阅读说明：本技术 汽车摄像头aa制程专用双重固化环氧胶及制备方法及应用 (Special dual-curing epoxy adhesive for automobile camera AA (acrylic acid) manufacturing process and preparation method and application thereof ) 是由 刘锋 霍应鹏 陈燕舞 彭琦 肖瑞雄 吴嘉培 洪丹 刘明宇 于 2021-06-30 设计创作，主要内容包括：本发明涉及一种汽车摄像头AA制程专用双重固化环氧胶及制备方法及应用,特点是包括环氧树脂、丙烯酸酯官能团的酸酐单体、酸酐单体、催化剂、增韧剂、硅烷偶联剂、紫外光引发剂、热引发剂、(甲基)丙烯酸酯类单体和填料,所述环氧树脂、丙烯酸酯官能团的酸酐单体、酸酐单体、催化剂、增韧剂、硅烷偶联剂、紫外光引发剂、热引发剂、(甲基)丙烯酸酯类单体和填料的质量比是1：0.2-0.4：0.1-0.5：0.001-0.005：0.2-0.5：0.001-0.006：0.001-0.002：0.0005-0.0015：1-2：0.1-3。其不仅可以作为环氧树脂的固化剂,还存在丙烯酸酯双键官能团,可进行紫外光引发固化,可以应用于汽车高清摄像头AA制程组装领域。(The invention relates to a dual-curing epoxy adhesive special for an automobile camera AA process, a preparation method and application thereof, and is characterized by comprising epoxy resin, an acrylate functional anhydride monomer, an anhydride monomer, a catalyst, a toughening agent, a silane coupling agent, an ultraviolet initiator, a thermal initiator, (meth) acrylate monomers and a filler, wherein the mass ratio of the epoxy resin to the acrylate functional anhydride monomer to the catalyst to the toughening agent to the silane coupling agent to the ultraviolet initiator to the thermal initiator to the (meth) acrylate monomers to the filler is 1: 0.2-0.4: 0.1-0.5: 0.001-0.005: 0.2-0.5: 0.001-0.006: 0.001-0.002: 0.0005-0.0015: 1-2: 0.1-3. The epoxy resin curing agent can be used as a curing agent of epoxy resin, has acrylate double bond functional groups, can be cured by ultraviolet initiation, and can be applied to the field of AA (acrylic acid) process assembly of automobile high-definition cameras.)

1. The special dual-curing epoxy adhesive for the AA processing procedure of the automobile camera is characterized by comprising epoxy resin, an acrylic ester functional anhydride monomer, an anhydride monomer, a catalyst, a toughening agent, a silane coupling agent, an ultraviolet initiator, a thermal initiator, a (methyl) acrylate monomer and a filler, wherein the mass ratio of the epoxy resin to the acrylic ester functional anhydride monomer to the catalyst to the toughening agent to the silane coupling agent to the ultraviolet initiator to the thermal initiator to the (methyl) acrylate monomer to the filler is 1: 0.2-0.4: 0.1-0.5: 0.001-0.005: 0.2-0.5: 0.001-0.006: 0.001-0.002: 0.0005-0.0015: 1-2: 0.1-3.

2. The special dual-curing epoxy adhesive for the AA processing procedure of the automobile camera head as claimed in claim 1, wherein the acid anhydride monomer of the acrylate functional group comprises 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride, 2-hydroxyethyl methacrylate, a solvent A and a basic catalyst, and the mass ratio of the 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride, the 2-hydroxyethyl methacrylate, the solvent A and the basic catalyst is 1: 0.6-2: 5-50: 0.5-4.

3. The special dual-curing epoxy adhesive for the AA processing procedure of the automobile camera head as claimed in claim 2, wherein the preparation method of the acrylate functional anhydride monomer comprises the following steps: adding 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride and 2-hydroxyethyl methacrylate into a solvent A, adding a basic catalyst, raising the temperature to 60-80 ℃, reacting for 30-120min, washing, and purifying to obtain an anhydride monomer containing acrylate functional groups, wherein the synthetic route is shown in the following figure:

。

4. the dual-curing epoxy adhesive special for the AA processing procedure of the automobile camera head as claimed in claim 2, wherein the solvent A is one or a mixture of toluene, p-xylene, acetonitrile, (methyl) isobutyl ketone, di (methyl) formamide or cyclohexanone; the alkaline catalyst is one or a mixture of more of sodium hydroxide, potassium hydroxide, ammonia water, calcium hydroxide or strontium hydroxide.

