CN113025247A - Low-water-absorption double-component thermosetting epoxy adhesive and preparation method and application thereof - Google Patents
Low-water-absorption double-component thermosetting epoxy adhesive and preparation method and application thereof Download PDFInfo
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- CN113025247A CN113025247A CN202110284057.9A CN202110284057A CN113025247A CN 113025247 A CN113025247 A CN 113025247A CN 202110284057 A CN202110284057 A CN 202110284057A CN 113025247 A CN113025247 A CN 113025247A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention provides a two-component thermosetting epoxy adhesive with low water absorption rate, a preparation method and application thereof, wherein the two-component thermosetting epoxy adhesive comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by mass: 20-50 parts of bisphenol epoxy resin, 5-15 parts of triglycidyl isocyanurate, 10-20 parts of halogen-free flame retardant resin, 5-10 parts of toughening resin, 30-50 parts of reactive diluent, 3-10 parts of liquid phosphate flame retardant and 0.5-2 parts of wetting agent; the component B comprises the following raw materials in parts by mass: 10-20 parts of alicyclic diamine, 3-10 parts of fluorine-containing aromatic diamine, 2-7 parts of phosphine oxide containing 2 aminophenyl groups, 2-4 parts of an accelerator and 10-20 parts of a reactive diluent. The two-component thermosetting epoxy adhesive provided by the invention is halogen-free, solvent-free, low-molecular-weight-volatilization-free, high in cured material hardness, good in toughness, bending-resistant and low in water absorption, and basically has no obvious adverse effect on dielectric property and dimensional stability in a double 85 test; the flame retardant reaches UL94VO flame retardant grade under the condition of low flame retardant dosage, and the adhesive film is transparent.
Description
Technical Field
The invention relates to the field of coating adhesives, in particular to a double-component thermosetting epoxy adhesive with low water absorption rate, and a preparation method and application thereof.
Background
The two-component epoxy adhesive has higher requirements in the field of electronic devices and the like needing adhesive insulation, and has industrial standards in various requirements such as low VOC, low halogen, three prevention, aging resistance, weather resistance, insulation, flame retardance and the like. Bromine-containing flame retardant is often added into the existing epoxy resin coating adhesive, so that the efficiency is high, the dosage is small, but with the social progress and the enhancement of environmental awareness, the development of halogen-free low-toxicity flame retardant technology is in great tendency in both scientific and industrial fields. The european union is pushing on the use of halogen-free or low-halogen flame retardants. It is specifically stipulated in the directive about coating electronic and electrical equipment and the directive about limiting the use of certain harmful components in electronic and electrical equipment that harmful substances are forbidden for electronic and electrical equipment, and includes halogen-containing flame retardants, particularly bromine-containing flame retardants, used in the field of epoxy adhesives. Therefore, the great development of halogen-free flame retardant technology and product research is of great significance.
Except for the consideration of environmental protection and safety, the adhesive film is required to be transparent in the application of products in the electronic industry, for example, a circuit board needs a visible circuit and an original piece, and the adhesive film is light in color and transparent. The halogen-free flame-retardant adhesive is prepared by adding inorganic and organic solid or liquid flame retardants, wherein the common inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, antimony oxide, molybdate and rare earth oxide; commonly used organic flame retardants are phosphorus-nitrogen intumescent flame retardants such as ammonium polyphosphate, melamine phosphate, liquid polyphosphonates. Usually, the powder flame retardant does not react with the resin and/or the curing agent, and the suspension is physically and mechanically mixed and added to a predetermined amount, so that the cured product is opaque or translucent. The phosphate liquid flame retardant is colorless and transparent, and because the phosphate liquid flame retardant does not participate in the reaction or has low participation degree in the reaction, the phosphate exists in a cured material in the form of a plasticizer, and migrates to the surface of the cured material after a long time, so that an adhesive film becomes soft, the strength is reduced, the surface insulativity is reduced, the addition amount is strictly controlled, and the phosphate liquid flame retardant can only be added as an auxiliary flame retardant.
