Curing agent composition, thermosetting resin composition and application thereof

Abstract

The invention provides a curing agent composition, a thermosetting resin composition and application of the curing agent composition and the thermosetting resin composition. The curing agent composition comprises the following components in parts by mass: 2-10 parts of dicyandiamide, 20-40 parts of first epoxy resin, 0.5-10 parts of a first solvent and 0.000001-0.12 part of white carbon black. The curing agent composition does not contain control solvents such as DMF (Dimethyl Formamide) and the like, can solve the problems of solvent residue and environment caused by the use of the DMF solvent in a dicyandiamide system copper-clad plate, has excellent dispersity and dispersion stability, and does not generate the phenomena of agglomeration, sedimentation and the like. The copper-clad plate prepared from the curing agent composition is excellent in appearance, has excellent insulativity, reliability, heat resistance, peel strength, long-term reliability and the like, and meets IPC performance requirement standards.

Description

Technical Field

[0001] The invention belongs to the technical field of copper clad laminates, and in particular relates to a curing agent composition, a thermosetting resin composition and applications thereof. Background Art

[0002] With the comprehensive development of electronic technology and the continuous upgrading of people's consumption demand for electronic products, the environmental pollution caused by electronic products has also received more and more attention. Copper clad laminate is an indispensable basic material in circuit boards. In the copper clad laminate industry, due to the low price of N, N-dimethylformamide solvent, it is a good solvent for low-cost latent epoxy curing agent dicyandiamide, which can ensure that the curing agent and epoxy are fully in contact and cured. In order to ensure the cost-effectiveness of copper clad laminates, there is no material to replace this type of solvent and curing agent combination, so N, N-dimethylformamide is widely used. On December 19, 2011, the European Chemicals Agency released the sixth batch of substances of high concern, including N, N-dimethylformamide (DMF). Products with DMF content exceeding 1000ppm cannot be sold in Europe. Due to the particularity of the copper clad laminate manufacturing process, it cannot be guaranteed that the solvent used will not have residues in the copper clad laminate.

[0003] In order to reduce the residual DMF in copper clad laminates, the industry has tried to use other types of solvents. For example, CN101925629A discloses a dimethylformamide-free formula using dicyandiamide as a curing agent for thermosetting epoxy resin, wherein the solvent includes at least one of alcohols, ketones, and glycol ethers, such as butanol, methyl ethyl ketone, propylene glycol methyl ether, etc. The aforementioned solvents can dissolve dicyandiamide for curing, but it does not take into account that the use of such solvents will greatly increase the cost of copper clad laminates and will also result in the residue of high-risk controlled solvents in the product.

[0004] CN1471552A discloses a varnish for laminates and laminated materials, wherein the solvent is selected from methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol, diethylene glycol, 2-methoxyethanol, 2-(2-methoxyethyl)ethanol, 2-ethoxyethanol, 2-(2-ethoxyethyl)ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclohexanone, one or more. In order to make epoxy fully contact and react with the curing agent and increase the uniformity of the copper-clad laminate, the preparation process of the laminate uses a heating method to treat the dicyandiamide solution with epoxy, but it does not take into account the nitrogen oxides emitted by the combustion of the solvent N,N-dimethylformamide used in the production process of the bonding sheet and the high-risk control solvents remaining in the product.

[0005] CN104589667A discloses a method for preparing a bonding sheet for copper clad laminates, comprising the following steps: uniformly mixing epoxy resin, ultrafine dicyandiamide, and ultrafine 2-methylimidazole at a temperature of 40-120°C, impregnating a reinforcing material at a temperature of 40-100°C, and drying to obtain a semi-cured bonding sheet. Since both the mixing process and the impregnation process of the reinforcing material require heating temperature for assistance, it does not match the current process flow, making it difficult to achieve large-scale application, and the uniformity after mixing is not easy to ensure, and the agglomeration of dicyandiamide will directly cause partial loss of sheet performance.

