanoanthraquinone, 1-3 parts of 2, 2-bis [4-(4-aminophenoxy) phenyl]-1, 1, 1, 3, 3, 4-tetramethyl-1, 3, 4, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1 The invention discloses a light-cured acrylic resin, which is prepared from the following components in parts by weight: 2 to 4 parts of 1, 1, 1, 3, 3-hexafluoropropane, 5 to 8 parts of other active monomers, 1 to 3 parts of photoinitiator, 25 to 35 parts of diluent and 0.5 to 1.5 parts of leveling wetting agent. The adhesive is excellent in water resistance, sufficient in damp-heat aging resistance and high in bonding strength.

Description

Technical Field

[0001] The invention relates to the technical field of adhesives, and in particular to an ultraviolet light curing adhesive. Background Art

[0002] UV-curing adhesives are widely used in precision bonding in the fields of optical devices, electronic components, digital optical disks, medical devices, etc., due to their many advantages such as fast curing speed, low energy consumption, environmental friendliness, and high bonding strength. However, existing UV-curing adhesives still have more or less technical defects such as poor water resistance, insufficient resistance to moisture and heat aging, and the bonding strength needs to be further improved, which greatly limits the application scope of UV-curing adhesives.

[0003] In order to solve the above problems, a Chinese invention patent with authorization announcement number CN117165247B discloses a high-performance UV-curable adhesive and a preparation method thereof. The adhesive comprises the following raw materials in parts by weight: 35 to 75 parts of polythiourethane-acrylate, 20 to 50 parts of acrylate monomer, 0.5 to 5 parts of photoinitiator, 0.5 to 2 parts of coupling agent and 0.01 to 0.1 parts of catalyst. The invention also provides a preparation method thereof. Compared with the prior art, the UV-curable adhesive prepared by the invention has excellent bonding strength, good adhesion, and good waterproofness, which greatly expands the scope of application and has good market application prospects. However, its resistance to wet heat aging still needs to be further improved.

[0004] It can be seen that the art still needs a UV-curable adhesive with good water resistance, sufficient resistance to moisture and heat aging, and high bonding strength. Summary of the invention

[0005] The main purpose of the present invention is to provide an ultraviolet light curing adhesive with good water resistance, sufficient moisture and heat aging resistance and high bonding strength.

[0006] To achieve the above purpose, the present invention provides a UV-curing adhesive, which comprises the following components in parts by weight: 30-45 parts of Atlac 430 epoxy bisphenol A vinyl resin, 10-15 parts of amino-terminated hyperbranched polyimide, 1-3 parts of 1,4-diamino-2,3-dicyanoanthraquinone, 2-4 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 5-8 parts of other active monomers, 1-3 parts of photoinitiator, 25-35 parts of diluent, and 0.5-1.5 parts of leveling wetting agent.

[0007] Preferably, there is no special requirement for the source of the amino-terminated hyperbranched polyimide. In one embodiment of the present invention, the amino-terminated hyperbranched polyimide is prepared according to the method of Example 3 of the Chinese invention patent with authorization announcement number CN102267940B.

[0008] Preferably, the other active monomer is a mixture of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, bis(1-vinylimidazol-2-yl)ketone, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonate inner salt, dicyclopentene methacrylate, N-vinyl oxazolidinone, and allethrin cyclopentylmethyl at a mass ratio of 2:(1-3):1:(0.8-1.2):1:(0.8-1.2).

[0009] Preferably, the photoinitiator is at least one of benzoin dimethyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

[0010] Preferably, the diluent is a mixture of butyl methacrylate, methyl methacrylate, and hydroxypropyl methacrylate at a mass ratio of 1:(1-2):(0.8-1.2).

[0011] Preferably, the leveling and wetting agent is one or a mixture of several of TEGO-410, TEGO-432, TEGO-4000, BYK-306, and BYK-307.

[0012] Another object of the present invention is to provide a method for preparing the ultraviolet curable adhesive, comprising the following steps: mixing the components evenly by weight, performing vacuum degassing for 0.8-1.5 h, then standing for defoaming and storing to obtain the ultraviolet curable adhesive.