5. The dual-curing epoxy adhesive special for the AA process of the automobile camera head as claimed in claim 1, wherein the epoxy resin is one or a mixture of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, alicyclic epoxy resin, biphenyl epoxy resin, naphthalene ring structure epoxy resin, hydrogenated epoxy resin or organosilicon epoxy resin, the molecular weight is 100-5000, the halogen content is below 200ppm, and the metal ion content is below 1 ppm.

6. The dual-curing epoxy adhesive special for the AA manufacturing process of the automobile camera head as claimed in claim 1, wherein the acid anhydride monomer is one or a mixture of more of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, (methyl) tetrahydrophthalic anhydride, (methyl) hexahydrophthalic anhydride, nadic anhydride, (methyl) nadic anhydride or trimellitic anhydride.

7. The dual curing epoxy adhesive of claim 1, wherein the catalyst is 2- (methyl) imidazole, 2-ethyl-4 (methyl) imidazole-carboxyl, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2- (methyl) imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2- (methyl) imidazole-isocyanurate, 2-phenyl-4-benzyl-5-hydroxy (methyl) imidazole, 1- β -aminoethyl-2-ethylimidazole, 2-phenyl-4-benzyl-5-hydroxy (methyl) imidazole, 2-cyano-methyl-isocyanurate, 2-cyano-amino-2-ethylimidazole, 2-hydroxy (methyl) imidazole, 2-cyano-amino-2-methyl-imidazole, or mixtures thereof, 1-beta-aminoethyl-2- (methyl) imidazole, 1-cyanoethyl-2-phenyl-4, 5-bis (cyanoethyl (methyl)) imidazole, 2-phenyl-4- (methyl) -5-hydroxy (methyl) imidazole, 2-phenylimidazole-isocyanurate or 2, 4-diamino-6 [2 '-undecylimidazole- (1') ] ethyl-S-triazine.

8. The dual-curing epoxy adhesive special for the AA processing procedure of the automobile camera head as claimed in claim 1, wherein the toughening agent is a butadiene elastomer system, an organosilicon modified system or a rubber system.

9. The special dual-curing epoxy adhesive for the AA processing procedure of the automobile camera head of claim 1, wherein the silane coupling agent is bis- (gamma-triethoxysilylpropyl) tetrasulfide, gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma- (meth) acryloxypropyltrimethoxysilane, gamma-mercaptopropyltri (meth) silane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, isopropyl triisostearate, a compound of isopropyl triisostearate, isopropyldioleate acyloxy (dioctylphosphate) titanate, isopropyltri (dioctylphosphate) titanate, bis (dioctyloxypyrophosphate) ethylene titanate, ethylene titanate, One or a mixture of a plurality of bis (diethyl citrate) dipropoxy zirconium chelate compounds or organic zirconate coupling agents.

10. The dual-curing epoxy adhesive special for the AA process of the automobile camera head of claim 1, wherein the ultraviolet initiator is one or a mixture of benzophenone, acetophenone, diethoxyacetophenone, benzoin isopropyl ether, N- (methyl) diethanolamine benzophenone, 2-hydroxy- (methyl) -1-phenylpropan-1-one, 2-benzyl-2- (di (methyl) amino) -1- [ di (methyl) amino ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone or diphenyl (2, 4, 6-tri (methyl) benzoyl) phosphine oxide.

11. The dual-curing epoxy adhesive special for the AA process of the automobile camera head of claim 1, wherein the thermal initiator is one or a mixture of more of tert-butyl peroxypivalate, tert-butyl peroxy2-ethylhexanoate, tert-butyl hydroperoxide, di-tert-butyl peroxide, di-tert-amyl peroxide, tert-butyl peroxymaleate, tert-butyl peroxybenzoate, tert-butyl peroxyoctodecanoate, bis (3-methoxybutyl) peroxydicarbonate, bis (ethoxyhexyl) peroxydicarbonate, 1,3, 3-tetra (methyl) butyl peroxyneodecanoate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, or diisopropyl peroxydicarbonate.

12. The dual-curing epoxy adhesive special for the AA process of the automobile camera head of claim 1, wherein the (meth) acrylate monomers are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, N-propyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, isoamyl (meth) acrylate, N-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-octyl (meth) acrylate, adamantyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N-ethyl (meth) acrylamide, N, -N-di (meth) acrylamide, N-isopropyl (meth) acrylamide, N-di (meth) acrylamide, N-isopropyl (meth) acrylate, N-butyl (meth) acrylate, N-di (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylate, N-ethyl (meth) acrylate, N-butyl (meth) acrylate, N-ethyl (meth) acrylate, N-di (meth) acrylate, N-N, 2- (2-ethoxyethoxy) ethyl acrylate, tetrahydrofurfuryl (meth) acrylate, lauric acid acrylate, isooctyl acrylate, 2-phenoxyethyl acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, morpholine (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetrahydrofuran methyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethylene glycol dicyclopentenyl ether methyl (meth) acrylate, or 2-hydroxypropyl (meth) acrylate.

