CN112679911B - Modified epoxy resin composition and prepreg and laminated board prepared from same - Google Patents
Modified epoxy resin composition and prepreg and laminated board prepared from same Download PDFInfo
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Abstract
The invention discloses a modified epoxy resin composition which comprises the following components in parts by weight: (a) modified phosphorus-containing nitrogen-containing epoxy resin: 10-100 parts; (b) curing agent: 1-200 parts. The resin composition has the characteristics of halogen-free flame retardance, high humidity and heat resistance, low water absorption, high flame retardance, high peel strength and good dielectric property; the prepreg and the laminated board prepared from the resin composition have the characteristics of halogen-free flame retardance, high humidity resistance, low water absorption, high flame retardance, high peel strength and good dielectric property, and can be used as printed circuit boards for electronic instruments.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a modified epoxy resin composition and a prepreg and a laminated board prepared by using the same.
Background
In the prior art, the traditional brominated flame retardant (such as brominated epoxy resin, tetrabromobisphenol A and the like) has excellent flame retardance and relatively low price, and is always the main flame retardant of the common FR-4 copper-clad plate. However, with the improvement of the quality of life and safety awareness of people, the safety requirements of people on electronic products at the sides are higher and higher. Bromine-containing flame retardants can generate hydrogen bromide, which is an irritant and corrosive toxic gas such as dioxin and polybrominated dibenzofuran, during combustion, and the hydrogen bromide seriously harms the health of people and causes pollution. In addition, the bond energy of the carbon-bromine bond in the bromine-containing flame retardant is weaker, so that the thermal decomposition temperature is lower, and the application of the bromine-containing flame retardant in a high-performance copper-clad plate is obviously insufficient.
Therefore, the development direction of the existing flame retardant tends to be non-halogenated increasingly, and manufacturers of flame retardant materials in various countries start to apply the brominated flame retardant to the high polymer in a strict attitude, and the halogen-free flame retardant, especially the phosphorus flame retardant, gradually becomes the mainstream.
At present, in the field of copper-clad plates, the more commonly used phosphorus flame retardants mainly comprise phosphate, aluminum phosphate, DOPO and the like, wherein the DOPO is used as a modifier and can be used for modifying functional resins such as epoxy resin, cyanate ester resin, maleimide resin and the like. However, the DOPO ring has high water absorption under high temperature, high humidity or alkaline conditions, which affects the dielectric properties and the wet and heat resistance of the circuit board.
Therefore, the halogen-free flame retardant modified epoxy resin composition with high humidity resistance, low water absorption, high flame retardance, high peel strength and good dielectric property is developed, and prepregs and laminated plates made of the composition have excellent comprehensive properties, so that the halogen-free flame retardant modified epoxy resin composition has positive practical significance.
Disclosure of Invention
The invention aims to provide a modified epoxy resin composition and a prepreg and a laminated board prepared by applying the same.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a modified epoxy resin composition comprises the following components in parts by weight:
(a) Modified phosphorus-containing and nitrogen-containing epoxy resin: 10-100 parts;
(b) Curing agent: 1-200 parts;
the preparation method of the modified phosphorus-containing nitrogen-containing epoxy resin comprises the following steps:
(1) Mixing a diamine compound and 3-vinyl-p-benzaldehyde according to a molar ratio of 1:2, reacting to obtain a powdery intermediate product;
(2) Mixing the powdery intermediate product with the phosphorus-containing compound containing active hydrogen according to a molar ratio of 1:2, reacting to obtain a phosphorus-containing nitrogen-containing compound;
(3) Mixing the phosphorus-containing and nitrogen-containing compound and the epoxy resin according to a molar ratio of 0.01-1: 1, and obtaining the modified phosphorus-containing nitrogen-containing epoxy resin.
In the above, the molar ratio of the phosphorus-containing and nitrogen-containing compound to the epoxy resin in the step (3) is 0.01 to 1:1, more preferably 0.1 to 1:1, more preferably 0.3 to 0.9:1, more preferably 0.4 to 0.7:1.
in the above, the nitrogen content in the modified phosphorus-containing and nitrogen-containing epoxy resin is 0.1-2.8%, and the phosphorus content is 0.22% -6.2%.
