CN110126430B - Flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board and preparation method thereof - Google Patents

Flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board and preparation method thereof Download PDF

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CN110126430B
CN110126430B CN201910509108.6A CN201910509108A CN110126430B CN 110126430 B CN110126430 B CN 110126430B CN 201910509108 A CN201910509108 A CN 201910509108A CN 110126430 B CN110126430 B CN 110126430B
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rectorite
flame
acid
glue
copper foil
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CN110126430A (en
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乔银娣
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Jiangmen Kingboard Laminates Holdings Ltd
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Jiangmen Kingboard Laminates Holdings Ltd
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    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • 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
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
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    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
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    • C08K7/14—Glass
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K9/00—Use of pretreated ingredients
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Abstract

The invention discloses a flame-retardant heat-resistant copper-clad foil epoxy fiberglass cloth-based laminated board and a preparation method thereof, wherein the preparation method comprises the following steps: (1) soaking glass fiber cloth in glue water, and drying to obtain a semi-solid sheet (PP); (2) stacking one or more semi-solid sheets according to the designed thickness; (3) covering copper foil on one side or two sides of the stacked semi-solid sheets; (4) and (5) hot pressing by a hot press. The flame-retardant heat-resistant copper-clad foil epoxy glass fiber cloth-based laminated board theoretically researches the performance of the copper-clad foil epoxy glass fiber cloth-based laminated board and related influence factors, the scheme is obtained through a large number of practical laminating forming experiments and performance test results of the prepared board, dicy curing is not adopted, excellent resin glue is prepared, and the flame-retardant heat-resistant copper-clad foil epoxy glass fiber cloth-based laminated board has excellent heat resistance, low Z thermal expansion coefficient and excellent through hole capacity and meets the requirements of IPC-4101/26.

Description

Flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board and preparation method thereof
Technical Field
The invention relates to a copper clad laminate, in particular to a flame-retardant heat-resistant copper clad epoxy fiberglass cloth-based laminate and a preparation method thereof.
Background
The material is the material basis for human survival and development, is a milestone for human progress, and is the lead of most inventions and creations. Therefore, the developed countries of the world do not place the research and development of materials at a very important position. The composite material is the key point of the development of the new material, has the advantages of various materials and supplements the disadvantages of various materials, thereby achieving the purposes of improving the comprehensive performance of the materials and saving resources by compounding different materials. The composite material is a product combining material science and material engineering, optimizes the material composition, structure, manufacture, performance and performance factors in the using process, designs according to requirements, adopts a new process or a new technology, and can manufacture the composite material with excellent performance. Thus, in particular, the composite material is composed of a matrix phase, a reinforcement phase and an interphase phase; in another aspect, the composite material is a material system which is artificially manufactured according to the purpose of use by skillfully combining raw materials.
The electronic industry is a high-technology industry which is rapidly developed in recent 20 years, electronic functional materials are the foundation and the support of electronic components and electronic equipment and are widely applied to various fields of the electronic industry, and composite materials have many excellent properties, such as high specific strength, high specific rigidity, good fatigue resistance, corrosion resistance, stable size, low density, unique material designability and the like, so the composite materials are used as structural members and structural functional members in the electronic industry, the products are endowed with the characteristics of light weight, high strength, high rigidity, high size precision and the like, the technical indexes of the products are improved, the composite materials better adapt to the development requirements of modern high technology, and although the composite materials are used as electronic functional materials, the composite materials are most represented by printed circuit board substrate materials (PCB). Printed wiring boards, which are used to connect and support electronic devices, are essential components for use in a wide variety of electronic products.
The basic process of manufacturing the copper-clad plate is to make a resin material, a reinforcing material and a copper foil into a substrate by hot press molding, namely the copper-clad plate, then to perform complex processing processes such as graphic development, drilling, electroplating, etching and the like on the substrate, and then to mount various electronic elements according to the designed circuit to form a complete module or product, thereby realizing the purposes of circuit conduction and electronic signal relay transmission. The insulating substrate is widely applied to various electronic and electromechanical products, skillfully realizes the combination of a conductor and an insulator, provides assembly, fixation, mechanical support and electrical connection of various electronic components in a circuit, collects all circuits on the insulating substrate, simplifies complicated wiring, and further leads the electronic products to be miniaturized, light and highly reliable.
In the current information age, the material is not only a basic material of the electronic information industry, but also widely used in electronic industry products such as televisions, radios, computers, mobile communication and the like, and plays an important role in scientific and technical progress and national economic development. The development of the copper-clad plate begins at the beginning of the 20 th century, and the development of the copper-clad plate is closely related to the development of the electronic information industry, particularly the technology, and is not separable. The resin for the copper-clad plate, the reinforcing material and the progress of the substrate manufacturing technology lay an important foundation for the development of the copper-clad plate industry and create necessary conditions. The invention and application of the integrated circuit, miniaturization and high performance of the electronic product promote the further development of the copper-clad plate technology and production.
The reinforced material of the copper-clad plate can be divided into organic and inorganic materials. The organic reinforced material mainly comprises various insulating organic papers, such as wood pulp insulating paper, fiber insulating paper, cotton fiber paper, kraft paper and the like, and the heat-resistant temperature of the organic paper is lower and only about 120 ℃, so the organic reinforced material is not generally used for a high-performance copper-clad plate. Synthetic fiber fabrics such as polyamide fabric, polyester fabric, aramid fabric and the like also belong to organic base materials, and the long-term use temperature is 150-inch high-temperature polyamide fiber fabric. The inorganic base material mainly refers to various alkali-free glass fiber cloth, alkali-free glass fiber felt, asbestos medium, quartz fiber and the like. Among them, glass fiber (or cloth) is used in practical production. The glass fiber contains silica as main component and also K, Ba, Al, etc. and is amorphous product obtained through fast condensation and solidification after melting. The glass fiber contains alkali and no alkali, and the alkali-free glass fiber is mainly used, because when the surface of the alkali-containing glass fiber adsorbs water, the internal alkali ions are bathed out on the surface, the conductivity of the surface is enhanced, and the reliability of the circuit is reduced. The alkali-free glass fiber has excellent electrical insulation performance, thermal stability, chemical resistance, high tensile strength and the like, and is widely applied.