13. The special dual-curing epoxy glue for the AA processing procedure of the automobile camera according to claim 1, wherein the filler is one or a mixture of amorphous silicon dioxide, spherical silicon dioxide, glass powder, aluminum nitride, magnesium oxide, aluminum oxide, boron nitride, calcium carbonate, talcum powder, calcium silicate, titanium dioxide, zeolite or talcum powder, and the particle size of the filler is 0.2-200 mu m.

14. The preparation method of the dual-curing epoxy adhesive special for the AA processing procedure of the automobile camera as claimed in claim 1, wherein the epoxy resin, the anhydride monomer with acrylate functional group, the anhydride monomer, the catalyst, the toughening agent, the silane coupling agent, the ultraviolet initiator, the thermal initiator, the (meth) acrylate monomer and the filler are put into a reaction kettle according to the mass ratio, the temperature of the reaction kettle is controlled within 20-40 ℃, the vacuum pumping is carried out while stirring, and the stirring speed is 200-1000rpm, so that the dual-curing epoxy adhesive special for the AA processing procedure of the automobile camera can be obtained.

15. The application of the dual-curing epoxy adhesive for the AA manufacturing process of the automobile camera as claimed in claim 1, which is characterized in that the dual-curing epoxy adhesive for the AA manufacturing process of the automobile camera is filled in the bonded automobile high-definition camera, and then the dual-curing epoxy adhesive is irradiated by ultraviolet light, wherein the wavelength of the ultraviolet light is 200-500nm, and the energy is 500-6000 mJ/cm²And (3) irradiating for 10-30s, pre-curing the dual-curing epoxy adhesive, and placing the fixed device in an oven, wherein the thermosetting temperature is set at 60-150 ℃, and the curing time is 30-120 min.

Technical Field

The invention belongs to the field of electronic adhesives, and particularly relates to a special dual-curing epoxy adhesive for an automobile camera AA (acrylic acid) process, and a preparation method and application thereof.

Background

The development of intelligent automobiles requires more and more cameras, wherein the cameras need to be structurally bonded with glue. Most currently used glues are mainly heat-curable glues. However, after the thermosetting glue is dispensed, the glue is easy to flow and overflow in the process of being transported to an oven, so that a glue capable of being UV pre-fixed is needed. The vehicle-mounted high-reliability glue requires high glass transition temperature and has extremely excellent high-temperature and high-humidity resistance. At present, the traditional camera glue is difficult to synchronously have the functions.

In addition, adopt more and more cameras among the intelligent automobile, the pixel of camera is more and more high now, requires that the equipment precision is more and more high. Traditional camera substrate adopts thermosetting gluing agent to bond. After the adhesive is dispensed, the moving assembly and the moving assembly are easy to displace, so that eccentricity is caused, and high pixels cannot be displayed.

Currently, the industry has a UV pre-fix + thermal cure glue that initially enables pre-estimated top of the assembly with UV and then re-heat to enable curing bonding. However, currently, such adhesives are mainly prepared by physically mixing a UV-cured glue part and a heat-cured glue part, and although UV and heat curing can be performed, in most cases, the two components are cured separately. Where the UV is irradiated, the UV component is fully cured. However, there are some places where UV irradiation is not possible, and this place cannot be thermally cured. Resulting in partial component failure to fully cure and residual uncured component in the coating affecting the final bond reliability.

In addition, compared with the mobile phone, the vehicle-mounted camera has the advantages that the service life of the vehicle-mounted camera is far longer than that of the mobile phone, the environment is worse, and the vehicle-mounted camera is exposed to severe natural environments such as high temperature, low temperature, wind, rain, salt mist, dirt and the like for a long time. Therefore, the UV + thermal dual-curing adhesive is required to have good heat resistance, good bonding strength and ultra-long service life. Currently, most UV + thermal dual-curing glue in the industry is mainly used for mobile phones, so that the service life of the glue needs to be further improved.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide the dual-curing epoxy adhesive special for the AA processing procedure of the automobile camera, and the preparation method and the application thereof.

