CN113172963A - Flame-retardant heat-resistant copper-clad plate and preparation method thereof - Google Patents

Flame-retardant heat-resistant copper-clad plate and preparation method thereof Download PDF

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CN113172963A
CN113172963A CN202110403160.0A CN202110403160A CN113172963A CN 113172963 A CN113172963 A CN 113172963A CN 202110403160 A CN202110403160 A CN 202110403160A CN 113172963 A CN113172963 A CN 113172963A
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resin
flame
clad plate
retardant heat
curing
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钱凯
王泳
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Hangzhou Honghe Electronic Technology Co ltd
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Hangzhou Honghe Electronic Technology Co 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/0007—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality
    • B32B37/003—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving treatment or provisions in order to avoid deformation or air inclusion, e.g. to improve surface quality to avoid air inclusion
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Abstract

The invention provides a flame-retardant heat-resistant copper-clad plate and a preparation method thereof, wherein the preparation method comprises the following steps: s1, preparing ingredients: dissolving a curing agent; resin reaction; dispersing the filler; curing and measuring S/G; s2, impregnation; s3, stacking; s4, combining; s5, pressing; and S6, checking. Compared with the prior art, the invention introduces a certain proportion of inorganic fillers (silicon dioxide, magnesium hydroxide and talcum powder, the thermal expansion coefficient of which is about 10-15 PPm/DEG C) to replace part of epoxy resin, effectively improves the heat resistance of the glass fiber cloth substrate, and the addition of the phenoxy resin and the DDS improves the crosslinking density and the glass state transition temperature of a resin system, thereby greatly improving the heat resistance of a base material.

Description

Flame-retardant heat-resistant copper-clad plate and preparation method thereof
Technical Field
The invention relates to the technical field of electronic materials, in particular to a flame-retardant heat-resistant copper-clad plate and a preparation method thereof.
Background
Copper Clad Laminate (CCL) is a product which is prepared by using wood pulp paper or glass fiber cloth as a reinforcing material, soaking the reinforcing material in resin, coating Copper foil on one side or two sides of the reinforcing material, and performing hot pressing.
The copper-clad plate is a basic material in the electronic industry, is mainly used for processing and manufacturing Printed Circuit Boards (PCBs), and is widely applied to electronic products such as televisions, radios, computers, mobile communication and the like.
The copper-clad plates available in the market can be mainly classified into the following types from the viewpoint of base materials: paper substrate, glass fiber cloth substrate, synthetic fiber cloth substrate, non-woven fabric substrate, composite substrate.
The preparation process flow of the glass fiber cloth substrate is as follows: cutting → pre-stacking → combining → pressing → disassembling → cutting → packaging → warehousing → delivering.
The traditional glass fiber cloth substrate is formed by the cross-linking reaction of epoxy resin and a curing agent, and the heat resistance of the glass fiber cloth substrate is poor because the thermal expansion coefficient of the epoxy resin is as high as 80 PPm/DEG C.
In addition, in general, the glass fiber cloth substrate uses polyamine, acid anhydride, polyphenol, polythiol, etc. as a curing agent, and has weak peel strength.
Disclosure of Invention
The invention aims to provide a flame-retardant heat-resistant copper-clad plate and a preparation method thereof, which are used for solving the problems of poor heat resistance and weak peeling strength of a glass fiber cloth substrate in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
the application discloses a preparation method of a flame-retardant heat-resistant copper-clad plate, which comprises the following steps
S1, preparing ingredients:
s11, dissolving a curing agent: adding 3-5 parts of dicyandiamide, 0.1-0.2 part of diethyl tetramethyl imidazole and 1-2 parts of DDS (direct digital Synthesis) of solid content of resin into a DMF (dimethyl formamide) solvent, continuously stirring to fully dissolve the dicyandiamide, and detecting that dicyandiamide-free crystals exist to obtain a curing agent solution for later use;
s12, resin reaction: 20-30 parts of phenoxy resin and 70-80 parts of bisphenol A type bromine epoxy resin are injected into a resin reaction kettle, all the curing agent solution obtained in the step S11 is injected into the resin reaction kettle, stirring reaction is carried out for 2-4 hours, and glue solution GT is detected for standby;
s13, filler dispersion: pumping all the reacted resin solution into a filler dispersing kettle, starting a stirrer, adding 50-80 parts of filler while stirring, accelerating the stirring and dispersing uniformly, starting an emulsifying pump, emulsifying, pumping into a curing kettle, and curing for later use;
s14, curing and measuring the ratio of S/G: after the blending glue solution formed in the step S13 is stirred and cured for 8 hours at a low speed, a sample is extracted, the S/G value of the sample is measured, and if the measured S/G range is within the range of 220S and 240S, the next step is carried out when the blending is qualified;
s2, impregnation: putting the glass fiber cloth into the ingredients prepared in the step S1, and drying to obtain a semi-solid piece;
s3, stacking: stacking a plurality of prepregs to a preset thickness according to a preset thickness requirement;
s4, combination: covering copper foil on the prepregs stacked in the step S3, combining the prepregs through a die, and sending the prepregs into a hot press after the prepregs are combined;
s5, pressing: melting the resin in the prepreg at high temperature, and expelling bubbles under high pressure to gradually harden the resin and bond the resin with the copper foil to form a substrate;
s6, checking: and cutting off the edge materials of the laminated substrate, and then checking the appearance, the thickness and the like to obtain a finished product.
