Vehicle-gauge-grade high-adhesion high-reliability ultraviolet curing adhesive composition

Abstract

The invention discloses a vehicle-gauge-grade ultraviolet curing adhesive composition with high adhesion and high reliability, and relates to the technical field of adhesives. The automobile-gauge-grade high-adhesion and high-reliability ultraviolet curing adhesive composition provided by the invention is prepared from the following components in parts by weight: 40 to 60 parts of acrylate oligomer, 20 to 50 parts of acrylate monomer, 1 to 5 parts of photoinitiator, 0.1 to 2 parts of adhesion aid, 0.1 to 4 parts of latent acid initiator and 1 to 5 parts of thixotropic agent, the above materials are mixed according to a certain process to obtain the adhesive. According to the present invention, the combination of the standard-grade high-adhesion high-reliability acrylic acid adhesive is provided, and the adhesive product has characteristics of high adhesion strength, high body strength, and low aging performance.

Description

Technical Field

[0001] The invention belongs to the technical field of adhesives, and in particular relates to an automotive-grade high-adhesion and high-reliability ultraviolet light-curing adhesive composition. Background Art

[0002] In modern industry and high-tech fields, automotive electronics plays a vital role. With the development of electronic products and changes in demand, various display screens and automotive modules have higher and higher requirements for material flexibility, bonding and aging performance. At the same time, the requirements for assembly are also getting higher and higher. UV technology can provide fast positioning and curing, only requiring 365nm or 405nm ultraviolet bands, and complete curing in 3-10 seconds, greatly improving production efficiency.

[0003] With the advancement of science and technology and the rapid development of the automobile industry, the materials used inside automobiles are also facing higher performance requirements, and the performance requirements for high adhesion and high reliability are also getting higher and higher. In particular, as components become more and more sophisticated, the flexibility of adhesives requires high adhesion and high reliability performance. Therefore, it is of great application value to study acrylic adhesives with high adhesion and high reliability to improve the performance and quality of products. Traditional adhesives for bonding automotive components are mainly epoxy-based. Epoxy adhesives have high strength and good aging performance, but lack flexibility and have high curing temperatures. Acrylic adhesives can cure quickly and have good flexibility, but most acrylic adhesives have poor aging performance. This patent application promotes the improvement of the bonding strength between acrylic resin and the interface by introducing a latent acid initiator, and the bonding strength has good resistance to wet and hot aging, so that this product meets the requirements of high reliability of automotive electronics. Therefore, in response to the above problems, a high-adhesion and high-reliability UV-curable adhesive composition for automotive standards is provided. Summary of the invention

[0004] The present invention provides an automotive-grade high-adhesion and high-reliability UV-curable adhesive composition. The curable adhesive composition includes an acrylate oligomer, an acrylate monomer, a photoinitiator, a silane bonding aid, a latent acid initiator and a thixotropic agent. After being mixed according to a certain process, the changes in the bulk before and after aging and the changes in the adhesion between glass and plastic parts are tested. The product has high bonding strength, high bulk strength and low aging performance degradation. In summary, the problems in the background technology are solved.

[0005] To solve the above technical problems, the present invention is achieved through the following technical solutions:

[0006] The automotive-grade high-adhesion and high-reliability ultraviolet light-curing adhesive composition of the present invention comprises the following components in parts by weight:

[0007] 40-60 parts of acrylate oligomer, 20-50 parts of acrylate monomer, 1-5 parts of photoinitiator, 0.1-2 parts of silane bonding aid, 0.1-4 parts of latent acid initiator and 1-5 parts of thixotropic agent are mixed according to a certain process to obtain an adhesive.

[0008] Furthermore, the acrylic monomer is an acrylic resin with a rigid structure, and the acrylic ester monomer is selected from at least one of hydroxyethyl acrylate, dicyclopentenyl ethoxylated acrylate, hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, tetraethylene glycol diacrylate, glycidyl methacrylate, tetrahydrofuran acrylate, diethyl acrylamide, trimethylcyclohexyl acrylate and ethoxylated trimethylolpropane triacrylate.

[0009] Furthermore, the acrylate oligomer is selected from at least one of polyester (meth) acrylate, polycarbonate (meth) acrylate, polyether (meth) acrylate, polyester polyurethane (meth) acrylate, polycarbonate polyurethane (meth) acrylate and polyether polyurethane (meth) acrylate; the polyester polyurethane acrylate is Guangzhou Runao FSP8982, LuCure8674, LuCure8722, Sartomer SARTOMER CN8880, CN8881, CN8888; the polyether acrylate is Zhongshan Qianyou DR34, DR334, Bomar resin BR5541M, BR 345, BR3641AA, Changxing resin DR-U379, DR-U384.