The epoxy adhesive also has the defect of poor stability in a humid environment, particularly a high-temperature and high-humidity environment. Generally, the epoxy resin cured material has high water absorption under high temperature and high humidity conditions, which affects the electrical properties of the encapsulated electrical material, and also causes the defects of reduced adhesion strength, dimensional change, easy water vapor permeation from the wire frame interface or the gap, or surface corrosion of the cured material, and poor dielectric properties, and dimensional instability of the epoxy resin adhesive under high temperature and high humidity conditions may cause the loosening of wiring structure. Therefore, the epoxy adhesive for the electronic industry is also required to have low water absorption. The usual method in the prior art is to add fillers or hydrophobic substances to suppress the water absorption. Such as hydrophobic inorganic fillers (silica, etc.), and organic fillers (foamed particles) are dispersed in the epoxy resin by means of physical blending, in order to desirably reduce the hydrophobicity of the epoxy material. However, the addition of these fillers adversely affects the mechanical and optical properties of the epoxy resin, particularly the decrease in light transmittance. Fluorine is also introduced into epoxy resin to form fluorine-containing epoxy resin, but the synthesis process is complex, the cost is high, and the method is not suitable for industrial production. The prior art also improves the hydrophobicity of the material by improving the crosslinking degree of the epoxy resin, but the toughness of the epoxy adhesive is insufficient.
In conclusion, the halogen-free epoxy resin is developed, the epoxy adhesive has good dielectric property, mechanical property, flame retardant property, optical property, aging resistance, dimensional stability and low water absorption rate, and the comprehensive performance is excellent, so that the epoxy adhesive has important significance and commercial value for the electronic and electrical appliance industry.
Disclosure of Invention
In order to overcome the defects that the performance of epoxy resin adhesive in the electronic industry is not satisfactory in part in the prior art, particularly the flame retardant performance, the optical performance and the low water absorption rate cannot be considered at the same time, the invention provides the two-component thermosetting epoxy adhesive with low water absorption rate, which does not need to add an inorganic flame retardant or a solid organic flame retardant, is halogen-free, solvent-free, low-molecular-weight-volatilization-free, high in hardness of a cured product, good in toughness, bending-resistant and low in water absorption rate, and basically has no obvious adverse effect on dielectric performance and dimensional stability in a double 85 test; the flame retardant reaches UL94VO flame retardant grade under the condition of low flame retardant dosage, and the adhesive film is transparent.
The invention solves the technical problems through the following technical scheme:
a low-water-absorption two-component thermosetting epoxy adhesive comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by mass: 20-50 parts of bisphenol epoxy resin, 5-15 parts of triglycidyl isocyanurate, 10-20 parts of halogen-free flame retardant resin, 5-10 parts of toughening resin, 30-50 parts of reactive diluent, 3-10 parts of liquid phosphate flame retardant and 0.5-2 parts of wetting agent; the component B comprises the following raw materials in parts by mass: 10-20 parts of alicyclic diamine, 3-10 parts of fluorine-containing aromatic diamine, 2-7 parts of phosphine oxide containing 2 aminophenyl groups, 2-4 parts of an accelerator and 10-20 parts of an active diluent.
In a preferred technical scheme of the invention, the low-water-absorption two-component thermosetting epoxy adhesive comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by mass: 20-40 parts of bisphenol epoxy resin, 5-10 parts of triglycidyl isocyanurate, 10-20 parts of halogen-free flame retardant resin, 5-10 parts of toughening resin, 30-50 parts of reactive diluent, 5-8 parts of liquid phosphate flame retardant and 0.5-1 part of wetting agent; the component B comprises the following raw materials in parts by mass: 10-20 parts of alicyclic diamine, 4-8 parts of fluorine-containing aromatic diamine, 3-5 parts of phosphine oxide containing 2 aminophenyl groups, 2-4 parts of an accelerator and 10-20 parts of an active diluent.