Although the world copper plate industry is developed more quickly, the copper-clad plate is produced by compounding an electric insulation laminated plate and a copper foil in the earliest time in China. In the early sixties, the main insulating material factories such as national 704 factories and Beijing insulating material factories use unbleached impregnated fiber paper, which is impregnated with phenolic resin as a core material, and then glass cloth impregnated with polyvinyl acetal glue as a surface layer to prepare the composite copper-clad plate. Then, the epoxy phenolic aldehyde type glass cloth-based copper-clad plate is developed, and the epoxy glass cloth-based copper-clad plate which has the product performance equivalent to G-10 and takes dicyandiamide as a curing agent is developed in turn by the Chinese academy of sciences and 704 factories until 1974. In the eighties, the electronic industry in China starts to start, black and white televisions, radio recorders, sound equipment, communication equipment and the like are greatly developed, and the production of copper-clad plates in China is promoted to step on a new step. In 1978, the annual output of the national copper-clad plate is only 1500 tons, but in 1984, the annual output is increased to 5000-. The varieties of copper clad plates are also increased, wherein the copper clad plates mainly comprise phenolic aldehyde paper plates and epoxy glass fiber cloth plates. Phenolic aldehyde paper board, mainly used for domestic electronic products. An epoxy fiberglass cloth board is mainly used for industrial electronic products. With the rapid development of the electronic industry, higher and higher requirements are put forward on the copper-clad plate. In recent years, new products are emerging and the level is improved in addition to the two main products.
Disclosure of Invention
The invention mainly solves the technical problem of providing the flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board and the preparation method thereof, theoretically researching the performance of the copper foil-coated epoxy fiberglass cloth-based laminated board and related influence factors thereof, and preparing an excellent resin solution; the scheme is obtained through a large number of actual laminating experiments and performance test results of the prepared plate.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board comprises the following steps:
(1) soaking glass fiber cloth in glue water, and drying to obtain a semi-solid sheet (PP);
(2) stacking one or more semi-solid sheets according to the designed thickness;
(3) covering copper foil on one side or two sides of the stacked semi-solid sheets;
(4) and (5) hot pressing by a hot press.
Hot pressing: the hot pressing is to melt p (B-stage) resin by high temperature and high pressure, completely expel gas and completely solidify the resin, and complete firm bonding between PP layers and with copper foil. According to the diffusion principle, the bonding is realized by mutual diffusion and permeation between macromolecules on the interface, and then interweaving is generated. A vacuum laminator is used, and the main process parameters are temperature rise conditions and pressure and vacuum degree control.
The glue comprises the following raw materials: epoxy resin, a curing agent, a catalyst and a solvent.
Epoxy resins are typically stored by dissolving them in acetone and holding them in an iron drum at about 80% by weight. The multifunctional phenolic resin is used as a curing agent, and the resin is subjected to crosslinking curing reaction at a proper temperature. 2-methylimidazole (2-MI) is used as a catalyst to initiate and accelerate the cure speed, which is evident from the adjustment of the cure time (S/G). Propylene glycol methyl ether acetate (PMA) is used as a solvent for adjusting the viscosity of the glue and maintaining a relatively uniform and stable system of the glue, which is important for gluing and semi-curing reactions.
Preferably, the glue is prepared from the following raw materials in percentage by mass: 70-80% of epoxy resin, 6-10% of curing agent, 0.08-0.13% of catalyst and the balance of solvent.
Preferably, the glue is prepared from the following raw materials in percentage by mass: 70-80% of epoxy resin, 3-9% of filler, 6-10% of curing agent, 1-4% of flame retardant, 0.08-0.13% of catalyst and the balance of solvent.
The epoxy resin is at least one of o-cresol type epoxy resin and multifunctional epoxy resin. Preferably, the epoxy resin consists of 30 to 70 wt% of o-cresol type epoxy resin and 30 to 70 wt% of multifunctional epoxy resin.
The filler is rectorite. Preferably, the filler is functionalized rectorite.
Rectorite is a rare layered silicate clay mineral with a special structure. Rectorite (Rectorite) is a dioctahedral mica and dioctahedral montmorillonite 1:1 regular interlayer clay mineral. It shares many similarities with kaolinite. Two 2:1 layers (TM-OM-TM-IM + Ts-Os-Ts-Is) exist in the rectorite structure unit layer. The interlayer cations IM of the 2:1 layers of the mica layer unit can be Na, K and Ca; and the 2:1 interlayer of the montmorillonite layer unit Is the exchangeable hydrated cation Ca, Na, Mg, Al, etc. (Is). The octahedral sheets in both types of layers are largely occupied by Al, occupying only two thirds of the octahedra, i.e. the dioctahedral subclass. The chemical formula of the crystal of the rectorite is as follows: kx(H2O){Al2[AlxSi4-xO10](OH)2}. Because the crystal structure of the rectorite contains a swelling montmorillonite layer, the crystal structure can be divided into a mica layer and a montmorillonite layer. Fine particle size of rectorite, general<5 μm. Rectorite is mostly in the form of thin scale, and lath-shaped and fibrous needle crystals can also be seen. The rectorite is gray white, gray green and yellow brown, the density is 2.8g/cm, and the hardness is<1, plasticity index 37. The acid treatment of the rectorite by the method not only improves the specific surface area of the rectorite, but also improves the adsorption performance of the rectorite, and the flame retardant property of the glue is improved through the subsequent flame retardant treatment.
The preparation method of the functionalized rectorite comprises the following steps: putting rectorite into 30-40% ethanol water solution by volume fraction, wherein the mass ratio of the rectorite to the 30-40% ethanol water solution is 1: (4-10), adjusting the pH to 2-3 with 0.5-1mol/L hydrochloric acid, and performing ultrasonic treatment for 20-30min to obtain a mixture; placing the mixture in dry ice at-78.5 deg.C, freezing for 4-8h, taking out, naturally reaching room temperature, centrifuging, washing the precipitate with 0.05-0.1mol/L carboxymethyl chitosan water solution for 2-5 times, and oven drying to obtain acid-treated rectorite; placing acid-treated rectorite in water with the weight 8-9 times of that of the acid-treated rectorite, adding melamine with the weight 10-15% of that of the acid-treated rectorite and 2-amino-4-dimethylamino-1, 3,5 triazine with the weight 4-10% of that of the acid-treated rectorite, heating to 70-80 ℃, adding cyanuric acid with the weight 4-10% of that of the acid-treated rectorite and phosphoric acid with the weight 10-15% of that of the acid-treated rectorite, continuing heating to 90-100 ℃, stirring for 2-3h, performing centrifugal separation, taking precipitates and drying to obtain the functionalized rectorite.