Hereinbefore, the reaction process of the modified phosphorus-containing nitrogen-containing epoxy resin can be represented by the following formula (taking DOPO as an example):
as described above, the resin composition further contains a curing accelerator selected from at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, and zinc isooctanoate, for example: a mixture of 4-dimethylaminopyridine and 2-methylimidazole, a mixture of 2-methylimidazole and 2-methyl-4-ethylimidazole, a mixture of 2-phenylimidazole and zinc isooctoate, and a mixture of 2-methylimidazole, 2-methyl-4-ethylimidazole and 2-phenylimidazole, although not limited thereto.
In the above technical scheme, the structural formula of the diamine compound is as follows: h 2 N-R 1 -NH 2 Wherein R is 1 Is selected from A: alkyl of 1 to 12 carbon atoms; b:
C：
D：
E：
F：
G：
H：
I：
one kind of (1).
In the technical scheme, the phosphorus-containing compound containing active hydrogen is DOPO or DPO, and the specific structure is as follows:
In the above technical solution, the epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol type epoxy resin, tetraphenylethane epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl novolac epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, and glycidylester type epoxy resin.
Preferably, the epoxy resin may be a naphthalene ring type epoxy resin, a biphenyl type epoxy resin, or a dicyclopentadiene type epoxy resin; the structural formula of the naphthalene ring-type epoxy resin is shown as the following structural formula (1), the structural formula of the biphenyl epoxy resin is shown as the following structural formula (2), and the structural formula of the dicyclopentadiene epoxy resin is shown as the following structural formula (3):
In the above technical scheme, the curing agent is selected from one or more of amine compounds, amide compounds, anhydride compounds, phenol compounds, benzoxazine compounds and active ester compounds.
The amine compound is selected from one or more of diaminodiphenylmethane, diaminodiphenyl sulfone, diethylenetriamine, dicarboxyphthalimide, imidazole, dicyandiamide and diaminodiphenyl ether; preferably diaminodiphenylmethane and/or diaminodiphenylsulfone; the amide-based compound may be a low-molecular polyamide;
the acid anhydride compound is selected from one or more of phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, maleimide tung oil anhydride, styrene-maleic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride and nadic anhydride; preferably styrene-maleic anhydride;
the phenolic compound is selected from one or more of phenolic resin (preferably bisphenol A phenolic resin, phenol phenolic resin and naphthol phenolic resin), benzoxazine resin, bisphenol, monophenol, polyhydric phenol, benzenediol, biphenol type phenolic resin, biphenol type naphthol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin and trimethylolmethane resin;
the active ester compound is preferably a compound represented by the following structural formula (4):
Still further preferably, the curing agent is selected from at least one of dicyandiamide, diaminodiphenyl sulfone, diaminodiphenyl methane, styrene-maleic anhydride copolymer, phenolic resin, active ester, or benzoxazine.
Preferably, in the step (3), the reaction temperature is 60-180 ℃. More preferably 80 to 160 deg.C, more preferably 90 to 150 deg.C, more preferably 100 to 140 deg.C, more preferably 110 to 130 deg.C, more preferably 120 deg.C.
In the above technical solution, the resin composition further includes a filler, and the filler is 0 to 200 parts by weight based on 100 parts by weight of the resin composition, and it is understood that the resin composition may or may not include the filler. When a filler is contained in the resin composition, the filler is preferably contained in an amount of 10 to 100 parts by weight, more preferably 30 to 70 parts by weight, for example, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight, or 200 parts by weight, based on 100 parts by weight of the resin composition.
Specifically, the filler is an organic filler and/or an inorganic filler, wherein the inorganic filler is selected from one or a mixture of any several of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder. More preferably, the inorganic filler is at least one selected from the group consisting of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder. Preferably, the filler is silica, more preferably, surface-treated spherical silica. The surface treating agent is a silane coupling agent, such as a silane coupling agent containing an epoxy group, an amino group, a vinyl group, an acrylate group or an allyl group. Preferably, the filler has a particle size median value of 1 to 15 microns, such as 1 micron, 2 microns, 5 microns, 8 microns, 10 microns, 11 microns, 12 microns, 13 microns, 14 microns. More preferably, the filler has a median particle size value of from 1 to 10 microns.
