CN111531985A - High-heat-resistance FR-4 material and preparation method thereof - Google Patents

High-heat-resistance FR-4 material and preparation method thereof Download PDF

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Publication number
CN111531985A
CN111531985A CN202010240622.7A CN202010240622A CN111531985A CN 111531985 A CN111531985 A CN 111531985A CN 202010240622 A CN202010240622 A CN 202010240622A CN 111531985 A CN111531985 A CN 111531985A
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adhesive
resin curing
epoxy resin
stirring
curing agent
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张运东
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Jiangxi Province Hangyu New Material Co ltd
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Jiangxi Province Hangyu New Material Co ltd
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Priority to CN202010240622.7A priority Critical patent/CN111531985A/en
Publication of CN111531985A publication Critical patent/CN111531985A/en
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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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/04—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • 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
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a high-heat-resistance FR-4 material which is prepared from an adhesive, glass fiber cloth and a copper foil, wherein the adhesive comprises the following components in percentage by weight: dicyandiamide 0.002-0.05%, high bromine resin 6-25%, inorganic filler 10-50%, isocyanic acid modified brominated epoxy resin 4-20%, high bromine resin curing agent 1-5%, phenolic resin curing agent 10-45%, epoxy resin curing accelerator 0.007-0.03%, and the balance of organic solvent. The high-heat-resistance FR-4 material prepared by the invention has higher glass transition temperature (Tg ≧ 190 ℃), has excellent heat resistance, low water absorption and good peeling strength, and can be suitable for halogen-free and environment-friendly lead-free processes and processing and manufacturing of multilayer boards (PCBs). The raw materials adopted by the invention are common and easily-obtained raw materials, the process is simple, and the cost is lower.

Description

High-heat-resistance FR-4 material and preparation method thereof
Technical Field
The invention relates to the field of copper-clad plates, in particular to a high-heat-resistance FR-4 material and a preparation method thereof.
Background
With the high density and high performance of the PCB, the HDI/BUM board, the embedded component multilayer board, the high-density multilayer board, and the like are rapidly developed, and the number of layers, thickness, and area of the PCB are increased, and when the high-temperature soldering is performed, particularly the lead-free soldering is performed, in order to ensure the reliability of the soldering, the high-temperature soldering temperature or the longer soldering time is required to be endured, so that higher requirements are made on the substrate material, and compared with the conventional material, the board material has higher glass transition temperature and heat resistance. Beginning at 7/1 in 2006, the official implementation of two directives (directive on the restriction of the use of hazardous substances in electrical and electronic products and directive on the scrapping of electrical and electronic products) in the european union indicates that the global electronics industry will enter the lead-free soldering era. Because the welding temperature is high, the thermal reliability of the copper-clad plate is correspondingly improved, the traditional lead-tin solder can not be reused, and the welding temperature required by the existing tin-silver-copper and other alternative solders is greatly improved. The traditional FR-4 copper-clad plate has low heat resistance, the glass transition temperature is only 130-.
Lead-free products developed in the industry at present mostly have a Tg of 150 ℃ or higher, and such copper clad laminate materials are in a wide variety and are becoming mature, and the materials are used for improving heat resistance.
The curing system adopted in the general formula is phenolic aldehyde curing: although the heat resistance of the material is improved, the material has disadvantages in peel strength and PCB processability, for example, due to the material being too hard and brittle, the drill bit may be worn seriously during the drilling process of PCB processing, the cost of drill bit loss is high, and the cost of PCB processing is increased.
Another design direction is for dicyandiamide curing systems: although the material of the curing system has relatively good toughness and good PCB processability, the material has a great defect in heat resistance, and cannot meet the requirement of PCB processing procedure on the heat resistance of the material, namely, the material cannot be applied to a lead-free procedure.
Therefore, it is imperative to develop a common Tg low-cost material with good heat resistance.
Disclosure of Invention
The invention aims to provide a high-heat-resistance FR-4 material and a preparation method thereof.
In order to achieve the aim, the invention provides a high-heat-resistance FR-4 material which is prepared from an adhesive, glass fiber cloth and copper foil;
the adhesive comprises the following components in percentage by weight:
dicyandiamide 0.002-0.05%, high bromine resin 6-25%, inorganic filler 10-50%, isocyanic acid modified brominated epoxy resin 4-20%, high bromine resin curing agent 1-5%, phenolic resin curing agent 10-45%, epoxy resin curing accelerator 0.007-0.03%, and the balance of organic solvent.
