CN114181496A - Epoxy resin composite material, prepreg and laminated board - Google Patents

Epoxy resin composite material, prepreg and laminated board Download PDF

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Publication number
CN114181496A
CN114181496A CN202111605941.4A CN202111605941A CN114181496A CN 114181496 A CN114181496 A CN 114181496A CN 202111605941 A CN202111605941 A CN 202111605941A CN 114181496 A CN114181496 A CN 114181496A
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epoxy resin
parts
prepreg
composite material
resin
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CN114181496B (en
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漆小龙
余家斌
郭永军
李进威
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Guangdong Ying Hua New Mstar Technology Ltd
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Guangdong Ying Hua New Mstar Technology Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses an epoxy resin composite material, a prepreg and a laminated board, wherein the epoxy resin composite material comprises the following raw material components: 15-50 parts of basic epoxy resin, 0.5-4 parts of first resin, 0.5-4 parts of silicon-based scratch resistant agent, 50-90 parts of nano filler and 0.5-2.5 parts of wetting dispersant; wherein the first resin is at least one selected from rubber modified epoxy resin and thermoplastic resin. The auxiliary materials are added to be matched for use to modify the basic epoxy resin, the first resin improves the resistance capacity and the deformation absorption capacity of the basic epoxy resin to external force, organic silicon in the silicon-based scratch-resistant agent is increased and is tangled with an epoxy group, so that polysiloxane molecules are better and uniform in surface distribution and are not precipitated, the raw materials are effectively filled by further utilizing the surface effect of the nano spherical filler, and the synergistic effect among the raw materials can improve the hardness and the scratch resistance of the epoxy resin composite material.

Description

Epoxy resin composite material, prepreg and laminated board
Technical Field
The invention relates to the field of organic materials, in particular to an epoxy resin composite material, a prepreg and a laminated board.
Background
The epoxy resin has excellent cohesiveness, corrosion resistance and dielectric insulation, so that the epoxy resin can be prepared into coatings, composite materials, casting materials, adhesives, molding materials and injection molding materials, and can be widely applied to various fields. However, the surface hardness of the common epoxy resin is only HB-4H in the pencil hardness test, and the common epoxy resin cannot be used in the field requiring materials with scratch resistance.
Conventionally, a layer of high-hardness material is plated on the surface of a composite material needing to improve the surface hardness to achieve the purpose of enhancing the surface hardness mainly through surface treatment technologies such as composite plating, however, the technologies are complex in manufacturing process, high in cost and uneven in plating thickness.
Disclosure of Invention
In view of the above, there is a need to provide an epoxy resin composite, a prepreg and a laminate having both a high surface hardness of 8H and a high scratch resistance.
The invention provides an epoxy resin composite material which comprises the following raw material components in parts by weight:
Figure BDA0003433851620000011
Figure BDA0003433851620000021
wherein the first resin is at least one selected from rubber-modified epoxy resins and thermoplastic resins.
In one embodiment, the base epoxy resin is selected from at least one of a bisphenol a type epoxy resin and a glycidyl ester type epoxy resin.
In one embodiment, the rubber in the rubber modified epoxy resin is selected from at least one of carboxyl-terminated liquid nitrile rubber, vinyl-terminated nitrile rubber, and amino-terminated nitrile rubber; and/or
The epoxy resin in the rubber modified epoxy resin is at least one selected from glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin and aliphatic epoxy resin; and/or
The mass ratio of the rubber to the epoxy resin in the rubber modified epoxy resin is 1 (5-12).
In one embodiment, the thermoplastic resin is selected from at least one of polysulfone, polyethersulfone, polyetherimide, and polyetherketone.
In one embodiment, the nano-filler is a nano-spherical filler selected from at least one of glass powder, silica, zirconia, alumina, and magnesia; and/or
The particle size of the nano spherical filler is 25 nm-80 nm.
In one embodiment, the raw material components further comprise 0.5-2 parts of a curing agent and 0.01-0.05 part of an accelerator.