Preferably, in step S11, the stirring speed is not lower than 2900 r/min.
Preferably, the filler in step S13 is one of silica, magnesium hydroxide and talc.
Preferably, in step S13, the stirring time is not less than 4 hours, the stirring speed is not less than 120r/Min, the emulsification temperature is less than 70 ℃, and the emulsification time is not less than 2 hours.
Preferably, the step S2 of putting the glass fiber cloth into the mixture prepared in the step S1 specifically includes the following operations: and (4) pouring the ingredients prepared in the step (S1) into an impregnation tank of an impregnation machine, installing the glass fiber cloth on a cloth rack of the impregnation machine, controlling the glass fiber cloth to advance by tension, and passing through the impregnation tank filled with the ingredient glue solution.
Preferably, the mold in step S4 is a high-hardness mirror-finished steel plate.
Preferably, in the pressing process of step S5, the temperature is increased to 1.5-2.5 ℃/min, the pressure is 0.5-3.5 Mpa, and the vacuum is 730 mmhg.
Preferably, the step S1 further includes a sub-step S15: if the S/G is longer, adding 0.01-0.1 part of catalyst for accelerating the reaction; and if the S/G is shorter, additionally preparing a new ingredient with the S/G length according to the steps S11-S14, uniformly mixing the new ingredient with the original ingredient, and then detecting the S/G, wherein in the preparation process of the new ingredient, the resins of all the components are added in equal proportion to ensure the stability of Tg and other related performances.
The flame-retardant heat-resistant copper-clad plate prepared by the preparation method.
The invention has the beneficial effects that: compared with the prior art, the preparation method of the flame-retardant heat-resistant copper-clad plate provided by the invention has the advantages that the traditional glass fiber cloth substrate is subjected to a crosslinking reaction by using epoxy resin and a curing agent, the thermal expansion coefficient of the epoxy resin is as high as 80 PPm/DEG C, the glass fiber cloth substrate is poor in heat resistance, a certain proportion of inorganic fillers (silicon dioxide, magnesium hydroxide and talcum powder, the thermal expansion coefficient of the inorganic fillers is about 10-15 PPm/DEG C) are introduced to replace part of the epoxy resin, the heat resistance of the glass fiber cloth substrate is effectively improved, meanwhile, the addition of the phenoxy resin and the DDS greatly improves the crosslinking density and glass state conversion temperature of a resin system, so that the heat resistance of the substrate is greatly improved, in addition, the common glass fiber cloth substrate adopts polyamine, anhydride, polyphenol, polythiol and the like as the curing agent, these curing agents have weak bonding force with the copper foil and weak peel strength due to the absence of polar substances between molecules. The invention adopts a certain proportion of curing agent dicyandiamide or Diamino Diphenyl Sulfone (DDS) with a molecular structure having polarity, and amine substances in the diamino diphenyl sulfone or dicyandiamide curing agent belong to a polar substance, so that the bonding force between the whole system and the copper foil can be improved, the adhesive force between an epoxy resin interface and the copper foil is enhanced, and the epoxy resin interface and the copper foil have higher peel strength.
The features and advantages of the present invention will be described in detail by embodiments in conjunction with the accompanying drawings.
