CN113528071B - Low-dielectric epoxy adhesive and preparation method thereof - Google Patents
Low-dielectric epoxy adhesive and preparation method thereof Download PDFInfo
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- CN113528071B CN113528071B CN202110967428.3A CN202110967428A CN113528071B CN 113528071 B CN113528071 B CN 113528071B CN 202110967428 A CN202110967428 A CN 202110967428A CN 113528071 B CN113528071 B CN 113528071B
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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
- 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
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
A low dielectric epoxy adhesive and a preparation method thereof belong to the field of adhesives. The technical problem to be solved by the invention is to improve the dielectric property of the adhesive. The cyanate ester resin is prepared from 10-40 parts by weight of cyanate ester resin, 90-60 parts by weight of epoxy resin A, 0-5 parts by weight of epoxy diluent, 5-30 parts by weight of toughening agent, 0-10 parts by weight of thixotropic agent, 0-140 parts by weight of filler, 5-10 parts by weight of epoxy resin B and 0.5-5 parts by weight of catalyst. The invention takes epoxy resin as main resin, adds a small amount of cyanate ester for modification, and adopts a nonmetal compound as a catalyst to prepare the cyanate ester modified epoxy resin paste (paste) glue which has low dielectric constant and low dielectric loss tangent tan delta, excellent adhesive property, high peel strength and heat resistance.
Description
Technical Field
The invention belongs to the field of adhesives; in particular to low dielectric epoxy glue and a preparation method thereof.
Background
The low dielectric epoxy resin and the adhesive are widely applied to the fields of printed circuit boards, low dielectric composite materials and the like. The dielectric constant epsilon of the epoxy resin and the adhesive under a high-frequency condition (10GHz) is 3.0-3.4, and the dielectric loss tangent tan delta is 0.010-0.030. The high dielectric constant and dielectric loss of the current common epoxy glue can not meet the requirements.
The method for improving the dielectric property of the epoxy mainly comprises the following steps: firstly, the curing process is optimized, the curing degree of the material is improved, the resin forms a more uniform network structure, and polar groups in the structure are effectively limited. Secondly, the hybrid material is hybridized with low dielectric inorganic materials, such as silicon dioxide, silsesquioxane and the like; thirdly, blending or copolymerizing the high polymer with low dielectric constant.
Cyanate ester resins are an important modifier of epoxy resins. Cyanate ester resin is a relatively new variety of thermosetting resin, and has low hygroscopicity, low dielectric constant (2.7-3.2, 10GHz), low dielectric loss tangent tan delta (0.004-0.010, 10GHz) and good flame retardance, so that the cyanate ester resin becomes an attractive composite material resin matrix. Thus, cyanate ester modified epoxy resins (CE/EP) can improve the performance of the epoxy resin, and the copolymer is more cost effective than cyanate ester alone. Cyanate ester/epoxy formulations (containing catalysts, fillers, coupling agents, etc.) are reported to have excellent moisture and thermal shock resistance. Can be used as an underfill material for chip semiconductor devices. The formulation of the patent has good filling property, crack resistance in thermal cycling and good moisture resistance [ JP11106,481, JP11106,480], and the application of cyanate/epoxy resin is mostly in copper clad laminates [ JP 76397026, JP85125661, JP1154886], airplane structures [ UP5045609] and semiconductor devices [ UP5855821 ]. Chinese patent CN106753218A discloses a low-dielectric high-toughness cyanate ester adhesive, bisphenol AF epoxy resin is adopted to modify cyanate ester, the proportion of cyanate ester resin is 70-95%, organic metal salt is used as a catalyst, and the curing temperature is 200 ℃. Patent zl201210187060.x discloses a low-temperature curing cyanate ester adhesive, and the catalyst is a mixture of phenolic compounds and transition metal complexes. The Chinese patent CN106381110A adopts isocyanate modified epoxy resin, and the patent content has no dielectric data, which is different from the matrix resin of the patent. The curing agent in the Chinese patent CN112080111A is a phenolic compound and participates in the copolymerization reaction of cyanate ester functional groups and epoxy functional groups, and the dielectric constant of the formula of the patent at 10GHz is higher and is 3.78-3.95.
Disclosure of Invention
The invention aims to provide a low dielectric epoxy adhesive with excellent dielectric property, high adhesive property and high peel strength and a preparation method thereof.