[0006] Therefore, developing a material that can avoid the solvent residue and environmental problems caused by the use of DMF solvent in dicyandiamide system copper clad laminates while ensuring the performance of the copper clad laminates is a research focus in this field. Summary of the invention

[0007] In view of the deficiencies in the prior art, the object of the present invention is to provide a curing agent composition, a thermosetting resin composition and applications thereof. Through the design and compounding of components, the curing agent composition can not only solve the residue and environmental problems caused by the use of DMF solvent in dicyandiamide system copper clad laminates, but also meet the excellent surface performance, insulation, reliability, heat resistance, peel strength, long-term reliability and other performance requirements of the copper clad laminates.

[0008] To achieve this object, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a curing agent composition, wherein the curing agent composition comprises the following components in parts by mass:

[0010]

[0011]

[0012] In the curing agent composition provided by the present invention, the white carbon black and the first solvent help dicyandiamide to be evenly dispersed in the epoxy resin, so that the thermosetting resin composition required for preparing the metal-clad laminate can undergo a uniform curing reaction. The curing agent composition does not contain controlled solvents such as DMF, and each component has excellent dispersibility, and the curing agent does not settle, so that the prepared metal-clad laminate not only meets the requirements of environmental management materials and nitrogen oxide emission requirements, but also has excellent and uniform surface properties, excellent insulation, reliability, heat resistance, peel strength and long-term reliability, and meets the high performance requirements of the plate.

[0013] In the curing agent composition provided by the present invention, the mass parts of the dicyandiamide are 2-10 parts, for example, it can be 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts or 9.5 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.

[0014] The mass parts of the first epoxy resin are 20-40 parts, for example, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 35 parts, 36 parts or 38 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 said range.

[0015] The mass proportion of the first solvent is 0.5-10 parts, for example, it can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts or 9.5 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 said range.

[0016] The mass proportion of the white carbon black is 0.000001-0.12 parts, for example, it can be 0.000005 parts, 0.00001 parts, 0.00002 parts, 0.00005 parts, 0.00008 parts, 0.0001 parts, 0.0002 parts, 0.0005 parts, 0.0008 parts, 0.001 parts, 0.002 parts, 0.005 parts, 0.008 parts, 0.01 parts, 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts or 0.11 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 said range.

[0017] The “parts” and “parts by mass” involved in the present invention are all calculated based on the solid content and do not include solvents, dispersants, etc.

[0018] 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.

[0019] Preferably, the D of dicyandiamide 50The particle size is 0.1-15 μm, for example, it can be 0.5 μm, 0.8 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm or 14 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 0.5-10 μm is further preferred.

[0020] In the present invention, D 50 The particle size indicates the average particle size, which can be obtained by testing with a laser particle size analyzer.

[0021] As a preferred technical solution of the present invention, the dicyandiamide has a suitable D 50 The particle size of dicyandiamide is such that the curing agent composition containing it has excellent dispersibility and stability, and avoids agglomeration and sedimentation. If the particle size of dicyandiamide is too small, it is difficult to disperse in the epoxy resin and is easy to agglomerate; if the particle size of dicyandiamide is too large, it is easy to sediment.

[0022] Preferably, the purity of the dicyandiamide is ≥99.9%, for example, it may be 99.91%, 99.92%, 99.95%, 99.98%, 99.99%, 99.992%, 99.995%, 99.998%, 99.999%, 99.9999%, etc.

[0023] Preferably, the mass percentage of dicyandiamide in the curing agent composition is 4%-30%, for example, it can be 4.5%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14%, 15%, 16%, 18%, 20%, 22%, 25% or 28%, 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 epoxy equivalent of the first epoxy resin is 180-800eq / 100g, for example, it can be 200eq / 100g, 250eq / 100g, 300eq / 100g, 350eq / 100g, 400eq / 100g, 450eq / 100g, 500eq / 100g, 550eq / 100g, 600eq / 100g, 650eq / 100g, 700eq / 100g or 750eq / 100g, 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.

[0025] Preferably, the first epoxy resin includes any one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, and brominated epoxy resin, or a combination of at least two thereof.

[0026] Preferably, the mass ratio of the first epoxy resin to dicyandiamide is (2-20):1, for example, it can be 2.5:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 12:1, 13:1, 15:1, 16:1, 18:1 or 19:1, etc.

[0027] Preferably, the mass percentage of the first epoxy resin in the curing agent composition is ≥60%, for example, it can be 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%, 92% or 95%, 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 enumerates the specific point values ​​included in the range, and 65%-90% is further preferred.

