CN114316590A - Resin composition and use thereof - Google Patents
Resin composition and use thereof Download PDFInfo
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- CN114316590A CN114316590A CN202111653624.XA CN202111653624A CN114316590A CN 114316590 A CN114316590 A CN 114316590A CN 202111653624 A CN202111653624 A CN 202111653624A CN 114316590 A CN114316590 A CN 114316590A
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Abstract
The invention relates to a resin composition, a prepreg, an insulating film and applications thereof. The resin composition comprises the following components in percentage by weight: 5-100 parts of bismaleimide resin and/or derivatives thereof; 1-30 parts of amine curing agent; 0.1-10 parts of antioxidant and 0.5-5 parts of accelerator; the accelerant comprises an imidazole compound and triphenyl phosphine, wherein the weight ratio of the imidazole compound to the triphenyl phosphine is (2-5) to (0.1-0.8). A prepreg includes a reinforcing material and a resin composition coated thereon. Insulating film: comprising a carrier film and a resin composition coated thereon. The invention improves the RTI value and the thermal decomposition temperature of the bismaleimide and obtains the resin composition with excellent comprehensive performance, wherein the RTI of the resin composition is higher than 110 ℃. The laminated board, the high-frequency circuit substrate and the like manufactured by adopting the bismaleimide resin composition have the characteristics of high RTI value and thermal decomposition temperature, excellent humidity resistance, higher peel strength, excellent manufacturability and the like.
Description
Technical Field
The invention belongs to the technical field of electronic materials, and particularly relates to a resin composition, a prepreg, an insulating film and applications thereof.
Background
The safety and reliability of electronic products relate to the safety of life and property, and the copper-clad plate is an important component of a printed circuit board in the electronic products. The copper clad laminate base material used in the field of civil electronic products requires that UL (Underwriter Laboratories, American authoritative safety test institute) Thermal Index (RTI) is not lower than 130 ℃. Bismaleimides (BMIs), one of high performance thermosetting resins, have been widely used in the fields of aerospace, electronic and electrical products, transportation and the like, especially in recent years, and have played an important role in the field of civil electronics, due to their outstanding heat resistance, dielectric properties, moisture and heat resistance, and excellent mechanical properties, chemical resistance, radiation resistance, wear resistance and dimensional stability. In the application of civil electronic field, BMI is required to meet the requirement of RTI 130 ℃ and above.
However, BMI undergoes radical oxidation, which results in a BMI with an RTI below 130 ℃. In the related art, the RTI of BMI is generally improved by: firstly, the modification is carried out through epoxy; and the other is to add polymerization inhibitor to improve RTI of BMI by capturing free radicals. However, although the former can improve RTI of BMI, BMI is not polyimide type (GPY) already; the latter has some effect on improving RTI of BMI, but does not meet the requirement that RTI is more than or equal to 140 ℃.
Therefore, it is one of the hot spots of the current research to develop a bismaleimide resin satisfying the requirements of the RTI of 130 ℃ and above, and a prepreg, an insulating film and related products made of the bismaleimide resin.
Disclosure of Invention
In order to prepare a bismaleimide resin with RTI higher than 130 ℃, a prepreg, an insulating film and related products prepared by using the bismaleimide resin, the invention provides a resin composition, the prepreg, the insulating film and applications of the resin composition, the prepreg, the insulating film and the related products.
In a first aspect, the present invention provides a resin composition, which adopts the following technical scheme:
a resin composition comprising, by weight:
5-100 parts of bismaleimide resin and/or derivatives thereof;
1-30 parts of amine curing agent;
0.1-10 parts of antioxidant;
and 0.5-5 parts of an accelerator;
the accelerant comprises an imidazole compound and triphenyl phosphine, wherein the weight ratio of the imidazole compound to the triphenyl phosphine is (2-5) to (0.1-0.8).
According to the technical scheme, on one hand, the manufacturability can be effectively improved by adopting the weight ratio of the imidazole compound to the triphenyl phosphine; on the other hand, the compound is matched with an antioxidant for use, so that the RTI of the bismaleimide resin and the derivative is effectively improved to be higher than 130 ℃, and the bismaleimide resin can better meet the requirement of civil electronic application.