Further, the alicyclic diamine is selected from 4, 4-diaminodicyclohexylmethane, 1, 4-diamino-2-N-propylcyclohexane, N '-dimethyl-1, 2-cyclohexanediamine, isophoronediamine, 1, 4-cyclohexanediamine (methylamine), 4' -methylenebis (2-methylcyclohexylamine); the fluorine-containing aromatic diamine is selected from 1-trifluoromethyl-3, 5-diaminobenzene, 3, 5-bis (trifluoromethyl) -1, 2-phenylenediamine, 1, 4-bis (4 '-amino-2' -trifluoromethylphenoxy) benzene, bis (3-aminophenyl) -3, 5-bis (trifluoromethyl) phenylphosphine oxide; the phosphine oxide containing a plurality of aminophenyl groups is selected from the group consisting of bis [4- (3-aminophenoxy) phenyl ] phenylphosphine oxide, 4' - [ (phenylphosphinoyl) bis (4, 1-phenoxy) ] bisaniline, bis (4-aminophenyl) phenylphosphine oxide, bis (3-aminophenyl) phenylphosphine oxide, bis (4-aminophenyl) ethylphosphine oxide, bis (3-aminophenyl) ethylphosphine oxide, bis (2-aminophenyl) ethylphosphine oxide, bis (4-aminophenyl) n-propylphosphine oxide, bis (3-aminophenyl) n-propylphosphine oxide, bis (4-aminophenyl) isopropylphosphine oxide, bis (3-aminophenyl) isopropylphosphine oxide, bis (4-aminophenyl) n-butylphosphine oxide, bis (3-aminophenyl) n-butylphosphine oxide, bis (4-aminophenyl), Bis (4-aminophenyl) isobutylphosphine oxide, bis (3-aminophenyl) isobutylphosphine oxide.
Further, the fluorine-containing aromatic diamine is selected from bis (3-aminophenyl) -3,5, -bis (trifluoromethyl) phenylphosphine oxide, and the 2-aminophenyl-containing phosphine oxide is selected from at least one of bis [4- (3-aminophenoxy) phenyl ] phenylphosphine oxide and 4,4' - [ (phenylphosphine) bis (4, 1-phenoxy) ] bis-aniline. The curing agent contains the structure of phenyl phosphine oxide, and can play a role in flame retardance and curing at the same time. The resulting cure is excellent in various properties. The V0 grade of flame retardance can be achieved under the condition of low flame retardant adding amount, and high light transmittance is kept.
Still further, the cycloaliphatic diamine is selected from the group consisting of 3,3' -dimethyl-4, 4-diaminodicyclohexylmethane; the fluorine-containing aromatic diamine is selected from bis (3-aminophenyl) -3,5, -bis (trifluoromethyl) phenylphosphine oxide; the phosphine oxide containing 2 aminophenyl groups is selected from 4,4' - [ (phenylphosphine) bis (4, 1-phenoxy) ] bis-aniline.
Bis [4- (3-aminophenoxy) phenyl ] phenylphosphine oxide, 4'- [ (phenylphosphinoyl) bis (4, 1-phenoxy) ] bis-aniline are phenylphosphine oxide derivatives differing only in the position of the amino group on the benzene ring, and the inventors have unexpectedly found that 4,4' - [ (phenylphosphinoyl) bis (4, 1-phenoxy) ] bis-aniline substituted with an amino group at the para-position of the benzene ring is more transparent to the cured film than bis [4- (3-aminophenoxy) phenyl ] phenylphosphine oxide substituted with an amino group at the meta-position of the benzene ring.