The curing agent is a multifunctional phenolic resin.
The catalyst is selected from any one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole or 2-phenylimidazole.
The solvent is any one or more of propylene glycol methyl ether acetate, acetone or butanone.
The flame retardant is one or more of melamine resin coated ammonium polyphosphate and ammonium polyphosphate containing a silane structure. Preferably, the flame retardant is melamine resin coated ammonium polyphosphate and ammonium polyphosphate containing a silane structure, and the mass ratio of the ammonium polyphosphate to the flame retardant is 1: (0.4-0.6).
The preparation method of the glue comprises the following steps:
s1, filler dispersion: adding 10-40 wt% of epoxy resin and solvent into a stirrer, stirring at a rotating speed of more than 1000rpm, adding a filler while stirring, and after the filler is added, continuously stirring at a rotating speed of more than 1000rpm for 4-5 hours to obtain an intermediate product A;
s2, adding the residual 60-90 wt% of epoxy resin into a batching tank, adding the intermediate product A, and stirring to obtain an intermediate product B;
s3, adding a curing agent, a catalyst and a flame retardant into the intermediate product B, stirring for at least 5 hours, sampling and detecting the curing time of the glue solution, and stopping stirring when the curing time of the glue solution is 280-320S to obtain the glue.
The parameters of the hot press are as follows:
the initial stage is as follows: the duration is 25-35 minutes, the temperature is kept at 80-140 ℃, and the pressure is 50-70 psi;
a heating stage: the heating rate is 1.2-2.0 ℃/min, the temperature is raised to 170-180 ℃, and the temperature is stopped, and the pressure is 50-70 psi;
and (3) hot pressing: the time duration is more than or equal to 45 minutes, the constant temperature is 170 ℃ and 180 ℃, and the pressure is 280 ℃ and 370 psi;
and (3) a cooling stage: cooling at a rate of less than 2.5 deg.C/min to room temperature under a pressure of 30-50 psi.
The invention provides a flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board which is prepared by the preparation method of the flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board.
The invention has the beneficial effects that:
the invention relates to a flame-retardant heat-resistant copper foil-clad epoxy glass fiber cloth-based laminated board, which theoretically researches the performance of the copper foil-clad epoxy glass fiber cloth-based laminated board and related influence factors, obtains the scheme through a large number of actual laminating experiments and performance test results of the prepared board, does not adopt dicy (namely dicyandiamide/cyanamide/dicyandiamide/cyanoguanidine/dicyandiamide), prepares excellent resin glue, has excellent heat resistance, low Z-direction thermal expansion coefficient and excellent through hole capability, and meets the requirements of IPC-4101/26.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The materials used are described below: a multifunctional phenol resin, model number 710HK65, epoxy equivalent 107g/eq, manufactured by south Asia electronic materials (Kunshan) Co. An o-cresol type epoxy resin having a type of 704K80 and an epoxy equivalent of 215g/eq, manufactured by south Asia electronic materials (Kunshan) Co., Ltd. The type of the multifunctional epoxy resin is 485HA80,epoxy equivalent 400g/eq, manufactured by south Asia electronic materials (Kunshan) Co., Ltd. Glass fiber cloth, electronic grade, model 7628M-127, gram weight 210g/M2Thickness 0.18mm, manufactured by Mount Taishan glass fibers Zhongji Co. Copper foil, 1 ounce in thickness, produced by lingbao jinyuan Kogyo GmbH. Rectorite is provided by mineral product processing factory in Lingshou county, and the granularity is 2000 meshes. Melamine resin coated ammonium polyphosphate was prepared according to the method shown in example 2 of chinese patent publication No. CN 103709445 a. Ammonium polyphosphate containing a silane structure was prepared according to the method shown in example 1 of chinese patent publication No. CN 104098789 a. The carboxymethyl chitosan is provided by Zhengzhou Wangbu chemical product Co., Ltd, and the type is as follows: and (4) food grade. The template material is alloy steel 4Cr5MoisVI, which can maintain high strength and surface hardness up to HRC44 at room temperature to 60 deg.c and maintain high toughness and laminated product performance.
Example 1
The preparation method of the flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board comprises the following steps:
(1) soaking glass fiber cloth into glue, placing the glass fiber cloth on a cloth rack of an impregnation machine, passing the glass fiber cloth through an impregnation groove which is fully impregnated with the glue, and placing the glass fiber cloth which is impregnated with the glue into an oven to be dried for 1min at the temperature of 170 ℃ to obtain a semi-solid piece;
(2) stacking 7 semi-fixed sheets;
(3) covering copper foils on the two sides of the stacked semi-solid sheets;
(4) and adding a die steel plate, sending into a hot press for hot pressing, and cutting according to requirements to obtain the flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth-based laminated board.
Hot pressing: the hot pressing is to melt p (B-stage) resin by high temperature and high pressure, completely expel gas and completely solidify the resin, and complete firm bonding between PP layers and with copper foil. According to the diffusion principle, the bonding is realized by mutual diffusion and permeation between macromolecules on the interface, and then interweaving is generated. A vacuum laminator is used, and the main process parameters are temperature rise conditions and pressure and vacuum degree control.
The glue is prepared from the following raw materials in percentage by mass: 36% of polyfunctional epoxy resin, 36% of o-cresol epoxy resin, 7% of filler, 8% of curing agent, 2.4% of flame retardant, 0.1% of catalyst and the balance of solvent.
The filler is functionalized rectorite.