Drawings
FIG. 1 is a preparation flow chart of a preparation method of a flame-retardant heat-resistant copper-clad plate of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood, however, that the description herein of specific embodiments is only intended to illustrate the invention and not to limit the scope of the invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
Example one (silica filler):
s1, preparing ingredients:
s11, dissolving a curing agent: adding 50g of dicyandiamide, 2g of 2-ethyl 4-methylimidazole and 20g of DDS into a 500g DMF solvent beaker, continuously stirring to fully dissolve the dicyandiamide, and detecting that dicyandiamide is not crystallized to obtain a curing agent solution for later use;
s12, resin reaction: adding 200g of phenoxy resin and 800g of bisphenol A type bromine epoxy resin into an experimental reaction kettle, pouring all curing agent solution obtained by 101 into the experimental resin reaction kettle, stirring and reacting for 2 hours, and detecting glue solution GT for later use;
s13, filler dispersion: starting a stirrer, adding 500g of silicon dioxide filler into an experimental resin reaction kettle while stirring, and after fully dispersing, accelerating the stirring and dispersing for 2 hours. Then placing the experimental high-shear stirrer into an experimental resin reaction kettle, emulsifying for 2 hours, taking out the high-shear stirrer, and pumping into a low-speed paddle type stirrer for stirring and curing for later use;
s14, curing and measuring the ratio of S/G: after stirring and curing the ingredient glue solution formed in the step (3) at a low speed for 8 hours, extracting a sample, measuring the S/G value of the sample, and if the measured S/G range is within the interval of 220S and 240S, gluing;
wherein the glue mainly comprises the following materials: phenoxy resin, epoxy resin, curing agent: dicyandiamide, 2-ethyl 4-methylimidazole, DDS, Dimethylformamide (DMF) solvent, silicon dioxide;
epoxy resins are typically stored by dissolving in butanone and storing in an iron drum at about 80% solids; the dicyandiamide and the DDS are used as curing agents, and resin is subjected to crosslinking curing reaction at a proper temperature; 2-ethyl-4-methylimidazole is used as a catalyst and is used for initiating and accelerating the curing speed, and the S/G adjustment is obvious; DMF is used as a solvent for adjusting the viscosity of the glue and maintaining a relatively uniform and stable system, which is important for the sizing and semi-curing reaction in the TREATING process.
S2, impregnation: the process comprises the steps of immersing glass fiber cloth into prepared glue, and then drying to obtain a semi-solid piece with appropriate parameters for subsequent production; the method comprises the following specific steps: arranging the electronic-grade glass fiber on a cloth rack of a dipping machine, controlling the glass fiber to advance by tension, leading the glass fiber cloth to pass through a dipping groove filled with glue solution (the glue solution is pumped into the dipping groove by a pipeline), leading the glass fiber cloth soaked with the glue solution to enter an oven, volatilizing a solvent and carrying out further reaction of resin and a curing agent. After drying, the product is a semi-finished product: prepreg (PP for short).
S3, stacking: and matching PP with different PP numbers according to different thicknesses and plan requirements. After stacking, sending the materials into a combination chamber;
s4, combination: covering a single-sided or double-sided copper foil on the PP stacked in front, adding a die-steel plate, combining, and then sending into a hot press;
s5, pressing: melting the resin in the prepreg at high temperature, and expelling bubbles under high pressure to gradually harden the resin and adhere the resin to the copper foil; the fluidity of the resin may be affected by the filler; hot-pressing procedure description: the hot pressing is to melt the (B-stage) semi-cured resin at high temperature and high pressure, completely expel the gas and completely cure the resin, and complete the firm bonding between the pp layers and the 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. In some embodiments, a cold and hot split vacuum laminator can be used for hot pressing, and the main process parameters are temperature rise condition, pressure and vacuum degree control, in this embodiment, the temperature rise is controlled to be 1.5-2.5 ℃/min, the pressure is 0.5-3.5 Mpa, and the vacuum is 730 mmhg.
S6, checking: and cutting off the edge materials of the laminated substrate, and then, inspecting the appearance, the thickness and the like and then discharging. And obtaining the finished product of the flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board.