Further, the bisphenol type epoxy resin is selected from at least one of bisphenol A type epoxy resins (such as NPEF-128EL, DEER331 or EP828EL), bisphenol S type epoxy resins and bisphenol F type epoxy resins (such as EXA-830LVP, EXA-835 LV); the epoxy equivalent of the epoxy resin is 150-200;
the halogen-free flame-retardant resin is at least one of cyanuric acid epoxy resin, hydantoin epoxy resin, liquid phosphorus-based epoxy resin and phosphaphenanthrene flame-retardant resin; more specifically, the halogen-free flame-retardant resin is at least one selected from A95 resin, MHR-070 resin, MHR-154 resin and EP360 resin;
the reactive diluent is selected from at least one of phenyl glycidyl ether, tertiary carbonic acid glycidyl ether and p-tert-butylphenol type glycidyl ether;
the toughening resin is at least one of polyurethane modified epoxy resin, polyurethane polyol resin, core-shell toughening resin and ABS triblock copolymer; specifically at least one of DER 791, Hypox UA-11, MX-125 and DY 965;
the liquid phosphate flame retardant is selected from at least one of tricresyl phosphate TCP, diethyl ethyl phosphate DEEP, dimethyl methyl phosphate DMMP and CNV-600A, and the liquid phosphate flame retardant is selected, so that the dosage is low, the viscosity is low, and the optical performance of a cured product is basically not influenced;
the wetting agent is selected from polyether modified polydimethylsiloxane, such as BYK-378, BYK-333, BYK-320 and BYK-330. The polyether modified polydimethylsiloxane is selected to reduce the surface tension, improve the infiltration capacity to the base material, improve the water contact angle after curing and avoid the permeation of water vapor to the interface in a damp and hot state.
Preferably, the invention can also add some conventional auxiliary materials of epoxy resin glue, such as anti-yellowing agent, antioxidant, defoaming agent, etc. into the A component and/or the B component. The specific type and amount thereof are well known in the art and will not be described further herein. The auxiliary material may be added to the A component and/or the B component without specific limitation. Preferably, the auxiliary materials are added into the component A in a whole.
The inventor unexpectedly found that the components of the provided two-component curing agent are matched with each other, particularly triglycidyl isocyanurate replaces part of bisphenol type epoxy resin, and the curing agent is a mixed curing agent formed by compounding alicyclic diamine, fluorine-containing aromatic diamine and phosphine oxide containing 2 aminophenyl according to certain mass. The two-component epoxy batch coating adhesive prepared by the invention is prepared by mixing the component A and the component B according to the mass ratio of 1-3:1, spraying the mixture on a PCB, and can be quickly cured under the medium temperature condition (80 ℃/1h +100 ℃/0.5h) to form a 50-80 mu m adhesive film, and the cured product has excellent comprehensive performance, particularly has low dilution rate and high light transmittance while meeting the mechanical property, flame retardant property and humidity and heat resistance stability of the epoxy adhesive, and can completely meet the requirements of the epoxy adhesive used for electronic and electric devices.
The invention also provides a preparation method of the low-water-absorption double-component thermosetting epoxy adhesive, which comprises the following steps:
(1) preparation of component A: according to the proportion, bisphenol type epoxy resin, triglycidyl isocyanurate and halogen-free flame retardant resin are stirred and mixed under the condition of heating, then reactive diluent and toughened resin are added, optionally auxiliary materials are added, after cooling, liquid phosphate flame retardant and wetting agent are added, and the component A is obtained after uniform mixing;
(2) preparation of the component B: adding alicyclic diamine, fluorine-containing aromatic diamine, phosphine oxide containing 2 aminophenyl groups, an accelerator, an active diluent and optionally auxiliary materials according to the mixture ratio, and mixing and stirring uniformly to obtain the component B.
