Epoxy resin composition and application thereof

Abstract

The invention provides an epoxy resin composition and application thereof. The epoxy resin composition is prepared from the following components in parts by mass: 100 parts of universal epoxy resin, 30 to 100 parts of alicyclic epoxy resin, 40 to 120 parts of phenolic curing agent and 40 to 300 parts of filler, the alicyclic epoxy resin has a structure as shown in a formula I. Through the design of the alicyclic epoxy resin and the phenolic curing agent and the mutual compounding of the alicyclic epoxy resin and the phenolic curing agent with the universal epoxy resin and the filler, the epoxy resin composition and the metal foil-clad laminated board containing the epoxy resin composition have high glass transition temperature and high thermal decomposition temperature, have excellent heat resistance and remarkably improved CTI (Comparative Tracking Index) performance, have the CTI reaching 600V or above, have good flame retardance, and can be used for preparing the metal foil-clad laminated board. Therefore, the reliability, safety and stability of the substrate and electronic and electrical products are greatly improved.

Description

Technical Field

[0001] The invention belongs to the technical field of copper clad laminates, and particularly relates to an epoxy resin composition and application thereof. Background Art

[0002] Copper clad laminates are referred to as "copper clad laminates". As the insulating substrate of printed circuit boards, they are widely used in various electronic and electrical products. Tracking resistance is an important reliability indicator of copper clad laminates. Copper clad laminates with poor tracking resistance are potential hazards of fires in electronic and electrical products. Therefore, it is very important to improve the tracking resistance of copper clad laminates.

[0003] Tracking resistance is measured by the comparative tracking index (CTI), and the higher the CTI, the better the tracking resistance. The production of traditional copper-clad laminates with high comparative tracking index is achieved by adding a resin composite material with a high CTI filler. For example, CN104151777A discloses a thermosetting resin composition, which includes 20-70% by mass of a thermosetting resin, 1-30% by mass of a curing agent, 0-10% by mass of an accelerator, and 1-70% by mass of a high CTI filler with an average particle size of 0.5-15 μm. The high CTI filler includes calcium fluoride, and can also include any one of aluminum hydroxide, barium sulfate, barium titanate, strontium titanate, talcum powder, and titanium dioxide, or a mixture of at least two of them; the CTI of the copper-clad laminate made of the thermosetting resin composition can reach up to 600V or more. CN105034492A discloses a method for preparing a CEM-1 copper clad laminate with a high CTI, wherein a resin emulsion for glass cloth comprises the following components: 45-65 parts of halogen-free epoxy resin, 1-2 parts of dicyandiamide, 24-33 parts of aluminum hydroxide and 8-25 parts of dimethylformamide; a resin emulsion for bleached wood pulp paper comprises the following components: 35-50 parts of halogen-free epoxy resin, 10-15 parts of nitrogen-containing phenolic resin, 5-10 parts of aluminum hydroxide, 8-15 parts of melamine cyanurate, 5-10 parts of melamine polyphosphate, 5-10 parts of phosphate ester and 10-15 parts of acetone; the above-mentioned glue solutions are used to prepare glass cloth impregnated sheets and bleached wood pulp paper impregnated sheets respectively, a plurality of bleached wood pulp paper impregnated sheets are overlapped, the upper and lower surfaces are covered with glass cloth impregnated sheets, and then copper foil is covered on one side or both sides, and hot pressing is performed to obtain a CEM-1 copper clad laminate. Although the method of adding high CTI fillers can obtain copper-clad laminates with a high comparative tracking index (CTI>600V), adding a large amount of fillers will reduce the processing performance of the board and make the heat resistance poor. Moreover, the most commonly used filler is aluminum hydroxide, and excessive use of it will also cause the alkali resistance of the board to deteriorate seriously.

