Resin composition and application of resin composition

Abstract

The present invention provides a resin composition, which comprises, by weight: (a) a modified maleimide prepolymer: 10 to 80 parts by weight; (b) an epoxy resin: 1 to 60 parts by weight; the modified maleimide prepolymer is prepared by modifying the maleimide resin with a diamine compound and a reactive phosphazene compound, wherein the reactive group in the reactive phosphazene compound is selected from at least one of allyl, amino, cyano, hydroxyl, and vinyl. The amino group or reactive group in the modified maleimide prepolymer can react with the epoxy group in the epoxy resin to increase the crosslinking density of the system, thereby improving the flame retardancy and heat resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of electronic materials, and in particular to a resin composition and application of the resin composition. Background Art

[0002] Traditional copper-clad laminates for printed circuits are mainly divided into halogen-containing copper-clad laminates and halogen-free copper-clad laminates according to whether they contain halogen or not. The two have great differences in achieving flame retardant functions. Among them, halogen-containing flame retardants will produce highly corrosive halogenated gases during combustion. Literature reports that in recent years, halogen-containing flame retardants produce carcinogens such as dioxins and dibenzofurans during high-temperature decomposition and combustion. At present, the method commonly used in the industry is to use phosphorus-containing compounds to replace the previous bromine-based flame retardants, but their products generally have problems such as insufficient heat resistance of tin immersion, easy moisture absorption, and insufficient heat resistance of tin immersion after moisture treatment.

[0003] As a kind of high-performance resin matrix, maleimide resin has the characteristics of high moisture / heat resistance, radiation resistance, high modulus, etc., and is widely used in aerospace, aviation and other materials. However, the current shortcomings of maleimide resin are: poor flame retardancy (UL94 V-1 grade), and can only be used in fields such as civil electronics. Therefore, it is necessary to improve the flame retardancy of maleimide resin. More importantly, on the basis of improving the halogen-free flame retardancy, the excellent properties of maleimide resin such as heat resistance, modulus, and coefficient of thermal expansion (CTE) are not affected. Among them, the added flame retardant cannot be effectively cross-linked with the main resin, and fails in extreme use environments such as multiple cold and hot shocks, affecting the heat resistance of the final cured product. Summary of the invention

[0004] The object of the present invention is to provide a resin composition and an application of the resin composition. The resin composition has good toughness, heat resistance and low CTE, and solves the problems of the additive flame retardant affecting the heat resistance and CTE of the system in the prior art.

[0005] In order to achieve one of the above-mentioned objects of the invention, one embodiment of the present invention provides a resin composition, which comprises, by weight:

[0006] (a) modified maleimide prepolymer: 10 to 80 parts by weight;

[0007] (b) epoxy resin: 1 to 60 parts by weight;

[0008] The modified maleimide prepolymer is prepared by modifying maleimide resin with a diamine compound and a reactive phosphazene compound, wherein the reactive phosphazene compound is represented by the following structural formula (1):

[0009] Wherein, R1 and R2 are the same or different and are selected from at least one of allyl, amino, cyano, hydroxyl and vinyl.

[0010] As a further improvement of one embodiment of the present invention, 100 parts by weight of maleimide resin is modified by using 5 to 60 parts by weight of a diamine compound and 1 to 50 parts by weight of a reactive phosphazene compound.

[0011] As a further improvement of one embodiment of the present invention, 100 parts by weight of maleimide resin is modified by using 15 to 50 parts by weight of a diamine compound and 5 to 30 parts by weight of a reactive phosphazene compound.

[0012] As a further improvement of one embodiment of the present invention, the phosphazene compound is at least one of the following structures:

[0013]

[0014]

[0015] As a further improvement of one embodiment of the present invention, the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl linear phenolic epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin, and glycidyl ester epoxy resin.

[0016] As a further improvement of one embodiment of the present invention, the epoxy resin is selected from at least one of the following structures:

[0017]

[0018] As a further improvement of one embodiment of the present invention, it also contains 1 to 60 parts by weight of a curing agent, wherein the curing agent is at least one of active ester compounds, phenolic compounds, acid anhydride compounds, amine compounds, benzoxazine compounds, cyanate compounds, and polyphenylene ether compounds.