As an alternative, the weight ratio of the imidazole compound to the triphenyl phosphine is (2-5) to (0.2-0.7); more preferably, the weight ratio of the imidazole compound to the triphenyl phosphine is (2-5) to (0.2-0.5), so that the ratio of the imidazole compound to the triphenyl phosphine is optimized.
When the weight ratio of the imidazole compound to the triphenylphosphine is higher than 50:1, the reaction of the system is too slow, and the dry-cracking phenomenon can occur due to large gummosis of the base material during pressing. When the weight ratio of the imidazole compound to the triphenyl phosphine is lower than 2.5:1, the system reaction is too fast, the viscosity of the glue solution is high, the gluing is difficult during pressing, and the production cannot be realized.
As an alternative, the imidazole-based compound includes at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole, and 1-cyanoethyl-2-methylimidazole.
Alternatively, the antioxidant is selected from at least one of naphthol compounds, thiol compounds, quinones, aromatic nitro compounds, electrophilic metal salts, aminophenols, phosphates, phosphites, and amine phosphates, such as antioxidant 1010 (Ciba chemical), 1076 (Ciba chemical), antioxidant 168 (Ciba chemical), triphenyl phosphite, antioxidant TBM-6 (Kyobo), 245(Basf) zinc bis-methyl terephthalate, and the like.
As an alternative, the bismaleimide resin is selected from at least one of the following structures:
R2is hydrogen, methyl or ethyl, R1Is methylene, ethylene or
in the structural formulas 6-10, n is an integer of 1-10.
Alternatively, the derivative of the bismaleimide resin is a modified product of the bismaleimide resin, and is a product modified with an allyl compound, a diamine compound, a polyphenylene ether compound, or a siloxane compound. Preferably, the bismaleimide resin is modified with an allyl compound or a diamine compound. A preparation method of modified bismaleimide resin belongs to the prior art.
The content of the bismaleimide resin or a derivative of the bismaleimide resin is preferably 5 to 50 parts.
Alternatively, the amine curing agent is an aromatic amine compound, preferably at least one selected from diaminodiphenylmethane, diaminodiphenylethane, and diaminodiphenylsulfone.
As an alternative, a filler is further included, and the filler is added in an amount of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the resin composition. The filler is an inorganic filler or an organic filler, wherein: the inorganic filler is at least one selected from the group consisting of fused boehmite, 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. The organic filler is at least one of polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder. Preferably, the filler is at least one of barium sulfate and boehmite.
As an alternative, the resin composition may further comprise other additives according to different requirements of the final product; preferably, the other auxiliaries are 0 to 5 parts by weight based on 100 parts by weight of the resin composition. Other auxiliary agents include coupling agents, dispersants, dyes.
Wherein: the coupling agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent.
The dispersant is selected from amino silane compounds having an amino group and having a hydrolyzable group or a hydroxyl group, such as γ -aminopropyltriethoxysilane and N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, epoxy silane compounds having an epoxy group and having a hydrolyzable group or a hydroxyl group, such as 3-acryloxypropyltrimethoxysilane, and vinyl silane compounds having a vinyl group and having a hydrolyzable group or a hydroxyl group, such as γ -methacryloxypropyltrimethoxysilane. Specific examples of the dispersant include Disperbyk-110, 111, 118, 180, 161, 903, 2009, BYK-W996, W9010, W903 and the like manufactured by BYK.
The dye is fluorescent dye or black dye, the fluorescent dye can be pyrazoline compound, and the black dye can be liquid or powder carbon black, pyridine complex, azo complex, aniline black, black talcum powder, cobalt chromium metal oxide, azine or phthalocyanine.
The invention also provides the application of the resin composition in prepregs, laminated boards, insulating films, insulating plates, high-frequency circuit substrates and electronic devices; the concrete description is as follows.
In a second aspect, the present invention provides a prepreg, which adopts the following technical scheme:
a prepreg comprising a reinforcing material and the resin composition as described above coated thereon; the resin composition is beneficial to improving the thermal index of the prepreg.
As an alternative, the prepreg is prepared by the following method: dissolving the resin composition with a solvent to prepare a glue solution, then soaking the reinforced material in the glue solution, and baking the soaked reinforced material at the temperature of 100-180 ℃ for 1-15 min; and drying to obtain the prepreg.
Wherein: the organic solvent may be at least one selected from acetone, methyl ethyl ketone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.