[0004] The molecular structure of the alicyclic epoxy resin does not contain a benzene ring structure, which greatly reduces the formation of carbon during the tracking process, and does not contain Cl, Na ions during the synthesis process, so the electrical properties are good, especially in terms of resistance to leakage tracking. CN102286190A discloses a resin composition, including the following components: 100 parts of hydrogenated bisphenol A epoxy resin, 10-25 parts of alicyclic epoxy resin, 25-40 parts of curing agent, 20-40 parts of aluminum hydroxide, and 10-20 parts of organic solvent; by using a resin with a high CTI value, the amount of inorganic filler aluminum hydroxide is reduced, so that the composition has a high CTI value and avoids a series of problems caused by excessive use of aluminum hydroxide, so that the copper clad laminate has good resistance to leakage tracking. CN102807735A discloses a halogen-free resin composition, the components of which are as follows: 10-30 parts by weight of phosphorus-containing epoxy resin, 5-15 parts by weight of alicyclic epoxy resin, 52-60 parts by weight of acid anhydride, 10 parts by weight of phenolic resin, and 3-5 parts by weight of phosphorus-containing flame retardant; the comparative tracking index (CTI) of the resin-coated copper foil and copper-clad laminate using the halogen-free resin composition is ≥600V. However, the traditional alicyclic epoxy resin has the characteristics of low viscosity and low boiling point. When used in the production of copper-clad laminates, it has the disadvantage of being volatile at high temperatures, resulting in a significant deterioration in the heat resistance of the board.

[0005] Therefore, developing resin materials with high CTI and high heat resistance to meet the performance requirements of copper-clad laminates is an urgent problem to be solved in this field. Summary of the invention

[0006] In view of the deficiencies in the prior art, the object of the present invention is to provide an epoxy resin composition and its application. By designing a cycloaliphatic epoxy resin with a specific structure and a phenolic curing agent and compounding them with a general-purpose epoxy resin and a filler, the epoxy resin composition and the metal-clad laminate containing the same have high CTI and excellent heat resistance, thereby greatly improving the reliability, safety and stability of substrates and electronic and electrical products.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides an epoxy resin composition, wherein the epoxy resin composition comprises the following components in parts by mass:

[0009]

[0010] The alicyclic epoxy resin has a structure as shown in Formula I:

[0011]

[0012] In formula I, R is selected from any one of H, C1-C5 straight chain or branched chain alkyl.

[0013] In formula I, n represents the number of structural units within the square brackets, and n≥1.

[0014] The present invention introduces an alicyclic epoxy resin having a specific structure as shown in Formula I, and adopts a phenolic curing agent. By designing the alicyclic epoxy resin and the phenolic curing agent and compounding them with a general-purpose epoxy resin and a filler, the glass transition temperature (T g ) high, thermal decomposition temperature (T d ) is high, with excellent heat resistance and CTI performance, which greatly improves the reliability, safety and stability of substrates and electronic and electrical products.

[0015] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0016] In the present invention, based on 100 parts by mass of the general-purpose epoxy resin, the mass of the alicyclic epoxy resin is 30-100 parts, for example, it can be 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts or 95 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0017] Based on 100 parts by weight of the general-purpose epoxy resin, the weight of the phenolic curing agent is 40-120 parts, for example, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts or 115 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0018] Based on 100 parts by mass of the general-purpose epoxy resin, the mass of the filler is 40-300 parts, for example, it can be 50 parts, 60 parts, 80 parts, 100 parts, 120 parts, 140 parts, 150 parts, 160 parts, 180 parts, 200 parts, 220 parts, 240 parts, 250 parts, 260 parts or 280 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0019] In the present invention, the C1-C5 straight chain or branched alkyl group can be a straight chain or branched alkyl group of C1, C2, C3, C4, or C5, illustratively including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, isopentyl, neopentyl, and the like.

[0020] Preferably, the general epoxy resin includes any one or a combination of at least two of brominated epoxy resin, bisphenol A epoxy resin, isocyanate modified epoxy resin, phenol formaldehyde epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol A formaldehyde epoxy resin, tetraphenol ethane epoxy resin, and phenol DCPD epoxy resin.

[0021] Preferably, the general-purpose epoxy resin includes brominated epoxy resin.

[0022] Preferably, based on 100 parts by mass of the general-purpose epoxy resin, the mass of the brominated epoxy resin is ≥50 parts, for example, it can be 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts or 100 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0023] Preferably, the mass percentage of bromine element in the brominated epoxy resin is 15-52%, for example, it can be 16%, 18%, 19%, 20%, 21%, 23%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48% or 50%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0024] Preferably, the brominated epoxy resin includes any one of a low-bromine epoxy resin, a high-bromine epoxy resin, and a bromine-containing isocyanate-modified epoxy resin, or a combination of at least two of them.