Example two (magnesium hydroxide filler):
s1, preparing ingredients:
s11, dissolving a curing agent: adding 50g of dicyandiamide, 2g of 2-ethyl 4-methylimidazole and 20g of DDS into a 500g DMF solvent beaker, continuously stirring to fully dissolve the dicyandiamide, and detecting that dicyandiamide is not crystallized to obtain a curing agent solution for later use;
s12, resin reaction: adding 200g of phenoxy resin and 800g of bisphenol A type bromine epoxy resin into an experimental reaction kettle, pouring all curing agent solution obtained by 101 into the experimental resin reaction kettle, stirring and reacting for 2 hours, and detecting glue solution GT for later use;
s13, filler dispersion: starting a stirrer, adding 500g of magnesium hydroxide filler into an experimental resin reaction kettle while stirring, and after fully dispersing, accelerating the stirring and dispersing for 2 hours. Then placing the experimental high-shear stirrer into an experimental resin reaction kettle, emulsifying for 2 hours, taking out the high-shear stirrer, and pumping into a low-speed paddle type stirrer for stirring and curing for later use;
s14, curing and measuring the ratio of S/G: after stirring and curing the ingredient glue solution formed in the step (3) at a low speed for 8 hours, extracting a sample, measuring the S/G value of the sample, and if the measured S/G range is within the interval of 220S and 240S, gluing;
wherein the glue mainly comprises the following materials: phenoxy resin, epoxy resin, curing agent: dicyandiamide, 2-ethyl 4-methylimidazole, DDS, Dimethylformamide (DMF) solvent and magnesium hydroxide;
epoxy resins are typically stored by dissolving in butanone and storing in an iron drum at about 80% solids; the dicyandiamide and the DDS are used as curing agents, and resin is subjected to crosslinking curing reaction at a proper temperature; 2-ethyl-4-methylimidazole is used as a catalyst and is used for initiating and accelerating the curing speed, and the S/G adjustment is obvious; DMF is used as a solvent for adjusting the viscosity of the glue and maintaining a relatively uniform and stable system, which is important for the sizing and semi-curing reaction in the TREATING process.
S2, impregnation: the process comprises the steps of immersing glass fiber cloth into prepared glue, and then drying to obtain a semi-solid piece with appropriate parameters for subsequent production; the method comprises the following specific steps: arranging the electronic-grade glass fiber on a cloth rack of a dipping machine, controlling the glass fiber to advance by tension, leading the glass fiber cloth to pass through a dipping groove filled with glue solution (the glue solution is pumped into the dipping groove by a pipeline), leading the glass fiber cloth soaked with the glue solution to enter an oven, volatilizing a solvent and carrying out further reaction of resin and a curing agent. After drying, the product is a semi-finished product: prepreg (PP for short).
S3, stacking: and matching PP with different PP numbers according to different thicknesses and plan requirements. After stacking, sending the materials into a combination chamber;
s4, combination: covering a single-sided or double-sided copper foil on the PP stacked in front, adding a die-steel plate, combining, and then sending into a hot press;
s5, pressing: melting the resin in the prepreg at high temperature, and expelling bubbles under high pressure to gradually harden the resin and adhere the resin to the copper foil; the fluidity of the resin may be affected by the filler; hot-pressing procedure description: the hot pressing is to melt the (B-stage) semi-cured resin at high temperature and high pressure, completely expel the gas and completely cure the resin, and complete the firm bonding between the pp layers and the 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. In some embodiments, a cold and hot split vacuum laminator can be used for hot pressing, and the main process parameters are temperature rise condition, pressure and vacuum degree control, in this embodiment, the temperature rise is controlled to be 1.5-2.5 ℃/min, the pressure is 0.5-3.5 Mpa, and the vacuum is 730 mmhg.
S6, checking: and cutting off the edge materials of the laminated substrate, and then, inspecting the appearance, the thickness and the like and then discharging. And obtaining the finished product of the flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board.