The preparation method of the functionalized rectorite comprises the following steps: putting rectorite into an ethanol water solution with the volume fraction of 35%, wherein the mass ratio of the rectorite to the 35% ethanol water solution is 1: 9, adjusting the pH value to 2 by using 0.6mol/L hydrochloric acid, and carrying out ultrasonic treatment for 25min at the ultrasonic power of 400W and the ultrasonic frequency of 20kHz to obtain a mixture; placing the mixture in dry ice at the temperature of-78.5 ℃ for freezing for 6h, taking out the mixture to naturally reach the room temperature of 20 ℃, then centrifugally separating for 20min at the rotating speed of 9000r/min, washing the precipitate for 3 times by using 0.08mol/L carboxymethyl chitosan aqueous solution, wherein the use amount of the carboxymethyl chitosan aqueous solution washed each time is 5 times of the weight of the precipitate, and drying the washed precipitate for 24h at the temperature of 80 ℃ to obtain acid-treated rectorite; placing acid-treated rectorite into deionized water 9 times of the weight of the acid-treated rectorite, adding melamine 12% of the weight of the acid-treated rectorite, 2-amino-4-dimethylamino-1, 3,5 triazine 6% of the weight of the acid-treated rectorite, heating to 75 ℃, adding cyanuric acid 8% of the weight of the acid-treated rectorite and phosphoric acid 12% of the weight of the acid-treated rectorite, continuing heating to 95 ℃, stirring at the rotating speed of 300r/min for 2.5h, centrifugally separating at the rotating speed of 9000r/min for 20min, taking the precipitate, and drying at the temperature of 80 ℃ for 24h to obtain the functionalized rectorite.
The curing agent is a multifunctional phenolic resin.
The catalyst is 2-methylimidazole.
The solvent is propylene glycol methyl ether acetate.
The flame retardant is melamine resin coated ammonium polyphosphate.
The preparation method of the glue comprises the following steps:
s1, filler dispersion: adding half of the total amount of the multifunctional epoxy resin and a solvent into a stirrer, stirring at 1500rpm, adding a filler while stirring, and continuously stirring at 1500rpm for 4.5 hours after the filler is added to obtain an intermediate product A;
s2, adding the remaining half of the multifunctional epoxy resin and the o-cresol epoxy resin into a batching tank, adding the intermediate product A, and stirring at 1500rpm to obtain an intermediate product B;
s3, adding a curing agent, a catalyst and a flame retardant into the intermediate product B, sampling and detecting the curing time of the glue solution after stirring at 1500rpm for at least 5 hours, and stopping stirring when the curing time of the glue solution is 280-320S to obtain the glue solution.
The parameters of the hot press are as follows:
the initial stage is as follows: the time is 30 minutes, the temperature is kept at 100 ℃, and the pressure is 60 psi;
a heating stage: the heating rate is 1.5 ℃/min, the temperature is increased to 180 ℃, and the temperature is stopped, and the pressure is 60 psi;
and (3) hot pressing: the time is 45 minutes, the temperature is kept at 180 ℃, and the pressure is 320 psi;
and (3) a cooling stage: the cooling rate was 2 deg.C/min, and cooling to room temperature was stopped at a pressure of 40 psi.
Example 2
The preparation method of the flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board comprises the following steps:
(1) soaking glass fiber cloth into glue, placing the glass fiber cloth on a cloth rack of an impregnation machine, passing the glass fiber cloth through an impregnation groove which is fully impregnated with the glue, and placing the glass fiber cloth which is impregnated with the glue into an oven to be dried for 1min at the temperature of 170 ℃ to obtain a semi-solid piece;
(2) stacking 7 semi-fixed sheets;
(3) covering copper foils on the two sides of the stacked semi-solid sheets;
(4) and adding a die steel plate, sending into a hot press for hot pressing, and cutting according to requirements to obtain the flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth-based laminated board.
Hot pressing: the hot pressing is to melt p (B-stage) resin by high temperature and high pressure, completely expel gas and completely solidify the resin, and complete firm bonding between PP layers and with copper foil. According to the diffusion principle, the bonding is realized by mutual diffusion and permeation between macromolecules on the interface, and then interweaving is generated. A vacuum laminator is used, and the main process parameters are temperature rise conditions and pressure and vacuum degree control.
The glue is prepared from the following raw materials in percentage by mass: 36 percent of polyfunctional epoxy resin, 36 percent of o-cresol epoxy resin, 8 percent of curing agent, 0.1 percent of catalyst and the balance of solvent.
The curing agent is a multifunctional phenolic resin.
The catalyst is 2-methylimidazole.
The solvent is propylene glycol methyl ether acetate.
The preparation method of the glue comprises the following steps:
s1, adding half of the total amount of the multifunctional epoxy resin and a solvent into a stirrer, and stirring at 1500rpm for 4.5 hours to obtain an intermediate product A;
s2, adding the remaining half of the multifunctional epoxy resin and the o-cresol epoxy resin into a batching tank, adding the intermediate product A, and stirring at 1500rpm to obtain an intermediate product B;
s3, adding a curing agent and a catalyst into the intermediate product B, sampling and detecting the curing time of the glue solution after stirring at 1500rpm for at least 5 hours, and stopping stirring when the curing time of the glue solution is 280-320S to obtain the glue.
The parameters of the hot press are as follows:
the initial stage is as follows: the time is 30 minutes, the temperature is kept at 100 ℃, and the pressure is 60 psi;
a heating stage: the heating rate is 1.5 ℃/min, the temperature is increased to 180 ℃, and the temperature is stopped, and the pressure is 60 psi;
and (3) hot pressing: the time is 45 minutes, the temperature is kept at 180 ℃, and the pressure is 320 psi;
and (3) a cooling stage: the cooling rate was 2 deg.C/min, and cooling to room temperature was stopped at a pressure of 40 psi.
Example 3
The preparation method of the flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board comprises the following steps:
(1) soaking glass fiber cloth into glue, placing the glass fiber cloth on a cloth rack of an impregnation machine, passing the glass fiber cloth through an impregnation groove which is fully impregnated with the glue, and placing the glass fiber cloth which is impregnated with the glue into an oven to be dried for 1min at the temperature of 170 ℃ to obtain a semi-solid piece;
(2) stacking 7 semi-fixed sheets;
(3) covering copper foils on the two sides of the stacked semi-solid sheets;
(4) and adding a die steel plate, sending into a hot press for hot pressing, and cutting according to requirements to obtain the flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth-based laminated board.