In one embodiment, the curing agent is at least one selected from the group consisting of cyanate-based curing agents, aliphatic polyamine-based curing agents, aromatic amine-based curing agents, polyamide-based curing agents, latent curing agents, and anhydride-based curing agents; and/or
The accelerator is at least one selected from amine accelerators, imidazole accelerators and peroxide accelerators.
The invention also provides a prepreg, which comprises a base material and the resin material loaded on the base material, wherein the resin material is the epoxy resin composite material.
Furthermore, the invention provides a laminated board, and the raw materials for preparing the laminated board comprise the prepreg.
Furthermore, the invention provides the application of the laminated board in preparing printed circuit boards, automobile parts, electric appliance housings or building materials.
The specific first resin, the silicon-based scratch-resistant agent, the nano filler and the wetting dispersant are matched to modify the basic epoxy resin, the first resin improves the resistance capacity and the deformation absorption capacity of the basic epoxy resin to external force, organic silicon in the silicon-based scratch-resistant agent is increased and tangled with an epoxy group, so that polysiloxane molecules are distributed on the surface more uniformly and are not precipitated, the raw materials are effectively filled by further utilizing the surface effect of the nano filler, and the hardness and the scratch-resistant performance of the epoxy resin composite material can be improved by the synergistic effect among the raw materials.
Detailed Description
The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.
The words "preferably," "more preferably," and the like, in the present disclosure mean embodiments of the disclosure that may, in some instances, provide certain benefits. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides an epoxy resin composite material which comprises the following raw material components in parts by weight:
Figure BDA0003433851620000041
wherein the first resin is at least one selected from rubber modified epoxy resin and thermoplastic resin.
The epoxy resin composite material preferably comprises the following raw material components in parts by weight:
Figure BDA0003433851620000042
in a specific example, the base epoxy resin is selected from at least one of a bisphenol a type epoxy resin and a glycidyl ester type epoxy resin.
It is understood that the silicon-based scratch resistant agent may be at least one selected from the group consisting of degussa 4042 and cantonese silicone technologies ltd TCP-8008.
In one specific example thereof, the rubber is selected from at least one of carboxyl-terminated liquid nitrile rubber, vinyl-terminated nitrile rubber, and amino-terminated nitrile rubber.
The rubber-modified epoxy resin is at least one epoxy resin selected from the group consisting of a gum-modified epoxy resin, a glycidyl ether epoxy resin, a glycidyl ester epoxy resin, a glycidyl amine epoxy resin and an aliphatic epoxy resin, and the rubber and the epoxy resin in the rubber-modified epoxy resin are modified in a mass ratio of 1 (5-12).
It is understood that the above rubber and epoxy resin may be, but not limited to, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, or 1: 12.
In a specific example thereof, the thermoplastic resin is selected from at least one of polysulfone, polyethersulfone, polyetherimide and polyetherketone.
It is understood that the wetting dispersant is selected from at least one of Effkoner 7520, BYK-9076, and BYK-W961.
The nano spherical filler is at least one selected from glass powder, silicon dioxide, zirconium oxide, aluminum oxide and magnesium oxide, and the particle size of the nano spherical filler is 25 nm-80 nm.
In a specific example, the raw material composition further comprises 0.5-2 parts of a curing agent and 0.01-0.05 part of an accelerator.
In a specific example, the curing agent is at least one selected from the group consisting of cyanate-based curing agents, aliphatic polyamine-based curing agents, aromatic amine-based curing agents, polyamide-based curing agents, latent curing agents, and acid anhydride-based curing agents.
Specifically, the curing agent may be at least one selected from the group consisting of methyl tetrahydrophthalic anhydride, methyl nadic anhydride, 4 '-diaminodiphenyl sulfone, and 4,4' -diaminodiphenyl methane.
It is to be understood that the above methyltetrahydrophthalic anhydride may not be limited to being a mixture of isomers.
In a specific example, the accelerator is selected from at least one of amine accelerators, imidazole accelerators and peroxide accelerators.
Specifically, the accelerator may be at least one selected from the group consisting of N, N-dimethylbenzylamine, triethylamine, and N, N-dimethylaniline.