[0010] Further, the photoinitiator is selected from at least one of 2-hydroxy-methylphenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, benzoin dimethyl ether BDK, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, isopropylthioxanthone (2, 4 isomer mixture), ethyl 4-(N,N-dimethylamino)benzoate, benzophenone, 4-chlorobenzophenone, methyl o-benzoylbenzoate, diphenyliodonium hexafluorophosphate, isooctyl para-N,N-dimethylaminobenzoate, 4-methylbenzophenone, methyl o-benzoylbenzoate and 4-phenylbenzophenone.

[0011] Furthermore, the silane bonding aid is selected from at least one of 3-methoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, 3-ethylenedioxypropyltrimethoxysilane and methoxyvinyltrimethoxysilane.

[0012] Furthermore, the latent acidic initiator is at least one of latent antimonates, latent phosphates and latent iodates, including ammonium hexafluorosilicate, iodonium salts, (4-hydroxyphenyl)(methyl)(benzyl)sulfonium hexafluoroantimonate initiators.

[0013] Furthermore, the thixotropic agent is fumed silica, including CABOT TS720, CABOT M5, Wacker HDK H18, Wacker HDK H2000, Evonik AEROSIL R974 and Evonik AEROSIL R8200.

[0014] A method for preparing an automotive-grade high-adhesion and high-reliability UV-curable adhesive is prepared using the above-mentioned automotive-grade high-adhesion and high-reliability UV-curable adhesive composition, comprising the following steps:

[0015] S1. Weigh 20-50 parts of acrylate monomer and 1-5 parts of photoinitiator, put them into a high-speed planetary stirrer and stir for 30 minutes to 1 hour to mix them evenly;

[0016] S2. Weigh 0.5-4 parts of latent acid initiator, put it into a high-speed planetary mixer, control the temperature below 30°C, and mix well;

[0017] S3, weigh 40-60 parts of acrylate oligomer and 1-5 parts of thixotropic agent in sequence, put them into a high-speed planetary stirrer, control the temperature below 30°C, stir for 1-2 hours under vacuum, and mix them evenly;

[0018] S4, take 0.1-2 parts of silane additive, put it into a high-speed planetary mixer, control the temperature below 30°C, mix it evenly for 30 minutes to 1 hour, and finally obtain the adhesive. Put the prepared adhesive into a container for storage.

[0019] The above-mentioned automotive-grade high-adhesion and high-reliability UV-curable adhesive composition is used in the rapid assembly and structural bonding of display screens, automotive modules or sensors.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The acrylic adhesive prepared by the present invention not only has strong bonding force, but also has improved strength after moisture and heat aging, instead of decreasing, and has moderate viscosity, which can meet the structural bonding requirements of different components and ensures the reliability of packaging modules and display modules.

[0022] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Specific embodiment 1:

[0025] (1) Weigh 12 parts of diethylacrylamide, 10 parts of isobornyl acrylate and 0.9 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, put them into a high-speed planetary stirrer and stir for 30 minutes to 1 hour to mix them evenly;

[0026] (2) Weigh 1.6 parts of hexafluoroantimonate and put it into a high-speed planetary stirrer, control the temperature below 30° C., and mix well;

[0027] (3) Weigh 25 parts of polyether acrylate oligomer and 1.5 parts of fumed silica in sequence, put them into a high-speed planetary stirrer, control the temperature below 30° C., stir for 1-2 hours under vacuum, and mix them evenly;

[0028] (4) Take 0.45 parts of 3-ethylenedioxypropyltrimethoxysilane and 0.45 parts of 3-propyleneoxypropyltrimethoxysilane, put them into a high-speed planetary stirrer, control the temperature below 30° C., and mix them evenly for 30 minutes to 1 hour to finally obtain the adhesive. The prepared adhesive is placed in a container for storage. Specific embodiment 2:

[0030] (1) Weigh 12 parts of diethylacrylamide, 10 parts of isobornyl acrylate and 0.9 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, put them into a high-speed planetary stirrer and stir for 30 minutes to 1 hour to mix them evenly;

[0031] (2) Weigh 0.5 parts of hexafluoroantimonate and put it into a high-speed planetary mixer, control the temperature below 30° C., and mix well;