[0013] Another object of the present invention is to provide an application of the ultraviolet curable adhesive, comprising the following steps: coating the ultraviolet curable adhesive on the surface of the material to be bonded, first curing by ultraviolet light irradiation for 10-50 seconds, and then drying at 70-80 °C for 1-2 hours.

[0014] Preferably, the wavelength of the ultraviolet light is 220-260 nm.

[0015] Due to the application of the above technical solution, the present invention has the following beneficial effects: (1) The preparation method of the ultraviolet curable adhesive disclosed by the present invention has a simple process, convenient operation control, high preparation efficiency and product qualification rate, low dependence on equipment, is suitable for continuous large-scale production, and has high popularization and application value.

[0016] (2) The UV curing adhesive disclosed in the present invention comprises the following components by weight: 30-45 parts of Atlac 430 epoxy bisphenol A vinyl resin, 10-15 parts of amino-terminated hyperbranched polyimide, 1-3 parts of 1,4-diamino-2,3-dicyanoanthraquinone, 2-4 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 5-8 parts of other active monomers, 1-3 parts of photoinitiator, 25-35 parts of diluent, and 0.5-1.5 parts of leveling wetting agent. Through the mutual cooperation between the components, the prepared adhesive has good water resistance, sufficient resistance to moisture and heat aging, high bonding strength, fast UV curing speed, and is suitable for the precise bonding of various materials, especially in the field of electronic and optical device manufacturing. It has broad application prospects.

[0017] (3) In the UV-curing adhesive disclosed in the present invention, the other active monomers are prepared by mixing 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, bis(1-vinylimidazole-2-one), 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, dicyclopentene methacrylate, N-vinyloxazolidinone and cyclopentylthrin in a mass ratio of 2:(1-3):1:(0.8-1.2):1:(0.8-1.2). Through the reasonable selection of the above-mentioned active monomer composition, triazinetrione, imidazolone, amphoteric organic ion salt, dicyclopentenyl ester, oxazolidinone, and cyclopentyl acetone structures are simultaneously introduced into the adhesive film formed after the adhesive is cured. These structures cooperate with the cyanoanthraquinone, fluorinated phenyl ether, hyperbranched polyimide and bisphenol A structures introduced by other components under the multiple effects of electronic effect, steric effect and conjugation effect, etc., to give the product excellent water resistance, moisture and heat aging resistance and bonding strength.

[0018] (4) In the UV-curable adhesive disclosed in the present invention, the component containing unsaturated olefinic bonds will undergo a copolymerization curing reaction under the initiation of a photoinitiator; at the same time, the component containing epoxy groups will undergo an epoxy ring-opening reaction with the component containing amino groups; and two different interpenetrating network structures are simultaneously introduced into the adhesive film, which cooperate with each other to further improve the water resistance, moisture-heat aging resistance and bonding strength of the product. DETAILED DESCRIPTION

[0019] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are only examples, and those skilled in the art may think of other obvious variations. Example 1

[0020] An ultraviolet curable adhesive, by weight, comprises the following components: 30 parts of Atlac 430 epoxy bisphenol A vinyl resin, 10 parts of amino-terminated hyperbranched polyimide, 1 part of 1,4-diamino-2,3-dicyanoanthraquinone, 2 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 5 parts of other reactive monomers, 1 part of photoinitiator, 25 parts of diluent, and 0.5 part of leveling and wetting agent.

[0021] The amino-terminated hyperbranched polyimide is prepared by the method of Example 3 of the Chinese invention patent with the authorization announcement number CN102267940B; the other reactive monomers are composed of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, bis(1-vinylimidazol-2-yl)ketone, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonate inner salt, dicyclopentene methacrylate, N-vinyl oxazolidinone, and cyclopentene allethrin in a mass ratio of 2:1:1:0.8:1:0.8; the photoinitiator is benzoin dimethyl ether; the diluent is composed of butyl methacrylate, methyl methacrylate, and hydroxypropyl methacrylate in a mass ratio of 1:1:0.8; the leveling and wetting agent is TEGO-410.