When the adhesive film is applied, the component A and the component B are uniformly mixed according to the mass ratio of 1-3:1, the mixture is cured for 1-1.5h at the temperature of 80-90 ℃ and cured for 0.5-1h at the temperature of 100-110 ℃, the spraying amount of the epoxy resin is controlled to ensure that the thickness of the cured adhesive film is 50-100 mu m, and the obtained adhesive film has low water absorption and high light transmittance. The two-component epoxy glue is simple and convenient to operate, high in hardness after curing, good in toughness, bending resistance, high-temperature and high-humidity resistance, good in dielectric property and size stability after a double 85 experiment for 300 hours, the surface insulation resistance value of the two-component epoxy glue is reduced by less than 30%, and the size change is not more than 0.8%; in the preferred embodiment, the surface insulation resistance value is reduced by less than 20%, and the dimensional change is not more than 0.5%. The two-component epoxy glue provided by the invention has the advantages of favorable moisture and heat resistance stability, small reduction range of dielectric property, stable size, and capability of ensuring that water vapor cannot permeate from an interface, thereby ensuring the safe and long-term operation of an electronic device.
Detailed Description
The technical solution of the present invention is further explained and illustrated by the following embodiments, but it should not be construed as limiting the protection content of the present invention.
Reagents and instruments used in the examples are commercially available. Unless otherwise specified, "parts" are parts by mass, and% are mass%.
20-40 parts of bisphenol epoxy resin, 5-10 parts of triglycidyl isocyanurate, 10-20 parts of halogen-free flame retardant resin, 5-10 parts of toughening resin, 30-50 parts of reactive diluent, 5-10 parts of liquid phosphate flame retardant and 1-2 parts of wetting agent; the component B comprises the following raw materials in parts by mass: 10-20 parts of alicyclic diamine, 4-8 parts of fluorine-containing aromatic diamine, 3-5 parts of phosphine oxide containing 2 aminophenyl groups, 2-4 parts of an accelerator and 10-20 parts of an active diluent.
Example 1
(1) Preparation of component A: stirring and mixing 30 parts of bisphenol A epoxy resin DEER331, 5 parts of triglycidyl isocyanurate and 15 parts of MHR-070 resin at 80 ℃, adding 40 parts of reactive diluent ED-509S, 5 parts of toughened resin Hypox UA-11, 1 part of wetting agent BYK-330, 0.3 part of defoaming agent Hamming 5300 and 0.5 part of anti-yellowing additive SKELA-0025, cooling, adding 5 parts of liquid phosphate flame retardant DEEP, and uniformly mixing to obtain a component A;
(2) preparation of the component B: uniformly mixing 15 parts of 4, 4-diaminodicyclohexylmethane, 5 parts of 1-trifluoromethyl-3, 5-diaminobenzene, 3 parts of bis (3-aminophenyl) phenylphosphine oxide, 3 parts of an accelerant AC399 and 20 parts of an active diluent ED-509S to obtain a component B.
When the composition is applied, the ratio of the component A to the component B is 3:1, uniformly mixing, spraying on a PCB, curing at a medium temperature (80 ℃/1h +100 ℃/0.5h), and controlling the spraying amount to enable the thickness of the formed adhesive film to be 50 μm.
A two-part epoxy adhesive was prepared in the same manner as in example 1, and its formulation is shown in Table 1 below, without the component representatives shown in Table 1 being the same as in example 1:
TABLE 1
Application example
The epoxy adhesives obtained in the above examples and comparative examples were tested for their properties after curing (wherein the viscosity was measured when the two-component epoxy adhesive was just mixed) and the results are shown in table 2 below:
viscosity of the solution: testing at 25 ℃; the viscosity test is the viscosity of the system when the two-component epoxy glue is just mixed.
Adhesion force: testing the number of the lost grids by a grid method according to the GB/T9286-1998 standard;
flexibility: referring to IPC-TM-6502.4.5.1 standard, the paint film is not cracked when being bent for 180 degrees;
surface insulation resistance value: with reference to the IPC-TM-6502.6.3.4A standard, in 1018 Ω; and (3) testing conditions are as follows: testing Mitsubishi chemical Loresta-GX MCP-T700 at 25 ℃ and 50% humidity.