[0019] As a further improvement of one embodiment of the present invention, it further comprises 0.01 to 5 parts by weight of a catalyst, wherein the catalyst is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

[0020] As a further improvement of one embodiment of the present invention, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and zinc octoate.

[0021] As a further improvement of one embodiment of the present invention, a filler is further included, and the filler content is 20 to 80 parts by weight based on 100 parts by weight of the resin composition. The filler is surface treated with a silane coupling agent, and the silane coupling agent is selected from the following structures:

[0022]

[0023] As a further improvement of one embodiment of the present invention, it also includes a silane coupling agent and a dispersant, the silane coupling agent is an epoxy silane coupling agent, the dispersant is a phosphate dispersant and / or a modified polyurethane dispersant, and the weight ratio of the silane coupling agent to the dispersant is (2 to 10):1.

[0024] One embodiment of the present invention further provides a use of the above-mentioned resin composition in a prepreg, a laminate, an insulating film, an insulating board, a copper-clad board, a circuit substrate and an electronic device.

[0025] One or more technical solutions provided by the present invention have at least the following technical effects or advantages:

[0026] In the resin composition provided by the present invention, a maleimide resin is modified by a diamine compound and a reactive phosphazene compound to obtain a prepolymer, and the flexible diamine compound and the rigid phosphazene compound work together to make the prepolymer have good toughness and rigidity, and the heat resistance of the prepolymer can be maintained or even improved while the toughness is enhanced; the modified maleimide prepolymer has a lower curing temperature than the maleimide resin; the amino group in the diamine compound in the prepolymer reacts with the epoxy group of the epoxy resin, which can increase the crosslinking density, make the curing system of the composition more compact, and improve the CTE of the resin composition. DETAILED DESCRIPTION

[0027] The present invention will be described in detail below in conjunction with specific embodiments, but these embodiments do not limit the present invention, and changes in reaction conditions, reactants or raw material amounts made by ordinary technicians in the field according to these embodiments are all included in the protection scope of the present invention.

[0028] The embodiment of the present invention provides a resin composition, which comprises, by weight:

[0029] (a) modified maleimide prepolymer: 10 to 80 parts by weight;

[0030] (b) epoxy resin: 1 to 60 parts by weight;

[0031] The modified maleimide prepolymer is prepared by modifying the maleimide resin with a diamine compound and a reactive phosphazene compound. The specific reaction is as follows:

[0032] After 100 parts by weight of maleimide resin and 5 to 60 parts by weight of diamine compound are reacted at a temperature of 60 to 100° C. for 60 minutes, 1 to 50 parts by weight of reactive phosphazene compound are added, and the temperature is raised to 100 to 150° C. and the reaction is continued for 30 minutes to obtain a modified maleimide prepolymer.

[0033] Wherein, the reactive phosphazene compound is shown in the following structural formula (1):

[0034] R1 and R2 are the same or different and are selected from at least one of allyl, amino, cyano, hydroxyl and vinyl.

[0035] Preferably, in the aforementioned modification reaction, the mass ratio of the maleimide resin, the diamine compound and the reactive phosphazene compound is 100:(15-50):(5-30).

[0036] Preferably, the phosphazene compound is at least one of the following structures:

[0037]

[0038]

[0039] Furthermore, the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl linear phenolic epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin, and glycidyl ester epoxy resin.

[0040] Furthermore, the epoxy resin is selected from at least one of the following structures:

[0041]

[0042] Furthermore, the resin composition further comprises 1 to 60 parts by weight of a styrene-based elastomer, the elastomer being selected from H1041, H1043, H1051, H1052, H1053, H1221, P1500, P2000, M1911 or M1913 produced by Asahi Kasei Corporation of Japan; 8004, 8006, 8076, 8104, V9827, 2002, 2005, 2006, 2007, 2104, 7125, 4033, 4044, 4055, 4077 or 4099 produced by Kuraray Co., Ltd.

[0043] Furthermore, the resin composition further comprises 1 to 60 parts by weight of a curing agent, wherein the curing agent is at least one of active ester compounds, phenolic compounds, acid anhydride compounds, amine compounds, benzoxazine compounds, cyanate compounds, and polyphenylene ether compounds.

[0044] Wherein, the amine compound is selected from diaminodiphenylmethane, diaminodiphenyl sulfone, diethylenetriamine, dicarboxyphthalimide, dicyandiamide or imidazole.