[0025] Preferably, the mass percentage of bromine element in the low-bromine epoxy resin is 19-21%, for example, it can be 19.2%, 19.5%, 19.8%, 20%, 20.2%, 20.5% or 20.8%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0026] Preferably, the mass percentage of bromine element in the high-bromine epoxy resin is 46-50%, for example, it can be 46.2%, 46.5%, 46.8%, 47%, 47.2%, 47.5%, 47.8%, 48%, 48.2%, 48.5%, 48.8%, 49%, 49.2%, 49.5% or 49.8%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0027] Preferably, the bromine-containing isocyanate-modified epoxy resin comprises bromine-containing MDI (diphenylmethane diisocyanate)-modified epoxy resin.

[0028] Preferably, the mass percentage of bromine element in the bromine-containing isocyanate-modified epoxy resin is 16-18%, for example, it can be 16.2%, 16.5%, 16.8%, 17%, 17.2%, 17.5% or 17.8%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0029] As a preferred technical solution of the present invention, the general-purpose epoxy resin includes a specific amount of brominated epoxy resin so that the mass percentage of bromine element in the resin phase of the epoxy resin composition is 6-16%, for example, it can be 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0030] Preferably, the epoxy equivalent of the general epoxy resin is 150-1200 g / eq, for example, it can be 160 g / eq, 170 g / eq, 180 g / eq, 200 g / eq, 250 g / eq, 300 g / eq, 350 g / eq, 400 g / eq, 450 g / eq, 500 g / eq, 550 g / eq, 600 g / eq, 650 g / eq, 700 g / eq, 750 g / eq, 800 g / eq, 850 g / eq, 900 g / eq, 950 g / eq, 1000 g / eq, 1050 g / eq, 1100 g / eq or 1150 g / eq, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0031] Preferably, the epoxy equivalent of the brominated epoxy resin is 300-500 g / eq, for example, it can be 320 g / eq, 350 g / eq, 380 g / eq, 400 g / eq, 420 g / eq, 450 g / eq or 480 g / eq, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0032] Preferably, the epoxy equivalent of the bisphenol A epoxy resin is 800-1100 g / eq, for example, it can be 820 g / eq, 850 g / eq, 880 g / eq, 900 g / eq, 920 g / eq, 950 g / eq, 980 g / eq, 1000 g / eq, 1020 g / eq, 1050 g / eq or 1080 g / eq, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0033] Preferably, the epoxy equivalent of the phenol formaldehyde epoxy resin is 150-200 g / eq, for example, it can be 155 g / eq, 160 g / eq, 165 g / eq, 170 g / eq, 175 g / eq, 180 g / eq, 185 g / eq, 190 g / eq or 195 g / eq, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0034] Preferably, the epoxy equivalent of the isocyanate modified epoxy resin, phenol formaldehyde epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol A formaldehyde epoxy resin, tetraphenol ethane epoxy resin, and phenol DCPD (dicyclopentadiene) epoxy resin is each independently 160-320 g / eq, for example, it can be 170 g / eq, 180 g / eq, 200 g / eq, 220 g / eq, 240 g / eq, 250 g / eq, 260 g / eq, 280 g / eq, 300 g / eq or 310 g / eq, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0035] Preferably, the isocyanate-modified epoxy resin includes MDI-modified epoxy resin.

[0036] In Formula I of the present invention, n represents the number of structural units in the square brackets, n≥1, for example, it can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, 20, 22, 24, 25, 26, 28, 30, and specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and preferably, n is an integer of 1-30.

[0037] Preferably, the epoxy equivalent of the alicyclic epoxy resin is 170-200 g / eq, for example, it can be 172 g / eq, 175 g / eq, 180 g / eq, 182 g / eq, 185 g / eq, 188 g / eq, 190 g / eq, 192 g / eq, 195 g / eq or 198 g / eq, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0038] Preferably, the softening point of the alicyclic epoxy resin is 70-90°C, for example, it can be 72°C, 75°C, 78°C, 80°C, 85°C, 85°C or 88°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0039] Preferably, the phenolic curing agent includes any one of bisphenol A, tetrabromobisphenol A, linear phenol formaldehyde resin, linear o-cresol formaldehyde resin, linear bisphenol A formaldehyde resin, and phenol DCPD resin, or a combination of at least two thereof.