[0032] (3) Weigh 25 parts of polyether acrylate oligomer and 1.5 parts of fumed silica, put them into a high-speed planetary stirrer, control the temperature below 30° C., stir for 1-2 hours under vacuum, and mix them evenly;

[0033] (4) Weigh 0.45 parts of 3-ethylenedioxypropyltrimethoxysilane and 0.45 parts of 3-propyleneoxypropyltrimethoxysilane, put them into a high-speed planetary stirrer, control the temperature below 30° C., and mix them evenly for 30 minutes to 1 hour to finally obtain the adhesive. The prepared adhesive is placed in a container for storage. Specific embodiment 3:

[0035] (1) Weigh 7 parts of diethyl acrylamide, 13 parts of trimethylcyclohexyl acrylate and 1.3 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, put them into a high-speed planetary stirrer and stir for 30 minutes to 1 hour to mix them evenly;

[0036] (2) Weigh 1.7 parts of hexafluoroantimonate, put it into a high-speed planetary mixer, control the temperature below 30° C., and mix it evenly;

[0037] (3) Weigh 26 parts of polyester acrylate oligomer and 1.7 parts of fumed silica, put them into a high-speed planetary mixer, control the temperature below 30° C., stir for 1-2 hours under vacuum, and mix them evenly;

[0038] (4) Weigh 0.3 parts of 3-ethylenedioxypropyltrimethoxysilane, put it into a high-speed planetary stirrer, control the temperature below 30° C., and mix it for 30 minutes to 1 hour to obtain the adhesive. The prepared adhesive is placed in a container for storage. Specific embodiment 4:

[0040] (1) Weigh 7 parts of diethyl acrylamide, 13 parts of trimethylcyclohexyl acrylate and 1.3 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, put them into a high-speed planetary stirrer and stir for 30 minutes to 1 hour to mix them evenly;

[0041] (2) Weigh 0.5 parts of hexafluoroantimonate and put it into a high-speed planetary mixer, control the temperature below 30° C., and mix well;

[0042] (3) Weigh 26 parts of polyester acrylate oligomer and 1.7 parts of fumed silica in sequence, put them into a high-speed planetary stirrer, control the temperature below 30° C., stir for 1-2 hours under vacuum, and mix them evenly;

[0043] (4) Weigh 0.3 parts of 3-ethylenedioxypropyltrimethoxysilane, put it into a high-speed planetary mixer, control the temperature below 30° C., mix it evenly for 30 minutes to 1 hour, and finally prepare the adhesive. Put the prepared adhesive into a container for storage;

[0044] Comparative Example 1:

[0045] (1) Weigh 12 parts of diethylacrylamide, 10 parts of isobornyl acrylate and 0.9 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, put them into a high-speed planetary stirrer and stir for 30 minutes to 1 hour to mix them evenly;

[0046] (2) Weigh 25 parts of polyether acrylate oligomer and 1.5 parts of fumed silica in sequence, put them into a high-speed planetary stirrer, and stir for 1-2 hours under vacuum to mix them evenly;

[0047] (3) Weighing 0.45 parts of 3-ethylenedioxypropyltrimethoxysilane and 0.45 parts of 3-propyleneoxypropyltrimethoxysilane, putting them into a high-speed planetary stirrer, and mixing them evenly for 30 minutes to 1 hour to finally prepare the adhesive, and putting the prepared adhesive into a container for storage;

[0048] Comparative Example 2:

[0049] (1) Weigh 12 parts of diethylacrylamide, 10 parts of isobornyl acrylate and 0.9 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, put them into a high-speed planetary stirrer and stir for 30 minutes to 1 hour to mix them evenly;

[0050] (2) Weigh 1.6 parts of hexafluoroantimonate and put it into a high-speed planetary stirrer, control the temperature below 30° C., and mix well;

[0051] (3) Weighing 25 parts of polyether acrylate oligomer and 1.5 parts of fumed silica in sequence, putting them into a high-speed planetary stirrer, controlling the temperature below 30° C., stirring for 1-2 hours under vacuum, and mixing evenly to finally obtain the adhesive, and putting the prepared adhesive into a container for storage;

[0052] Comparative Example 3:

[0053] (1) Weigh 7 parts of diethyl acrylamide, 13 parts of trimethylcyclohexyl acrylate and 1.3 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, put them into a high-speed planetary stirrer and stir for 30 minutes to 1 hour to mix them evenly;

[0054] (2) Weigh 26 parts of polyester acrylate oligomer and 1.7 parts of fumed silica in sequence, put them into a high-speed planetary mixer, and stir for 1-2 hours under vacuum to mix them evenly;

[0055] (3) Weigh 0.3 parts of 3-ethylenedioxypropyltrimethoxysilane, put it into a high-speed planetary stirrer, and mix it evenly for 30 minutes to 1 hour to finally obtain the adhesive. The prepared adhesive is placed in a container for storage.