Hot pressing: the hot pressing is to melt p (B-stage) resin by high temperature and high pressure, completely expel gas and completely solidify the resin, and complete firm bonding between PP layers and with copper foil. According to the diffusion principle, the bonding is realized by mutual diffusion and permeation between macromolecules on the interface, and then interweaving is generated. A vacuum laminator is used, and the main process parameters are temperature rise conditions and pressure and vacuum degree control.
The glue is prepared from the following raw materials in percentage by mass: 36% of polyfunctional epoxy resin, 36% of o-cresol epoxy resin, 7% of filler, 8% of curing agent, 2.4% of flame retardant, 0.1% of catalyst and the balance of solvent.
The filler is rectorite.
The curing agent is a multifunctional phenolic resin.
The catalyst is 2-methylimidazole.
The solvent is propylene glycol methyl ether acetate.
The flame retardant is melamine resin coated ammonium polyphosphate.
The preparation method of the glue comprises the following steps:
s1, filler dispersion: adding half of the total amount of the multifunctional epoxy resin and a solvent into a stirrer, stirring at 1500rpm, adding a filler while stirring, and continuously stirring at 1500rpm for 4.5 hours after the filler is added to obtain an intermediate product A;
s2, adding the remaining half of the multifunctional epoxy resin and the o-cresol epoxy resin into a batching tank, adding the intermediate product A, and stirring at 1500rpm to obtain an intermediate product B;
s3, adding a curing agent, a catalyst and a flame retardant into the intermediate product B, sampling and detecting the curing time of the glue solution after stirring at 1500rpm for at least 5 hours, and stopping stirring when the curing time of the glue solution is 280-320S to obtain the glue solution.
The parameters of the hot press are as follows:
the initial stage is as follows: the time is 30 minutes, the temperature is kept at 100 ℃, and the pressure is 60 psi;
a heating stage: the heating rate is 1.5 ℃/min, the temperature is increased to 180 ℃, and the temperature is stopped, and the pressure is 60 psi;
and (3) hot pressing: the time is 45 minutes, the temperature is kept at 180 ℃, and the pressure is 320 psi;
and (3) a cooling stage: the cooling rate was 2 deg.C/min, and cooling to room temperature was stopped at a pressure of 40 psi.
Example 4
The preparation method of the flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board comprises the following steps:
(1) soaking glass fiber cloth into glue, placing the glass fiber cloth on a cloth rack of an impregnation machine, passing the glass fiber cloth through an impregnation groove which is fully impregnated with the glue, and placing the glass fiber cloth which is impregnated with the glue into an oven to be dried for 1min at the temperature of 170 ℃ to obtain a semi-solid piece;
(2) stacking 7 semi-fixed sheets;
(3) covering copper foils on the two sides of the stacked semi-solid sheets;
(4) and adding a die steel plate, sending into a hot press for hot pressing, and cutting according to requirements to obtain the flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth-based laminated board.
Hot pressing: the hot pressing is to melt p (B-stage) resin by high temperature and high pressure, completely expel gas and completely solidify the resin, and complete firm bonding between PP layers and with copper foil. According to the diffusion principle, the bonding is realized by mutual diffusion and permeation between macromolecules on the interface, and then interweaving is generated. A vacuum laminator is used, and the main process parameters are temperature rise conditions and pressure and vacuum degree control.
The glue is prepared from the following raw materials in percentage by mass: 36% of polyfunctional epoxy resin, 36% of o-cresol epoxy resin, 7% of filler, 8% of curing agent, 2.4% of flame retardant, 0.1% of catalyst and the balance of solvent.
The filler is functionalized rectorite.
The preparation method of the functionalized rectorite comprises the following steps: putting rectorite into deionized water 9 times of the weight of the rectorite, adding melamine 12 percent of the weight of the rectorite and 2-amino-4-dimethylamino-1, 3,5 triazine 6 percent of the weight of the rectorite, heating to 75 ℃, adding cyanuric acid 8 percent of the weight of the rectorite and phosphoric acid 12 percent of the weight of the rectorite, continuing heating to 95 ℃, stirring for 2.5h at the rotating speed of 300r/min, centrifugally separating for 20min at the rotating speed of 9000r/min, taking the precipitate, and drying for 24h at the temperature of 80 ℃ to obtain the functionalized rectorite.
The curing agent is a multifunctional phenolic resin.
The catalyst is 2-methylimidazole.
The solvent is propylene glycol methyl ether acetate.
The flame retardant is melamine resin coated ammonium polyphosphate.
The preparation method of the glue comprises the following steps:
s1, filler dispersion: adding half of the total amount of the multifunctional epoxy resin and a solvent into a stirrer, stirring at 1500rpm, adding a filler while stirring, and continuously stirring at 1500rpm for 4.5 hours after the filler is added to obtain an intermediate product A;
s2, adding the remaining half of the multifunctional epoxy resin and the o-cresol epoxy resin into a batching tank, adding the intermediate product A, and stirring at 1500rpm to obtain an intermediate product B;
s3, adding a curing agent, a catalyst and a flame retardant into the intermediate product B, sampling and detecting the curing time of the glue solution after stirring at 1500rpm for at least 5 hours, and stopping stirring when the curing time of the glue solution is 280-320S to obtain the glue solution.
The parameters of the hot press are as follows:
the initial stage is as follows: the time is 30 minutes, the temperature is kept at 100 ℃, and the pressure is 60 psi;
a heating stage: the heating rate is 1.5 ℃/min, the temperature is increased to 180 ℃, and the temperature is stopped, and the pressure is 60 psi;
and (3) hot pressing: the time is 45 minutes, the temperature is kept at 180 ℃, and the pressure is 320 psi;
and (3) a cooling stage: the cooling rate was 2 deg.C/min, and cooling to room temperature was stopped at a pressure of 40 psi.
Example 5
The preparation method of the flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board comprises the following steps:
(1) soaking glass fiber cloth into glue, placing the glass fiber cloth on a cloth rack of an impregnation machine, passing the glass fiber cloth through an impregnation groove which is fully impregnated with the glue, and placing the glass fiber cloth which is impregnated with the glue into an oven to be dried for 1min at the temperature of 170 ℃ to obtain a semi-solid piece;
(2) stacking 7 semi-fixed sheets;
(3) covering copper foils on the two sides of the stacked semi-solid sheets;
(4) and adding a die steel plate, sending into a hot press for hot pressing, and cutting according to requirements to obtain the flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth-based laminated board.