The invention is realized by the following technical scheme:
a low-dielectric epoxy adhesive is mainly prepared from 10-40 parts by weight of cyanate ester resin, 90-60 parts by weight of epoxy resin A, 0-5 parts by weight of epoxy diluent, 5-30 parts by weight of toughening agent, 0-10 parts by weight of thixotropic agent, 0-140 parts by weight of filler, 5-10 parts by weight of epoxy resin B and 0.5-5 parts by weight of catalyst.
The cyanate ester resin is one or a combination of bisphenol A cyanate ester, bisphenol A cyanate ester prepolymer, bisphenol E cyanate ester, bisphenol M cyanate ester, phenolic cyanate ester, dicyclopentadiene cyanate ester and cardanol cyanate ester resin.
The epoxy resin A is one or a mixture of more of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether and trifunctional glycidyl amine, and the epoxy equivalent is 100-240 g/eq.
The low dielectric epoxy adhesive is characterized in that the diluent is one or a mixture of more of dipropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, resorcinol diglycidyl ether and ethylene glycol diglycidyl ether.
The low dielectric epoxy glue is characterized in that the toughening agent is rubber particles with a core-shell structure, and the toughening agent is one or a mixture of more of commercially available S-2001, EXL2691, S-2006, S-2030, SX-005, SX-006, MR-501, P52 and EXL 2330.
The low dielectric epoxy adhesive is prepared by mixing one or more of fumed silica and surface-treated fumed silica.
The low dielectric epoxy adhesive is characterized in that the filler is fused spherical silica micropowder, and the average particle size D of the filler 95 Less than or equal to 15 microns.
According to the low dielectric epoxy adhesive, the epoxy resin B is one or a mixture of more of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether and trifunctional glycidyl amine, and the epoxy equivalent is 100-240 g/eq.
The catalyst of the low dielectric epoxy adhesive is one or a combination of 2-methylimidazole, 1-methylimidazole and 2-ethyl-4-methylimidazole.
The invention relates to a preparation method of low dielectric epoxy glue, which comprises the following steps:
weighing 10-40 parts by weight of cyanate ester resin, adding 90-60 parts by weight of epoxy resin A, uniformly stirring, adding 0-5 parts by weight of epoxy diluent, adding 5-30 parts by weight of toughening agent, 0-10 parts by weight of thixotropic agent and 0-140 parts by weight of filler, and obtaining the resin in the first step for later use;
step two, weighing 5-10 parts of epoxy resin B, adding 0.5-5 parts of catalyst, and uniformly mixing to obtain resin in step two for later use;
and step three, mixing the resin obtained in the step one and the resin obtained in the step two, and uniformly stirring to obtain the low dielectric epoxy glue.
The low dielectric epoxy adhesive is prepared by modifying epoxy resin with cyanate ester and nonmetal compound, adding flexibilizer, thixotropic agent and filler, and copolymerizing cyanate ester and epoxy in the way that cyanate ester undergoes self polymerization to form triazine ring structure, epoxy group is inserted into triazine ring to isomerize into isocyanurate, and then the structure is rearranged into oxazolidinone structure. In addition to self-polymerization to form a triazine ring structure, cyanate ester groups may also form a four-membered ring dimer. The more four-membered ring dimer structure is present in the phenol/transition metal complex catalyzed cyanate/epoxy resin system, while the more isocyanurate ring structure is present in the non-metal ion catalyzed resin system. The addition of the catalyst generally affects the formation mechanism of the mixed network and changes the material performance. Therefore, compared with the prior art, the cyanate ester modified epoxy resin paste (paste) adhesive has the characteristics of low dielectric constant, low dielectric loss tangent tan delta, excellent bonding performance, high peel strength, heat resistance and good process performance, and can be used for bonding and repairing low dielectric cyanate ester and bismaleimide composite materials.
The low dielectric epoxy adhesive disclosed by the invention is prepared by taking epoxy resin as a main resin, adding a small amount of cyanate ester for modification and adopting a non-metallic compound as a catalyst, and the prepared cyanate ester modified epoxy resin paste (paste) adhesive has the advantages of lower dielectric constant, low dielectric loss tangent tan delta and higher room temperature and high temperature bonding strength.
Detailed Description
The first specific implementation way is as follows:
a preparation method of low dielectric epoxy glue comprises the following steps:
step one, weighing 50 parts of bisphenol F epoxy resin and 40 parts of bisphenol E cyanate ester according to parts by weight, and uniformly blending;
step two, weighing 10 parts of bisphenol F epoxy resin according to the parts by weight, adding 1 part of 2-ethyl-4-methylimidazole, and uniformly stirring;
and step three, uniformly mixing the resins obtained in the step one and the step two to prepare the low dielectric epoxy glue.