Test for double 85 (temperature 85 degree, humidity 85 degree) aging: the solidified sample is placed for 300h under the conditions of 85 +/-1 ℃ and 85 +/-2 RH percent.
UL94 flame retardant test method：
HB: the lowest flame retardant rating in the UL94 standard. Requiring a burn rate of less than 40 mm per minute for samples 3 to 13 mm thick; a sample less than 3 mm thick with a burning rate less than 70 mm per minute; or a mark at 100 mm.
V-2 after two 10 second burn tests on the samples, the flame extinguished within 60 seconds. There may be combustion products falling.
V-1 after two 10 second burn tests on the samples, the flame extinguished within 60 seconds. No combustible material can fall off.
V-0 after two 10 second burn tests on the samples, the flame extinguished within 30 seconds. No combustible material can fall off.
Measurement of light transmittance: refer to GB/T2410-.
Water absorption test: reference IPC-TM-6502.6.2.1 test
TABLE 2
Claims (10)
1. The two-component thermosetting epoxy adhesive with low water absorption is characterized by comprising a component A and a component B, wherein the component A comprises the following raw materials in parts by mass: 20-50 parts of bisphenol epoxy resin, 5-15 parts of triglycidyl isocyanurate, 10-20 parts of halogen-free flame retardant resin, 5-10 parts of toughening resin, 30-50 parts of reactive diluent, 3-10 parts of liquid phosphate flame retardant and 0.5-2 parts of wetting agent; the component B comprises the following raw materials in parts by mass: 10-20 parts of alicyclic diamine, 3-10 parts of fluorine-containing aromatic diamine, 2-7 parts of phosphine oxide containing 2 aminophenyl groups, 2-4 parts of an accelerator and 10-20 parts of an active diluent.
2. The two-component thermosetting epoxy adhesive with low water absorption according to claim 1, which is characterized by comprising a component A and a component B, wherein the component A comprises the following raw materials in parts by mass: 20-40 parts of bisphenol epoxy resin, 5-10 parts of triglycidyl isocyanurate, 10-20 parts of halogen-free flame retardant resin, 5-10 parts of toughening resin, 30-50 parts of reactive diluent, 5-8 parts of liquid phosphate flame retardant and 0.5-1 part of wetting agent; the component B comprises the following raw materials in parts by mass: 10-20 parts of alicyclic diamine, 4-8 parts of fluorine-containing aromatic diamine, 3-5 parts of phosphine oxide containing 2 aminophenyl groups, 2-4 parts of an accelerator and 10-20 parts of an active diluent.
3. The two-component thermosetting epoxy adhesive with low water absorption according to claim 1, wherein the alicyclic diamine is at least one selected from the group consisting of 4, 4-diaminodicyclohexylmethane, 1, 4-diamino-2-N-propylcyclohexane, N '-dimethyl-1, 2-cyclohexanediamine, isophoronediamine, 1, 4-cyclohexanediamine, 4' -methylenebis (2-methylcyclohexylamine); the fluorine-containing aromatic diamine is selected from at least one of 1-trifluoromethyl-3, 5-diaminobenzene, 3, 5-bis (trifluoromethyl) -1, 2-phenylenediamine, 1, 4-bis (4 '-amino-2' -trifluoromethylphenoxy) benzene, bis (3-aminophenyl) -3, 5-bis (trifluoromethyl) phenylphosphine oxide; the phosphine oxide containing a plurality of aminophenyl groups is selected from the group consisting of bis [4- (3-aminophenoxy) phenyl ] phenylphosphine oxide, 4' - [ (phenylphosphinoyl) bis (4, 1-phenoxy) ] bisaniline, bis (4-aminophenyl) phenylphosphine oxide, bis (3-aminophenyl) phenylphosphine oxide, bis (4-aminophenyl) ethylphosphine oxide, bis (3-aminophenyl) ethylphosphine oxide, bis (2-aminophenyl) ethylphosphine oxide, bis (4-aminophenyl) n-propylphosphine oxide, bis (3-aminophenyl) n-propylphosphine oxide, bis (4-aminophenyl) isopropylphosphine oxide, bis (3-aminophenyl) isopropylphosphine oxide, bis (4-aminophenyl) n-butylphosphine oxide, bis (3-aminophenyl) n-butylphosphine oxide, bis (4-aminophenyl), At least one of bis (4-aminophenyl) isobutylphosphine oxide and bis (3-aminophenyl) isobutylphosphine oxide.