[0040] Preferably, the hydroxyl equivalent of the phenolic curing agent is 100-250 g / eq, for example, it can be 110 g / eq, 120 g / eq, 140 g / eq, 150 g / eq, 160 g / eq, 180 g / eq, 200 g / eq, 220 g / eq or 240 g / eq, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0041] Preferably, the molar amount of phenolic hydroxyl groups in the phenolic curing agent is n1, the total molar amount of epoxy groups in the general-purpose epoxy resin and the alicyclic epoxy resin is n2, 0.8≤n1 / n2≤1.1, for example, n1 / n2 can be 0.82, 0.85, 0.88, 0.9, 0.92, 0.95, 0.98, 1, 1.02, 1.05 or 1.08, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0042] Preferably, the filler includes any one or a combination of at least two of aluminum hydroxide, silica powder, kaolin, talc, magnesium hydroxide, barium sulfate, and boehmite, and more preferably any one or a combination of at least two of aluminum hydroxide, barium sulfate, and boehmite.

[0043] Preferably, the average particle size (D 50 The particle size) is 0.1-30 μm, for example, it can be 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm or 28 μm, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and 0.5-20 μm is further preferred.

[0044] Exemplarily, the particle size of the filler is measured using a MS3000 Malvern laser particle size analyzer.

[0045] Preferably, the epoxy resin composition further comprises any one of a promoter, a dispersant, a coupling agent, a UV absorber, and a colorant, or a combination of at least two thereof.

[0046] As a preferred technical solution of the present invention, in order to achieve the regulation of reactivity, an accelerator can be added to the epoxy resin composition.

[0047] Preferably, the accelerator includes any one of a tertiary amine accelerator, an imidazole accelerator, and a boron trifluoride amine complex, or a combination of at least two of them.

[0048] Preferably, based on 100 parts by mass of the general-purpose epoxy resin, the mass of the accelerator is ≤5 parts, for example, it can be 0, 0.001 parts, 0.005 parts, 0.01 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts, as well as specific point values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0049] As a preferred technical solution of the present invention, in order to achieve good filler dispersion, a dispersant and / or a coupling agent may be added to the epoxy resin composition.

[0050] Preferably, based on 100 parts by mass of the general-purpose epoxy resin, the mass of the dispersant is ≤5 parts, for example, it can be 0, 0.001 parts, 0.005 parts, 0.01 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts, as well as specific point values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0051] As a preferred technical solution of the present invention, in order to obtain a UV shielding effect, a UV absorber may be added to the epoxy resin composition.

[0052] As a preferred technical solution of the present invention, in order to obtain different colors, a colorant may be added to the epoxy resin composition, and the colorant includes a pigment.

[0053] It should be noted that the present invention does not have any special restrictions on the specific types and amounts of dispersants, coupling agents, UV absorbers, and colorants. Those skilled in the art can add dispersants, coupling agents, UV absorbers, and colorants according to their types and needs.

[0054] A solvent may also be added to the above epoxy resin composition, and the amount of solvent added is selected by a person skilled in the art based on experience and process requirements, so that the epoxy resin composition reaches a viscosity suitable for use, so as to facilitate impregnation, coating, etc. of the epoxy resin composition. In the subsequent drying, semi-curing or full curing stage, the solvent in the epoxy resin composition will partially or completely volatilize.

[0055] The solvent of the present invention is not particularly limited, and exemplarily includes but is not limited to: ketones such as acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and mesitylene, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol, and butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, propylene glycol methyl ether, carbitol, and butyl carbitol, nitrogen-containing compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; the solvent can be used alone or in combination of two or more. Preferably, any one of acetone, butanone, cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether, and N,N-dimethylformamide or a combination of at least two of them is used.

[0056] The epoxy resin composition provided by the present invention is prepared by the following method, which comprises: mixing and uniformly dispersing the components in the epoxy resin composition to obtain the epoxy resin composition.

[0057] In a second aspect, the present invention provides a resin film, wherein the material of the resin film includes the epoxy resin composition as described in the first aspect.

[0058] Preferably, the resin film is obtained by coating the epoxy resin composition on a release material and then drying and / or semi-curing the epoxy resin composition.