[0045] The anhydride compound is selected from phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride or styrene-maleic anhydride.

[0046] The phenolic compound is selected from bisphenol A phenolic resin, phenol phenolic resin, naphthalene phenolic resin, biphenyl phenolic resin, biphenyl phenol naphthol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin.

[0047] The active ester compound is selected from the compound represented by the following structural formula (18):

[0048]

[0049] Wherein, X is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; and n represents a repeating unit, which is 0.25 to 1.25.

[0050] Preferably, the active ester compound is an active ester compound with a brand name of HPC-8000 or EXB-8150 produced by DIC Corporation.

[0051] Furthermore, the resin composition further comprises 0.01 to 5 parts by weight of a catalyst, wherein the catalyst is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

[0052] Preferably, the catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and zinc octoate.

[0053] Furthermore, the resin composition further comprises a filler, and the content of the filler is 20 to 80 parts by weight based on 100 parts by weight of the resin composition.

[0054] Fillers include inorganic fillers, organic fillers and composite fillers.

[0055] Preferably, the filler is spherical silica, alumina or aluminum hydroxide, more preferably spherical silica.

[0056] Further, the filler is surface treated with a silane coupling agent, and the silane coupling agent is at least one of an aminosilane coupling agent, a carbon-carbon double bond-containing silane coupling agent, or an epoxysilane coupling agent. Preferably, the silane coupling agent is selected from the following structures:

[0057] The brands are KBM-573 produced by Shin-Etsu Chemical Co., Ltd. and Z-6883 produced by Dow Corning Corporation;

[0058] The brand is KBM-1003 produced by Shin-Etsu Chemical Co., Ltd.

[0059] The brand is KBM-1403 produced by Shin-Etsu Chemical Co., Ltd.

[0060] Furthermore, the resin composition also includes a silane coupling agent and a dispersant, the silane coupling agent is an epoxy silane coupling agent, the dispersant is a phosphate dispersant and / or a modified polyurethane dispersant, and the weight ratio of the silane coupling agent to the dispersant is (2-10):1.

[0061] Furthermore, a dye may be added to the resin composition, which may be a fluorescent dye or a black dye. The fluorescent dye may be a pyrazoline compound, and the black dye may be a liquid or powdered carbon black, a pyridine complex, an azo complex, a quinone compound, zirconium nitride, titanium oxide, titanium nitride, black talc, cobalt chromium metal oxide, azine or phthalocyanine, etc.

[0062] The present invention also provides the use of the resin composition in prepregs, laminates, insulating films, insulating boards, circuit substrates and electronic devices, which are specifically described as follows:

[0063] The present invention also provides a prepreg, comprising a reinforcing material and the above-mentioned resin composition. The preparation method of the prepreg is: dissolving the resin composition with a solvent to prepare a glue solution, then immersing the reinforcing material in the above-mentioned glue solution, taking out the immersed reinforcing material and baking it at 100-180°C for 1-15 minutes; after drying, the prepreg is obtained.

[0064] The solvent is selected from at least one of acetone, butanone, toluene, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene and cyclohexane.

[0065] The reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics. Preferably, the reinforcing material is glass fiber cloth; among the glass fiber cloth, open fiber cloth or flat cloth is preferably used; and the glass fiber cloth is preferably E glass fiber cloth, S glass fiber cloth, or Q glass fiber cloth.

[0066] In addition, when the reinforcing material is glass fiber cloth, the glass fiber cloth is chemically treated with a coupling agent to improve the interface bonding between the resin composition and the glass fiber cloth. The coupling agent is preferably an epoxy silane coupling agent or an amino silane coupling agent to provide good water resistance and heat resistance.

[0067] An embodiment of the present invention also provides a laminate, comprising a piece of the aforementioned prepreg and a metal foil disposed on at least one side of the prepreg; or comprising a composite sheet formed by overlapping a plurality of the aforementioned prepregs and a metal foil disposed on at least one side of the composite sheet.

[0068] The laminate is prepared by the following method: a metal foil is coated on one or both sides of a prepreg, or at least two prepregs are stacked to form a composite sheet, a metal foil is coated on one or both sides of the composite sheet, and the metal foil laminate is obtained by hot pressing. The pressing conditions of hot pressing are: pressing at 0.2-2MPa and 150-250°C for 2-4 hours.