Example three (talc filler):
s1, preparing ingredients:
s11, dissolving a curing agent: adding 50g of dicyandiamide, 2g of 2-ethyl 4-methylimidazole and 20g of DDS into a 500g DMF solvent beaker, continuously stirring to fully dissolve the dicyandiamide, and detecting that dicyandiamide is not crystallized to obtain a curing agent solution for later use;
s12, resin reaction: adding 200g of phenoxy resin and 800g of bisphenol A type bromine epoxy resin into an experimental reaction kettle, pouring all curing agent solution obtained by 101 into the experimental resin reaction kettle, stirring and reacting for 2 hours, and detecting glue solution GT for later use;
s13, filler dispersion: starting a stirrer, adding 500g of talcum powder filler into an experimental resin reaction kettle while stirring, and after full dispersion, accelerating stirring and dispersion for 2 hours. Then placing the experimental high-shear stirrer into an experimental resin reaction kettle, emulsifying for 2 hours, taking out the high-shear stirrer, and pumping into a low-speed paddle type stirrer for stirring and curing for later use;
s14, curing and measuring the ratio of S/G: after stirring and curing the ingredient glue solution formed in the step (3) at a low speed for 8 hours, extracting a sample, measuring the S/G value of the sample, and if the measured S/G range is within the interval of 220S and 240S, gluing;
wherein the glue mainly comprises the following materials: phenoxy resin, epoxy resin, curing agent: dicyandiamide, 2-ethyl 4-methylimidazole, DDS, Dimethylformamide (DMF) solvent and talcum powder;
epoxy resins are typically stored by dissolving in butanone and storing in an iron drum at about 80% solids; the dicyandiamide and the DDS are used as curing agents, and resin is subjected to crosslinking curing reaction at a proper temperature; 2-ethyl-4-methylimidazole is used as a catalyst and is used for initiating and accelerating the curing speed, and the S/G adjustment is obvious; DMF is used as a solvent for adjusting the viscosity of the glue and maintaining a relatively uniform and stable system, which is important for the sizing and semi-curing reaction in the TREATING process.
S2, impregnation: the process comprises the steps of immersing glass fiber cloth into prepared glue, and then drying to obtain a semi-solid piece with appropriate parameters for subsequent production; the method comprises the following specific steps: arranging the electronic-grade glass fiber on a cloth rack of a dipping machine, controlling the glass fiber to advance by tension, leading the glass fiber cloth to pass through a dipping groove filled with glue solution (the glue solution is pumped into the dipping groove by a pipeline), leading the glass fiber cloth soaked with the glue solution to enter an oven, volatilizing a solvent and carrying out further reaction of resin and a curing agent. After drying, the product is a semi-finished product: prepreg (PP for short).
S3, stacking: and matching PP with different PP numbers according to different thicknesses and plan requirements. After stacking, sending the materials into a combination chamber;
s4, combination: covering a single-sided or double-sided copper foil on the PP stacked in front, adding a die-steel plate, combining, and then sending into a hot press;
s5, pressing: melting the resin in the prepreg at high temperature, and expelling bubbles under high pressure to gradually harden the resin and adhere the resin to the copper foil; the fluidity of the resin may be affected by the filler; hot-pressing procedure description: the hot pressing is to melt the (B-stage) semi-cured resin at high temperature and high pressure, completely expel the gas and completely cure the resin, and complete the firm bonding between the pp layers and the 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. In some embodiments, a cold and hot split vacuum laminator can be used for hot pressing, and the main process parameters are temperature rise condition, pressure and vacuum degree control, in this embodiment, the temperature rise is controlled to be 1.5-2.5 ℃/min, the pressure is 0.5-3.5 Mpa, and the vacuum is 730 mmhg.
S6, checking: and cutting off the edge materials of the laminated substrate, and then, inspecting the appearance, the thickness and the like and then discharging. And obtaining the finished product of the flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board.
Comparative example 1 (no filler, pure resin system):
s1, preparing ingredients:
s11, dissolving a curing agent: adding 50g of dicyandiamide, 2g of 2-ethyl 4-methylimidazole and 20g of DDS into a 500g DMF solvent beaker, continuously stirring to fully dissolve the dicyandiamide, and detecting that dicyandiamide is not crystallized to obtain a curing agent solution for later use;
s12, resin reaction: adding 200g of phenoxy resin and 800g of bisphenol A type bromine epoxy resin into an experimental reaction kettle, pouring all curing agent solution obtained by 101 into the experimental resin reaction kettle, stirring and reacting for 2 hours, and detecting glue solution GT for later use;
s13, curing and measuring the ratio of S/G: after stirring and curing the ingredient glue solution formed in the step (3) at a low speed for 8 hours, extracting a sample, measuring the S/G value of the sample, and if the measured S/G range is within the interval of 220S and 240S, gluing;
the glue mainly comprises the following materials: phenoxy resin, epoxy resin, curing agent: dicyandiamide, 2-ethyl 4-methylimidazole, DDS, Dimethylformamide (DMF) solvent; epoxy resins are typically stored by dissolving in butanone and storing in an iron drum at about 80% solids; the dicyandiamide and the DDS are used as curing agents, and resin is subjected to crosslinking curing reaction at a proper temperature; 2-ethyl-4-methylimidazole is used as a catalyst and is used for initiating and accelerating the curing speed, and the S/G adjustment is obvious; DMF is used as a solvent for adjusting the viscosity of the glue and maintaining a relatively uniform and stable system, which is important for the sizing and semi-curing reaction in the TREATING process.