[0059] In a third aspect, the present invention provides a resin-coated copper foil, wherein the resin-coated copper foil comprises a copper foil layer and a resin layer, wherein the material of the resin layer comprises the epoxy resin composition as described in the first aspect.

[0060] Preferably, the resin-coated copper foil is obtained by coating the epoxy resin composition on a copper foil and then drying and / or semi-curing the composition.

[0061] In a fourth aspect, the present invention provides a prepreg, comprising a reinforcing material and the epoxy resin composition as described in the first aspect attached to the reinforcing material.

[0062] Preferably, the epoxy resin composition is attached to the reinforcing material by impregnation and drying.

[0063] Preferably, the raw material of the reinforcing material includes any one of natural fibers, organic synthetic fibers, inorganic fibers, and organic fabrics, or a combination of at least two thereof; for example, glass fiber cloth, quartz glass fiber blended cloth, non-woven fabric, and the like.

[0064] Illustratively, the method for preparing the prepreg comprises: impregnating a reinforcing material with a resin glue of the epoxy resin composition, and then drying to obtain the prepreg.

[0065] Preferably, the drying temperature is 100-180°C, for example, it can be 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C or 175°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0066] Preferably, the drying time is 1-30 min, for example, it can be 2 min, 5 min, 8 min, 10 min, 15 min, 20 min or 25 min, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0067] In another aspect, the present invention provides a laminate comprising at least one prepreg as described in the fourth aspect.

[0068] In a fifth aspect, the present invention provides a metal foil-clad laminate, the metal foil-clad laminate comprising at least one of the resin film as described in the second aspect, the resin-coated copper foil as described in the third aspect, and the prepreg as described in the fourth aspect.

[0069] Preferably, the metal foil in the metal foil-clad laminate includes any one of copper foil, aluminum foil, nickel foil, alloy foil, or a combination of at least two of them, and copper foil is more preferred.

[0070] Preferably, the metal foil is copper foil, and the metal foil-clad laminate is a copper-clad laminate.

[0071] Preferably, the number of prepregs in the metal foil-clad laminate is 1-20, for example, 2, 3, 5, 7, 9, 10, 11, 13, 15, 17 or 19, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0072] Exemplarily, the method for preparing the metal foil-clad laminate comprises: laminating metal foil on one side or both sides of a prepreg and curing to obtain the metal foil-clad laminate; or, stacking at least two prepregs into a laminate, and then laminating metal foil on one side or both sides of the laminate and curing to obtain the metal foil-clad laminate.

[0073] Preferably, the curing is carried out in a press.

[0074] Preferably, the curing temperature is 160-280°C, for example, it can be 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C or 270°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and 200-220°C is further preferred.

[0075] Preferably, the curing pressure is 10-60 kgf / cm 2 , for example, it can be 15kgf / cm 2 、20kgf / cm 2 、25kgf / cm 2 、30kgf / cm 2 、35kgf / cm 2 、40kgf / cm 2 、45kgf / cm 2 、50kgf / cm 2 or 55kgf / cm 2 , as well as specific point values ​​between the above point values, due to space limitations and for the sake of brevity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0076] Preferably, the curing time is 30-300 min, for example, 40 min, 60 min, 80 min, 100 min, 120 min, 150 min, 180 min, 200 min, 220 min, 240 min, 260 min or 280 min, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0077] In a sixth aspect, the present invention provides a printed circuit board, comprising at least one of the resin film as described in the second aspect, the resin-coated copper foil as described in the third aspect, the prepreg as described in the fourth aspect, and the metal foil-clad laminate as described in the fifth aspect.

[0078] Compared with the prior art, the present invention has the following beneficial effects:

[0079] (1) In the epoxy resin composition provided by the present invention, the glass transition temperature (T) of the epoxy resin composition and the metal foil-clad laminate containing the epoxy resin is increased by designing the alicyclic epoxy resin and the phenolic curing agent and compounding them with the general-purpose epoxy resin and the filler. g ) high, thermal decomposition temperature (T d ) is high, has excellent heat resistance and significantly improved CTI performance, CTI reaches more than 600V, and has good flame retardancy, which greatly improves the reliability, safety and stability of substrates and electronic and electrical products.