In order to achieve the above primary object, the technical scheme of the dual-curing epoxy adhesive special for the AA process of the automobile camera is realized by the following steps, and the dual-curing epoxy adhesive is characterized by comprising epoxy resin, an acrylate functional anhydride monomer, an anhydride monomer, a catalyst, a toughening agent, a silane coupling agent, an ultraviolet initiator, a thermal initiator, a (meth) acrylate monomer and a filler, wherein the mass ratio of the epoxy resin, the acrylate functional anhydride monomer, the catalyst, the toughening agent, the silane coupling agent, the ultraviolet initiator, the thermal initiator, the (meth) acrylate monomer and the filler is 1: 0.2-0.4: 0.1-0.5: 0.001-0.005: 0.2-0.5: 0.001-0.006: 0.001-0.002: 0.0005-0.0015: 1-2: 0.1-3.

In order to achieve the second purpose, the technical scheme of the preparation method of the dual-curing epoxy adhesive special for the AA process of the automobile camera is realized, and the preparation method is characterized in that epoxy resin, an acrylic ester functional anhydride monomer, an anhydride monomer, a catalyst, a toughening agent, a silane coupling agent, an ultraviolet initiator, a thermal initiator, a (methyl) acrylate monomer and a filler are put into a reaction kettle according to the mass ratio, the temperature of the reaction kettle is controlled within 20-40 ℃, the reaction kettle is stirred and vacuumized at the stirring speed of 200 plus 1000rpm, and the dual-curing epoxy adhesive can be obtained.

In the technical scheme, the anhydride monomer of the acrylate functional group comprises 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride, 2-hydroxyethyl methacrylate, a solvent A and an alkaline catalyst, wherein the mass ratio of the 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride, the 2-hydroxyethyl methacrylate, the solvent A and the alkaline catalyst is 1: 0.6-2: 5-50: 0.5-4.

In the technical scheme, the preparation method of the acrylate functional anhydride monomer comprises the following steps: adding 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride and 2-hydroxyethyl methacrylate into a solvent A, adding a basic catalyst, raising the temperature to 60-80 ℃, reacting for 30-120min, washing, and purifying to obtain an anhydride monomer containing acrylate functional groups, wherein the synthetic route is shown in the following figure:

in the technical scheme, the solvent A is one or a mixture of more of toluene, p-xylene, acetonitrile, (methyl) isobutyl ketone, di (methyl) formamide or cyclohexanone; the alkaline catalyst is one or a mixture of more of sodium hydroxide, potassium hydroxide, ammonia water, calcium hydroxide or strontium hydroxide.

In the technical scheme, the epoxy resin is one or a mixture of more of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, alicyclic epoxy resin, biphenyl epoxy resin, naphthalene ring structure epoxy resin, hydrogenated epoxy resin or organic silicon epoxy resin, the molecular weight of the epoxy resin is between 100 and 5000, the halogen content is below 200ppm, and the metal ion content is below 1 ppm.

The anhydride monomer is one or a mixture of more of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, (methyl) tetrahydrophthalic anhydride, (methyl) hexahydrophthalic anhydride, nadic anhydride, (methyl) nadic anhydride or trimellitic anhydride.

In the present technical scheme, the catalyst is 2- (methyl) imidazole, 2-ethyl-4 (methyl) imidazole-carboxyl, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2- (methyl) imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2- (methyl) imidazole-isocyanurate, 2-phenyl-4-benzyl-5-hydroxy (methyl) imidazole, 1-beta-aminoethyl-2-ethylimidazole, 1-beta-aminoethyl-2- (methyl) imidazole, 2-methyl-imidazole, or a mixture thereof, 1-cyanoethyl-2-phenyl-4, 5-di (cyanoethyl (methyl)) imidazole, 2-phenyl-4- (methyl) -5-hydroxy (methyl) imidazole, 2-phenylimidazole-isocyanurate or 2, 4-diamino-6 [2 '-undecylimidazole- (1') ] ethyl-S-triazine.

In the technical scheme, the dual-curing epoxy adhesive special for the AA process of the automobile camera is characterized in that the toughening agent is a butadiene elastomer system, such as commercialized MX137, MX154 or MX533 series (KANEKA company of Japan); silicone modification systems such as commercial KMP-605 (shines); rubber systems, such as ATBN or CTBN (of the Japan department of Japan).

In the technical scheme, the silane coupling agent is bis- (gamma-triethoxysilylpropyl) tetrasulfide, gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma- (methyl) acryloxypropyltrimethoxysilane, gamma-mercaptopropyltri (methyl) silane and vinyl triethoxysilane, one or a mixture of more of vinyl tri (2-methoxyethoxy) silane, isopropyl triisostearate, a compound of isopropyl triisostearate, isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate, isopropyl tri (dioctyl pyrophosphate acyloxy) titanate, bis (dioctyl pyrophosphate ester) ethylene titanate, bis (diethyl citrate) dipropoxy zirconium chelate or organic zirconate coupling agent.