According to the invention, the specific first resin, the silicon-based scratch-resistant agent, the nano filler and the wetting dispersant are matched for use to modify the basic epoxy resin, the first resin improves the resistance and deformation absorption capacity of the basic epoxy resin to external force, the entanglement of organic silicon in the silicon-based scratch-resistant agent and an epoxy group is increased, so that polysiloxane molecules are distributed on the surface more uniformly without precipitation, the raw materials are effectively filled by further utilizing the surface effect of the nano filler, and the hardness and scratch resistance of the epoxy resin composite material can be improved by the synergistic effect among the raw materials.
It can be understood that the preparation method of the epoxy resin composite material comprises the following steps S10 to S20:
step S10: mixing a curing agent with a first solvent to prepare a first mixture;
step S20: mixing basic epoxy resin, first resin, a silicon-based scratch-resistant agent, an accelerator, a nano filler, a wetting dispersant and a second solvent to prepare a second mixture;
step S30: the first mixture is mixed with the second mixture.
In a specific example, the first solvent and the second solvent are each independently selected from at least one of N, N-dimethylformamide and cyclohexanone.
Step S20 includes: the basic epoxy resin, the first resin, the silicon-based scratch resistant agent and the accelerator are primarily mixed for 0.2 to 1 hour at the dispersion speed of 800 to 1200r/min, the nano filler and the second solvent are added for stirring, and the wetting dispersant is added for secondary mixing for 1 to 5 hours at the dispersion speed of 1600 to 2400 r/min.
The invention also provides a prepreg, which comprises a base material and a resin material loaded on the base material, wherein the resin material is the epoxy resin composite material.
Specifically, the substrate may be selected from, but not limited to, glass fibers.
The preparation method of the prepreg comprises the steps of soaking the base material in the epoxy resin composite material, and carrying out heat treatment for 1-5 min at 150-200 ℃.
Preferably, the material is immersed in the epoxy resin composite material and is subjected to heat treatment at 160-190 ℃ for 2-4 min.
Furthermore, the invention provides a laminated board, and the raw materials for preparing the laminated board comprise the prepreg.
The preparation steps of the laminated board comprise: stacking the prepregs in a vacuum state at 20kgf/cm2～40kgf/cm2At a temperature of 150-200 ℃ for 50-80 min under the pressure of (2).
Preferably, the prepreg is stacked in a vacuum state at 20kgf/cm2～30kgf/cm2At 160-190 ℃ for 50-70 min.
Furthermore, the invention provides the application of the laminated board in preparing printed circuit boards, automobile parts, electric appliance housings or building materials.
Specific examples are provided below to further illustrate the epoxy resin composite material of the present invention in detail. The raw materials in the following embodiments are commercially available unless otherwise specified.
The particle size of the nano-scale spherical glass powder used in the following examples and comparative examples is 25-80nm, the particle size of the nano-scale spherical talcum powder is 25-80nm, and the carboxyl-terminated butyronitrile modified epoxy resin E51 and the epoxy resin E51 used in the following examples: bisphenol A diglycidyl ether (E51 type), the mass ratio of carboxyl terminated butyronitrile to epoxy resin E51: 1:9.
Example 1:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 20 parts of bisphenol A type epoxy resin, 2 parts of Texaco 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 55 parts of nano-scale spherical glass powder and 30 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at the rotating speed of 2000r/min for 2 hours at a high speed, adding all the compositions in the batching bottle II into the batching bottle I, and continuously dispersing at the rotating speed of 2000r/min for 1 hour at a high speed; preparing the epoxy resin composite material.