[0022] A preparation method of the ultraviolet curable adhesive comprises the following steps: after mixing each component evenly by weight, evacuating and defoaming for 0.8 h, then standing for defoaming and storing to obtain the ultraviolet curable adhesive.

[0023] An application of the ultraviolet curable adhesive comprises the following steps: coating the ultraviolet curable adhesive on the surface of the material to be bonded, first curing by ultraviolet light irradiation for 10 seconds, and then drying at 70 °C for 1 hour; the wavelength of the ultraviolet light is 220 nm. Example 2

[0024] An ultraviolet curable adhesive, by weight, comprises the following components: 35 parts of Atlac 430 epoxy bisphenol A vinyl resin, 12 parts of amino-terminated hyperbranched polyimide, 1.5 parts of 1,4-diamino-2,3-dicyanoanthraquinone, 2.5 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 6 parts of other reactive monomers, 1.5 parts of photoinitiator, 27 parts of diluent, and 0.7 part of leveling and wetting agent.

[0025] The amino-terminated hyperbranched polyimide is prepared by the method of Example 3 of the Chinese invention patent with the authorized announcement number of CN102267940B; the other reactive monomer is composed of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, bis(1-vinylimidazol-2-yl)ketone, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonate inner salt, dicyclopentenyloxy methacrylate, N-vinyl oxazolidinone, and cyclopentene allethrin, which are mixed in a mass ratio of 2:1.5:1:0.9:1:0.9; the photoinitiator is benzoin ethyl ether; the diluent is composed of butyl methacrylate, methyl methacrylate, and hydroxypropyl methacrylate, which are mixed in a mass ratio of 1:1.2:0.9; the leveling and wetting agent is TEGO-432.

[0026] A preparation method of the ultraviolet curable adhesive comprises the following steps: after mixing each component evenly by weight, vacuum degassing is carried out for 1 h, then standing for defoaming and storing to obtain the ultraviolet curable adhesive.

[0027] An application of the ultraviolet curable adhesive comprises the following steps: coating the ultraviolet curable adhesive on the surface of the material to be bonded, first curing by ultraviolet light irradiation for 20 s, and then drying at 73 °C for 1.2 h; the wavelength of the ultraviolet light is 230 nm. Example 3

[0028] An ultraviolet curable adhesive, by weight, comprises the following components: 39 parts of Atlac 430 epoxy bisphenol A vinyl resin, 13 parts of amino-terminated hyperbranched polyimide, 2 parts of 1,4-diamino-2,3-dicyanoanthraquinone, 3 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 6.5 parts of other reactive monomer, 2 parts of photoinitiator, 30 parts of diluent, and 1 part of leveling and wetting agent.

[0029] The amino-terminated hyperbranched polyimide is prepared according to the method of Example 3 of the Chinese invention patent with authorization announcement number CN102267940B; the other active monomers are 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, bis(1-vinylimidazole-2-)ketone, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, dicyclopentene methacrylate, N-vinyloxazolidinone, and cyclopentylthrin in a mass ratio of 2:2:1:1:1:1; the photoinitiator is benzoin isopropyl ether; the diluent is butyl methacrylate, methyl methacrylate, and hydroxypropyl methacrylate in a mass ratio of 1:1.5:1; and the leveling wetting agent is TEGO-4000.

[0030] A method for preparing the ultraviolet light curing adhesive comprises the following steps: mixing the components uniformly according to weight, vacuuming and degassing for 1.2 hours, and then standing and degassing the mixture before storing to obtain the ultraviolet light curing adhesive.

[0031] An application of the UV-curing adhesive comprises the following steps: applying the UV-curing adhesive to the surface of the material to be bonded, first curing it by UV irradiation for 30 seconds, and then drying it at 75° C. for 1.5 hours; the wavelength of the UV light is 240 nm. Example 4

[0032] A UV-curing adhesive comprises the following components, measured by weight: 43 parts of Atlac 430 epoxy bisphenol A vinyl resin, 14 parts of amino-terminated hyperbranched polyimide, 2.5 parts of 1,4-diamino-2,3-dicyanoanthraquinone, 3.5 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 7.5 parts of other active monomers, 2.5 parts of a photoinitiator, 33 parts of a diluent, and 1.3 parts of a leveling wetting agent.