In the technical scheme, the ultraviolet initiator is one or a mixture of more of benzophenone, acetophenone, diethoxyacetophenone, benzoin isopropyl ether, N- (methyl) diethanolamine benzophenone, 2-hydroxy- (methyl) -1-phenylpropan-1-one, 2-benzyl-2- (di (methyl) amino) -1- [ di (methyl) amino ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone or diphenyl (2, 4, 6-tri (methyl) benzoyl) phosphine oxide.

In the technical scheme, the thermal initiator is one or a mixture of more of tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl hydroperoxide, di-tert-butyl peroxide, di-tert-amyl peroxide, tert-butyl peroxymaleate, tert-butyl peroxybenzoate, tert-butyl peroxyoctodecanoate, bis (3-methoxybutyl) peroxydicarbonate, bis (ethoxyhexyl) peroxydicarbonate, 1,3, 3-tetra (methyl) butyl peroxyneodecanoate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, or diisopropyl peroxydicarbonate.

In the present embodiment, the (meth) acrylate monomer is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, N-propyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, isoamyl (meth) acrylate, N-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-octyl (meth) acrylate, adamantyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N-ethyl (meth) acrylamide, N, -N-di (meth) acrylamide, N-isopropyl (meth) acrylamide, 2- (2-ethoxyethoxy) ethyl acrylate, N-isopropyl (meth) acrylamide, N-di (meth) acrylamide, N-isopropyl (meth) acrylamide, N-ethoxyethoxy) ethyl acrylate, N-butyl (meth) acrylate, N-di (meth) acrylate, N-2- (2-ethoxyethoxy) ethyl acrylate, N-butyl (meth) acrylate, N-di (meth) acrylate, N-2- (2-di (meth) acrylate, N-butyl (meth) acrylate, N-2- (2-ethyl acrylate, N-2-ethyl (2-ethyl acrylate, N-2-ethyl acrylate, N-2-ethyl (meth) acrylate, N-2-ethyl acrylate, N-2-ethyl acrylate, N-2-N-ethyl acrylate, N-2-N-ethyl acrylate, N-2-N-2-N-ethyl acrylate, N-ethyl acrylate, N-2-N-2-ethyl acrylate, N-ethyl acrylate, N-2-N-2-N-, Tetrahydrofurfuryl (meth) acrylate, lauric acid acrylate, isooctyl acrylate, 2-phenoxyethyl acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, morpholine (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetrahydrofuran methyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethylene glycol dicyclopentenyl ether methyl (meth) acrylate, or 2-hydroxypropyl (meth) acrylate.

In the technical scheme, the filler is one or a mixture of more of amorphous silicon dioxide, spherical silicon dioxide, glass powder, aluminum nitride, magnesium oxide, aluminum oxide, boron nitride, calcium carbonate, talcum powder, calcium silicate, titanium dioxide, zeolite or talcum powder, and the particle size of the filler is 0.2-200 mu m.

In order to achieve the third object, the technical scheme of the application of the dual-curing epoxy adhesive special for the AA processing procedure of the automobile camera is realized by filling the dual-curing epoxy adhesive special for the AA processing procedure of the automobile camera in the bonded automobile high-definition camera, and then irradiating the dual-curing epoxy adhesive by using ultraviolet light, wherein the wavelength of the ultraviolet light is 200-500nm, and the energy is 500-6000 mJ/cm²And (3) irradiating for 10-30s, pre-curing the dual-curing epoxy adhesive, and placing the fixed device in an oven, wherein the thermosetting temperature is set at 60-150 ℃, and the curing time is 30-120 min.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) the invention synthesizes a brand new anhydride monomer, two acrylate functional groups with double bonds are introduced on the monomer, then the monomer is added into the formula of the epoxy resin adhesive, the anhydride functional groups contained in the anhydride monomer with the new structure can react with the epoxy resin for crosslinking reaction under the heating condition, simultaneously, the newly introduced double bond functional groups can participate in UV reaction, and simultaneously, the double bonds can also participate in thermosetting reaction.

(2) The anhydride monomer is anhydride with perylene tetracarboxylic dianhydride as a skeleton, and the structure is a monomer with a plane rigid structure containing four benzene rings, so that the prepared epoxy resin adhesive has high glass transition temperature and good heat resistance, the problem that the epoxy resin adhesive cured by the anhydride curing agent is not water-resistant can be solved, and the long-term reliability of the AA adhesive is improved.