[0069] Preferably, the metal foil is selected from copper foil or aluminum foil. The thickness of the metal foil is 5 micrometers, 8 micrometers, 12 micrometers, 18 micrometers, 35 micrometers or 70 micrometers.

[0070] An embodiment of the present invention further provides an insulating board, comprising at least one of the aforementioned prepreg sheets.

[0071] The embodiment of the present invention further provides an insulating film, comprising a carrier film and the above-mentioned resin composition coated thereon, and the thermal index of the insulating film is significantly improved.

[0072] The insulating film is prepared by the following method: the resin composition is dissolved in a solvent to prepare a glue solution, the glue solution is then coated on a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the insulating film.

[0073] The aforementioned solvent is selected from at least one of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0074] The carrier film is selected from at least one of PET film, PP film, PE film and PVC film.

[0075] An embodiment of the present invention further provides a circuit substrate, comprising one or more of the aforementioned prepreg, laminate, insulating plate, and insulating film.

[0076] An embodiment of the present invention further provides an electronic device, comprising the aforementioned circuit substrate; since the heat resistance of the circuit substrate is greatly improved, the safety of the electronic device is significantly improved.

[0077] The technical solution of the present application is further described below in conjunction with some specific synthesis examples and comparative examples.

[0078] Synthesis Example 1: Modified maleimide prepolymer Y1

[0079] Step 1: Add 200 g of bismaleimide resin (manufactured by Yamato Chemical Industry, BMI-2300), 30 g of diaminodiphenylmethane and an appropriate amount of organic solvent into a beaker, and react at 80° C. for 60 min to obtain a pre-reactant;

[0080] Step 2: Raise the temperature to 110° C., add 20 g of allyl phosphazene compound, and continue the reaction at 110° C. for 60 min to obtain modified maleimide prepolymer Y1.

[0081] Synthesis Example 2: Modified bismaleimide prepolymer Y2

[0082] Step 1: Add 200 g of bismaleimide resin (MIR-3000 manufactured by Nippon Kayaku), 60 g of diaminodiphenylmethane and an appropriate amount of organic solvent into a beaker, and react at 90° C. for 60 min to obtain a pre-reactant;

[0083] Step 2: Raise the temperature to 110° C., add 20 g of allyl phosphazene compound, and continue the reaction at 110° C. for 60 min to obtain a modified maleimide prepolymer Y2.

[0084] Synthesis Example 3: Modified maleimide prepolymer Y3

[0085] 200 g of bismaleimide resin (manufactured by Yamato Chemical Industry, BMI-2300), 30 g of diaminodiphenylmethane, 20 g of allylphosphazene compound and an appropriate amount of organic solvent were added to a beaker, and the mixture was reacted at 100° C. for 150 min to obtain a modified maleimide prepolymer Y3.

[0086] Comparative Synthesis Example 1: Modified Maleimide Prepolymer Y5

[0087] 200 g of bismaleimide resin (BMI-2300 manufactured by Yamato Chemical Industry Co., Ltd.), 30 g of diaminodiphenylmethane and an appropriate amount of organic solvent were added to a beaker, and the mixture was reacted at 100° C. for 150 min to obtain a modified maleimide prepolymer Y5.

[0088] Comparative Synthesis Example 2: Modified Maleimide Prepolymer Y5

[0089] 200 g of bismaleimide resin (BMI-2300 manufactured by Yamato Chemical Industry Co., Ltd.), 20 g of allylphosphazene compound and an appropriate amount of organic solvent were added to a beaker, and the mixture was reacted at 100° C. for 150 min to obtain a modified maleimide prepolymer Y6.

[0090] According to the component contents in Table 1, the components and an appropriate amount of butanone solvent were stirred and mixed to obtain a glue solution with a solid content of 60%. The glue solution was impregnated and coated on E glass fiber cloth (2116), and baked in an oven at 160°C for 5 minutes to obtain a prepreg.

[0091] The prepreg was cut to 300×300 mm, and an electrolytic copper foil was placed on each side of the prepreg to form a certain stacking structure, and then sent to a vacuum press for pressing to obtain a metal foil laminate (or copper-clad laminate). The specific performance tests are shown in Table 2.