[0080] (2) The present invention designs and optimizes the components of the epoxy resin composition to make the CTI of the copper-clad laminate prepared using the epoxy resin composition ≥ 625V, T g ≥159℃,T d ≥351℃, T288≥27.6min, thermal stress>300s, V-0 flame retardancy can be achieved, and it has excellent heat resistance, tracking resistance, flame retardancy and reliability. DETAILED DESCRIPTION

[0081] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0082] In the specific implementation of the present invention, the materials for which the preparation method is not provided are all commercially available chemicals, and the specific information is shown in the following table:

[0083]

[0084]

[0085]

[0086] The epoxy resin composition and the metal-clad laminate of the present invention will be described in detail below by taking a number of embodiments as examples, but the epoxy resin composition and the metal-clad laminate are not limited to these embodiments.

[0087] Examples 1-10, Comparative Examples 1-6

[0088] An epoxy resin composition, the types and amounts of each component are shown in Table 1 and Table 2, and the amount units of each component are all "parts" (parts by mass); n1 / n2 represents the molar ratio of the curing group (phenolic hydroxyl or amino group) in the curing agent to the epoxy group in the resin system, which is calculated based on the feed amount of each material and the median value of the group equivalent range; the bromine content (mass content) of the resin phase is calculated based on the feed amount of the brominated epoxy resin and the median value of the bromine content range.

[0089] A prepreg and a copper-clad laminate comprising the epoxy resin composition, the preparation method of which is as follows:

[0090] (1) adding a general-purpose epoxy resin, an alicyclic epoxy resin and a curing agent to butanone according to the formula amount, dissolving them into a resin solution with a solid content of 60%, then adding a filler and a dispersant, dispersing them evenly, adding an accelerator, adjusting the gelation time to 200-300 s (tested at 171° C.), and preparing a resin glue solution;

[0091] (2) The 7628E glass fiber cloth is immersed in the resin glue obtained in step (1), and then baked at 170°C for 3min20s to remove the solvent and semi-cure to obtain the corresponding prepreg.

[0092] (3) Stack the four prepregs obtained in step (2) and cover the upper and lower surfaces of the stack with a copper foil respectively. Place the stack in a laminator and heat at 180°C and 30 kgf / cm 2 The copper clad laminate was obtained by hot pressing and curing for 60 minutes.

[0093] The copper clad laminate is subjected to a performance test, and the specific method is as follows:

[0094] (1) Glass transition temperature (T g ): According to the method in IPC TM-650, DSC (differential scanning calorimeter) was used for testing, and the heating rate was 20°C / min;

[0095] (2) Thermal decomposition temperature (T d ): According to the method in IPC TM-650, 5% weight loss temperature under N2 protection, TGA (thermogravimetric analyzer) test, heating rate 10℃ / min;

[0096] (3) T288: According to the method in IPC TM-650, the time that the plate can resist thermal expansion without cracking at 288°C is tested. TMA (thermomechanical analysis) test, the heating rate is 10°C / min, and the temperature is kept constant at 288°C for a period of time;

[0097] (4) Thermal stress: According to the method in IPC TM-650, 288℃ solder immersion time;

[0098] (5) Flame retardancy: Test and classify according to the material flammability method of UL-94;

[0099] (6) CTI: Tested according to the method in IEC60112:2020;

[0100] The test results are shown in Table 1 and Table 2.

[0101] Table 1

[0102]

[0103]

[0104] In Example 1 and Comparative Examples 1-6 of Table 1, the equivalent ratio (n1 / n2) of the curing agent functional group (phenolic hydroxyl or amino group) to the epoxy group in the resin system is 1.0, the bromine content of the resin phase is 11%, and the mass ratio of the resin phase to the filler is 100:(43±1).

[0105] Table 2

[0106]

[0107]

[0108]

[0109] According to the data in Table 1 and Table 2, the present invention makes the epoxy resin composition and the copper clad laminate containing the epoxy resin have high CTI and excellent heat resistance through the design of alicyclic epoxy resin and phenolic curing agent with specific structure and compounding with general epoxy resin and filler. Among them, the CTI of the copper clad laminates of Examples 1-10 is 625V, T g ≥159℃, thermal decomposition temperature T d ≥351℃, T288≥27.6min, thermal stress>300s, achieving V-0 flame retardancy, improving the reliability, safety and stability of substrates and electronic and electrical products.