The reinforcing material may be selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics. Preferably, the reinforcing material adopts glass fiber cloth; among the glass fiber cloth, a spread cloth or a flat cloth is preferably used. In addition, when the reinforcing material is 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 chemical treatment method is 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.
In a third aspect, the present invention provides a laminate, which adopts the following technical scheme:
the laminated board comprises a prepreg and a metal foil arranged on at least one side surface of the prepreg; or the prepreg comprises a composition sheet formed by mutually laminating a plurality of prepregs and a metal foil arranged on at least one side surface of the composition sheet.
The heat index of the laminate with the prepreg is remarkably improved.
As an alternative, the laminate is prepared by the following method: covering a metal foil on one side or two sides of a prepreg, and performing hot press forming to obtain a metal foil laminated board; or laminating at least two prepregs to form a sheet, coating metal foils on one or two surfaces of the sheet, and performing hot press forming to obtain the metal foil laminated board. The pressing conditions of the above laminate were: pressing at a pressure of 0.2-2MPa and a temperature of 150 ℃ and 250 ℃ for 2-4 hours.
The number of prepregs in the laminate may be determined according to the desired thickness of the laminate, and may be one or more. The metal foil can be copper foil, aluminum foil or other conventional metal foils; the thickness of the metal foil can be freely set according to practical situations, such as 5 microns, 8 microns, 12 microns, 18 microns, 35 microns or 70 microns.
In a fourth aspect, the invention discloses an insulating plate, which adopts the following technical scheme:
an insulating board comprising at least one prepreg; the thermal index of the resulting insulating panel can be improved.
In a fifth aspect, the invention discloses an insulating film, which adopts the following technical scheme:
an insulation film comprising a support film and the resin composition coated thereon, the insulation film having a significantly improved heat index.
As an alternative, the insulating film is prepared by the following method: dissolving the resin composition with a solvent to prepare a glue solution, coating the glue solution on a carrier film, and heating and drying the carrier film coated with the glue solution to obtain the insulating film.
The organic solvent may be at least one selected from acetone, methyl ethyl ketone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.
The support film may be at least one selected from the group consisting of a PET film, a PP film, a PE film, and a PVC film.
In a sixth aspect, the invention discloses a high-frequency circuit substrate, which adopts the following technical scheme:
a high-frequency circuit substrate comprises one or more of the prepreg, the laminated board, the insulating board and the insulating film.
Through the technical scheme, the heat resistance and the heat index of the high-frequency circuit substrate are greatly improved.
In a seventh aspect, the present invention discloses an electronic device, which adopts the following technical scheme:
an electronic device comprising the high-frequency circuit substrate; since the heat resistance of the high-frequency circuit board is greatly improved, the safety of the electronic device is remarkably improved.
The invention has the beneficial technical effects that: provided are a resin composition, a prepreg, an insulating film, and applications thereof. The invention improves the RTI value and the thermal decomposition temperature of the bismaleimide, improves the manufacturability and obtains the resin composition with excellent comprehensive performance, and the RTI of the resin composition is higher than 160 ℃. The laminated board, the high-frequency circuit substrate and the like made of the bismaleimide resin composition have the characteristics of high RTI value, high thermal decomposition temperature, excellent moist heat resistance, higher peel strength, excellent manufacturability and the like.
Detailed Description
The present invention will now be illustrated in further detail by way of examples, which are given by way of illustration only, and are not to be construed as limiting the scope of the present invention.
The invention discloses a resin composition, which comprises 5-100 parts by weight of bismaleimide resin and/or derivatives thereof, 1-30 parts by weight of amine curing agent, 0.1-10 parts by weight of antioxidant and 0.5-5 parts by weight of accelerator.
Wherein: the bismaleimide resin is selected from at least one of the following structures:
R2is hydrogen, methyl or ethyl, R1Is methylene, ethylene or
in the structural formulas 6-10, n is an integer of 1-10.
The derivative of the bismaleimide resin is a modified product of the bismaleimide resin, and is a product modified by an allyl compound, a diamine compound, a polyphenyl ether compound or a siloxane compound; the derivative of the bismaleimide resin is preferably an allyl compound-modified bismaleimide resin or a diamine compound-modified bismaleimide resin.