(3) The cured material of the invention can meet the strict reliability tests of high temperature, high humidity, cold and hot shock, boiling and long-term vibration.

Detailed Description

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

Example one

Step one preparation of acrylate-functional anhydride monomers

Adding 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride (CAS: 118129-60-5) and 2-hydroxyethyl methacrylate (CAS: 868-77-9) into a solvent A, adding a basic catalyst, raising the temperature to 60 ℃, reacting for 30min, washing, and purifying to obtain an anhydride monomer containing an acrylate functional group, wherein the synthetic route of the anhydride monomer is shown in the following figure:

wherein the mass ratio of the 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride (CAS: 118129-60-5), the 2-hydroxyethyl methacrylate (CAS: 868-77-9), the solvent A and the alkaline catalyst is as follows: 1: 0.6: 5: 0.5, wherein the solvent A is toluene; the alkaline catalyst is sodium hydroxide.

Step two, preparation of special dual-curing epoxy adhesive for AA (acrylic acid) process of automobile camera

Epoxy resin, an acrylic ester functional anhydride monomer, an anhydride monomer, a catalyst, a toughening agent, a silane coupling agent, an ultraviolet initiator, a thermal initiator, a (meth) acrylate monomer and a filler are added into a stirrer, the temperature of a reaction kettle is controlled within 20 ℃, the stirring is carried out while vacuumizing, and the stirring speed is 200rpm, so that the dual-curing epoxy adhesive special for the automobile camera AA preparation process can be obtained.

Wherein the mass ratio of the epoxy resin, the acrylate functional anhydride monomer, the catalyst, the toughening agent, the silane coupling agent, the ultraviolet initiator, the thermal initiator, the (methyl) acrylate monomer and the filler is 1: 0.2: 0.1: 0.001: 0.2: 0.001: 0.001: 0.0005: 1: 0.2.

the epoxy resin is bisphenol A epoxy resin, the molecular weight of the epoxy resin is 1000, the halogen content is below 200ppm, and the metal ion content is below 1 ppm;

the anhydride monomer is phthalic anhydride;

the catalyst is 2- (methyl) imidazole;

the toughening agent is MX137 (KANEKA, Japan);

the silane coupling agent is bis- (gamma-triethoxysilylpropyl) tetrasulfide;

the ultraviolet initiator is benzophenone;

the thermal initiator is tert-butyl peroxypivalate;

the (methyl) acrylate monomer is methyl (methyl) acrylate;

the filler is amorphous silicon dioxide, and the particle size of the filler is 0.5 mu m.

Application of dual-curing epoxy glue filling special for automobile camera AA (acrylic acid) manufacturing process

Filling the dual-curing epoxy adhesive special for the AA processing procedure of the automobile camera prepared in the step two in the LCP material and PC material pair for bonding the automobile high-definition camera, and then irradiating the dual-curing epoxy adhesive by using ultraviolet light, wherein the wavelength of the ultraviolet light is 365nm, and the energy is 1500 mJ/cm²And (3) irradiating for 15s, pre-curing the dual-curing epoxy adhesive, and placing the fixed device in an oven at 100 ℃ for thermal curing for 120 min.

Example two

Step one preparation of acrylate-functional anhydride monomers

Adding 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride (CAS: 118129-60-5) and 2-hydroxyethyl methacrylate (CAS: 868-77-9) into a solvent A, adding a basic catalyst, raising the temperature to 80 ℃, reacting for 120min, washing, and purifying to obtain an anhydride monomer containing acrylate functional groups; the synthetic route is shown as the following figure:

wherein the mass ratio of the 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride (CAS: 118129-60-5), the 2-hydroxyethyl methacrylate (CAS: 868-77-9), the solvent A and the alkaline catalyst is as follows: 1: 2: 50: 4, the solvent A is p-xylene; the alkaline catalyst is potassium hydroxide.

Step two, preparation of special dual-curing epoxy adhesive for AA (acrylic acid) process of automobile camera

Epoxy resin, an acrylic ester functional anhydride monomer, an anhydride monomer, a catalyst, a toughening agent, a silane coupling agent, an ultraviolet initiator, a thermal initiator, a (meth) acrylate monomer and a filler are added into a stirrer while controlling the temperature of a reaction kettle within 40 ℃, and the stirring is carried out while vacuumizing at the stirring speed of 1000rpm, so that the dual-curing epoxy adhesive special for the AA processing procedure of the automobile camera can be obtained.