The low dielectric epoxy adhesive prepared by the embodiment is used for a dielectric sample, the sample size is phi 25mm multiplied by 2mm, the curing process is carried out for 12h at 100 ℃, and then the curing process is carried out for 12h at 150 ℃.
Comparative example one: the catalyst is a mixture of 4 parts of nonyl phenol and 0.0666 part of copper acetylacetonate, and the rest is the same as the first embodiment.
The second embodiment is as follows:
a preparation method of low dielectric epoxy glue comprises the following steps:
weighing 50 parts of bisphenol F epoxy resin and 40 parts of bisphenol E cyanate ester according to parts by weight, uniformly blending, adding 20 parts of EXL2691 core-shell particles, and dispersing in a high-speed dispersion machine at the speed of 5000-13000 r/min for 3-10 min;
weighing 10 parts of bisphenol F epoxy resin according to parts by weight, adding 1 part of 2-ethyl-4-methylimidazole, and uniformly stirring;
and step three, uniformly mixing the resins obtained in the step one and the step two to prepare the low dielectric epoxy glue.
The low dielectric epoxy adhesive prepared by the embodiment is used for a dielectric sample, the sample size is phi 25mm multiplied by 2mm, the sample is bonded, and the curing process is performed for 12 hours at 100 ℃ and then for 12 hours at 150 ℃.
Comparative example two: the catalyst is a mixture of 4 parts of nonyl phenol and 0.0666 part of copper acetylacetonate, and the rest is the same as the second embodiment.
The third concrete implementation mode:
a preparation method of low dielectric epoxy glue comprises the following steps:
weighing 50 parts of bisphenol F epoxy resin and 40 parts of bisphenol E cyanate ester according to parts by weight, uniformly blending, adding 30 parts of EXL2691 core-shell particles, and dispersing in a high-speed dispersion machine at a speed of 10000-13000 r/min for 3-10 min;
step two, weighing 10 parts of bisphenol F epoxy resin according to parts by weight, adding 1 part of 2-ethyl-4-methylimidazole, and uniformly stirring;
and step three, uniformly mixing the resins obtained in the step one and the step two to prepare the low dielectric epoxy glue.
The low dielectric epoxy adhesive prepared by the embodiment is used for a dielectric sample, the sample size is phi 25mm multiplied by 2mm, the sample is bonded, and the curing process is performed for 12 hours at 100 ℃ and then for 12 hours at 150 ℃.
Comparative example three: the catalyst is a mixture of 4 parts of nonyl phenol and 0.0666 part of copper acetylacetonate, and the rest is the same as the third embodiment.
Shear strength test reference is made to HB5164 tensile shear strength test method, sample material: 2a12 aluminum alloy. The peel strength test refers to a GJB446-88 adhesive 90-degree peel strength test method, and the sample material comprises the following components: 2a12 aluminum alloy. The test specimens were tested with a dielectric constant tester (Keysight E5071c, USA). Room temperature test, frequency 10.1 GHz. The test results are shown in table 1:
TABLE 1 adhesive and dielectric Properties of the Adhesives
As can be seen from Table 1, the 2-ethyl-4-methyl catalyzed cyanate ester modified epoxy resin (CE/EP) has a high adhesive strength, especially 150 ℃ shear strength. The adding amount of the core-shell particles EXL2691 is increased from 0 to 30 parts by weight, and the shear strength at 150 ℃ is increased from 26.75MPa to 29.81 MPa; the 90 DEG peel strength increased from 17.84N/cm to 60.53N/cm, increasing the peel strength by 42.69N/cm. The dielectric constant and the dielectric loss tangent tan delta are basically reduced along with the increase of the core-shell particles EXL2691A, the dielectric constant is reduced from 2.88 to 2.71, the dielectric loss tangent tan delta is reduced from 0.01831 to 0.01720, and the dielectric property is improved.
As can be seen from table 1, the comparative example nonylphenol/copper acetylacetonate catalyzed cyanate-modified epoxy resin had a lower shear strength. The addition amount of the core-shell particles EXL2691 is increased from 0 to 30 parts by weight, the shear strength at 150 ℃ is in a descending trend, and the shear strength is reduced from 23.79MPa to 19.0 MPa; the 90 DEG peel strength is increased from 13.52N/cm to 44.04N/cm, and the peel strength is only increased by 30.52N/cm. After curing, the dielectric constant of the adhesive increased from 2.74 to 2.82, the dielectric loss tangent tan delta increased from 0.01750 to 0.01808, and the dielectric properties deteriorated.