With the epoxy1067 glass fiber cloth (basis weight 30 g/m) impregnated with resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71 percent. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Example 2:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 30 parts of bisphenol A type epoxy resin, 2 parts of Texaco 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 55 parts of nano spherical glass powder and 30 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 70%. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Example 3:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 40 parts of bisphenol A type epoxy resin, 2 parts of Texaco 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 55 parts of nano spherical glass powder and 30 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 69 percent. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Example 4:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 20 parts of bisphenol A type epoxy resin, 2 parts of Texaco 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 60 parts of nano spherical glass powder and 30 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71 percent. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Example 5:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 20 parts of bisphenol A type epoxy resin, 2 parts of Texaco 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 70 parts of nano-scale spherical glass powder and 35 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 72 percent. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Example 6:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 20 parts of bisphenol A type epoxy resin, 2 parts of Texaco 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 80 parts of nano spherical glass powder and 40 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 72 percent. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Example 7:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 30 parts of bisphenol A type epoxy resin, 2 parts of Texaco 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 60 parts of nano spherical glass powder and 30 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 70%. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Example 8:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 30 parts of bisphenol A type epoxy resin, 2 parts of Texaco 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 70 parts of nano-scale spherical glass powder and 35 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71 percent. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Example 9:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 30 parts of bisphenol A type epoxy resin, 2 parts of Texaco 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 80 parts of nano spherical glass powder and 40 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71 percent. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Example 10:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 40 parts of bisphenol A type epoxy resin, 2 parts of Texaco 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 60 parts of nano spherical glass powder and 30 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 69 percent. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure condition of (1), curing the product at 180 ℃ for 60 minutes to prepare the productInto a laminate of 0.5mm thickness.
Example 11:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 40 parts of bisphenol A type epoxy resin, 2 parts of Texaco 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 70 parts of nano-scale spherical glass powder and 35 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 70%. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Example 12:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 40 parts of bisphenol A type epoxy resin, 2 parts of Texaco 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 80 parts of nano spherical glass powder and 40 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 70%. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, and placing the laminate in a programmable machineIn a vacuum press with controlled temperature and pressure at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Comparative example 1:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 20 parts of bisphenol A type epoxy resin, 2 parts of Texaco 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 55 parts of nanoscale spherical talcum powder and 30 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at the high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at the high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71 percent. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Comparative example 2:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 20 parts of bisphenol A epoxy resin, 2 parts of degussa 4042 and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 55 parts of nano spherical glass powder and 30 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71 percent.Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Comparative example 3:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 20 parts of bisphenol A epoxy resin, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 55 parts of nano spherical glass powder and 30 parts of cyclohexanone into a batching bottle II, adding 1 part of Aifuken 7520 under the stirring condition, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71 percent. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Comparative example 4:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 20 parts of bisphenol A epoxy resin, 2 parts of Texaco 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 55 parts of nano-scale spherical glass powder and 30 parts of cyclohexanone into a batching bottle II, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the batching bottle II into the batching bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) In aBaking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71 percent. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Comparative example 5:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle (I), fully stirring and dissolving, and then sequentially adding 20 parts of bisphenol A epoxy resin, 4 parts of degussa 4042 and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 80 parts of nano-scale spherical glass powder and 40 parts of cyclohexanone into a proportioning bottle II, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the proportioning bottle II into the proportioning bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71 percent. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Comparative example 6:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 20 parts of bisphenol A epoxy resin, 4 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 80 parts of nano-scale spherical glass powder and 40 parts of cyclohexanone into a proportioning bottle II, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the proportioning bottle II into the proportioning bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) In the heatAnd baking for 3min at 180 ℃ in a wind circulation oven to obtain the prepreg with the resin content of 71 percent. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Comparative example 7:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a proportioning bottle, fully stirring and dissolving, and then sequentially adding 20 parts of bisphenol A epoxy resin, 2 parts of polytetrafluoroethylene micropowder, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5 h; adding 80 parts of nano-scale spherical glass powder and 40 parts of cyclohexanone into a proportioning bottle II, dispersing at a high speed of 2000r/min for 2 hours, adding all the composition in the proportioning bottle II into the proportioning bottle I, and continuously dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
1067 glass fiber cloth (basis weight 30 g/m) was impregnated with this epoxy resin composite2) And baking the prepreg for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71 percent. Overlapping 10 prepregs, covering a release film on each of the upper and lower surfaces of the laminate, placing in a vacuum press with programmable temperature and pressure control at 25kgf/cm in vacuum state2Under the pressure conditions of (1) and at a temperature of 180 ℃ for 60 minutes, to form a laminate having a thickness of 0.5 mm.