4. The low water absorption two-component thermosetting epoxy adhesive according to claim 3, wherein the fluorine-containing aromatic diamine is selected from bis (3-aminophenyl) -3,5, -bis (trifluoromethyl) phenylphosphine oxide, and the phosphine oxide containing 2 aminophenyl groups is selected from at least one of bis [4- (3-aminophenoxy) phenyl ] phenylphosphine oxide and 4,4' - [ (phenylphosphinoyl) bis (4, 1-phenoxy) ] bis-aniline.
5. The low water absorption two-component thermosetting epoxy adhesive according to claim 3, wherein the cycloaliphatic diamine is selected from the group consisting of 3,3' -dimethyl-4, 4-diaminodicyclohexylmethane; the fluorine-containing aromatic diamine is selected from bis (3-aminophenyl) -3,5, -bis (trifluoromethyl) phenylphosphine oxide; the phosphine oxide containing 2 aminophenyl groups is selected from 4,4' - [ (phenylphosphine) bis (4, 1-phenoxy) ] bis-aniline.
6. The low water absorption two-component thermosetting epoxy resin according to claim 1, wherein the bisphenol type epoxy resin is at least one selected from the group consisting of bisphenol a type epoxy resin, bisphenol S type epoxy resin, and bisphenol F type epoxy resin; the epoxy equivalent of the epoxy resin is 150-200; and/or
The halogen-free flame-retardant resin is at least one of cyanuric acid epoxy resin, hydantoin epoxy resin, liquid phosphorus-based epoxy resin and phosphaphenanthrene flame-retardant resin; and/or
The reactive diluent is selected from at least one of phenyl glycidyl ether, tertiary carbonic acid glycidyl ether and p-tert-butylphenol type glycidyl ether; and/or
The toughening resin is at least one of polyurethane modified epoxy resin, polyurethane polyol resin, core-shell toughening resin and ABS triblock copolymer; and/or
The liquid phosphate flame retardant is selected from at least one of TCP, DEEP, DMMP and CNV-600A; and/or
The wetting agent is selected from polyether modified polydimethylsiloxane.
7. The method for preparing the low water absorption two-component thermosetting epoxy adhesive according to any one of claims 1 to 6, comprising the steps of:
(1) preparation of component A: according to the proportion, bisphenol type epoxy resin, triglycidyl isocyanurate and halogen-free flame retardant resin are stirred and mixed under the condition of heating, then reactive diluent and toughened resin are added, optionally auxiliary materials are added, after cooling, liquid phosphate flame retardant and wetting agent are added, and the component A is obtained after uniform mixing;
(2) preparation of the component B: adding alicyclic diamine, fluorine-containing aromatic diamine, phosphine oxide containing 2 aminophenyl groups, an accelerator, an active diluent and optionally auxiliary materials according to the mixture ratio, and mixing and stirring uniformly to obtain the component B.
8. Use of the low water absorption two-component thermosetting epoxy adhesive according to any one of claims 1 to 6 in electronic and electrical appliance coating adhesives.
9. The use as claimed in claim 8, wherein the component A and the component B are uniformly mixed according to the mass ratio of 1-3:1, sprayed on the surface of the base material, cured for 1-1.5h at 80-90 ℃ and cured for 0.5-1h at 100-110 ℃.
10. The use according to claim 9, wherein the spraying amount of the two-component epoxy resin is controlled so that the thickness of the cured adhesive film is 50-100 μm.
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