In conclusion, the CE/EP modified by the nonmetal catalyst and the core-shell particles EXL2691A improves the bonding performance of the cyanate adhesive and further ensures the dielectric performance of the low dielectric epoxy adhesive.
The fourth concrete implementation mode:
a preparation method of low dielectric epoxy glue comprises the following steps:
weighing 50 parts of bisphenol F epoxy resin, 30 parts of bisphenol E cyanate and 10 parts of bisphenol A cyanate prepolymer according to parts by weight, uniformly blending, adding 20 parts of p52 core-shell particles and 2 parts of fumed silica, and dispersing in a high-speed dispersion machine at the speed of 5000-13000 r/min for 3-10 min;
weighing 10 parts of bisphenol F epoxy resin according to parts by weight, adding 1 part of 2-ethyl-4-methylimidazole, and uniformly stirring;
and step three, uniformly mixing the resins obtained in the step one and the step two to prepare the low dielectric epoxy glue.
The low dielectric epoxy adhesive prepared by the embodiment is used for a dielectric sample, the sample size is phi 25mm multiplied by 2mm, the sample is bonded, and the curing process is performed for 12 hours at 100 ℃ and then for 12 hours at 150 ℃.
The fifth concrete implementation mode:
a preparation method of low dielectric epoxy glue comprises the following steps:
weighing 50 parts of bisphenol F epoxy resin, 30 parts of bisphenol E cyanate and 10 parts of bisphenol A cyanate prepolymer according to parts by weight, uniformly blending, adding 30 parts of p52 core-shell particles and 2 parts of fumed silica, and dispersing in a high-speed dispersion machine at the speed of 5000-13000 r/min for 3-10 min;
step two, weighing 10 parts of bisphenol F epoxy resin according to the parts by weight, adding 1 part of 2-ethyl-4-methylimidazole, and uniformly stirring;
and step three, uniformly mixing the resins obtained in the step one and the step two to prepare the low dielectric epoxy glue.
The low dielectric epoxy adhesive prepared by the embodiment is used for a dielectric sample, the sample size is phi 25mm multiplied by 2mm, the sample bonding is carried out, the curing process is carried out for 12h at 100 ℃, and then the curing process is carried out for 12h at 150 ℃.
The performance tests of a low dielectric epoxy adhesive prepared in the fourth embodiment and the fifth embodiment are shown in table 2:
TABLE 2 shear strength, bond strength and dielectric Properties of the Adhesives
As can be seen from Table 2, 2-ethyl-4-methylimidazole and organosilicon core-shell particles P52 in the low dielectric epoxy adhesive cooperate with each other to generate a synergistic effect. With the increase of the use amount of the core-shell particles, the bonding strength is increased, and the dielectric constant is reduced.
The sixth specific implementation mode:
a preparation method of low dielectric epoxy glue comprises the following steps:
weighing 60 parts of bisphenol F epoxy resin, 30 parts of bisphenol E cyanate ester and 5 parts of ethylene glycol diglycidyl ether according to parts by weight, uniformly blending, adding 10 parts of EXL2691 core-shell particles, dispersing in a high-speed dispersion machine at a dispersion speed of 10000-13000 r/min for 3-10 min, adding 100 parts of silicon micropowder and 4 parts of fumed silica, and dispersing on a high-speed mixer at a speed of 1000-2000 r/min for 30-60 min;
step two, weighing 5 parts of bisphenol F epoxy resin according to parts by weight, adding 1 part of 2-ethyl-4-methylimidazole, and uniformly stirring;
and step three, uniformly mixing the resins obtained in the step one and the step two to prepare the low dielectric epoxy glue.
The low dielectric epoxy adhesive prepared by the embodiment is used for a dielectric sample, the sample size is phi 25mm multiplied by 2mm, the sample is bonded, and the curing process is performed for 12 hours at 100 ℃ and then for 12 hours at 150 ℃.