[0028] Preferably, the first solvent includes any one of an alcohol ether solvent, a ketone solvent, and an alcohol solvent, or a combination of at least two thereof, and an alcohol solvent is more preferred.

[0029] Preferably, the first solvent includes any one of propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, ethylene glycol methyl ether, acetone, butanone, cyclohexanone, ethanol, methanol, isopropanol, propylene glycol, ethylene glycol, butanol, hexanol, and n-butanol, or a combination of at least two thereof; further preferably, any one of ethanol, methanol, isopropanol, propylene glycol, ethylene glycol, butanol (preferably n-butanol), and hexanol, or a combination of at least two thereof.

[0030] Preferably, the particle size of the white carbon black is 1-50nm, for example, it can be 2nm, 5nm, 8nm, 10nm, 12nm, 15nm, 18nm, 20nm, 22nm, 25nm, 28nm, 30nm, 35nm, 40nm, 45nm or 48nm, 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 5-20nm is further preferred.

[0031] Preferably, the BET surface area of ​​the white carbon black is 300-450 g / m 2 , for example, it can be 320g / m 2 , 340g / m 2 , 350g / m 2 , 360g / m 2 , 380g / m 2, 400g / m 2 , 420g / m 2 or 440g / m 2 , 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. It is further preferred that the range is 350-410 g / m 2 .

[0032] As a preferred technical solution of the present invention, the white carbon black has a nanometer-scale particle size and a large specific surface area. It is compounded with the first solvent, dicyandiamide, and the first epoxy resin to solve the sedimentation problem of dicyandiamide after dispersion in the epoxy resin, so that the curing agent composition has excellent dispersibility and dispersion stability.

[0033] Preferably, the purity of the white carbon black is ≥99%, for example, it can be 99.1%, 99.2%, 99.5%, 99.8%, 99.9%, 99.91%, 99.92%, 99.95%, 99.98%, 99.99%, 99.992%, 99.995%, 99.998%, 99.999%, 99.9999%, etc.

[0034] Preferably, the pH value of the white carbon black is 3.7-4.7, for example, it can be 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5 or 4.6, 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, based on the mass of the dicyandiamide as 100%, the mass of the white carbon black is 0.0001%-1%, for example, it can be 0.0002%, 0.0005%, 0.0008%, 0.001%, 0.002%, 0.005%, 0.008%, 0.01%, 0.02%, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9% or 0.95%, 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 enumerates the specific point values ​​included in the range.

[0036] In a second aspect, the present invention provides a method for preparing the curing agent composition according to the first aspect, the preparation method comprising the following steps:

[0037] (1) mixing and uniformly dispersing dicyandiamide and a first solvent to obtain a dicyandiamide slurry;

[0038] (2) mixing the dicyandiamide slurry and white carbon black and dispersing them uniformly to obtain a premix;

[0039] (3) The premix and the first epoxy resin are mixed and dispersed uniformly to obtain the curing agent composition.

[0040] In the preparation method of the present invention, the first solvent is firstly mixed with dicyandiamide, so that the first solvent fully infiltrates and contacts the dicyandiamide, so that the surface of the dicyandiamide has a large number of hydroxyl groups (preferably an alcohol solvent, which is adsorbed on the surface of the dicyandiamide after contact and infiltration), and then fully dispersed with white carbon black, and finally mixed with the first epoxy resin to form the curing agent composition with excellent dispersion, uniformity and good stability, thereby avoiding the agglomeration and sedimentation of the curing agent.

[0041] Preferably, the mixing in step (1) is performed by a disperser.

[0042] Preferably, the mixing rotation speed in step (1) is 500-2000 rpm, for example, it can be 800 rpm, 1000 rpm, 1200 rpm, 1500 rpm or 1800 rpm, 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.

[0043] Preferably, the mixing time in step (1) is 5-60 min, for example, 10 min, 20 min, 30 min, 40 min or 50 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.

[0044] Preferably, the dispersion in step (2) is carried out by a disperser.