Furthermore, according to different requirements of final products, the resin composition also comprises 0-5 parts of other auxiliary agents. The other auxiliary agents comprise a coupling agent, a dispersing agent and a dye. The coupling agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent; the dispersant is amino silane compound having amino group and having hydrolytic group or hydroxyl group such as gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, epoxy silane compound having epoxy group and having hydrolytic group or hydroxyl group such as 3-acryloxypropyltrimethoxysilane, vinyl silane compound having vinyl group and having hydrolytic group or hydroxyl group such as gamma-methacryloxypropyltrimethoxysilane, cationic silane coupling agent; the dispersant can be Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010 and W903 (all product names) made by BYK; the dye is a fluorescent dye and a black dye, wherein the fluorescent dye is pyrazoline and the like, and the black dye is carbon black (liquid or powder), a pyridine complex, an azo complex, aniline black, black talcum powder, cobalt chromium metal oxide, azine, phthalocyanine and the like.
The invention also discloses a prepreg manufactured by the resin composition, the resin composition is dissolved by a solvent to prepare a glue solution, then the reinforcing material is soaked in the glue solution, and the soaked reinforcing material is heated and dried to obtain the prepreg. Wherein the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric; preferably, the reinforcing material is glass fiber cloth, and open fiber cloth or flat cloth is preferably used in the glass fiber cloth. In addition, when the reinforcing material is a glass cloth, the glass cloth generally needs to be chemically treated to improve the interface between the resin composition and the glass cloth. The main method of the chemical treatment is a coupling agent treatment. The coupling agent used is preferably an epoxy silane, an aminosilane or the like to provide good water resistance and heat resistance.
The preparation method of the prepreg comprises the following steps: and (2) soaking the reinforcing material in the resin composition glue solution, then baking the soaked reinforcing material for 1-10min at the temperature of 50-170 ℃, and drying to obtain the prepreg.
The invention also discloses a laminated board, wherein a metal foil is coated on one side or two sides of one prepreg, or after at least 2 prepregs are stacked, a metal foil is coated on one side or two sides of the prepreg, and the laminated board is obtained by hot press forming. The preparation steps of the laminated board are as follows: and covering a metal foil on one or two sides of one prepreg, or covering a metal foil on one or two sides of at least 2 prepregs after laminating, and performing hot press forming to obtain the metal foil laminated board. The pressing conditions of the above laminate were: pressing for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃. Specifically, the number of prepregs may be determined according to the thickness of a desired laminate, and one or more prepregs may be used. The metal foil can be copper foil or aluminum foil, and the material is not limited; the thickness of the metal foil is also not particularly limited, such as 5 microns, 8 microns, 12 microns, 18 microns, 35 microns, or 70 microns.
The invention also provides a printed wiring board which comprises at least one prepreg or/and a laminated board.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention develops a novel modified epoxy resin composition, which is mainly modified phosphorus-containing and nitrogen-containing epoxy resin, wherein the modified phosphorus-containing and nitrogen-containing epoxy resin simultaneously has double bonds and epoxy groups, so that the resin has two curing reactions in the curing process: firstly, the free radical polymerization of double bond, secondly, the polymerization of epoxy group to can improve its cross-linking density greatly, and then promote Tg and modulus, the experiment proves: compared with the prior art, the resin system can improve Tg by at least 5 ℃, and has remarkable effect;
2. the modified phosphorus-containing and nitrogen-containing epoxy resin has a double bond structure, so that the dielectric property of a system can be improved besides the improvement of Tg; meanwhile, the nitrogen and phosphorus compounds in the modified epoxy resin can enable the epoxy resin to realize N-P synergistic flame retardance, so that the using amount of phosphorus is greatly reduced, low water absorption (large water absorption of P) can be realized, the dielectric property of the system is more excellent, and the dielectric property of the resin system is more excellent due to the cooperation of the nitrogen and phosphorus compounds;
3. experiments prove that: the resin composition has the characteristics of halogen-free flame retardance, high humidity and heat resistance, low water absorption, high flame retardance, high peel strength and good dielectric property; the prepreg and the laminated board prepared from the resin composition have the characteristics of halogen-free flame retardance, high humidity resistance, low water absorption, high flame retardance, high peel strength and good dielectric property, and can be used as printed circuit boards for electronic instruments.
