CN114181496B - 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
CN114181496B
CN114181496B CN202111605941.4A CN202111605941A CN114181496B CN 114181496 B CN114181496 B CN 114181496B CN 202111605941 A CN202111605941 A CN 202111605941A CN 114181496 B CN114181496 B CN 114181496B
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epoxy resin
parts
composite material
resin composite
rubber
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CN114181496A (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 to 50 parts of basic epoxy resin, 0.5 to 4 parts of first resin, 0.5 to 4 parts of silicon-based scratch resistant agent, 50 to 90 parts of nano filler and 0.5 to 2.5 parts of wetting dispersant; wherein the first resin is selected from at least one of a rubber modified epoxy resin and a thermoplastic resin. The auxiliary materials are added for being matched for use to modify the basic epoxy resin, the first resin improves the resistance capability and deformation absorption capability of the basic epoxy resin to external force, and the organic silicon in the silicon-based scratch-resistant agent increases entanglement with epoxy groups, so that polysiloxane molecules are distributed better and more uniformly on the surface and are not separated out, the raw materials are effectively filled by further utilizing the surface effect of the nano spherical filler, and the synergy among the raw materials can improve the hardness and 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 is widely applied to various fields. However, the pencil hardness test of the common epoxy resin is only between HB-4H, and the epoxy resin cannot be used in the field requiring scratch resistance.
The traditional method mainly adopts surface treatment technologies such as composite plating and the like to plate a layer of high-hardness material on the surface of the composite material with the surface hardness to achieve the purpose of enhancing the surface hardness, however, the technologies have complex manufacturing processes, high cost and uneven plating thickness.
Disclosure of Invention
Based on this, it is necessary to provide an epoxy resin composite material, prepreg and laminate having both high surface hardness of 8H and high scratch resistance.
The invention provides an epoxy resin composite material which comprises the following raw material components in parts by weight:
wherein the first resin is at least one selected from the group consisting of rubber modified epoxy resins and thermoplastic resins.
In one embodiment, the base epoxy resin is selected from at least one of bisphenol a type epoxy resin and glycidyl ester type epoxy resin.
In one embodiment, the rubber in the rubber modified epoxy resin is selected from at least one of a carboxyl terminated liquid nitrile rubber, a vinyl terminated nitrile rubber, and an 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 frit, 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 component further comprises 0.5-2 parts of a curing agent and 0.01-0.05 parts of an accelerator.
In one embodiment, the curing agent is at least one selected from the group consisting of cyanate ester curing agents, aliphatic polyamine curing agents, aromatic amine curing agents, polyamide type curing agents, latent curing agents, and acid anhydride 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 a resin material loaded on the base material, wherein the resin material is the epoxy resin composite material.
Further, the invention provides a laminated board, and the preparation raw materials of the laminated board comprise the prepreg.
Still further, the present invention provides the use of the laminate as described above for the preparation of printed wiring boards, automotive parts, electrical housings or building materials.
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 capability and deformation absorption capability of the basic epoxy resin to external force, the organic silicon in the silicon-based scratch resistant agent increases entanglement with epoxy groups, so that polysiloxane molecules are distributed on the surface more uniformly and are not separated out, the surface effect of the nano filler is further utilized to effectively fill the raw materials, and the synergy among the raw materials can improve the hardness and scratch resistance of the epoxy resin composite material.
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. They are, of course, merely examples and are not intended to limit the 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 invention refer to embodiments of the invention that may provide certain benefits in some instances. 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 for 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 description 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 include 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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein 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:
wherein the first resin is selected from at least one of a rubber modified epoxy resin and a thermoplastic resin.
Preferably, the epoxy resin composite material comprises the following raw material components in parts by weight:
in a specific example, the base epoxy resin is selected from at least one of bisphenol a type epoxy resin and glycidyl ester type epoxy resin.
It is understood that the silicon-based scratch resistant agent may be selected from at least one of Degusse 4042 and Guangzhou Tianci organosilicon technology Co., ltd. TCP-8008.