[0092] Table 1 Resin composition composition

[0093]

[0094] The prepregs and copper-clad laminates prepared in all the above Examples 1 to 5 and Comparative Examples 1 to 2 were subjected to performance tests. The performance test methods are as follows:

[0095] (1) Glass transition temperature: DMA, heating rate of 10 °C / min, frequency of 10 Hz;

[0096] (2) XY axis CTE (α1): TMA, heating rate 5°C / min;

[0097] (3) Dielectric properties: The dielectric constant and dielectric loss at 10 GHz were measured using a Keysight network analyzer.

[0098] (4) Water absorption: Test the water absorption of state A according to the method specified in IPC-TM-650 2.6.2.1.

[0099] (5) Flame retardancy: UL94 vertical burning (UL94 V), tested according to ASTM (D63-77) method.

[0100] Table 2 Performance table

[0101]

[0102] It can be seen from the above experimental data that the performance of the embodiments of the present application is significantly superior to that of the comparative examples. Among them, compared with the comparative example 1 without adding reactive phosphinothrene, the flame retardancy of embodiment 1 is significantly superior, and the glass transition temperature Tg is significantly improved, and the water absorption rate and CTE value are significantly excellent; in addition, compared with the comparative example 2 without adding aromatic amine compounds, the glass transition temperature of embodiment 3 is significantly increased. This is because the overall reaction uniformity is poor after the amine compound is not added, resulting in the crosslinking density not being achieved, which seriously affects the heat resistance index, and the water absorption rate is significantly improved.

[0103] It should be understood that although this specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each implementation mode may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

[0104] The series of detailed descriptions listed above are only specific descriptions of feasible implementation methods of the present invention. They are not intended to limit the scope of protection of the present invention. Any equivalent implementation methods or changes that do not deviate from the technical spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A resin composition, It is characterized in that By weight, including: (a) modified maleimide prepolymer: 10 to 80 parts by weight; (b) epoxy resin: 1 to 60 parts by weight; The modified maleimide prepolymer is prepared by modifying maleimide resin with a diamine compound and a reactive phosphazene compound, wherein the reactive phosphazene compound is represented by the following structural formula (1): Among them, R 1 and R 2 are the same and are selected from allyl; The modified maleimide prepolymer is prepared by the following method: 100 parts by weight of maleimide resin and 5 to 60 parts by weight of diamine compound are reacted at a temperature of 60 to 100° C. for 60 minutes, 1 to 50 parts by weight of reactive phosphazene compound are added, the temperature is raised to 100 to 150° C., and the reaction is continued for 30 minutes to obtain the modified maleimide prepolymer; The epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl linear novolac epoxy resin, alicyclic epoxy resin, glycidylamine epoxy resin, and glycidylester epoxy resin.

2. The resin composition according to claim 1, It is characterized in that 100 parts by weight of maleimide resin is modified by using 15 to 50 parts by weight of diamine compound and 5 to 30 parts by weight of reactive phosphazene compound.

3. The resin composition according to claim 1, It is characterized in that The epoxy resin is selected from at least one of the following structures:

4. The resin composition according to claim 1, It is characterized in that The invention also contains 1 to 60 parts by weight of a curing agent, wherein the curing agent is at least one of active ester compounds, phenol compounds, acid anhydride compounds, amine compounds, benzoxazine compounds, cyanate compounds and polyphenylene ether compounds.

5. The resin composition according to claim 1, It is characterized in that The invention also comprises 0.01 to 5 parts by weight of a catalyst, wherein the catalyst is at least one of an imidazole catalyst, a pyridine catalyst and an organic metal salt catalyst.

6. The resin composition according to claim 5, It is characterized in that The catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and zinc octanoate.

7. The resin composition according to claim 1, It is characterized in that The resin composition further comprises a filler, wherein the filler content is 20 to 80 parts by weight based on 100 parts by weight of the resin composition, and the filler is surface treated with a silane coupling agent, and the silane coupling agent is selected from the following structures:

8. The resin composition according to claim 1, It is characterized in that It also includes a silane coupling agent and a dispersant, wherein the silane coupling agent is an epoxy silane coupling agent, and the dispersant is a phosphate dispersant or / and a modified polyurethane dispersant, and the weight ratio of the silane coupling agent to the dispersant is (2-10):

1.

9. Use of the resin composition according to any one of claims 1 to 8 in prepregs, laminates, insulating films, insulating boards, circuit substrates and electronic devices.

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