The invention provides a preparation method of a high-heat-resistance FR-4 material, which comprises the following specific steps:
s1, adhesive preparation:
(1) adding part of organic solvent, dicyandiamide and high-bromine resin into a stirring tank according to the formula amount, starting a stirrer, rotating at 500-1000 rpm, continuously stirring for 1.5-2.5 hours to ensure that all solids in the tank are completely dissolved, and simultaneously controlling the temperature of the tank body to be 20-45 ℃; then adding an inorganic filler, and continuously stirring for 80-120 minutes after the inorganic filler is added;
(2) adding isocyanic acid modified brominated epoxy resin, a high-bromine resin curing agent and a phenolic resin curing agent into a stirring tank in a formula ratio in sequence, stirring at a rotating speed of 900-1400 rpm in the feeding process, starting efficient shearing and emulsifying for 1-3 hours after the addition is finished, and simultaneously performing cooling water circulation to keep the temperature of the tank body controlled at 20-45 ℃;
(3) weighing the epoxy resin curing accelerator according to the formula amount, adding the epoxy resin curing accelerator into the rest organic solvent, adding the solution into a stirring tank after the epoxy resin curing accelerator is completely dissolved, and continuously stirring for 4-12 hours at 1000-1500 rpm to obtain the adhesive for later use;
s2, prepreg preparation:
(1) circulating the adhesive to a gluing machine, and uniformly coating the adhesive on glass fiber cloth through pre-dipping and main dipping;
(2) baking the glass fiber cloth coated with the adhesive in a drying oven at 110-250 ℃ to volatilize the solvent, and carrying out primary reaction and solidification on the adhesive to obtain a prepreg; wherein the linear speed of gluing is controlled to be 5-25 m/min;
s3, copper-clad plate preparation:
and cutting the prepreg into a group of 1-18 pieces with the same size, overlapping the prepreg with the copper foil, and pressing to obtain the copper-clad laminated paper.
Wherein the parameters of the pressing are controlled as follows:
a. pressure: 100-550 psi;
b. temperature of the hot plate: 80-200 ℃;
c. vacuum degree: 0.030-0.080 Mpa;
d. pressing time: 140-180 minutes;
e. curing time: keeping the temperature of more than 190 ℃ for 40-100 minutes.
The invention has the beneficial effects that:
the high-heat-resistance FR-4 material prepared by the invention has higher glass transition temperature (Tg is more than or equal to 190 ℃), has excellent heat resistance, low water absorption and good peeling strength, and can be suitable for halogen-free and environment-friendly lead-free manufacturing procedures and processing and manufacturing of multilayer boards (PCBs). The raw materials adopted by the invention are common and easily-obtained raw materials, the process is simple, and the cost is lower.
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further described in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention.
Example 1
The high-heat-resistance FR-4 material is prepared from an adhesive, glass fiber cloth and copper foil, wherein the adhesive comprises the following components in percentage by weight:
dicyandiamide 0.05%, high bromine resin 8%, inorganic filler 45%, isocyanic acid modified brominated epoxy resin 10%, high bromine resin curing agent 5%, phenolic resin curing agent 20%, epoxy resin curing accelerator 0.03%, and the balance of organic solvent.
A preparation method of a high heat resistance FR-4 material comprises the following specific steps:
s1, adhesive preparation:
(1) adding part of organic solvent, dicyandiamide and high-bromine resin into a stirring tank according to the formula amount, starting a stirrer, rotating at 1000 rpm, continuously stirring for 1.5 hours to ensure that all solids in the tank are completely dissolved, and simultaneously controlling the temperature of the tank body to be 20 ℃; then adding inorganic filler, and continuously stirring for 120 minutes after the addition is finished;
(2) adding isocyanic acid modified brominated epoxy resin, a high-bromine resin curing agent and a phenolic resin curing agent into a stirring tank in a formula ratio in sequence, stirring at a rotating speed of 1000 revolutions per minute in the feeding process, starting efficient shearing and emulsifying for 2.5 hours after the addition is finished, and simultaneously performing cooling water circulation to keep the temperature of the tank body controlled at 30 ℃;
(3) weighing the epoxy resin curing accelerator according to the formula amount, adding the epoxy resin curing accelerator into the rest organic solvent, adding the solution into a stirring tank after the epoxy resin curing accelerator is completely dissolved, and continuously stirring for 6 hours at 1500 rpm to obtain the adhesive for later use;
s2, prepreg preparation:
(1) circulating the adhesive to a gluing machine, and uniformly coating the adhesive on glass fiber cloth through pre-dipping and main dipping;
(2) baking the glass fiber cloth coated with the adhesive in a drying oven at 200 ℃ to volatilize the solvent, and carrying out primary reaction and solidification on the adhesive to obtain a prepreg; wherein the linear speed of gluing is controlled to be 5 m/min;
s3, copper-clad plate preparation:
and cutting the prepreg into a group of 1-18 pieces with the same size, overlapping the prepreg with the copper foil, and pressing to obtain the copper-clad laminated paper.