Test methods and results analysis
The formulations and properties of the epoxy resin composites prepared in the above examples and comparative examples are shown in the following table.
Wherein, the pencil hardness test: surface hardness was measured according to ASTM D3363;
scratch resistance: the GM W14688Method A-Code2(10N) Method was used to test scratch resistance.
Figure BDA0003433851620000181
Figure BDA0003433851620000182
Figure BDA0003433851620000191
As can be seen from the above examples and comparative examples, in comparative examples 1 to 4, epoxy resin based compositions having good hardness and scratch resistance could not be obtained without adding the corresponding nano filler, first resin, scratch resistance agent and wetting dispersant, respectively. Further, comparative example 5 and comparative example 6 and example 9 did not satisfy the requirements for increasing the hardness and scratch resistance of the final epoxy resin composition of the silicon-based scratch resistant agent or the first resin when the first resin or the silicon-based scratch resistant agent was not added. In addition, in comparative example 7, the silicon-based scratch resistant agent was changed to another scratch resistant agent, and the scratch resistance and hardness were also somewhat reduced.
The specific first resin, the silicon-based scratch-resistant agent, the nano filler and the wetting dispersant are matched for use to modify the basic epoxy resin, the first resin improves the resistance and deformation absorption capacity of the basic epoxy resin to external force, the organic silicon in the silicon-based scratch-resistant agent is increased to be tangled with an epoxy group, so that polysiloxane molecules are distributed on the surface more uniformly and are not precipitated, the raw materials are effectively filled by further utilizing the surface effect of the nano filler, and the hardness and scratch resistance of the epoxy resin composite material can be improved by the synergistic effect of the raw materials.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The epoxy resin composite material is characterized by comprising the following raw material components in parts by weight:
Figure FDA0003433851610000011
wherein the first resin is at least one selected from rubber-modified epoxy resins and thermoplastic resins.
2. The epoxy resin composite according to claim 1, wherein the base epoxy resin is at least one selected from the group consisting of a bisphenol a type epoxy resin and a glycidyl ester type epoxy resin.
3. The epoxy composite of claim 1, wherein the rubber in the rubber modified epoxy is selected from at least one of carboxyl terminated liquid nitrile rubber, vinyl terminated nitrile rubber, and amino terminated nitrile rubber; and/or
The epoxy resin in the rubber modified epoxy resin is at least one selected from glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin and aliphatic epoxy resin; and/or
The mass ratio of the rubber to the epoxy resin in the rubber modified epoxy resin is 1 (5-12).
4. The epoxy composite of claim 1, wherein the thermoplastic resin is selected from at least one of polysulfone, polyethersulfone, polyetherimide, and polyetherketone.
5. The epoxy composite of claim 1, wherein the nano-filler is a nano-spherical filler selected from at least one of glass frit, silica, zirconia, alumina, and magnesia; and/or
The particle size of the nano spherical filler is 25 nm-80 nm.
6. The epoxy resin composite material according to any one of claims 1 to 5, wherein the raw material composition further comprises 0.5 to 2 parts of a curing agent and 0.01 to 0.05 part of an accelerator.
7. The epoxy resin composite according to claim 6, wherein the curing agent is at least one selected from the group consisting of cyanate-based curing agents, aliphatic polyamine-based curing agents, aromatic amine-based curing agents, polyamide-based curing agents, latent curing agents, and acid anhydride-based curing agents; and/or
The accelerator is at least one selected from amine accelerators, imidazole accelerators and peroxide accelerators.
8. A prepreg, comprising a substrate and a resin material supported on the substrate, wherein the resin material is the epoxy resin composite material according to any one of claims 1 to 7.
9. A laminate, characterized in that the starting materials for the preparation of the laminate comprise a prepreg according to claim 8.
10. Use of the laminate of claim 9 for the manufacture of printed wiring boards, automotive parts, appliance housings or building materials.
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