Hot pressing: the hot pressing is to melt p (B-stage) resin by high temperature and high pressure, completely expel gas and completely solidify the resin, and complete firm bonding between PP layers and with copper foil. According to the diffusion principle, the bonding is realized by mutual diffusion and permeation between macromolecules on the interface, and then interweaving is generated. A vacuum laminator is used, and the main process parameters are temperature rise conditions and pressure and vacuum degree control.
The glue is prepared from the following raw materials in percentage by mass: 36% of polyfunctional epoxy resin, 36% of o-cresol epoxy resin, 7% of filler, 8% of curing agent, 2.4% of flame retardant, 0.1% of catalyst and the balance of solvent.
The filler is functionalized rectorite.
The preparation method of the functionalized rectorite comprises the following steps: putting rectorite into an ethanol water solution with the volume fraction of 35%, wherein the mass ratio of the rectorite to the 35% ethanol water solution is 1: 9, adjusting the pH value to 2 by using 0.6mol/L hydrochloric acid, and carrying out ultrasonic treatment for 25min at the ultrasonic power of 400W and the ultrasonic frequency of 20kHz to obtain a mixture; placing the mixture in dry ice at the temperature of-78.5 ℃ for freezing for 6h, taking out the mixture to naturally reach the room temperature of 20 ℃, then carrying out centrifugal separation for 20min at the rotating speed of 9000r/min, washing the precipitate with deionized water for 3 times, wherein the use amount of the deionized water for each time is 5 times of the weight of the precipitate, and drying the washed precipitate for 24h at the temperature of 80 ℃ to obtain acid-treated rectorite; placing acid-treated rectorite into deionized water 9 times of the weight of the acid-treated rectorite, adding melamine 18% of the weight of the acid-treated rectorite, heating to 75 ℃, adding cyanuric acid 8% of the weight of the acid-treated rectorite and phosphoric acid 12% of the weight of the acid-treated rectorite, continuing heating to 95 ℃, stirring at the rotating speed of 300r/min for 2.5h, centrifugally separating at the rotating speed of 9000r/min for 20min, taking the precipitate, and drying at the temperature of 80 ℃ for 24h to obtain the functionalized rectorite.
The curing agent is a multifunctional phenolic resin.
The catalyst is 2-methylimidazole.
The solvent is propylene glycol methyl ether acetate.
The flame retardant is melamine resin coated ammonium polyphosphate.
The preparation method of the glue comprises the following steps:
s1, filler dispersion: adding half of the total amount of the multifunctional epoxy resin and a solvent into a stirrer, stirring at 1500rpm, adding a filler while stirring, and continuously stirring at 1500rpm for 4.5 hours after the filler is added to obtain an intermediate product A;
s2, adding the remaining half of the multifunctional epoxy resin and the o-cresol epoxy resin into a batching tank, adding the intermediate product A, and stirring at 1500rpm to obtain an intermediate product B;
s3, adding a curing agent, a catalyst and a flame retardant into the intermediate product B, sampling and detecting the curing time of the glue solution after stirring at 1500rpm for at least 5 hours, and stopping stirring when the curing time of the glue solution is 280-320S to obtain the glue solution.
The parameters of the hot press are as follows:
the initial stage is as follows: the time is 30 minutes, the temperature is kept at 100 ℃, and the pressure is 60 psi;
a heating stage: the heating rate is 1.5 ℃/min, the temperature is increased to 180 ℃, and the temperature is stopped, and the pressure is 60 psi;
and (3) hot pressing: the time is 45 minutes, the temperature is kept at 180 ℃, and the pressure is 320 psi;
and (3) a cooling stage: the cooling rate was 2 deg.C/min, and cooling to room temperature was stopped at a pressure of 40 psi.
Example 6
The preparation method of the flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board comprises the following steps:
(1) soaking glass fiber cloth into glue, placing the glass fiber cloth on a cloth rack of an impregnation machine, passing the glass fiber cloth through an impregnation groove which is fully impregnated with the glue, and placing the glass fiber cloth which is impregnated with the glue into an oven to be dried for 1min at the temperature of 170 ℃ to obtain a semi-solid piece;
(2) stacking 7 semi-fixed sheets;
(3) covering copper foils on the two sides of the stacked semi-solid sheets;
(4) and adding a die steel plate, sending into a hot press for hot pressing, and cutting according to requirements to obtain the flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth-based laminated board.
Hot pressing: the hot pressing is to melt p (B-stage) resin by high temperature and high pressure, completely expel gas and completely solidify the resin, and complete firm bonding between PP layers and with copper foil. According to the diffusion principle, the bonding is realized by mutual diffusion and permeation between macromolecules on the interface, and then interweaving is generated. A vacuum laminator is used, and the main process parameters are temperature rise conditions and pressure and vacuum degree control.
The glue is prepared from the following raw materials in percentage by mass: 36% of polyfunctional epoxy resin, 36% of o-cresol epoxy resin, 7% of filler, 8% of curing agent, 2.4% of flame retardant, 0.1% of catalyst and the balance of solvent.
The filler is functionalized rectorite.
The preparation method of the functionalized rectorite comprises the following steps: putting rectorite into an ethanol water solution with the volume fraction of 35%, wherein the mass ratio of the rectorite to the 35% ethanol water solution is 1: 9, adjusting the pH value to 2 by using 0.6mol/L hydrochloric acid, and carrying out ultrasonic treatment for 25min at the ultrasonic power of 400W and the ultrasonic frequency of 20kHz to obtain a mixture; placing the mixture in dry ice at the temperature of-78.5 ℃ for freezing for 6h, taking out the mixture to naturally reach the room temperature of 20 ℃, then centrifugally separating for 20min at the rotating speed of 9000r/min, washing the precipitate for 3 times by using 0.08mol/L carboxymethyl chitosan aqueous solution, wherein the use amount of the carboxymethyl chitosan aqueous solution washed each time is 5 times of the weight of the precipitate, and drying the washed precipitate for 24h at the temperature of 80 ℃ to obtain acid-treated rectorite; placing acid-treated rectorite into deionized water 9 times of the weight of the acid-treated rectorite, adding melamine 12% of the weight of the acid-treated rectorite, 2-amino-4-dimethylamino-1, 3,5 triazine 6% of the weight of the acid-treated rectorite, heating to 75 ℃, adding cyanuric acid 8% of the weight of the acid-treated rectorite and phosphoric acid 12% of the weight of the acid-treated rectorite, continuing heating to 95 ℃, stirring at the rotating speed of 300r/min for 2.5h, centrifugally separating at the rotating speed of 9000r/min for 20min, taking the precipitate, and drying at the temperature of 80 ℃ for 24h to obtain the functionalized rectorite.