In a specific example thereof, the rubber is selected from at least one of a carboxyl terminated liquid nitrile rubber, a vinyl terminated nitrile rubber, and an amino terminated nitrile rubber.
It is to be understood that the epoxy resin in the rubber-modified epoxy resin is at least one selected from the group consisting of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin and aliphatic epoxy resin, and further that the mass ratio of the rubber to the epoxy resin in the rubber-modified epoxy resin is 1 (5-12).
It is understood that the rubber and epoxy resin may be, but are 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 the group consisting of Epfukan 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 further has a particle size of 25-80 nm.
In a specific example, the raw material component further includes 0.5 to 2 parts of a curing agent and 0.01 to 0.05 parts of an accelerator.
In a specific example, the curing agent is selected from at least one of a cyanate ester curing agent, a fatty polyamine curing agent, an aromatic amine curing agent, a polyamide type curing agent, a latent curing agent, and an acid anhydride curing agent.
Specifically, the curing agent may be at least one selected from the group consisting of methyltetrahydrophthalic anhydride, methylnadic anhydride, 4 '-diaminodiphenyl sulfone, and 4,4' -diaminodiphenyl methane.
It will be appreciated that the methyltetrahydrophthalic anhydride described above may not be limited to being a mixture of various isomers.
In a specific example, the accelerator is selected from at least one of an amine accelerator, an imidazole accelerator, and a peroxide accelerator.
Specifically, the accelerator may be selected from at least one 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 capability and deformation absorption capability of the basic epoxy resin to external force, the organic silicon in the silicon-based scratch-resistant agent increases entanglement with epoxy groups, so that polysiloxane molecules are distributed on the surface more uniformly and are not separated out, the surface effect of the nano filler is further utilized to effectively fill the raw materials, and the synergy among the raw materials can improve the hardness and scratch resistance of the epoxy resin composite material.
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 a base epoxy resin, a first resin, a silicon-based scratch resistant agent, an accelerator, a nanofiller, a wetting dispersant and a second solvent to prepare a second mixture;
step S30: the first mixture and the second mixture are mixed.
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.
The step S20 includes: primary mixing of the basic epoxy resin, the first resin, the silicon-based scratch resistant agent and the accelerator is carried out for 0.2 to 1 hour at a dispersion speed of 800 to 1200r/min, the nano filler and the second solvent are added for stirring, and then the wetting dispersant is added for secondary mixing for 1 to 5 hours at a 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.
In particular, the above substrate may be, but is not limited to, selected from glass fibers.
The preparation method of the prepreg comprises the steps of immersing the base material in the epoxy resin composite material and carrying out heat treatment at 150-200 ℃ for 1-5 min.
Preferably, the material is immersed in the epoxy resin composite material and subjected to heat treatment at 160-190 ℃ for 2-4 min.
Furthermore, the invention provides a laminated board, and the preparation raw materials of the laminated board comprise the prepreg.
The preparation steps of the laminated board comprise: stacking prepregs in a vacuum state at 20kgf/cm 2 ～40kgf/cm 2 The heat treatment is carried out for 50 to 80 minutes at the temperature of between 150 and 200 ℃.
Preferably, the prepreg is stacked in a vacuum state at 20kgf/cm 2 ～30kgf/cm 2 The heat treatment is carried out for 50 to 70 minutes at the temperature of 160 to 190 ℃ under the pressure of (2).
Still further, the present invention provides the use of the laminate as described above for the preparation of printed wiring boards, automotive parts, electrical housings or building materials.
Specific examples are provided below to illustrate the epoxy resin composite of the present invention in further detail. The raw materials according to the following embodiments may be commercially available unless otherwise specified.
The particle diameter of the nano-sized spherical glass powder used in the following examples and comparative examples is 25 to 80nm, the particle diameter of the nano-sized spherical talc powder is 25 to 80nm, and the carboxyl terminated butyronitrile modified epoxy resin E51, epoxy resin E51 used in the following examples: bisphenol A diglycidyl ether (E51 type), carboxyl terminated butyronitrile and epoxy resin E51 mass ratio: 1:9.