Detailed Description
The invention is further described below with reference to examples:
synthesis example 1: modified epoxy resin A
The method comprises the following specific steps:
(1) Adding 0.1mol of p-phenylenediamine, 0.2mol of 3-vinyl-p-benzaldehyde and 70g of dimethylbenzene into a four-port reaction kettle provided with stirring and condensing equipment and nitrogen, heating to 110 ℃, reacting for 4 hours, and distilling under reduced pressure to remove the dimethylbenzene to obtain a powder intermediate product;
(2) Adding 0.1mol of intermediate product, 0.2mol of DOPO and 150g of dimethylbenzene into a four-port reaction kettle provided with stirring and condensing equipment and nitrogen, heating to 130 ℃, reacting for 6 hours, and removing the dimethylbenzene by reduced pressure distillation to obtain a final product, namely a phosphorus-nitrogen-containing compound;
(3) Adding 0.12mol of the phosphorus-nitrogen-containing compound, 1mol of biphenyl epoxy resin (structural formula 2 in the specification), 300g of dimethylbenzene and 0.5g of tributylamine into a four-port reaction kettle provided with stirring and condensing equipment and nitrogen, heating to 170 ℃, reacting for 4 hours, and removing the dimethylbenzene by reduced pressure distillation to obtain the modified epoxy resin A with the phosphorus content of 2.02%.
Synthesis example 2: modified epoxy resin B
Reaction conditions are as follows: 0.12mol of the phosphorus-nitrogen-containing compound in synthesis example 1, 1mol of naphthalene ring epoxy resin (structural formula 1 in the specification), 280g of xylene and 0.4g of tributylamine are added into a four-port reaction kettle provided with stirring and condensing equipment and nitrogen, the temperature is increased to 180 ℃, the reaction is carried out for 4 hours, and the xylene is removed by reduced pressure distillation, so that modified epoxy resin B with the phosphorus content of 2.31 percent is obtained.
Synthesis example 3: modified epoxy resin C
Reaction conditions are as follows: 0.12mol of the phosphorus-nitrogen-containing compound in synthesis example 1, 1mol of DCPD epoxy resin (i.e., structural formula 3 in the specification), 290g of xylene and 0.4g of tributylamine are added into a four-port reaction kettle provided with stirring and condensing equipment and nitrogen, the temperature is raised to 150 ℃, the reaction is carried out for 8 hours, and the xylene is removed by reduced pressure distillation, thus obtaining modified epoxy resin C with the phosphorus content of 2.17 percent.
Synthesis example 4: modified epoxy resin D
The method comprises the following specific steps:
(1) Adding 0.1mol of p-phenylenediamine, 0.2mol of 3-vinyl-p-benzaldehyde and 70g of dimethylbenzene into a four-port reaction kettle provided with stirring and condensing equipment and nitrogen, heating to 110 ℃, reacting for 4 hours, and distilling under reduced pressure to remove the dimethylbenzene to obtain a powder intermediate product;
(2) Adding 0.1mol of intermediate product, 0.2mol of DPO and 150g of dimethylbenzene into a four-port reaction kettle provided with stirring and condensing equipment and nitrogen, heating to 130 ℃, reacting for 6 hours, and removing the dimethylbenzene by reduced pressure distillation to obtain a final product, namely a phosphorus-nitrogen-containing compound;
(3) Adding 0.1mol of the phosphorus-nitrogen-containing compound, 1mol of biphenyl epoxy resin (structural formula 3), 300g of dimethylbenzene and 0.5g of tributylamine into a four-port reaction kettle provided with stirring and condensing equipment and nitrogen, heating to 170 ℃, reacting for 4 hours, and removing the dimethylbenzene by reduced pressure distillation to obtain phosphide-modified epoxy resin D with the phosphorus content of 1.77%.
Synthesis example 5: modified epoxy resin E
0.1mol of phosphorus-containing and nitrogen-containing compound in synthesis example 4, 1mol of naphthalene ring epoxy resin (structural formula 2), 280g of xylene and 0.4g of tributylamine are added into a four-port reaction kettle provided with stirring and condensing equipment and nitrogen, the temperature is increased to 180 ℃, the reaction is carried out for 4 hours, and the xylene is removed by reduced pressure distillation, so as to obtain phosphide-modified epoxy resin E with the phosphorus content of 2.04%.
Comparative synthesis example 1: modified epoxy resin curing agent F
The following epoxy resin curing agent was prepared according to the technique disclosed in chinese patent No. CN107400196A and used to cure epoxy resin.