[0045] Preferably, the dispersion rotation speed in step (2) is 500-2000 rpm, for example, it can be 800 rpm, 1000 rpm, 1200 rpm, 1500 rpm or 1800 rpm, 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.

[0046] Preferably, the dispersion time in step (2) is 5-60 min, for example, it can be 10 min, 20 min, 30 min, 40 min or 50 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.

[0047] Preferably, the mixing in step (3) is performed by a disperser, and / or the dispersing in step (3) is performed by a disperser and / or a sand mill.

[0048] Preferably, the dispersion rotation speed in step (3) is 500-5000 rpm, for example, it can be 1000 rpm, 1500 rpm, 2000 rpm, 2500 rpm, 3000 rpm, 3500 rpm, 4000 rpm or 4500 rpm, 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.

[0049] Preferably, the dispersion time in step (3) is 5-60 min, for example, it can be 10 min, 20 min, 30 min, 40 min or 50 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.

[0050] In a third aspect, the present invention provides a thermosetting resin composition, comprising a thermosetting resin and the curing agent composition as described in the first aspect.

[0051] Preferably, the thermosetting resin comprises a second epoxy resin.

[0052] Preferably, the second epoxy resin includes any one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, and brominated epoxy resin, or a combination of at least two thereof.

[0053] Preferably, the epoxy equivalent of the second epoxy resin is 180-800 g / eq, for example, it can be 200 g / eq g, 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 or 750 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.

[0054] Preferably, the mass percentage of the thermosetting resin (second epoxy resin) in the thermosetting resin composition is ≥40%, for example, it can be 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90%, 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.

[0055] Preferably, based on the mass of the thermosetting resin as 100%, the mass of the curing agent composition is 20%-90%, for example, it can be 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%, 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 enumerates the specific point values ​​included in the range, and 25%-85% is further preferred.

[0056] Preferably, the thermosetting resin composition further comprises a curing accelerator.

[0057] Preferably, the curing accelerator includes an imidazole compound, and further preferably any one of 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-propylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-cyanoethyl-2-methylimidazole, or a combination of at least two thereof.

[0058] Preferably, based on the mass of the curing agent composition as 100%, the mass of the curing accelerator is 0.002%-0.5%, for example, it can be 0.005%, 0.008%, 0.01%, 0.02%, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 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.

[0059] Preferably, the thermosetting resin composition further comprises a filler.

[0060] Preferably, the filler includes any one of silicon micropowder, kaolin, talc, magnesium hydroxide, barium sulfate, aluminum hydroxide, aluminum oxide, titanium dioxide, and calcium carbonate, or a combination of at least two thereof.

[0061] Preferably, based on the mass of the thermosetting resin as 100%, the mass of the filler is ≤70%, for example, it can be 0, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% or 65%, 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.

[0062] Preferably, the mass content of filler in the thermosetting resin composition is ≤60%, for example, it can be 0, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or 55%, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0063] Preferably, the thermosetting resin composition further comprises other additives that a person skilled in the art is motivated to add, such as any one or a combination of at least two of an antioxidant, a viscosity modifier, a flame retardant, a coupling agent, etc.

[0064] Preferably, the method for preparing the thermosetting resin composition comprises: uniformly mixing the components of the thermosetting resin composition to obtain the thermosetting resin composition.

[0065] An optional second solvent may also be added to the thermosetting resin composition. On the other hand, the present invention provides a resin adhesive, which comprises the thermosetting resin composition as described in the third aspect and a second solvent, wherein the thermosetting resin composition is dispersed and / or dissolved in the second solvent.

[0066] The amount of the second solvent added is selected by those skilled in the art based on experience and process requirements to make the resin glue reach a suitable viscosity for use, so as to facilitate the impregnation and coating of the resin glue. The solvent will partially or completely evaporate in the subsequent drying, semi-curing or complete curing stages.

[0067] The second solvent of the present invention is not particularly limited and includes any one of ketone solvents, alcohol solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents, or a combination of at least two thereof.

[0068] Preferably, the second solvent includes ketones such as acetone, butanone, cyclohexanone, etc., aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol or butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, carbitol or butyl carbitol, etc. The second solvent can be used alone or in combination of two or more. Preferably, any one of acetone, butanone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, methyl acetate, toluene, xylene, and methanol or a combination of at least two thereof is used.