The low dielectric epoxy adhesive prepared in this embodiment was used to test a sample using a dielectric constant tester (keysight e5071c, usa). Testing at room temperature, wherein the frequency range is 2-18.3 GHz, and the test results are shown in Table 3:
TABLE 3 dielectric constant and dielectric loss tangent tan delta of the adhesive
| frequency/GHz | Dielectric constant of | Dielectric loss tangent tan delta |
| 2 | 2.75 | 0.00890 |
| 6 | 2.73 | 0.00808 |
| 10.1 | 2.72 | 0.00787 |
| 14.2 | 2.71 | 0.00623 |
| 18.3 | 2.70 | 0.00454 |
As can be seen from Table 3, the addition of the silica powder to the modified epoxy adhesive catalyzed by the nonmetallic compound can further effectively reduce the dielectric constant and the dielectric loss tangent tan delta of the adhesive, the dielectric constant is reduced to 2.70-2.75, and the dielectric loss tangent tan delta is reduced to 0.00454-0.00890.
The seventh embodiment:
a low-dielectric epoxy adhesive is mainly prepared from 10-40 parts by weight of cyanate ester resin, 90-60 parts by weight of epoxy resin A, 0-5 parts by weight of epoxy diluent, 5-30 parts by weight of toughening agent, 0-10 parts by weight of thixotropic agent, 0-140 parts by weight of filler, 5-10 parts by weight of epoxy resin B and 0.5-5 parts by weight of catalyst.
In the low dielectric epoxy adhesive of the embodiment, the epoxy resin is modified by the cyanate ester and the nonmetal compound, the toughening agent, the thixotropic agent and the filler are added, the copolymerization reaction route of the cyanate ester and the epoxy is that the cyanate ester generates a self-polymerization reaction to form a triazine ring structure, the epoxy group is inserted into the triazine ring to isomerize into the isocyanurate, and then the structure is rearranged into an oxazolidinone structure. In addition to self-polymerization to form a triazine ring structure, cyanate ester groups may also form a four-membered ring dimer. The more four-membered ring dimer structure is present in the phenol/transition metal complex catalyzed cyanate/epoxy resin system, while the more isocyanurate ring structure is present in the non-metal ion catalyzed resin system. The addition of the catalyst generally affects the formation mechanism of a mixed network and changes the material performance. Therefore, compared with the prior art, the embodiment has the characteristics that the cyanate ester modified epoxy resin paste adhesive has low dielectric constant and low dielectric loss tangent tan delta, excellent bonding performance, high peel strength and heat resistance, and good process performance, and can be used for bonding and repairing low-dielectric cyanate ester and bismaleimide composite materials.
The low dielectric epoxy adhesive provided by the invention takes epoxy resin as main resin, is modified by adding a small amount of cyanate ester and adopts a non-metallic compound as a catalyst, and the prepared cyanate ester modified epoxy resin paste (paste) adhesive has the advantages of low dielectric constant, low dielectric loss tangent tan delta, and high bonding strength at room temperature and high temperature
The specific implementation mode is eight:
according to a seventh embodiment, the cyanate ester resin is one or a combination of bisphenol a cyanate ester, bisphenol a cyanate ester prepolymer, bisphenol E cyanate ester, bisphenol M cyanate ester, phenolic cyanate ester, dicyclopentadiene cyanate ester, and cardanol cyanate ester resin.
The specific implementation method nine:
according to a seventh embodiment of the low dielectric epoxy resin, the epoxy resin a is one or a mixture of several of diglycidyl ether of bisphenol a, diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol a, diglycidyl ether of hydrogenated bisphenol F, and trifunctional glycidyl amine, and the epoxy equivalent is 100 to 240 g/eq.
The detailed implementation mode is ten:
according to a seventh embodiment of the low dielectric epoxy adhesive, the diluent is one or a mixture of dipropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, resorcinol diglycidyl ether, and ethylene glycol diglycidyl ether.
The concrete implementation mode eleven:
according to the seventh embodiment, the toughening agent is rubber particles with a core-shell structure, and the toughening agent is one or a mixture of more of commercially available S-2001, EXL2691, S-2006, S-2030, SX-005, SX-006, MR-501, P52 and EXL 2330.
The specific implementation mode twelve:
according to a seventh embodiment, the thixotropic agent is one or a mixture of fumed silica and surface-treated fumed silica.
The specific implementation mode is thirteen:
according to the seventh embodiment, the filler is fused spherical silica powder, and the average particle diameter D of the filler is 95 Less than or equal to 15 microns.