The amine curing agent is aromatic amine compound, and is selected from at least one of diaminodiphenylmethane, diaminodiphenylethane, and diaminodiphenylsulfone.
The antioxidant is at least one selected from naphthol compound, thiol compound, quinones, aromatic nitro compound, variable valence metal salt electrophilic substance, aminophenol, phosphate ester, phosphite ester, and amine phosphate.
The accelerator comprises imidazole compounds and triphenyl phosphine, and the weight ratio of the imidazole compounds to the triphenyl phosphine is (2-5): 0.1-0.8, preferably (2-5): 0.2-0.7, more preferably (2-5): 0.2-0.5. The imidazole compound is at least one selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole and 1-cyanoethyl-2-methylimidazole.
In addition, the resin composition may further include a filler. The filler is added in an amount of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the resin composition. The filler is inorganic filler or organic filler; wherein: the inorganic filler is at least one selected from the group consisting of fused boehmite, 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; the organic filler is at least one of polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder. The filler is preferably at least one of barium sulfate and boehmite.
The invention also discloses a prepreg, which comprises a reinforcing material and the resin composition coated on the reinforcing material. Wherein the reinforcing material is selected from at least one of natural fiber fabric, organic synthetic fiber fabric and inorganic fiber fabric. Preferably, the reinforcing material adopts glass fiber cloth; among the glass fiber cloth, a spread cloth or a flat cloth is preferably used.
The preparation method of the prepreg comprises the following steps: dissolving the resin composition with a solvent to prepare a glue solution, then soaking the reinforcing material in the glue solution, and heating and drying the soaked reinforcing material to obtain the prepreg.
The invention also discloses a laminated board which comprises a prepreg and the metal foil arranged on the surface of at least one side of the prepreg; or comprises a composition sheet formed by mutually laminating a plurality of prepregs and a metal foil arranged on at least one side surface of the composition sheet. Wherein: the metal foil is selected from copper foil, aluminum foil or other conventional metal foils.
The preparation method of the laminated board comprises the following steps: covering a metal foil on one side or two sides of a prepreg, and performing hot press forming to obtain a laminated board; or laminating at least two prepregs to form a sheet, coating a metal foil on one or both surfaces of the sheet, and hot-press forming to obtain the laminated board.
The invention also discloses an insulating plate which comprises at least one prepreg.
The invention also discloses an insulating film, which comprises a carrier film and the resin composition coated on the carrier film. Wherein: the carrier film is at least one selected from PET film, PP film, PE film and PVC film.
The preparation method of the insulating film comprises the following steps: and dissolving the resin composition by using a solvent to prepare a glue solution, coating the glue solution on the carrier film, and heating and drying the carrier film coated with the glue solution to obtain the insulating film.
The invention also discloses a high-frequency circuit substrate which comprises the prepreg, a laminated board formed by the prepreg and/or the insulating film.
The invention discloses an electronic device, which comprises the high-frequency circuit substrate.
The compositions and their use according to the invention are described in detail in the following examples.
Example 1
The present example discloses a resin composition comprising: 100g of bismaleimide resin, 5g of diaminodiphenylmethane, 2g of 2-methyl-4-ethylimidazole, 0.75g of triphenylphosphine and 1g of antioxidant.
Wherein: the bismaleimide resin is MIR-3000 of Japanese chemical, and the structural formula is as follows:
The antioxidant is antioxidant 1010 of Ciba chemistry.
The embodiment also discloses a prepreg, which comprises a reinforcing material and the resin composition coated on the reinforcing material.
The preparation method of the prepreg comprises the following steps:
s1, weighing the resin composition according to the components and the proportion thereof, adding a certain amount of butanone, and uniformly stirring to obtain a glue solution with a solid content of 65 wt%.
S2, coating the glue solution on E glass fiber cloth (7628, with the single weight of 198 g/m) as a reinforcing material by a dipping method2) Then, the prepreg with the resin content of 50 percent is prepared by baking the prepreg in an oven at 175 ℃ for 6min, and the film thickness of the resin composition is controlled to be 0.20 mm.
This example also discloses a copper-clad laminate, which is composed of a composite sheet in which eight prepregs as described above are laminated on each other, and metal copper foils (18 μm thick) disposed on both surfaces of the composite sheet.
The preparation method of the laminated board comprises the following steps:
p1, laminating eight prepregs to form a composite sheet, and then laminating a metal copper foil on both surfaces of the composite sheet.