Wherein the parameters of the pressing are controlled as follows:
a. pressure: 550 psi;
b. temperature of the hot plate: 80 ℃;
c. vacuum degree: 0.080 Mpa;
d. pressing time: 180 minutes;
e. curing time: held at 195 ℃ for 100 minutes.
Example 2
The high-heat-resistance FR-4 material is prepared from an adhesive, glass fiber cloth and copper foil, wherein the adhesive comprises the following components in percentage by weight:
dicyandiamide 0.03%, high bromine resin 15%, inorganic filler 50%, isocyanic acid modified brominated epoxy resin 5%, high bromine resin curing agent 1%, phenolic resin curing agent 10%, epoxy resin curing accelerator 0.03%, and the balance of organic solvent.
A preparation method of a high heat resistance FR-4 material comprises the following specific steps:
s1, adhesive preparation:
(1) adding part of organic solvent, dicyandiamide and high-bromine resin into a stirring tank according to the formula amount, starting a stirrer, rotating at 750 revolutions per minute, continuously stirring for 2 hours to ensure that all solids in the tank are completely dissolved, and simultaneously controlling the temperature of the tank body to be 35 ℃; then adding inorganic filler, and continuously stirring for 100 minutes after the addition is finished;
(2) adding isocyanic acid modified brominated epoxy resin, a high-bromine resin curing agent and a phenolic resin curing agent into a stirring tank in a formula ratio in turn, stirring at a rotating speed of 1200 revolutions per minute in the feeding process, starting efficient shearing and emulsifying for 2 hours after the addition is finished, and simultaneously performing cooling water circulation to keep the temperature of the tank body controlled at 35 ℃;
(3) weighing the epoxy resin curing accelerator according to the formula amount, adding the epoxy resin curing accelerator into the rest organic solvent, adding the solution into a stirring tank after the epoxy resin curing accelerator is completely dissolved, and continuously stirring at 1300 rpm for 6 hours to obtain the adhesive for later use;
s2, prepreg preparation:
(1) circulating the adhesive to a gluing machine, and uniformly coating the adhesive on glass fiber cloth through pre-dipping and main dipping;
(2) baking the glass fiber cloth coated with the adhesive in a drying oven at 250 ℃ to volatilize the solvent, and carrying out primary reaction and solidification on the adhesive to obtain a prepreg; wherein the linear speed of gluing is controlled to be 15 m/min;
s3, copper-clad plate preparation:
and cutting the prepreg into a group of 1-18 pieces with the same size, overlapping the prepreg with the copper foil, and pressing to obtain the copper-clad laminated paper.
Wherein the parameters of the pressing are controlled as follows:
a. pressure: 300 psi;
b. temperature of the hot plate: 150 ℃;
c. vacuum degree: 0.05 Mpa;
d. pressing time: 140 minutes;
e. curing time: the temperature was maintained at 200 ℃ for 40 minutes.
Example 3
The high-heat-resistance FR-4 material is prepared from an adhesive, glass fiber cloth and copper foil, wherein the adhesive comprises the following components in percentage by weight:
dicyandiamide 0.002%, high bromine resin 25%, inorganic filler 35%, isocyanic acid modified brominated epoxy resin 14%, high bromine resin curing agent 3%, phenolic resin curing agent 30%, epoxy resin curing accelerator 0.007% and the balance of organic solvent.
A preparation method of a high heat resistance FR-4 material comprises the following specific steps:
s1, adhesive preparation:
(1) adding part of organic solvent, dicyandiamide and high-bromine resin into a stirring tank according to the formula amount, starting a stirrer, rotating at 500 rpm, continuously stirring for 1.5 hours to ensure that all solids in the tank are completely dissolved, and simultaneously controlling the temperature of the tank body to be 20 ℃; then adding inorganic filler, and continuously stirring for 80 minutes after the addition is finished;
(2) adding isocyanic acid modified brominated epoxy resin, a high-bromine resin curing agent and a phenolic resin curing agent into a stirring tank in a formula ratio in sequence, stirring at a rotation speed of 900 revolutions per minute in the feeding process, starting efficient shearing and emulsifying for 3 hours after the addition is finished, and simultaneously performing cooling water circulation to keep the temperature of the tank body controlled at 20 ℃;
(3) weighing the epoxy resin curing accelerator according to the formula amount, adding the epoxy resin curing accelerator into the rest organic solvent, adding the solution into a stirring tank after the epoxy resin curing accelerator is completely dissolved, and continuously stirring for 4 hours at 1500 rpm to obtain the adhesive for later use;
s2, prepreg preparation:
(1) circulating the adhesive to a gluing machine, and uniformly coating the adhesive on glass fiber cloth through pre-dipping and main dipping;
(2) baking the glass fiber cloth coated with the adhesive in a drying oven at 110 ℃ to volatilize the solvent, and carrying out primary reaction and solidification on the adhesive to obtain a prepreg; wherein the linear speed of gluing is controlled to be 25 m/min;
s3, copper-clad plate preparation:
and cutting the prepreg into a group of 1-18 pieces with the same size, overlapping the prepreg with the copper foil, and pressing to obtain the copper-clad laminated paper.