The components and contents of the resin compositions of the examples and comparative examples are shown in the following table 1:
TABLE 1
Note: wherein the DOPO modified epoxy resin is an epoxy resin (with 75 percent of solid content) with the model number XZ92530 of the United states Olin;
the phenolic resin is PSM-4357 of Nippon gordon chemical; styrene maleic anhydride was XIRAN EF10 from Polyscope, the Netherlands.
According to the component content in the table 1, the modified epoxy resin, the curing agent, the filler, the catalyst and a proper amount of butanone solvent are stirred and mixed uniformly to obtain a glue solution with the solid content of 65 weight percent. The glue solution is dipped and coated on E glass fiber cloth (7628) and is dried in an oven at 160 ℃ for 5min to prepare a prepreg.
Preparation of performance evaluation sample laminates:
and (3) placing a 18-micron metal copper foil on each of the prepregs from top to bottom, and placing the prepregs in a vacuum hot press for pressing to obtain the laminated board. The specific pressing process is pressing for 2 hours under the pressure of 1.5MPa and the temperature of 180-220 ℃.
The performance test method is as follows:
(1) Flame retardance: measured by the UL94 method.
(2) Water absorption: the test was carried out according to IPC-TM-650.2.6.2.1.
(3) Dielectric properties: the frequency of the test was 1GHz using the plate method according to IPC-TM-650.5.5.9.
(4) Glass transition temperature Tg (. Degree. C.): the measurement was carried out by Differential Scanning Calorimetry (DSC) method according to the DSC method defined by IPC-TM-650.4.25.
(5) Peel strength (PS, N/mm):
the peel strength of the metal cap was tested according to the "post thermal stress" experimental conditions in the IPC-TM-650.2.4.8 method.
(6) Tin immersion heat resistance after moist heat treatment:
3 samples of 10cm thick and 0.80mm thick with the metal foil removed on both sides were dried at 100 ℃ for 2 hours, and then treated with a Pressure Cooker test (Pressure Cooker test) at 121 ℃ under 2 atmospheres for 1 hour, and then dipped in tin in a tin furnace at 288 ℃ for 20 seconds, and visually observed whether or not there was any delamination. If there are 0,1,2,3 of the 3 blocks, the delamination is recorded as 0/3,1/3,2/3,3/3, respectively.
The properties of the laminate obtained are shown in table 2.
TABLE 2
| E1 | E2 | E3 | E4 | E5 | E6 | E7 | E8 | C1 | C2 | |
| Phosphorus content (%) | 1.79 | 1.85 | 1.81 | 1.76 | 1.91 | 1.55 | 1.59 | 1.56 | 2.76 | 2.26 |
| Flame retardancy | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-1 |
| Water absorption (%) | 0.20 | 0.19 | 0.18 | 0.19 | 0.20 | 0.18 | 0.17 | 0.16 | 0.25 | 0.25 |
| Dk | 3.76 | 3.79 | 3.68 | 3.73 | 3.82 | 3.74 | 3.76 | 3.65 | 3.85 | 3.97 |
| Df | 0.006 | 0.006 | 0.005 | 0.006 | 0.006 | 0.006 | 0.006 | 0.005 | 0.007 | 0.007 |
| Tg(℃) | 162 | 159 | 155 | 157 | 161 | 165 | 162 | 158 | 150 | 143 |
| Peel strength | 1.4 | 1.3 | 1.2 | 1.4 | 1.4 | 1.4 | 1.3 | 1.2 | 1.3 | 1.2 |
| PCT 1Hr | 0/3 | 0/3 | 0/3 | 0/3 | 0/3 | 0/3 | 0/3 | 0/3 | 3/3 | 3/3 |
From the above table it can be seen that: comparative example 1 the modified epoxy resin curing agent F of comparative synthesis example 1 was used to cure DCPD epoxy resin (i.e., formula 3 in the specification), and it was found that the water absorption and wet heat resistance were both significantly reduced compared to the examples; comparative example 2 the use of phenol novolac resin (PSM-4357, NJ chemical Co., ltd.) to cure DOPO modified epoxy resin (Olin XZ92530, USA) is inferior to examples and comparative example 1 in flame retardancy, water absorption, wet heat resistance, dielectric properties and peel strength; the embodiments of the present invention have the characteristics of high flame retardancy, low dielectric constant, low dielectric loss tangent, low water absorption, high heat resistance, excellent moisture and heat resistance, and good adhesion with copper foil.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The modified epoxy resin composition is characterized by comprising the following components in parts by weight:
(a) Modified phosphorus-containing and nitrogen-containing epoxy resin: 10-100 parts;
(b) Curing agent: 1-200 parts;
the preparation method of the modified phosphorus-containing nitrogen-containing epoxy resin comprises the following steps:
(1) Mixing a diamine compound and 3-vinyl-p-benzaldehyde according to a molar ratio of 1:2, reacting to obtain a powdery intermediate product;
(2) Mixing the powdery intermediate product with the phosphorus-containing compound containing active hydrogen according to a molar ratio of 1:2, reacting to obtain a phosphorus-containing nitrogen-containing compound;
(3) Mixing the phosphorus-containing and nitrogen-containing compound and the epoxy resin according to a molar ratio of 0.01-1: 1 to obtain the modified phosphorus-containing and nitrogen-containing epoxy resin.