P2, placing in a vacuum hot press, and hot pressing at 180-220 ℃ for 1-4 h under the pressure of 1.5MPa to obtain the copper clad laminate. The properties of the copper-clad laminate obtained are shown in Table 1.
The embodiment also discloses an insulating film, which comprises a carrier film and the resin composition coated on the carrier film.
The preparation method of the insulating film comprises the following steps:
s10, weighing the resin composition according to the components and the proportion thereof, adding a certain amount of butanone, and uniformly stirring to obtain a glue solution with a solid content of 65 wt%.
S20, uniformly coating the glue solution on a PET film (G2, Mitsubishi chemical) with the thickness of 10-150 microns serving as a carrier film, and drying in an oven at the temperature of 50-170 ℃ for 1-10 min to obtain the interlayer insulating film.
The embodiment also discloses a high-frequency circuit substrate which is composed of the copper-clad laminate; the high-frequency circuit board has a high RTI value, a high thermal decomposition temperature and excellent moisture and heat resistance. In another embodiment, the high-frequency circuit board may further include the insulating film.
The embodiment also discloses an electronic device, which comprises the high-frequency circuit substrate; since the high-frequency circuit board has good heat resistance, the safety of the electronic device is remarkably improved.
Example 2
The present example discloses a resin composition comprising: 100g of allyl-modified bismaleimide resin, 5g of diaminodiphenylethane, 0.8g of 2-methylimidazole, 0.2g of triphenylphosphine and 1g of antioxidant.
Wherein: the allyl modified bismaleimide resin is prepared by reacting bismaleimide resin with a structural formula 1 and an allyl bisphenol A compound. The antioxidant is antioxidant 1010 of Ciba chemistry.
The antioxidant is antioxidant 1010 of Ciba chemistry.
The preparation methods of the prepreg, the copper clad laminate, the insulating film, the high frequency circuit board, and the electronic device were the same as in example 1.
Example 3
The present example discloses a resin composition comprising: 100g of bismaleimide resin, 5g of diaminodiphenylmethane, 3g of 1-benzyl-2-methylimidazole, 0.25g of triphenylphosphine and 1g of antioxidant.
Wherein: the bismaleimide resin adopts a structural formula 6.
The antioxidant is antioxidant 1010 of Ciba chemistry.
The preparation methods of the prepreg, the copper clad laminate, the insulating film, the high frequency circuit board, and the electronic device were the same as in example 1.
Example 4
The present example discloses a resin composition comprising: 100g of bismaleimide resin, 15g of diaminodiphenyl sulfone, 3g of 2-phenyl-imidazole, 0.1g of triphenyl phosphine, and 1g of antioxidant.
Wherein: the bismaleimide resin is prepared from structural formula 2 and structural formula 6 according to a mass ratio of 1:1, mixing; the antioxidant is antioxidant 1010 of Ciba chemistry.
The preparation methods of the prepreg, the copper clad laminate, the insulating film, the high frequency circuit board, and the electronic device were the same as in example 1.
Example 5
This example is substantially the same as example 3, except that: the resin compositions have different composition ratios.
The method specifically comprises the following steps: the resin composition comprises: 100g of bismaleimide resin, 5g of diaminodiphenylmethane, 2g of 1-benzyl-2-methylimidazole, 0.8g of triphenylphosphine and 1g of antioxidant.
Wherein: the bismaleimide resin adopts a structural formula 6. The antioxidant is antioxidant 1010 of Ciba chemistry.
Comparative example 1
The main differences between this comparative example and example 1 are: the raw materials have different composition ratios.
The method specifically comprises the following steps: the resin composition comprises: 100g of bismaleimide resin, 5g of diaminodiphenylmethane, 1g of 2-methyl-4-ethylimidazole, 1g of triphenylphosphine and 1g of antioxidant.
Comparative example 2
The main differences between this comparative example and example 2 are: the raw materials have different composition ratios.
The method specifically comprises the following steps: the resin composition comprises: 100g of allyl-modified bismaleimide resin, 5g of diaminodiphenylethane, 1.2g of 2-methylimidazole, 0.023g of triphenylphosphine and 1.0g of antioxidant.
Comparative example 3
The main differences between this comparative example and example 3 are: the raw materials have different composition ratios.