Wherein the mass ratio of the epoxy resin, the acrylate functional anhydride monomer, the catalyst, the toughening agent, the silane coupling agent, the ultraviolet initiator, the thermal initiator, the (methyl) acrylate monomer and the filler is 1: 0.4: 0.5: 0.005: 0.5: 0.006: 0.002: 0.0015: 1: 0.4.

the epoxy resin is bisphenol F epoxy resin, the molecular weight of the epoxy resin is 2000, the halogen content is below 200ppm, and the metal ion content is below 1 ppm;

the acid anhydride monomer is nadic acid anhydride;

the catalyst is 2-ethyl-4 (methyl) imidazole-carboxyl;

the toughening agent is KMP-605 (Xinyue);

the silane coupling agent is gamma-mercaptopropyl tri (methyl) silane;

the ultraviolet initiator is N- (methyl) diethanolamine benzophenone;

the thermal initiator is tert-butyl peroxy-2-ethylhexanoate;

the acrylate monomer is tetrahydrofurfuryl (meth) acrylate;

the filler is spherical silicon dioxide, and the particle size of the filler is 5 mu m.

Application of dual-curing epoxy glue filling special for automobile camera AA (acrylic acid) manufacturing process

Filling the prepared dual-curing epoxy adhesive special for the AA processing procedure of the automobile camera in the LCP materialBonding the automobile high-definition camera with a PC material, and then irradiating the dual-curing epoxy adhesive by using ultraviolet light, wherein the wavelength of the ultraviolet light is 405nm, and the energy is 2000 mJ/cm²And irradiating for 20s, pre-curing the dual-curing epoxy adhesive, and placing the fixed device in an oven at 120 ℃ for 100 min.

EXAMPLE III

Step one preparation of acrylate-functional anhydride monomers

Adding 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride (CAS: 118129-60-5) and 2-hydroxyethyl methacrylate (CAS: 868-77-9) into a solvent A, adding a basic catalyst, raising the temperature to 70 ℃, reacting for 100min, washing, and purifying to obtain an anhydride monomer containing an acrylate functional group: the synthetic route is shown as the following figure:

wherein the mass ratio of the 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride (CAS: 118129-60-5), the 2-hydroxyethyl methacrylate (CAS: 868-77-9), the solvent A and the alkaline catalyst is as follows: 1: 1: 20: 2; the solvent A is acetonitrile; the alkaline catalyst is calcium hydroxide.

Step two, preparation of special dual-curing epoxy adhesive for AA (acrylic acid) process of automobile camera

Epoxy resin, an acrylic ester functional anhydride monomer, an anhydride monomer, a catalyst, a toughening agent, a silane coupling agent, an ultraviolet initiator, a thermal initiator, a (meth) acrylate monomer and a filler are added into a stirrer, the temperature of a reaction kettle is controlled within 30 ℃, the stirring is carried out while vacuumizing, and the stirring speed is 800rpm, so that the dual-curing epoxy adhesive special for the automobile camera AA preparation process can be obtained.

Wherein the mass ratio of the epoxy resin, the acrylate functional anhydride monomer, the catalyst, the toughening agent, the silane coupling agent, the ultraviolet initiator, the thermal initiator, the (methyl) acrylate monomer and the filler is 1: 0.3: 0.4: 0.004: 0.4: 0.005: 0.001: 0.001: 1.5: 0.6.

the epoxy resin is alicyclic epoxy resin, the molecular weight of the epoxy resin is 3000, the halogen content is below 200ppm, and the metal ion content is below 1 ppm;

the acid anhydride monomer is methyl nadic anhydride;

the catalyst is 1-benzyl-2- (methyl) imidazole;

the toughening agent is MX533 (KANEKA, Japan);

the silane coupling agent is bis (dioctyloxy pyrophosphate) ethylene titanate;

the ultraviolet initiator is 2-benzyl-2- (di (methyl) amino) -1- [ di (methyl) amino ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone;

the thermal initiator is 1,1,3, 3-tetra (methyl) butyl peroxyneodecanoate;

the acrylate monomer is trimethylolpropane tri (methyl) acrylate;

the filler is talcum powder, and the particle size of the filler is 10 mu m.

Application of dual-curing epoxy glue filling special for automobile camera AA (acrylic acid) manufacturing process

Filling the dual-curing epoxy adhesive special for the AA processing procedure of the automobile camera prepared in the step two in the LCP material and PC material pair for bonding the automobile high-definition camera, and then irradiating the dual-curing epoxy adhesive by using ultraviolet light, wherein the wavelength of the ultraviolet light is 365nm, and the energy is 1000 mJ/cm²And irradiating for 25s, pre-curing the dual-curing epoxy adhesive, and placing the fixed device in an oven at 130 ℃ for 60 min.