[0069] Preferably, the mass percentage of the solvent in the resin glue is 15%-85%, for example, it can be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 62%, 65%, 68%, 70%, 72%, 75% or 80%, 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 said range.

[0070] Preferably, the method for preparing the resin adhesive comprises: mixing each component in the thermosetting resin composition with a second solvent, and dispersing them uniformly to obtain the resin adhesive.

[0071] In a fourth aspect, the present invention provides a prepreg, the prepreg comprising a reinforcing material and the thermosetting resin composition as described in the third aspect attached to the reinforcing material.

[0072] Preferably, the thermosetting resin composition is attached to the reinforcing material by impregnation and drying.

[0073] Preferably, the reinforcement material comprises glass fiber cloth.

[0074] Illustratively, the method for preparing the prepreg is: using the resin glue of the thermosetting resin composition to infiltrate a reinforcing material, and then drying to obtain the prepreg.

[0075] Preferably, the drying temperature is 80-200°C, for example, it can be 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C or 200°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.

[0076] Preferably, the drying time is 1-20 min, for example, it can be 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, 19 min or 20 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 fifth aspect, the present invention provides a laminate comprising at least one prepreg sheet as described in the fourth aspect.

[0078] In a sixth aspect, the present invention provides a metal foil-clad laminate, comprising a metal foil and at least one of the prepreg as described in the fourth aspect and the laminate as described in the fifth aspect.

[0079] Preferably, the number of prepregs in the metal foil-clad laminate is 1-30, for example, 2, 3, 5, 6, 8, 10, 12, 15, 18, 20, 22, 25 or 28, 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.

[0080] Preferably, the metal foil is a copper foil, and thus the metal foil-clad laminate is a copper foil-clad laminate (CCL).

[0081] Exemplarily, the method for preparing the metal-clad laminate comprises: laminating metal foil on one side or both sides of a semi-cured sheet and curing to obtain the metal-clad laminate; or, stacking at least two semi-cured sheets into a laminate, and then laminating metal foil on one side or both sides of the laminate and curing to obtain the metal-clad laminate.

[0082] Preferably, the curing is carried out in a press.

[0083] Preferably, the curing temperature is 120-280°C, for example, 130°C, 140°C, 150°C, 160°C, 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.

[0084] Preferably, the curing pressure is 1-10 MPa, for example 1.5 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa or 9 MPa, 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.

[0085] 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, and 30-180 min is further preferred.

[0086] In a seventh aspect, the present invention provides a printed circuit board, comprising at least one of the prepreg as described in the fourth aspect, the laminate as described in the fifth aspect, and the metal foil-clad laminate as described in the sixth aspect.

[0087] Compared with the prior art, the present invention has the following beneficial effects:

[0088] The curing agent composition provided by the present invention does not contain controlled solvents such as DMF, and can solve the solvent residue and environmental problems caused by the use of DMF solvent in the dicyandiamide system copper clad laminate, and make the nitrogen oxide emission 0ppm. At the same time, each component in the curing agent composition has excellent dispersibility and dispersion stability, and does not agglomerate and settle. The copper clad laminate obtained therefrom has excellent appearance, excellent insulation, reliability, heat resistance, peel strength and long-term reliability, etc., and meets the IPC performance requirements. DETAILED DESCRIPTION

[0089] 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.

[0090] In the following specific implementation of the present invention, the materials involved are as follows:

[0091]

[0092]

[0093] Examples 1-8, Comparative Examples 1-3

[0094] A curing agent composition, the types and amounts of each component are shown in Table 1, and the unit of amount of each component is "part".

[0095] The preparation method of each curing agent composition in Table 1 comprises the following steps:

[0096] (1) mixing dicyandiamide and a first solvent according to the formula amount, and dispersing them for 30 minutes using a dispersing disc disperser at 1000 rpm to obtain a dicyandiamide slurry;

[0097] (2) mixing the dicyandiamide slurry obtained in step (1) with white carbon black, and dispersing them for 30 minutes using a dispersing disc disperser at 1000 rpm to obtain a uniform premix;

[0098] (3) The premix obtained in step (2) and the first epoxy resin are firstly stirred uniformly using a dispersing disc disperser, and then dispersed using a horizontal sand mill at 3000 rpm for 30 minutes to fully disperse them uniformly to obtain the curing agent composition.