[0056] Comparative Example 4:

[0057] (1) Weigh 7 parts of diethyl acrylamide, 13 parts of trimethylcyclohexyl acrylate and 1.3 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, put them into a high-speed planetary stirrer and stir for 30 minutes to 1 hour to mix them evenly;

[0058] (2) Weigh 1.7 parts of hexafluoroantimonate, put it into a high-speed planetary mixer, control the temperature below 30° C., and mix it evenly;

[0059] (3) Weighing 26 parts of polyester acrylate oligomer and 1.7 parts of fumed silica in sequence, putting them into a high-speed planetary stirrer, controlling the temperature below 30° C., stirring for 1-2 hours under vacuum, and mixing evenly to finally obtain the adhesive, and putting the prepared adhesive into a container for storage;

[0060] In order to further illustrate the beneficial technical effects of the adhesives involved in the embodiments of the present invention, relevant performance tests were conducted on the automotive-grade adhesives involved in the specific embodiments 1-4 and the comparative examples 1-4. The test results are shown in Tables 1 and 2. The test methods are as follows:

[0061] Adhesion test: adhesive layer thickness is 30-50 microns, adhesive material sheet is 5*5mm 2 ,The test materials are glass and Japan Otsuka Chemical PA NTB982G3, glass and polycarbonate PC, which are cured by LED UV lamp, 365nm curing such as IGE's XC210 (wavelength is 365nm). The light intensity is 500-1000mw / cm2, and the time is 3-4 seconds.

[0062] The experiment was divided into two groups: one group of samples was taken out after curing, and after standing for 1 day, the bonding strength was tested with a thrust machine Dage4000, and the values ​​were recorded. The other group of samples was placed in a double 85 test (85°C and 85% humidity), taken out after 1000 hours, and then the bonding strength was tested with a thrust machine Dage4000, and the values ​​were recorded.

[0063] Body strength test: used to characterize the strength of the adhesive composition to the sheet after it is fully cured. The thickness of the adhesive layer is usually 1.2-2 mm. Inject the glue into a mold that can control the thickness of the adhesive layer to make a 2mm thick adhesive film. The prepared adhesive film is cured with 365nm UV, and the light intensity is 500-1000mw / cm2 for 3-4 seconds. The cured adhesive film is cut into a dumb bell shape with a dumb bell cutter (the size of the cutter is 115mm*25mm), and the cut samples are divided into two groups, each with 3 samples. The test is divided into two groups: one group of samples is tested for the performance of the body at room temperature using a microcomputer-controlled electronic universal testing machine (Instron 3367, Instron Inc.), and the elongation at break and body strength are recorded. The test speed is 500mm / min. The other group of samples is placed in a double 85 test (85℃ and 85% humidity), taken out after 1000 hours, and tested for elongation at break and body strength using a microcomputer-controlled electronic universal testing machine.

[0064]

[0065] Table 1 Initial performance parameter table;

[0066]

[0067]

[0068] Table 2 Aging performance (85°C and 85% humidity) Performance parameters after 1000 hours

[0069] As can be seen from Table 1, comparing the effect of the coupling agent on the bonding strength of glass to plastic, the strengths of Example 1 and Comparative Example 2 using polyether acrylic resin are 10.3Mpa and 9.1Mpa respectively, which are close in strength; the strengths of Example 3 and Comparative Example 4 using polyester acrylic resin are 20.6Mpa and 19Mpa respectively, which are also close in strength, indicating that the change in bonding strength has no obvious correlation with the silane coupling agent. And comparing the effect of the amount of latent acid initiator used in this patent on the bonding strength of glass to plastic, the strengths of Example 3, Example 4 and Comparative Example 3 using polyester acrylic resin are 20.6Mpa, 18.5Mpa and 18.1Mpa respectively, and the strengths decrease in sequence, indicating that the amount of latent acid initiator used in this patent has a certain effect on the bonding strength of glass to plastic.