Example four

Step one preparation of acrylate-functional anhydride monomers

Adding 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride (CAS: 118129-60-5) and 2-hydroxyethyl methacrylate (CAS: 868-77-9) into a solvent A, adding a basic catalyst, raising the temperature to 65 ℃, reacting for 110min, washing, and purifying to obtain an anhydride monomer containing acrylate functional groups; the synthetic route is shown as the following figure:

wherein the mass ratio of the 1, 7-dibromo-3, 4,9, 10-perylene tetracarboxylic dianhydride (CAS: 118129-60-5), the 2-hydroxyethyl methacrylate (CAS: 868-77-9), the solvent A and the alkaline catalyst is as follows: 1: 1: 30: 3, the solvent A is methyl isobutyl ketone; the alkaline catalyst is strontium hydroxide.

Step two, preparation of special dual-curing epoxy adhesive for AA (acrylic acid) process of automobile camera

Epoxy resin, an acrylic ester functional anhydride monomer, an anhydride monomer, a catalyst, a toughening agent, a silane coupling agent, an ultraviolet initiator, a thermal initiator, a (meth) acrylate monomer and a filler are added into a stirrer while controlling the temperature of a reaction kettle within 30 ℃, and the stirring is carried out while vacuumizing at the stirring speed of 600rpm, so that the dual-curing epoxy adhesive special for the AA processing procedure of the automobile camera can be obtained.

Wherein the mass ratio of the epoxy resin, the acrylate functional anhydride monomer, the catalyst, the toughening agent, the silane coupling agent, the ultraviolet initiator, the thermal initiator, the (methyl) acrylate monomer and the filler is 1: 0.3: 0.25: 0.003: 0.45: 0.004: 0.0013: 0.0012: 1.3: 0.8.

the epoxy resin is hydrogenated epoxy resin, the molecular weight of the epoxy resin is 2500, the halogen content is below 200ppm, and the metal ion content is below 1 ppm;

the anhydride monomer is trimellitic anhydride;

the catalyst is 2-phenylimidazole-isocyanurate;

the toughening agent is ATBN (product of Japan ministry of Japan);

the silane coupling agent is gamma- (methyl) acryloyloxy propyl trimethoxy silane;

the ultraviolet initiator is 2-hydroxy- (methyl) -1-phenylpropan-1-one;

the thermal initiator is 1,1,3, 3-tetra (methyl) butyl peroxyneodecanoate;

the acrylate monomer is trimethylolpropane tri (methyl) acrylate;

the filler is calcium silicate, and the particle size of the filler is 20 mu m.

Application of dual-curing epoxy glue filling special for automobile camera AA (acrylic acid) manufacturing process

Filling the dual-curing epoxy adhesive special for the AA processing procedure of the automobile camera prepared in the step two in the LCP material and PC material pair for bonding the automobile high-definition camera, and then irradiating the dual-curing epoxy adhesive by using ultraviolet light, wherein the wavelength of the ultraviolet light is 405nm, and the energy is 1200 mJ/cm²And irradiating for 25s, pre-curing the dual-curing epoxy adhesive, and placing the fixed device in an oven at 150 ℃ for 30 min.

The test specimens prepared in examples one to four were subjected to the performance test, and the test results are shown in table 1.

Table 1 performance parameters of dual cure epoxy adhesives prepared in examples one through four

Measurement of viscosity: the viscosity values were measured using a Brookfield rotational viscometer at 25 ℃ with spindle # 52 and at 10 rpm.

Testing of adhesive strength: and dispensing 100mg of glue between the LCP material and the PC material to the bonded automobile high-definition camera, and testing thrust by using a push-pull force testing machine after dual curing to obtain bonding strength.

And (3) testing the glass transition temperature Tg by adopting a DSC method, putting 3mg of a sample into equipment, controlling the temperature to be 20-250 ℃ and the temperature rise speed to be 10 ℃/min, and analyzing the obtained curve to obtain Tg data.

The CTE (coefficient of expansion) test method refers to the standard JISK7197 method. The test instrument references two data of CTE were obtained in the resulting curves tested using a thermomechanical analyzer, one above the Tg point and one below the Tg point.

The modulus testing method adopts a DMA dynamic thermomechanical analyzer and a three-point bending method, the temperature rise speed is-50-200 ℃, and modulus data at 25 ℃ can be obtained by analyzing and testing a curve.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.