[0099] The sedimentation of each curing agent composition in Table 1 was tested by weighing the same amount of the mixture in a transparent sealable glass bottle, and observing the sedimentation after leaving it for 24 hours.

[0100] Table 1

[0101]

[0102]

[0103] Example 9

[0104] A curing agent composition N9, whose components are the same as those of Example 4, differing only in that the preparation method is different, specifically as follows: dicyandiamide, a first epoxy resin, white carbon black and a first solvent are mixed according to the formula amount, and a dispersing disc disperser is used to stir and disperse for 90 minutes at 1000 rpm to obtain the curing agent composition, which has obvious sedimentation after being placed for 24 hours.

[0105] Application Example 1-9, Comparative Application Example 1-6

[0106] A thermosetting resin composition, the types and amounts of each component are shown in Table 2 and Table 3, and the amount unit of each component is "part".

[0107] A prepreg comprising the thermosetting resin composition and a metal foil-clad laminate (copper-clad laminate), the preparation method of which is as follows:

[0108] (1) The thermosetting resin composition and the second solvent are mixed according to the formula amount, and stirred for 1 hour to prepare a uniform resin glue solution; glass fiber cloth is used as a reinforcing material, and the reinforcing material impregnated with glue through an extrusion roller is dried in an oven at an oven temperature of 170° C. and a drying time of 5 minutes to prepare a semi-cured sheet with a thickness of 0.2 mm.

[0109] (2) Five prepregs obtained in step (1) were stacked, and both outer sides of the stack were covered with 35 μm copper foil, which was placed in a vacuum press and hot-pressed at 3.0 MPa and 170° C. for 40 min to produce a copper-clad laminate.

[0110] The copper clad laminate is subjected to a performance test, and the specific method is as follows:

[0111] (1) Residue of controlled substances in board materials: tested by gas chromatography-mass spectrometry (GC-MS);

[0112] (2) Nitrogen oxide emissions: determined based on the formulation materials (using the amount of DMF used for determination);

[0113] (3) Thermal stress: Thermal stress test was conducted in 288°C soldering furnace according to the method in IPC-TM-650 2.4.13.1-1994 Thermal Stress of Laminates.

[0114] (4) Board appearance: Visually observe the board, if there is no dry flower on the board surface, record it as "OK";

[0115] (5) Cost comparison: The cost is calculated using the single sheet cost method. If the cost is lower than the existing DMF product formula, it will be recorded as "low", if the cost is the same as the existing DMF product formula, it will be recorded as "medium", and if the cost is higher than the existing DMF product formula, it will be recorded as "high";

[0116] The test results are shown in Table 2 and Table 3.

[0117] Table 2

[0118]

[0119]

[0120] Table 3

[0121]

[0122]

[0123] According to the performance data in Table 2, the curing agent composition provided by the present invention is compounded with the epoxy resin commonly used in copper-clad laminates, and is combined with a viscosity-adjusting solvent (second solvent) controlled by non-DMF, a curing accelerator, and a filler. The 288°C thermal stress of the copper-clad laminate produced according to the general copper-clad laminate process is greater than 100s, and there are no apparent defects such as dried flowers, and the secondary appearance is excellent. It has excellent reliability, heat resistance, insulation, peel strength and long-term reliability, and has excellent comprehensive performance, meeting the IPC performance requirements. At the same time, the DMF content of the copper-clad laminate is 0ppm, and the nitrogen oxide emission is 0ppm, which meets environmental protection requirements.

[0124] The present invention designs and optimizes the preparation process of the curing agent composition, so that it has excellent dispersibility and dispersion stability, and does not have agglomeration, sedimentation and the like, so that the resin glue prepared by the curing agent composition has good uniformity and excellent board appearance. The curing agent composition N9 of Example 9 is prepared by a conventional mixing process, and sedimentation occurs, resulting in uneven glue, which affects the appearance of the board.