S2, impregnation: the process comprises the steps of immersing glass fiber cloth into prepared glue, and then drying to obtain a semi-solid piece with appropriate parameters for subsequent production; the method comprises the following specific steps: arranging the electronic-grade glass fiber on a cloth rack of a dipping machine, controlling the glass fiber to advance by tension, leading the glass fiber cloth to pass through a dipping groove filled with glue solution (the glue solution is pumped into the dipping groove by a pipeline), leading the glass fiber cloth soaked with the glue solution to enter an oven, volatilizing a solvent and carrying out further reaction of resin and a curing agent. After drying, the product is a semi-finished product: prepreg (PP for short).
S3, stacking: and matching PP with different PP numbers according to different thicknesses and plan requirements. After stacking, sending the materials into a combination chamber;
s4, combination: covering a single-sided or double-sided copper foil on the PP stacked in front, adding a die-steel plate, combining, and then sending into a hot press;
s5, pressing: melting the resin in the prepreg at high temperature, and expelling bubbles under high pressure to gradually harden the resin and adhere the resin to the copper foil. The fluidity of the resin may be affected by the filler; hot-pressing procedure description: the hot pressing is to melt the (B-stage) semi-cured resin at high temperature and high pressure, completely expel the gas and completely cure the resin, and complete the firm bonding between the pp layers and the 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. In some embodiments, a hot and cold split vacuum laminator can be used for hot pressing, and the main process parameters are temperature rise, pressure and vacuum degree control. In the embodiment, the temperature is controlled to be 1.5-2.5 ℃/min, the pressure is 0.5-3.5 Mpa, and the vacuum is 730 mmhg;
s6, checking: and cutting off the edge materials of the laminated substrate, and then, inspecting the appearance, the thickness and the like and then discharging. And obtaining the finished product of the flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board.
Comparative example 2 (pure resin system and other curing agents):
s1, preparing ingredients:
s11, dissolving a curing agent: adding 50g of polyamine, 2g of 2-ethyl 4-methylimidazole and 20g of DDS into a 500g DMF solvent beaker, continuously stirring to fully dissolve the polyamine, and detecting that no polyamine crystal exists to obtain a curing agent solution for later use;
s12, resin reaction: adding 200g of phenoxy resin and 800g of bisphenol A type bromine epoxy resin into an experimental reaction kettle, pouring all curing agent solution obtained by 101 into the experimental resin reaction kettle, stirring and reacting for 2 hours, and detecting glue solution GT for later use;
s13, curing and measuring the ratio of S/G: after stirring and curing the ingredient glue solution formed in the step (3) at a low speed for 8 hours, extracting a sample, measuring the S/G value of the sample, and if the measured S/G range is within the interval of 220S and 240S, gluing;
the glue mainly comprises the following materials: phenoxy resin, epoxy resin, curing agent: polyamine, 2-ethyl 4-methylimidazole, DDS, Dimethylformamide (DMF) solvent;
epoxy resins are typically stored by dissolving in butanone and storing in an iron drum at about 80% solids; the polyamine and the DDS are used as curing agents, and the resin is subjected to crosslinking curing reaction at a proper temperature; 2-ethyl-4-methylimidazole is used as a catalyst and is used for initiating and accelerating the curing speed, and the S/G adjustment is obvious; DMF is used as a solvent for adjusting the viscosity of the glue and maintaining a relatively uniform and stable system, which is important for the sizing and semi-curing reaction in the TREATING process.
S2, impregnation: the process comprises the steps of immersing glass fiber cloth into prepared glue, and then drying to obtain a semi-solid piece with appropriate parameters for subsequent production; the method comprises the following specific steps: arranging the electronic-grade glass fiber on a cloth rack of a dipping machine, controlling the glass fiber to advance by tension, leading the glass fiber cloth to pass through a dipping groove filled with glue solution (the glue solution is pumped into the dipping groove by a pipeline), leading the glass fiber cloth soaked with the glue solution to enter an oven, volatilizing a solvent and carrying out further reaction of resin and a curing agent. After drying, the product is a semi-finished product: prepreg (PP for short).