[0033] The amino-terminated hyperbranched polyimide is prepared according to the method of Example 3 of the Chinese invention patent with the authorization announcement number CN102267940B; the other active monomers are 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, bis(1-vinylimidazole-2-)ketone, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, dicyclopentene methacrylate, N-vinyl oxazolidine The ketone and cyclopentylthrin are mixed in a mass ratio of 2:2.5:1:1.1:1:1.1; the photoinitiator is a mixture of benzoin dimethyl ether, benzoin ethyl ether and benzoin isopropyl ether in a mass ratio of 1:2:1; the diluent is a mixture of butyl methacrylate, methyl methacrylate and hydroxypropyl methacrylate in a mass ratio of 1:1.8:1.1; the leveling wetting agent is a mixture of TEGO-410, TEGO-432, TEGO-4000, BYK-306 and BYK-307 in a mass ratio of 1:1:2:3:1.

[0034] A method for preparing the ultraviolet light-curing adhesive comprises the following steps: uniformly mixing the components according to weight, vacuuming and degassing for 1.3 hours, and then standing and degassing the components before storing to obtain the ultraviolet light-curing adhesive.

[0035] An application of the UV-curing adhesive comprises the following steps: applying the UV-curing adhesive to the surface of the material to be bonded, first curing it by UV irradiation for 40 seconds, and then drying it at 78° C. for 1.8 hours; the wavelength of the UV light is 250 nm. Example 5

[0036] A UV-curing adhesive comprises the following components, measured by weight: 45 parts of Atlac 430 epoxy bisphenol A vinyl resin, 15 parts of amino-terminated hyperbranched polyimide, 3 parts of 1,4-diamino-2,3-dicyanoanthraquinone, 4 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 8 parts of other active monomers, 3 parts of a photoinitiator, 35 parts of a diluent, and 1.5 parts of a leveling wetting agent.

[0037] The amino-terminated hyperbranched polyimide is prepared according to the method of Example 3 of the Chinese invention patent with the authorized announcement number CN102267940B; the other reactive monomers are composed of 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, bis(1-vinylimidazol-2-yl)ketone, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium] propane-1-sulfonate inner salt, dicyclopentene methacrylate, N-vinyl oxazolidinone, and cyclopentene allethrin, which are mixed in a mass ratio of 2:3:1:1.2:1:1.2; the photoinitiator is benzoin dimethyl ether; the diluent is composed of butyl methacrylate, methyl methacrylate, and hydroxypropyl methacrylate, which are mixed in a mass ratio of 1:2:1.2; the leveling and wetting agent is BYK-307.

[0038] A preparation method of the ultraviolet curable adhesive includes the following steps: after mixing each component evenly by weight, evacuating and defoaming for 1.5 h, then standing for defoaming and storing to obtain the ultraviolet curable adhesive.

[0039] An application of the ultraviolet curable adhesive includes the following steps: coating the ultraviolet curable adhesive on the surface of the material to be bonded, first curing by ultraviolet light irradiation for 50 seconds, and then drying at 80 °C for 2 hours; the wavelength of the ultraviolet light is 260 nm.

[0040] Comparative Example 1 An ultraviolet curable adhesive is basically the same as that in Example 1, except that 1,4-diamino-2,3-dicyanoanthraquinone and other reactive monomers are not added.

[0041] Comparative Example 2 An ultraviolet curable adhesive is basically the same as that in Example 1, except that an equal amount of Atlac 430 epoxy bisphenol A vinyl resin is used to replace the amino-terminated hyperbranched polyimide.