[0070] As can be seen from Table 2, by comparing the changes in the bonding strength of glass to plastic after aging at double 85 (85°C and 85% humidity) for 1000 hours, the strength of Example 1, Example 2 and Comparative Example 1 using polyether acrylic resin increased by 22%, 25% and decreased by 30%, respectively; the strength of Example 3, Example 4 and Comparative Example 3 using polyester acrylic resin increased by 12%, 0% and decreased by 65%, respectively; this indicates that after aging at 85°C and 85% humidity for 1000 hours using the latent acid initiator described in this patent, the bonding strength of glass to plastic not only does not decay, but can even be better than the initial strength; and it increases with the increase in dosage, and the high temperature and high humidity resistance performance has obvious advantages.

[0071] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An automotive grade high-adhesion and high-reliability UV-curable adhesive composition, characterized in that: In parts by weight, it includes the following components: 40-60 parts of acrylate oligomer, 20-50 parts of acrylate monomer, 1-5 parts of photoinitiator, 0.1-2 parts of silane adhesion promoter, 0.1-4 parts of latent acid initiator and 1-5 parts of thixotropic agent.

2. The automotive-grade high-adhesion and high-reliability UV-curable adhesive composition according to claim 1, characterized in that: The acrylate monomer is selected from at least one of hydroxyethyl acrylate, dicyclopentenyl ethoxylated acrylate, hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, glycidyl methacrylate tetraethylene glycol diacrylate, tetrahydrofuran acrylate, diethyl acrylamide, trimethylcyclohexyl acrylate and ethoxylated trimethylolpropane triacrylate.

3. The automotive-grade high-adhesion and high-reliability UV-curable adhesive composition according to claim 1, characterized in that: The acrylate oligomer is selected from at least one of polyester (meth) acrylate, polycarbonate (meth) acrylate, polyether (meth) acrylate, polyester polyurethane (meth) acrylate, polycarbonate polyurethane (meth) acrylate and polyether polyurethane (meth) acrylate.

4. The automotive-grade high-adhesion and high-reliability UV-curable adhesive composition according to claim 1, characterized in that: The photoinitiator is selected from at least one of free 2-hydroxy-methylphenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, benzoin dimethyl ether BDK, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, isopropylthioxanthone (2, 4 isomer mixture), ethyl 4-(N,N-dimethylamino)benzoate, benzophenone, 4-chlorobenzophenone, methyl o-benzoylbenzoate, diphenyliodonium hexafluorophosphate, isooctyl para-N,N-dimethylaminobenzoate, 4-methylbenzophenone, methyl o-benzoylbenzoate and 4-phenylbenzophenone.

5. The automotive-grade high-adhesion and high-reliability UV-curable adhesive composition according to claim 1, characterized in that: The silane bonding aid is selected from at least one of 3-methoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, 3-ethylenedioxypropyltrimethoxysilane and methoxyvinyltrimethoxysilane.

6. The automotive-grade high-adhesion and high-reliability UV-curable adhesive composition according to claim 1, characterized in that: The latent acid initiator is at least one of latent antimonate, latent phosphate and latent iodate.

7. The automotive-grade high-adhesion and high-reliability UV-curable adhesive composition according to claim 1, characterized in that: The thixotropic agent is fumed silica.

8. A method for preparing an automotive-grade high-adhesion and high-reliability UV-curable adhesive, which is prepared using an automotive-grade high-adhesion and high-reliability UV-curable adhesive composition as described in claims 1-7, characterized in that: The steps include: S1, adding corresponding weight portions of acrylate monomer, photoinitiator, and latent acid initiator into a mixing container in sequence; S2. Start the stirring equipment to fully mix the raw materials in the mixing container to ensure that the various raw materials are fully and evenly mixed together. During the stirring process, the temperature of the glue stirring container must be controlled not to be higher than 30° C. to finally form a uniform mixture; S3, gradually add corresponding weight portions of acrylate oligomer and thixotropic agent, stir for 1 to 2 hours under vacuum, mix evenly, and ensure that the temperature of the stirring container is not higher than 30° C. during the whole process; S4. Add silane adhesive additive, stir for 1 to 2 hours under vacuum, mix evenly, and ensure that the temperature of the stirring container is not higher than 30° C. during the whole process. The adhesive is finally obtained and the prepared adhesive is placed in a container for storage.

9. Application of an automotive-grade high-adhesion and high-reliability UV-curable adhesive composition as described in any one of claims 1 to 7 in rapid assembly and structural bonding of display screens, automotive modules or sensors.

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