The curing agent is a multifunctional phenolic resin.
The catalyst is 2-methylimidazole.
The solvent is propylene glycol methyl ether acetate.
The flame retardant is melamine resin coated ammonium polyphosphate.
The preparation method of the glue comprises the following steps:
s1, filler dispersion: adding half of the total amount of the multifunctional epoxy resin and a solvent into a stirrer, stirring at 1500rpm, adding a filler while stirring, and continuously stirring at 1500rpm for 4.5 hours after the filler is added to obtain an intermediate product A;
s2, adding the remaining half of the multifunctional epoxy resin and the o-cresol epoxy resin into a batching tank, adding the intermediate product A, and stirring at 1500rpm to obtain an intermediate product B;
s3, adding a curing agent, a catalyst and a flame retardant into the intermediate product B, sampling and detecting the curing time of the glue solution after stirring at 1500rpm for at least 5 hours, and stopping stirring when the curing time of the glue solution is 280-320S to obtain the glue solution.
The parameters of the hot press are as follows:
the initial stage is as follows: the time is 30 minutes, the temperature is kept at 100 ℃, and the pressure is 60 psi;
a heating stage: the heating rate is 1.5 ℃/min, the temperature is increased to 180 ℃, and the temperature is stopped, and the pressure is 60 psi;
and (3) hot pressing: the time is 45 minutes, the temperature is kept at 180 ℃, and the pressure is 320 psi;
and (3) a cooling stage: the cooling rate was 2 deg.C/min, and cooling to room temperature was stopped at a pressure of 40 psi.
Example 7
The preparation method of the flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board comprises the following steps:
(1) soaking glass fiber cloth into glue, placing the glass fiber cloth on a cloth rack of an impregnation machine, passing the glass fiber cloth through an impregnation groove which is fully impregnated with the glue, and placing the glass fiber cloth which is impregnated with the glue into an oven to be dried for 1min at the temperature of 170 ℃ to obtain a semi-solid piece;
(2) stacking 7 semi-fixed sheets;
(3) covering copper foils on the two sides of the stacked semi-solid sheets;
(4) and adding a die steel plate, sending into a hot press for hot pressing, and cutting according to requirements to obtain the flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth-based laminated board.
Hot pressing: the hot pressing is to melt p (B-stage) resin by high temperature and high pressure, completely expel gas and completely solidify the resin, and complete firm bonding between PP layers and with copper foil. According to the diffusion principle, the bonding is realized by mutual diffusion and permeation between macromolecules on the interface, and then interweaving is generated. A vacuum laminator is used, and the main process parameters are temperature rise conditions and pressure and vacuum degree control.
The glue is prepared from the following raw materials in percentage by mass: 36% of polyfunctional epoxy resin, 36% of o-cresol epoxy resin, 7% of filler, 8% of curing agent, 1.6% of melamine resin coated ammonium polyphosphate, 0.8% of ammonium polyphosphate containing a silane structure, 0.1% of catalyst and the balance of solvent.
The filler is functionalized rectorite.
The preparation method of the functionalized rectorite comprises the following steps: putting rectorite into an ethanol water solution with the volume fraction of 35%, wherein the mass ratio of the rectorite to the 35% ethanol water solution is 1: 9, adjusting the pH value to 2 by using 0.6mol/L hydrochloric acid, and carrying out ultrasonic treatment for 25min at the ultrasonic power of 400W and the ultrasonic frequency of 20kHz to obtain a mixture; placing the mixture in dry ice at the temperature of-78.5 ℃ for freezing for 6h, taking out the mixture to naturally reach the room temperature of 20 ℃, then centrifugally separating for 20min at the rotating speed of 9000r/min, washing the precipitate for 3 times by using 0.08mol/L carboxymethyl chitosan aqueous solution, wherein the use amount of the carboxymethyl chitosan aqueous solution washed each time is 5 times of the weight of the precipitate, and drying the washed precipitate for 24h at the temperature of 80 ℃ to obtain acid-treated rectorite; placing acid-treated rectorite into deionized water 9 times of the weight of the acid-treated rectorite, adding melamine 12% of the weight of the acid-treated rectorite, 2-amino-4-dimethylamino-1, 3,5 triazine 6% of the weight of the acid-treated rectorite, heating to 75 ℃, adding cyanuric acid 8% of the weight of the acid-treated rectorite and phosphoric acid 12% of the weight of the acid-treated rectorite, continuing heating to 95 ℃, stirring at the rotating speed of 300r/min for 2.5h, centrifugally separating at the rotating speed of 9000r/min for 20min, taking the precipitate, and drying at the temperature of 80 ℃ for 24h to obtain the functionalized rectorite.
The curing agent is a multifunctional phenolic resin.
The catalyst is 2-methylimidazole.
The solvent is propylene glycol methyl ether acetate.
The preparation method of the glue comprises the following steps:
s1, filler dispersion: adding half of the total amount of the multifunctional epoxy resin and a solvent into a stirrer, stirring at 1500rpm, adding a filler while stirring, and continuously stirring at 1500rpm for 4.5 hours after the filler is added to obtain an intermediate product A;
s2, adding the remaining half of the multifunctional epoxy resin and the o-cresol epoxy resin into a batching tank, adding the intermediate product A, and stirring at 1500rpm to obtain an intermediate product B;
s3, adding a curing agent, a catalyst, melamine resin coated ammonium polyphosphate and ammonium polyphosphate containing a silane structure into the intermediate product B, stirring at 1500rpm for at least 5 hours, sampling, detecting the curing time of the glue solution, and stopping stirring when the curing time of the glue solution is at 280 plus 320 seconds to obtain the glue solution.