The method specifically comprises the following steps: the resin composition comprises: 100g of bismaleimide resin, 5g of diaminodiphenylmethane, 2g of 1-benzyl-2-methylimidazole, 0.9g of triphenylphosphine and 1g of antioxidant.
Comparative example 4, the main differences from example 1 are: the raw material composition does not contain an antioxidant.
The method specifically comprises the following steps: the resin composition comprises: 100g of bismaleimide resin, 5g of diaminodiphenylmethane, 2g of 2-ethyl-4-ethylimidazole and 0.75g of triphenyl phosphine.
Sample detection
The resin compositions, copper-clad laminates and high-frequency circuit boards obtained in examples 1 to 5 and comparative examples 1 to 4 were subjected to performance tests, and the results are shown in Table 1.
1) And (3) evaluating the manufacturability: good-the viscosity of the glue is suitable for sizing, the substrate has no dry thread (marked as ^), in general-the viscosity of the glue is somewhat large, but sizing can be performed, the substrate has no dry thread (marked as ^), poor-the viscosity of the glue is large, sizing can not be performed, or the viscosity of the glue can be sized, but the substrate produced by flowing glue is too large, dry thread cannot be used (marked as x)
2) And (3) RTI test: the bending strength is tested according to GB/T9341-2000 by using a domestic KQL microcomputer controlled electronic universal tester. Wherein: the test speed is 2 mm/min; the test sample was an etched high-frequency circuit board having a size of 100X 25 (weft) X1.60 mm. At least 5 effective results are obtained in each group of tests of the mechanical property, and the average value is taken as the final result. The samples were placed in ovens at 280, 260, 240, 220 ℃ respectively, sampled for the specified time to test the flexural strength, calculated using the equation y-a 0+ a1t + a2t2+ a3t3 to calculate the time for the flexural strength to decay to 50% at each temperature, and then calculated to RTI using Arrhenius equation (k-Ae-Ea/RT).
3) Thermogravimetric (TG) test: the thermal stability of the high-frequency circuit substrate in an air environment is characterized by adopting a Perkinelmer TGA-7 thermal weight loss analysis instrument in the United states. Wherein: the heating rate is 10 ℃/min, the temperature range is 50-800 ℃, and the atmosphere is air. The onset thermal decomposition temperature (Tdi) is defined as the temperature at which 5% weight loss occurs.
4) Resistance to moist Heat (PCT) test: taking 3 copper clad laminates with 10cm multiplied by 10cm, thickness of 0.80mm and metal foil removed on two sides; after drying at 100 ℃ for 2 hours, a cooking test (Pressure Cooker test) was carried out using an autoclave; after treatment at 121 ℃ for 3 hours under 2 atmospheres, the mixture was immersed in tin for 20 seconds at 288 ℃ in a tin furnace, and then visually observed for delamination. If there are 0, 1, 2, 3 blocks in the 3 blocks, the layering phenomena are respectively recorded as 0/3, 1/3, 2/3, 3/3.
5) And (3) testing combustibility: the test was performed with reference to UL 94.
6) And (3) testing the peel strength: the peel strength of the metal cap was tested with reference to the "post thermal stress" experimental conditions in the IPC-TM-6502.4.8 method.
TABLE 1 examination of the Properties of the samples obtained in examples 1-16 and comparative examples 1-3
Referring to table 1, the high-frequency circuit substrates obtained in the embodiments of the present invention all have a high RTI value (greater than 160 ℃) thermal decomposition temperature, and the combustion grade is 0 grade, which shows good heat resistance; meanwhile, the laminated board obtained by each embodiment of the invention has excellent humidity resistance and high peel strength; also, the resin polymer obtained in each example of the present invention has excellent processability.
Comparing example 1 with comparative example 1, it can be found that the weight ratio of the imidazole compound to the triphenyl phosphine is 1:1, and the ratio is too low, so that the glue solution has too high viscosity, the glue can not be glued, and the sample can not be prepared; the manufacturability of comparative example 1 is poor. Similarly, comparative example 3 and comparative example 3 can find that, because the weight ratio of the imidazole compound and the triphenylphosphine is 2.22: 1, the proportion is too low, which causes too high viscosity of the glue solution and can not glue.