[0110] Combining the data of Example 1 and Comparative Examples 1-6 in Table 1, it can be seen that Comparative Example 1 does not contain alicyclic epoxy resin, and its CTI is significantly reduced; Comparative Example 2 does not contain alicyclic epoxy resin, and the curing agent is dicyandiamide, which leads to a slight decrease in the CTI of the board and a serious deterioration in heat resistance reliability. Although alicyclic epoxy resin is introduced into Comparative Example 3, it does not have the structure of Formula I defined in the present invention, resulting in a T g The heat resistance is significantly reduced. In Comparative Example 4, dicyandiamide is used as a curing agent, resulting in a significant decrease in heat resistance and flame retardancy. In Comparative Example 5, the amount of alicyclic epoxy resin is too low, resulting in a decrease in CTI performance. In Comparative Example 6, the amount of alicyclic epoxy resin is too high, resulting in a significant decrease in flame retardancy.

[0111] The applicant declares that the present invention illustrates the epoxy resin composition and its application through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An epoxy resin composition, characterized in that The epoxy resin composition comprises the following components in parts by mass: The alicyclic epoxy resin has a structure as shown in Formula I: Wherein, R is selected from any one of H, C1-C5 straight chain or branched chain alkyl; n≥1。 2. The epoxy resin composition according to claim 1, characterized in that The general epoxy resin includes any one or a combination of at least two of brominated epoxy resin, bisphenol A epoxy resin, isocyanate modified epoxy resin, phenol formaldehyde epoxy resin, o-cresol formaldehyde epoxy resin, bisphenol A formaldehyde epoxy resin, tetraphenol ethane epoxy resin, and phenol DCPD epoxy resin; Preferably, the mass percentage of bromine element in the brominated epoxy resin is 15-52%; Preferably, n is an integer of 1-30; Preferably, the epoxy equivalent of the alicyclic epoxy resin is 170-200 g / eq; Preferably, the softening point of the alicyclic epoxy resin is 70-90°C.

3. The epoxy resin composition according to claim 1 or 2, characterized in that The phenolic curing agent includes any one or a combination of at least two of bisphenol A, tetrabromobisphenol A, linear phenol formaldehyde resin, linear o-cresol formaldehyde resin, linear bisphenol A formaldehyde resin, and phenol DCPD resin; Preferably, the molar amount of phenolic hydroxyl groups in the phenolic curing agent is n1, the total molar amount of epoxy groups in the general-purpose epoxy resin and the alicyclic epoxy resin is n2, and 0.8≤n1 / n2≤1.

1.

4. The epoxy resin composition according to any one of claims 1 to 3, characterized in that The filler comprises any one or a combination of at least two of aluminum hydroxide, silicon powder, kaolin, talc, magnesium hydroxide, barium sulfate, and boehmite, preferably any one or a combination of at least two of aluminum hydroxide, barium sulfate, and boehmite; Preferably, the average particle size of the filler is 0.1-30 μm, more preferably 0.5-20 μm.

5. The epoxy resin composition according to any one of claims 1 to 4, characterized in that The epoxy resin composition further comprises any one of a promoter, a dispersant, a coupling agent, a UV absorber, and a colorant, or a combination of at least two of them.

6. A resin film, characterized in that: The material of the resin film comprises the epoxy resin composition according to any one of claims 1 to 5.

7. A resin-coated copper foil, characterized in that: The resin-coated copper foil comprises a copper foil layer and a resin layer, and the material of the resin layer comprises the epoxy resin composition according to any one of claims 1 to 5.

8. A prepreg, characterized in that: The prepreg comprises a reinforcing material and the epoxy resin composition according to any one of claims 1 to 5 attached to the reinforcing material.

9. A metal foil-clad laminate, characterized in that: The metal foil-clad laminate includes at least one of the resin film according to claim 6 , the resin-coated copper foil according to claim 7 , and the prepreg according to claim 8 .

10. A printed circuit board, characterized in that: The printed circuit board comprises at least one of the resin film according to claim 6, the resin-coated copper foil according to claim 7, the prepreg according to claim 8, and the metal foil-clad laminate according to claim 9.

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