Example 1:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, and sequentially adding 20 parts of bisphenol A type epoxy resin, 2 parts of Desolid 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 0.5h; adding 55 parts of nano-scale spherical glass powder and 30 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukan 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Example 2:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, and sequentially adding 30 parts of bisphenol A type epoxy resin, 2 parts of Desolid 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 0.5h; adding 55 parts of nano-scale spherical glass powder and 30 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukuna 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 70%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Example 3:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, sequentially adding 40 parts of bisphenol A type epoxy resin, 2 parts of Desolid 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 0.5h; adding 55 parts of nano-scale spherical glass powder and 30 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukuna 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 69%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Example 4:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, and sequentially adding 20 parts of bisphenol A type epoxy resin, 2 parts of Desolid 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 0.5h; adding 60 parts of nano-scale spherical glass powder and 30 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukuna 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Example 5:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, and sequentially adding 20 parts of bisphenol A type epoxy resin, 2 parts of Desolid 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 0.5h; adding 70 parts of nano-scale spherical glass powder and 35 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukuna 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 72%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Example 6:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, and sequentially adding 20 parts of bisphenol A type epoxy resin, 2 parts of Desolid 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 0.5h; adding 80 parts of nano-scale spherical glass powder and 40 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukuna 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 72%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Example 7:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, and sequentially adding 30 parts of bisphenol A type epoxy resin, 2 parts of Desolid 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 0.5h; adding 60 parts of nano-scale spherical glass powder and 30 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukuna 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 70%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Example 8:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, and sequentially adding 30 parts of bisphenol A type epoxy resin, 2 parts of Desolid 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 0.5h; adding 70 parts of nano-scale spherical glass powder and 35 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukuna 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Example 9:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, and sequentially adding 30 parts of bisphenol A type epoxy resin, 2 parts of Desolid 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 0.5h; adding 80 parts of nano-scale spherical glass powder and 40 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukuna 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71%. Overlapping 10 prepregs, covering a release film on the upper and lower surfaces of the laminated body, placing in a vacuum press with programmable temperature and pressure control, andvacuum state at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Example 10:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, sequentially adding 40 parts of bisphenol A type epoxy resin, 2 parts of Desolid 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 0.5h; adding 60 parts of nano-scale spherical glass powder and 30 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukuna 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 69%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Example 11:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, sequentially adding 40 parts of bisphenol A type epoxy resin, 2 parts of Desolid 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 0.5h; adding 70 parts of nano-scale spherical glass powder and 35 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukuna 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) Baking at 180deg.C for 3min in hot air circulation oven to obtain semi-cured resin with 70%And (3) a sheet. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Example 12:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, sequentially adding 40 parts of bisphenol A type epoxy resin, 2 parts of Desolid 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 0.5h; adding 80 parts of nano-scale spherical glass powder and 40 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukuna 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 70%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Comparative example 1:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, and sequentially adding 20 parts of bisphenol A type epoxy resin, 2 parts of Desolid 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 0.5h; adding 55 parts of nano-scale spherical talcum powder and 30 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukuna 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Compounding with the epoxy resinComposite impregnated 1067 fiberglass cloth (basis weight 30g/m 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Comparative example 2:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, sequentially adding 20 parts of bisphenol A epoxy resin, 2 parts of Desolid 4042 and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5h; adding 55 parts of nano-scale spherical glass powder and 30 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukuna 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Comparative example 3:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, 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 0.5h; adding 55 parts of nano-scale spherical glass powder and 30 parts of cyclohexanone into a batching bottle (2), adding 1 part of Epfukuna 7520 under stirring, dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into the batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Comparative example 4:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, and sequentially adding 20 parts of bisphenol A type epoxy resin, 2 parts of Desolid 4042, 2 parts of carboxyl-terminated butyronitrile modified epoxy resin and 0.03 part of 2-methylimidazole to disperse at a high speed of 1000r/min for 0.5h; adding 55 parts of nano-scale spherical glass powder and 30 parts of cyclohexanone into a batching bottle (2), dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into a batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Comparative example 5:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, sequentially adding 20 parts of bisphenol A epoxy resin, 4 parts of Desolid 4042 and 0.03 part of 2-methylimidazole, and dispersing at a high speed of 1000r/min for 0.5h; adding 80 parts of nano-scale spherical glass powder and 40 parts of cyclohexanone into a batching bottle (2), dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into a batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Comparative example 6:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, 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 0.5h; adding 80 parts of nano-scale spherical glass powder and 40 parts of cyclohexanone into a batching bottle (2), dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into a batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Comparative example 7:
adding 1 part of dicyandiamide and 10 parts of N, N-dimethylformamide into a batching bottle (1), fully stirring and dissolving, sequentially adding 20 parts of bisphenol A type epoxy resin, 2 parts of polytetrafluoroethylene micro powder, 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 0.5h; adding 80 parts of nano-scale spherical glass powder and 40 parts of cyclohexanone into a batching bottle (2), dispersing at a high speed of 2000r/min for 2 hours, adding all the compositions in the batching bottle (2) into a batching bottle (1), and continuing dispersing at a high speed of 2000r/min for 1 hour; preparing the epoxy resin composite material.