The specific implementation mode is fourteen:
according to a seventh embodiment of the low dielectric epoxy resin, the epoxy resin B is one or a mixture of several of diglycidyl ether of bisphenol a, diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol a, diglycidyl ether of hydrogenated bisphenol F, and trifunctional glycidyl amine, and the epoxy equivalent is 100 to 240 g/eq.
The concrete implementation mode is fifteen:
according to a seventh embodiment of the low dielectric epoxy adhesive, the catalyst is one or a combination of 2-methylimidazole, 1-methylimidazole and 2-ethyl-4-methylimidazole.
The specific implementation mode is sixteen:
according to a seventh embodiment, the method for preparing a low dielectric epoxy adhesive comprises the following steps:
step one, weighing 10-40 parts by weight of cyanate ester resin, adding 90-60 parts by weight of epoxy resin A, uniformly stirring, adding 0-5 parts by weight of epoxy diluent, adding 5-30 parts by weight of flexibilizer, 0-10 parts by weight of thixotropic agent and 0-140 parts by weight of filler, and obtaining resin in step one for later use;
step two, weighing 5-10 parts of epoxy resin B, adding 0.5-5 parts of catalyst, and uniformly mixing to obtain resin in step two for later use;
and step three, mixing the resin obtained in the step one with the resin obtained in the step two, and uniformly stirring to obtain the low dielectric epoxy glue.
Claims (7)
1. A low dielectric epoxy adhesive is characterized in that: the low-dielectric epoxy resin is mainly prepared from 10-40 parts by weight of cyanate ester resin, 90-60 parts by weight of epoxy resin A, 0-5 parts by weight of epoxy diluent, 5-30 parts by weight of toughening agent, 0-10 parts by weight of thixotropic agent, 0-140 parts by weight of filler, 5-10 parts by weight of epoxy resin B and 0.5-5 parts by weight of catalyst;
the toughening agent is rubber particles with a core-shell structure, and is one or a mixture of more of commercially available S-2001, EXL2691, S-2006, S-2030, SX-005, SX-006, MR-501, P52 and EXL 2330;
the epoxy resin B is one or a mixture of more of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether and trifunctional glycidyl amine, and the epoxy equivalent is 100-240 g/eq;
the catalyst is one or a combination of 2-methylimidazole, 1-methylimidazole and 2-ethyl-4-methylimidazole.
2. The low dielectric epoxy adhesive of claim 1, wherein: the cyanate resin is one or a combination of bisphenol A cyanate, bisphenol A cyanate prepolymer, bisphenol E cyanate, bisphenol M cyanate, phenolic cyanate, dicyclopentadiene cyanate and cardanol cyanate resin.
3. The low dielectric epoxy adhesive of claim 1 or 2, wherein: the epoxy resin A is one or a mixture of more of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether and trifunctional glycidyl amine, and the epoxy equivalent is 100-240 g/eq.
4. The low dielectric epoxy adhesive of claim 3, wherein: the diluent is one or a mixture of more of dipropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, resorcinol diglycidyl ether and ethylene glycol diglycidyl ether.
5. The low dielectric epoxy adhesive of claim 4, wherein: the thixotropic agent is one or a mixture of more of fumed silica and surface-treated fumed silica.
6. The low dielectric epoxy adhesive of claim 5, wherein: the filler is fused spherical silicon micropowder, and the average particle diameter D of the filler 95 Less than or equal to 15 microns.
7. A method for preparing a low dielectric epoxy glue according to any of claims 1 to 6, characterized in that: the method comprises the following steps:
weighing 10-40 parts by weight of cyanate ester resin, adding 90-60 parts by weight of epoxy resin A, uniformly stirring, adding 0-5 parts by weight of epoxy diluent, adding 5-30 parts by weight of toughening agent, 0-10 parts by weight of thixotropic agent and 0-140 parts by weight of filler, and obtaining the resin in the first step for later use;
step two, weighing 5-10 parts of epoxy resin B, adding 0.5-5 parts of catalyst, and uniformly mixing to obtain resin in step two for later use;
and step three, mixing the resin obtained in the step one with the resin obtained in the step two, and uniformly stirring to obtain the low dielectric epoxy glue.
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| CN114149764A (en) * | 2021-12-14 | 2022-03-08 | 长春长光宇航复合材料有限公司 | Ultrathin high-toughness cyanate ester adhesive film and preparation method thereof |
| CN114702927B (en) * | 2022-04-26 | 2024-03-26 | 苏州艾迪亨斯胶粘技术有限公司 | Epoxy thermosetting packaging adhesive for probe card and preparation method thereof |
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