The parameters of the hot press are as follows:
the initial stage is as follows: the time is 30 minutes, the temperature is kept at 100 ℃, and the pressure is 60 psi;
a heating stage: the heating rate is 1.5 ℃/min, the temperature is increased to 180 ℃, and the temperature is stopped, and the pressure is 60 psi;
and (3) hot pressing: the time is 45 minutes, the temperature is kept at 180 ℃, and the pressure is 320 psi;
and (3) a cooling stage: the cooling rate was 2 deg.C/min, and cooling to room temperature was stopped at a pressure of 40 psi.
Test example 1
The main performance of the flame-retardant and heat-resistant copper foil-clad epoxy glass fiber fabric base laminate prepared in example 1 was tested according to the requirements of IPC-4101/24, and the test results are shown in Table 1.
Table 1: EXAMPLE 1 Performance data sheet
Figure BDA0002092846380000181
Figure BDA0002092846380000191
Test example 2
The flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth base laminate prepared in the example was subjected to an oxygen index test in accordance with GB/T8924-.
Table 2: oxygen index test result table
Figure BDA0002092846380000192
Figure BDA0002092846380000201
Test example 3
The interlayer shear strength test is carried out on the flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth base laminated board prepared in the embodiment according to GB/T3357-82, the length of a test sample is 10mm, the width of the test sample is 6mm, the average value is taken after 10 times of test of each test sample, and the test results are shown in Table 3.
Table 3: interlaminar shear strength test result table
Interlaminar shear strength/MPa
Example 1 47.6
Example 2 34.5
Example 3 40.0
Example 4 44.2
Example 5 41.9
Example 6 47.1
Example 7 52.3
Test example 4
The heat distortion temperature of the flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth base laminated board prepared in the embodiment is tested according to GB 1634-79. The samples were 100mm long and 25mm wide, and the average was taken 5 times per sample test, and the test results are shown in table 4.
Table 4: heat distortion temperature test result table
Figure BDA0002092846380000202
Figure BDA0002092846380000211
The invention relates to a flame-retardant heat-resistant copper foil-clad epoxy glass fiber cloth-based laminated board, which theoretically researches the performance of the copper foil-clad epoxy glass fiber cloth-based laminated board and related influence factors, obtains the scheme through a large number of actual laminating experiments and performance test results of the prepared board, does not adopt dicy (namely dicyandiamide/cyanamide/dicyandiamide/cyanoguanidine/dicyandiamide), prepares excellent resin glue, has excellent heat resistance, low Z-direction thermal expansion coefficient and excellent through hole capability, and meets the requirements of IPC-4101/26.

Claims (5)

1. The preparation method of the flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board is characterized by comprising the following steps of:
(1) soaking glass fiber cloth in glue water, and drying to obtain a semi-solid sheet;
(2) stacking one or more semi-solid sheets according to the designed thickness;
(3) covering copper foil on one side or two sides of the stacked semi-solid sheets;
(4) hot pressing by a hot press;
the glue is prepared from the following raw materials in percentage by mass: 70-80% of epoxy resin, 3-9% of filler, 6-10% of curing agent, 1-4% of flame retardant, 0.08-0.13% of catalyst and the balance of solvent;
the filler is functionalized rectorite; the preparation method of the functionalized rectorite comprises the following steps: putting rectorite into 30-40% ethanol water solution by volume fraction, wherein the mass ratio of the rectorite to the 30-40% ethanol water solution is 1: (4-10), adjusting the pH to 2-3 with 0.5-1mol/L hydrochloric acid, and performing ultrasonic treatment for 20-30min to obtain a mixture; placing the mixture in dry ice at-78.5 deg.C, freezing for 4-8h, taking out, naturally reaching room temperature, centrifuging, washing the precipitate with 0.05-0.1mol/L carboxymethyl chitosan water solution for 2-5 times, and oven drying to obtain acid-treated rectorite; placing acid-treated rectorite in water with the weight 8-9 times of that of the acid-treated rectorite, adding melamine with the weight 10-15% of that of the acid-treated rectorite and 2-amino-4-dimethylamino-1, 3,5 triazine with the weight 4-10% of that of the acid-treated rectorite, heating to 70-80 ℃, adding cyanuric acid with the weight 4-10% of that of the acid-treated rectorite and phosphoric acid with the weight 10-15% of that of the acid-treated rectorite, continuing heating to 90-100 ℃, stirring for 2-3h, performing centrifugal separation, taking precipitates and drying to obtain the functionalized rectorite.
2. The method for preparing the flame-retardant and heat-resistant copper foil-coated epoxy fiberglass cloth-based laminate according to claim 1, wherein the epoxy resin is at least one of o-cresol type epoxy resin and polyfunctional epoxy resin.
3. The method for preparing the flame-retardant and heat-resistant copper foil-coated epoxy fiberglass cloth-based laminate according to claim 1, wherein the curing agent is a multifunctional phenolic resin; the catalyst is selected from any one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole or 2-phenylimidazole; the solvent is any one or more of propylene glycol methyl ether acetate, acetone or butanone; the flame retardant is one or more of melamine resin coated ammonium polyphosphate and ammonium polyphosphate containing a silane structure.
4. The preparation method of the flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board as claimed in claim 1, wherein the preparation method of the glue comprises the following steps:
s1, filler dispersion: adding 10-40 wt% of epoxy resin and solvent into a stirrer, stirring at a rotating speed of more than 1000rpm, adding a filler while stirring, and after the filler is added, continuously stirring at a rotating speed of more than 1000rpm for 4-5 hours to obtain an intermediate product A;
s2, adding the residual 60-90 wt% of epoxy resin into a batching tank, adding the intermediate product A, and stirring to obtain an intermediate product B;
s3, adding a curing agent, a catalyst and a flame retardant into the intermediate product B, stirring for at least 5 hours, sampling and detecting the curing time of the glue solution, and stopping stirring when the curing time of the glue solution is 280-320S to obtain the glue.
5. A flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board, which is characterized by being prepared by the preparation method of the flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board according to any one of claims 1 to 4.
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CN102633990A (en) * 2012-04-05 2012-08-15 广东生益科技股份有限公司 Epoxy resin composition, prepreg made of epoxy resin composition and copper-coated laminate made of epoxy resin composition
JP2016065250A (en) * 2015-11-25 2016-04-28 パナソニックＩｐマネジメント株式会社 Prepreg, laminate sheet and metal laminate sheet

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