2. The resin composition according to claim 1, characterized in that: the diamine compound has the following structural formula: h 2 N-R 1 -NH 2 Wherein R is 1 Is selected from A: alkyl of 1 to 12 carbon atoms; b:
C：
D：
E：
F：
G：
H：
I：
one kind of (1).
3. The resin composition according to claim 1, characterized in that: the phosphorus-containing compound containing active hydrogen is DOPO or DPO.
4. The resin composition according to claim 1, characterized in that: the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol type epoxy resin, tetraphenylethane epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl novolac type epoxy resin, alicyclic epoxy resin, glycidyl amine type epoxy resin and glycidyl ester type epoxy resin.
5. The resin composition according to claim 1, characterized in that: the curing agent is selected from one or more of amine compounds, amide compounds, anhydride compounds, phenol compounds, benzoxazine compounds and active ester compounds.
6. The resin composition according to claim 1, characterized in that: the resin composition also comprises a filler, wherein the filler is selected from at least one of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talcum powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica and glass fiber powder.
7. The resin composition according to claim 1, characterized in that: in the step (3), the reaction temperature is 60-180 ℃.
8. A prepreg manufactured using the resin composition according to any one of claims 1 to 7, characterized in that: dissolving the resin composition according to any one of claims 1 to 7 with a solvent to prepare a glue solution, then impregnating the reinforcing material in the glue solution, and then heating and drying the impregnated reinforcing material to obtain the prepreg.
9. A laminate which is obtained by laminating a metal foil on one side or both sides of a sheet of the prepreg according to claim 8 or by laminating at least 2 sheets of the prepreg according to claim 8, laminating a metal foil on one side or both sides of the sheet, and hot press molding the laminate.
10. A circuit board comprising the prepreg according to claim 8 or/and the laminate according to claim 9.
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| CN1618830A (en) * | 2003-11-19 | 2005-05-25 | 北京化工大学 | Epoxy resin containing double bonds and curing system |
| JP2012111807A (en) * | 2010-11-22 | 2012-06-14 | Uniplus Electronics Co Ltd | Thermosetting resin composition and prepreg sheet or laminated board using the thermosetting resin composition |
| CN103073746A (en) * | 2013-01-10 | 2013-05-01 | 苏州安鸿泰新材料有限公司 | Reactive phosphorus flame retardant containing DOPO and active double bond and preparation method and application thereof |
| CN104693421A (en) * | 2015-03-27 | 2015-06-10 | 厦门大学 | Self-inflaming-retarding epoxy resin curing agent containing phosphorus-nitrogen and preparation method thereof |
| CN107501492A (en) * | 2017-08-10 | 2017-12-22 | 长春工业大学 | Schiff bases formula phosphorus nitrogen expansion type combustion inhibitor and its production and use |
| CN109608619A (en) * | 2018-11-21 | 2019-04-12 | 苏州生益科技有限公司 | A kind of phosphorous epoxy resin composition and prepreg and laminate using its preparation |
| CN109535715A (en) * | 2018-11-28 | 2019-03-29 | 苏州生益科技有限公司 | A kind of flame resistance resin composite and prepreg and laminate using its preparation |
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| CN112679911A (en) | 2021-04-20 |
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