Comparing example 2 with comparative example 2, it can be seen that the weight ratio of the imidazole compound to the triphenylphosphine is 52.17: 1, the proportion is too large, the glue flow of the prepreg in the pressing process is too large, the base material and the glass fiber are not well infiltrated (dry fibers), and the sample cannot meet the requirement. The embodiment 2 of the invention obviously improves the defects, and has good manufacturability and high RTI.
Comparing example 4 with example 1, it can be seen that the accelerator does not act synergistically with the antioxidant in the absence of the antioxidant, and the resulting prepreg cannot be prepared.
In light of the foregoing description of the preferred embodiment of the present invention, it is to be understood that various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A resin composition characterized by: comprises the following components in parts by weight:
5-100 parts of bismaleimide resin and/or derivatives thereof;
1-30 parts of amine curing agent;
0.1-10 parts of antioxidant;
and 0.5-5 parts of an accelerator;
the accelerant comprises an imidazole compound and triphenyl phosphine, wherein the weight ratio of the imidazole compound to the triphenyl phosphine is (2-5) to (0.1-0.8).
2. The resin composition according to claim 1, characterized in that: the weight ratio of the imidazole compound to the triphenyl phosphine is (2-5) to (0.2-0.7).
3. The resin composition according to claim 2, characterized in that: the weight ratio of the imidazole compound to the triphenyl phosphine is (2-5) to (0.2-0.5).
4. The resin composition according to claim 1, characterized in that: the imidazole compound is at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole and 1-cyanoethyl-2-methylimidazole.
5. The resin composition according to any one of claims 1 to 4, wherein: the antioxidant is at least one of naphthol compound, thiol compound, quinones, aromatic nitro compound, variable valence metal salt electrophilic substance, phosphate ester, phosphite ester or amine phosphate.
6. The resin composition according to claim 1, characterized in that: the bismaleimide resin is selected from at least one of the following structures:
r2 is hydrogen or methylOr ethyl, R1 is methylene, ethylene or
n is an integer of 1 to 10,
n is an integer of 1 to 10,
n is an integer of 1 to 10,
n is an integer of 1 to 10,
r is hydrogen, methyl or ethyl, and n is an integer of 1 to 10.
7. The resin composition according to claim 1, characterized in that: the derivative of the bismaleimide resin is a product obtained by modifying the bismaleimide resin by adopting an allyl compound, a diamine compound, a polyphenyl ether compound or a siloxane compound.
8. The resin composition according to claim 1, characterized in that: the amine curing agent is aromatic amine.
9. The resin composition according to claim 1, characterized in that: also comprises a filler; the filler includes an inorganic filler or an organic filler.
10. Use of the high-frequency resin composition according to any one of claims 1 to 9 in prepregs, laminates, insulating films, insulating plates, copper-clad plates, high-frequency circuit substrates and electronic devices.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019346A (en) * | 2019-12-26 | 2020-04-17 | 艾蒙特成都新材料科技有限公司 | Flame-retardant high-heat-resistance resin composition, copper-clad plate and preparation method thereof |
| CN111732817A (en) * | 2020-06-19 | 2020-10-02 | 林州致远电子科技有限公司 | Halogen-free low-loss copper-clad plate and glue solution and preparation method thereof |
| CN112062914A (en) * | 2020-09-22 | 2020-12-11 | 常熟生益科技有限公司 | Resin composition, and prepreg and laminated board manufactured by using same |
| CN112679700A (en) * | 2020-12-23 | 2021-04-20 | 江苏东材新材料有限责任公司 | Preparation method of high-heat-resistance brominated epoxy resin |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019346A (en) * | 2019-12-26 | 2020-04-17 | 艾蒙特成都新材料科技有限公司 | Flame-retardant high-heat-resistance resin composition, copper-clad plate and preparation method thereof |
| CN111732817A (en) * | 2020-06-19 | 2020-10-02 | 林州致远电子科技有限公司 | Halogen-free low-loss copper-clad plate and glue solution and preparation method thereof |
| CN112062914A (en) * | 2020-09-22 | 2020-12-11 | 常熟生益科技有限公司 | Resin composition, and prepreg and laminated board manufactured by using same |
| CN112679700A (en) * | 2020-12-23 | 2021-04-20 | 江苏东材新材料有限责任公司 | Preparation method of high-heat-resistance brominated epoxy resin |
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