S3, stacking: and matching PP with different PP numbers according to different thicknesses and plan requirements. After stacking, sending the materials into a combination chamber;
s4, combination: covering a single-sided or double-sided copper foil on the PP stacked in front, adding a die-steel plate, combining, and then sending into a hot press;
s5, pressing: melting the resin in the prepreg at high temperature, and expelling bubbles under high pressure to gradually harden the resin and adhere the resin to the copper foil. The fluidity of the resin may be affected by the filler; hot-pressing procedure description: the hot pressing is to melt the (B-stage) semi-cured resin at high temperature and high pressure, completely expel the gas and completely cure the resin, and complete the firm bonding between the pp layers and the 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. In some embodiments, a hot and cold split vacuum laminator can be used for hot pressing, and the main process parameters are temperature rise, pressure and vacuum degree control. In the embodiment, the temperature is controlled to be 1.5-2.5 ℃/min, the pressure is 0.5-3.5 Mpa, and the vacuum is 730 mmhg;
s6, checking: and cutting off the edge materials of the laminated substrate, and then, inspecting the appearance, the thickness and the like and then discharging. And obtaining the finished product of the flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board.
The following table is a table of performance parameters of the flame-retardant and heat-resistant copper foil-clad epoxy fiberglass cloth-based laminate obtained in each example:
performance in number Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2
Tg（℃，DSC） 148 145 148 147 143
Td（5%，N2） 345 343 335 345 330
T288(min, tin stove) 3 3 3 1.5 2
Breakdown voltage, kv ＞50 ＞50 ＞50 ＞50 ＞50
Flame retardancy, UL94 V0 V0 V0 V0 V0
Flexural Strength (W), MPa 540 524 560 585 578
Flexural Strength (F), MPa 487 465 498 521 520
Peel strength, LBS/IN 7.8 8.1 8.2 7.3 6.5
The performance parameter table T288 of each example indicates the longest time that the substrate can be subjected to high welding temperature at 288 ℃ without generating decomposition phenomena such as foaming, delamination and the like; as can be seen from the above table, the Tg in comparative example 1 is significantly lower than that in examples 1 to 3 of the present invention, because the present invention introduces a certain proportion of inorganic filler (such as silica, whose thermal expansion coefficient is about 10-15 PPm/DEG C) to replace part of epoxy resin, which effectively improves the heat resistance of the glass fiber cloth substrate;
the peel strength in the comparative example 2 is obviously lower than that in the examples 1 to 3, because the amine substance in the diaminodiphenyl sulfone (DDS) or dicyandiamide curing agent belongs to a polar substance, the bonding force between the whole system and the copper foil can be improved, the adhesive force between an epoxy resin interface and the copper foil is enhanced, and the epoxy resin interface and the copper foil have higher peel strength;
according to the invention, the glass fiber cloth-based laminated board prepared by the reasonable proportioning of the ingredients has good performance, low manufacturing cost and high cost performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (9)

1. The preparation method of the flame-retardant heat-resistant copper-clad plate is characterized by comprising the following steps: s1, preparing ingredients: s11, dissolving a curing agent: adding 3-5 parts of dicyandiamide, 0.1-0.2 part of diethyl tetramethyl imidazole and 1-2 parts of DDS (direct digital Synthesis) of solid content of resin into a DMF (dimethyl formamide) solvent, continuously stirring to fully dissolve the dicyandiamide, and detecting that dicyandiamide-free crystals exist to obtain a curing agent solution for later use; s12, resin reaction: 20-30 parts of phenoxy resin and 70-80 parts of bisphenol A type bromine epoxy resin are injected into a resin reaction kettle, all the curing agent solution obtained in the step S11 is injected into the resin reaction kettle, stirring reaction is carried out for 2-4 hours, and glue solution GT is detected for standby; s13, filler dispersion: pumping all the reacted resin solution into a filler dispersing kettle, starting a stirrer, adding 50-80 parts of filler while stirring, accelerating the stirring and dispersing uniformly, starting an emulsifying pump, emulsifying, pumping into a curing kettle, and curing for later use; s14, curing and measuring the ratio of S/G: after the blending glue solution formed in the step S13 is stirred and cured for 8 hours at a low speed, a sample is extracted, the S/G value of the sample is measured, and if the measured S/G range is within the range of 220S and 240S, the next step is carried out when the blending is qualified; s2, impregnation: putting the glass fiber cloth into the ingredients prepared in the step S1, and drying to obtain a semi-solid piece; s3, stacking: stacking a plurality of prepregs to a preset thickness according to a preset thickness requirement; s4, combination: covering copper foil on the prepregs stacked in the step S3, combining the prepregs through a die, and sending the prepregs into a hot press after the prepregs are combined; s5, pressing: melting the resin in the prepreg at high temperature, and expelling bubbles under high pressure to gradually harden the resin and bond the resin with the copper foil to form a substrate; s6, checking: and cutting off the edge materials of the laminated substrate, and then checking the appearance, the thickness and the like to obtain a finished product.