[0125] Comparing the data in Table 2 and Table 3, it can be seen that if conventional dicyandiamide is used as a curing agent (Comparative Application Examples 1-3), the preparation of uniform resin glue and semi-cured sheets requires the use of controlled solvents such as DMF and ethylene glycol monomethyl ether, resulting in controlled substances remaining in the plate, and DMF will also cause nitrogen oxide emissions; and solvents such as ethylene glycol monomethyl ether will increase the cost of the plate. If the curing agent composition does not contain the white carbon black of the content specified in the present invention, it has a shorter shelf life, the composition is easy to settle, and the appearance and thermal stress of the plate are significantly affected by the composition after sedimentation; if the amount of white carbon black is too much, it will cause the curing system to be extremely difficult to disperse, thereby seriously affecting the performance of the thermosetting resin composition and the plate.

[0126] The applicant declares that the present invention illustrates the curing agent composition, thermosetting resin composition and application of the present invention 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. A curing agent composition, characterized in that The curing agent composition comprises the following components in parts by mass:

2. The curing agent composition according to claim 1, characterized in that The D 50 The particle size is 0.1-15 μm, preferably 0.5-10 μm; Preferably, the epoxy equivalent of the first epoxy resin is 180-800 g / eq; Preferably, the first solvent comprises any one of alcohol ether solvents, ketone solvents, and alcohol solvents, or a combination of at least two thereof, and an alcohol solvent is further preferred; Preferably, the first solvent includes any one of propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, ethylene glycol methyl ether, acetone, butanone, cyclohexanone, ethanol, methanol, isopropanol, propylene glycol, ethylene glycol, butanol, and hexanol, or a combination of at least two thereof.

3. The curing agent composition according to claim 1 or 2, characterized in that The particle size of the white carbon black is 1-50nm, preferably 5-20nm; Preferably, the BET surface area of ​​the white carbon black is 300-450 g / m 2 , further preferably 350-410g / m 2 ; Preferably, based on 100% of the mass of the dicyandiamide, the mass of the white carbon black is 0.0001%-1%.

4. A method for preparing a curing agent composition according to any one of claims 1 to 3, characterized in that: The preparation method comprises the following steps: Mixing and dispersing dicyandiamide and the first solvent uniformly to obtain dicyandiamide slurry; The dicyandiamide slurry is mixed with white carbon black and dispersed evenly to obtain a premix; The premix is ​​mixed with the first epoxy resin and dispersed uniformly to obtain the curing agent composition.

5. A thermosetting resin composition, characterized in that: The thermosetting resin composition comprises a thermosetting resin and the curing agent composition according to any one of claims 1 to 3.

6. The thermosetting resin composition according to claim 5, characterized in that The thermosetting resin includes a second epoxy resin; Preferably, the second epoxy resin comprises any one or a combination of at least two of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, and brominated epoxy resin; Preferably, the epoxy equivalent of the second epoxy resin is 180-800 g / eq; Preferably, based on 100% of the mass of the thermosetting resin, the mass of the curing agent composition is 20%-90%, more preferably 25%-85%; Preferably, the thermosetting resin composition further comprises a curing accelerator; Preferably, the curing accelerator comprises an imidazole compound, and more preferably any one or a combination of at least two of 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-propylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-cyanoethyl-2-methylimidazole; Preferably, based on 100% of the mass of the curing agent composition, the mass of the curing accelerator is 0.002%-0.5%; Preferably, the thermosetting resin composition further comprises a filler; Preferably, the filler includes any one or a combination of at least two of silica powder, kaolin, talc, magnesium hydroxide, barium sulfate, aluminum hydroxide, aluminum oxide, titanium dioxide, and calcium carbonate; Preferably, based on the mass of the thermosetting resin being 100%, the mass of the filler is ≤70%.

7. A prepreg, characterized in that: The prepreg comprises a reinforcing material and the thermosetting resin composition according to claim 5 or 6 attached to the reinforcing material; Preferably, the thermosetting resin composition is attached to the reinforcing material by impregnation and drying.

8. A laminated board, characterized in that: The laminate comprises at least one prepreg according to claim 7.

9. A metal foil-clad laminate, characterized in that: The metal foil-clad laminate comprises a metal foil and at least one of the prepreg according to claim 7 and the laminate according to claim 8.

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

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