Glass fiber cloth (basis weight 30 g/m) was impregnated 1067 with the epoxy resin composite material 2 ) And (3) baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 71%. Overlapping 10 prepregs, covering the upper and lower surfaces of the laminated body with a release film, placing in a vacuum press with programmable temperature and pressure control, and vacuum-treating at 25kgf/cm 2 The product temperature was cured at 180℃for 60 minutes to produce a laminate of 0.5mm thickness.
Test method and result 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, pencil hardness test: surface hardness was measured according to ASTM D3363;
scratch resistance: the GM W14688Method A-Code2 (10N) Method tested scratch resistance.
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As can be seen from the above examples and comparative examples, in comparative examples 1 to 4, epoxy resin-based compositions excellent in hardness and scratch resistance could not be obtained without adding the corresponding nanofiller, the first resin, the scratch resistance agent, and the wetting dispersant, respectively. Further, the hardness and scratch resistance of the final epoxy resin composition of comparative example 5 and comparative example 6 and example 9 could not be satisfied by the corresponding increase in the silicon-based scratch resistance or the first resin, rather than the first resin or the silicon-based scratch resistance. In addition, in comparative example 7, the silicon-based scratch resistant agent was replaced with another scratch resistant agent, and the scratch resistance and hardness thereof were also somewhat lowered.
The invention further proves that 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 capability and deformation absorption capability of the basic epoxy resin to external force, the organic silicon in the silicon-based scratch-resistant agent increases entanglement with epoxy groups, so that polysiloxane molecules are distributed on the surface more uniformly and are not separated out, the surface effect of the nano-filler is further utilized to effectively fill the raw materials, and the synergy between the raw materials can improve the hardness and scratch resistance of the epoxy resin composite material.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. The epoxy resin composite material is characterized by comprising the following raw material components in parts by weight:
the first resin is rubber modified epoxy resin, 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 the nano filler is glass powder; the wetting dispersant is elvudine 7520; the silicon-based scratch resistant agent is Degusse 4042.
2. The epoxy resin composite of claim 1, wherein the base epoxy resin is selected from at least one of bisphenol a type epoxy resins and glycidyl ester type epoxy resins.
3. The epoxy resin composite material according to claim 1, wherein the epoxy resin in the rubber-modified epoxy resin is at least one selected from the group consisting of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, and aliphatic type 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 resin 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 nanofiller is a nanospherer filler; and/or
The particle size of the nano spherical filler is 25 nm-80 nm.
6. The epoxy resin composite of 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 parts 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 ester curing agents, aliphatic polyamine curing agents, aromatic amine curing agents, polyamide type curing agents, latent curing agents, and acid anhydride 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 of any one of claims 1 to 7.
9. A laminate, characterized in that the raw material for the preparation of the laminate comprises the prepreg according to claim 8.
10. Use of the laminate of claim 9 for the preparation of printed wiring boards, automotive parts, electrical housings or building materials.
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