2. The method for preparing the flame-retardant heat-resistant copper-clad plate according to claim 1, wherein in the step S11, the stirring rotation speed is not lower than 2900 r/min.
3. The method for preparing a flame-retardant heat-resistant copper-clad plate according to claim 1, wherein the filler in the step S13 is one of silica, magnesium hydroxide and talc.
4. The method for preparing the flame-retardant heat-resistant copper-clad plate according to claim 1, wherein in the step S13, the stirring time is not less than 4 hours, the stirring speed is not less than 120r/Min, the emulsifying temperature is less than 70 ℃, and the emulsifying time is not less than 2 hours.
5. The method for preparing the flame-retardant heat-resistant copper-clad plate according to claim 1, wherein the step S2 of putting the glass fiber cloth into the ingredients prepared in the step S1 specifically comprises the following operations: and (4) pouring the ingredients prepared in the step (S1) into an impregnation tank of an impregnation machine, installing the glass fiber cloth on a cloth rack of the impregnation machine, controlling the glass fiber cloth to advance by tension, and passing through the impregnation tank filled with the ingredient glue solution.
6. The method for preparing the flame-retardant heat-resistant copper-clad plate according to claim 1, wherein the mold in the step S4 is a high-hardness mirror steel plate.
7. The method for preparing the flame-retardant heat-resistant copper-clad plate according to claim 1, wherein in the pressing process of step S5, the temperature is raised to 1.5-2.5 ℃/min, the pressure is 0.5-3.5 MPa, and the vacuum is 730 mmhg.
8. The method for preparing a flame-retardant heat-resistant copper-clad plate according to claim 1, wherein the step S1 further comprises a substep S15: if the S/G is longer, adding 0.01-0.1 part of catalyst for accelerating the reaction; and if the S/G is shorter, additionally preparing a new ingredient with the S/G length according to the steps S11-S14, uniformly mixing the new ingredient with the original ingredient, and then detecting the S/G, wherein in the preparation process of the new ingredient, the resins of all the components are added in equal proportion to ensure the stability of Tg and other related performances.
9. A flame-retardant heat-resistant copper-clad plate prepared by the preparation method according to any one of claims 1 to 8.
CN202110403160.0A 2021-04-15 2021-04-15 Flame-retardant heat-resistant copper-clad plate and preparation method thereof Pending CN113172963A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101240109A (en) * 2007-09-30 2008-08-13 广东生益科技股份有限公司 Resin composition and semi-solidifying sheet for printed board prepared from the same
CN109181225A (en) * 2018-08-09 2019-01-11 陕西生益科技有限公司 A kind of heat conductive flame-retarding resin combination and its application
CN109575523A (en) * 2018-12-11 2019-04-05 广州联茂电子科技有限公司 A kind of highly thermal-conductive resin composition for copper-clad plate
CN110588116A (en) * 2019-09-04 2019-12-20 重庆德凯实业股份有限公司 Flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth-based laminated board and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101240109A (en) * 2007-09-30 2008-08-13 广东生益科技股份有限公司 Resin composition and semi-solidifying sheet for printed board prepared from the same
CN109181225A (en) * 2018-08-09 2019-01-11 陕西生益科技有限公司 A kind of heat conductive flame-retarding resin combination and its application
CN109575523A (en) * 2018-12-11 2019-04-05 广州联茂电子科技有限公司 A kind of highly thermal-conductive resin composition for copper-clad plate
CN110588116A (en) * 2019-09-04 2019-12-20 重庆德凯实业股份有限公司 Flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth-based laminated board and preparation method thereof

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