[0042] To further illustrate the beneficial technical effects of the ultraviolet curable adhesives involved in each embodiment of the present invention, relevant performance tests are carried out on the ultraviolet curable adhesives involved in Examples 1-5 and Comparative Examples 1-2. The test results are shown in Table 1, and the test methods are as follows: (1) Tensile shear strength: Coating the adhesive of each example on the adherend test piece to form a uniform film layer with a thickness of 0.2 mm, and measuring the tensile shear strength at room temperature of 20 °C after curing by using GB / T 7124-2008. The curing method adopts the method involved in the application steps of the adhesive of each example.

[0043] (2)Damp heat aging resistance performance: Place the cured adhesive samples of each example in an environment with a temperature of 85°C and a relative humidity of 85% for 500 hours. After cooling to room temperature, detect the tensile shear strength again according to the method in (1), and calculate the retention rate of the tensile shear strength. The larger the value, the better the damp heat aging resistance performance.

[0044] (3)Water resistance performance: Subject the cured adhesive samples of each example to water immersion treatment. The temperature of the water is 25°C, and the immersion time is 5 days. After taking them out and drying, detect the tensile shear strength again according to the method in (1), and count and calculate the retention rate of the tensile shear strength after water immersion. The larger the value, the better the water resistance performance.

[0045] Table 1 Project Tensile shear strength Wet heat aging resistance performance Water resistance Unit MPa % % Example 1 34.0 98.5 99.0 Example 2 34.5 99.1 99.2 Example 3 34.8 99.5 99.5 Example 4 35.0 99.7 99.6 Example 5 35.3 99.9 99.8 Comparative example 1 30.9 95.4 93.7 Comparative example 2 32.4 96.0 94.3 As can be seen from Table 1, the UV-curable adhesives disclosed in the embodiments of the present invention have higher tensile shear strength, better damp heat aging resistance performance and water resistance performance than the products of the comparative examples; the combined use of 1,4-diamino-2,3-dicyanoanthraquinone, other reactive monomers and amino-terminated hyperbranched polyimide is beneficial to improving the above performances.

[0046] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. What is described in the above embodiments and the specification is only the principle of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed. The scope of protection claimed by the present invention is defined by the appended claims and their equivalents.

Claims

1. A UV-curable adhesive, characterized in that: The invention comprises the following components in parts by weight: 30-45 parts of Atlac 430 epoxy bisphenol A vinyl resin, 10-15 parts of amino-terminated hyperbranched polyimide, 1-3 parts of 1,4-diamino-2,3-dicyanoanthraquinone, 2-4 parts of 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 5-8 parts of other active monomers, 1-3 parts of photoinitiator, 25-35 parts of diluent and 0.5-1.5 parts of leveling wetting agent.

2. The UV curing adhesive according to claim 1, characterized in that: The other active monomers are prepared by mixing 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, bis(1-vinylimidazole-2-)ketone, 3-[N,N-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]ammonium]propane-1-sulfonic acid inner salt, dicyclopentene methacrylate, N-vinyloxazolidinone, and cyclopentylthrin in a mass ratio of 2:(1-3):1:(0.8-1.2):1:(0.8-1.2).

3. The UV curing adhesive according to claim 1, characterized in that: The photoinitiator is at least one of benzoin dimethyl ether, benzoin ethyl ether and benzoin isopropyl ether.

4. The UV curing adhesive according to claim 1, characterized in that: The diluent is a mixture of butyl methacrylate, methyl methacrylate and hydroxypropyl methacrylate in a mass ratio of 1:(1-2):(0.8-1.2).

5. The UV-curable adhesive according to claim 1, characterized in that: The leveling wetting agent is one of TEGO-410, TEGO-432, TEGO-4000, BYK-306 and BYK-307 or a mixture of several thereof.

6. A method for preparing the UV-curable adhesive according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: uniformly mixing the components according to weight, vacuuming and degassing for 0.8-1.5 hours, and then standing to degas and storing to obtain an ultraviolet light curing adhesive.

7. An application of the UV-curable adhesive according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: applying the ultraviolet light curing adhesive to the surface of the material to be bonded, curing it by ultraviolet light irradiation for 10-50 seconds, and then drying it at 70-80°C for 1-2 hours.

8. The use of the UV curing adhesive according to claim 7, characterized in that: The wavelength of the ultraviolet light is 220-260nm.