Wherein the parameters of the pressing are controlled as follows:
a. pressure: 100 psi;
b. temperature of the hot plate: 80 ℃;
c. vacuum degree: 0.030 MPa;
d. pressing time: 140 minutes;
e. curing time: 198 ℃ for 100 minutes.
The properties of the highly heat-resistant FR-4 materials of examples 1-4 were measured by the following method (see IPC-TM-650). The results are shown in Table 1.
(1) Glass transition temperature (Tg), detection method: differential Scanning Calorimetry (DSC) is used to refer to the temperature (. degree. C.) at which the sheet changes from a glassy state to a highly elastic (rubbery) state when heated.
(2) Thermal stratification time (T-288): the T-288 thermal delamination time is the time that the sheet material is delaminated due to the action of heat at a set temperature of 288 ℃, and the time is kept before.
The detection method comprises the following steps: thermomechanical analysis (TMA) was used.
(3) Peel strength: the test was carried out according to the IPC-TM-650-2.4.8C method.
(4) Solder heat resistance
Solder heat resistance refers to the duration of time during which the sheet is immersed in molten solder at 288 ℃ without delamination and blistering.
The detection method comprises the following steps: cutting the etched substrate into 5.0cm × 5.0cm, sequentially polishing the edges of the substrate with 120-mesh and 800-mesh abrasive paper, cooking for a certain time with a pressure cooker, putting into a tin melting furnace at 288 ℃, and observing whether layering occurs or not.
Water absorption: the test was carried out according to the IPC-TM-650-2.6.2.1 method.
Table 1 results of performance testing of examples
Item Example 1 Example 2 Example 3
Glass transition temperature (Tg) of DEG C 193 190 192
Copper foil peel Strength (1oz), lb/in 9.2 9.0 9.0
T-288(TMA),min ＞60 ＞60 ＞60
Soldering tin heat resistance (288 ℃ tin immersion) for min ＞10 ＞10 ＞10
Water absorption percentage% 0.09 0.11 0.09
Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, rather than limitations, and that many variations and modifications of the invention are possible to those skilled in the art, without departing from the spirit and scope of the invention.

Claims (7)

1. The FR-4 material with high heat resistance is characterized in that the material is prepared from an adhesive, glass fiber cloth and copper foil;
the adhesive comprises the following components in percentage by weight:
dicyandiamide 0.002-0.05%, high bromine resin 6-25%, inorganic filler 10-50%, isocyanic acid modified brominated epoxy resin 4-20%, high bromine resin curing agent 1-5%, phenolic resin curing agent 10-45%, epoxy resin curing accelerator 0.007-0.03%, and the balance of organic solvent.
2. The method for preparing a high heat resistant FR-4 material of claim 1, comprising the steps of:
s1, adhesive preparation:
(1) adding part of organic solvent, dicyandiamide and high-bromine resin into a stirring tank according to the formula amount, starting a stirrer, continuously stirring until all solids in the tank are completely dissolved, and simultaneously controlling the temperature of the tank body to be 20-45 ℃; then adding an inorganic filler, and continuously stirring for 80-120 minutes after the inorganic filler is added;
(2) adding isocyanic acid modified brominated epoxy resin, a high-bromine resin curing agent and a phenolic resin curing agent into a stirring tank in a formula ratio in sequence, stirring at a rotating speed of 900-1400 rpm in the feeding process, starting efficient shearing and emulsification after the addition is finished, and simultaneously performing cooling water circulation to keep and control the temperature of the tank body at 20-45 ℃;
(3) weighing the epoxy resin curing accelerator according to the formula ratio, adding the epoxy resin curing accelerator into the rest organic solvent, adding the solution into a stirring tank after the epoxy resin curing accelerator is completely dissolved, and continuously stirring to obtain the adhesive for later use;
s2, prepreg preparation:
(1) circulating the adhesive to a gluing machine, and uniformly coating the adhesive on glass fiber cloth through pre-dipping and main dipping;
(2) baking the glass fiber cloth coated with the adhesive in a drying oven at 110-250 ℃ to volatilize the solvent, and carrying out primary reaction and solidification on the adhesive to obtain a prepreg;
s3, copper-clad plate preparation:
and cutting the prepreg into a group of 1-18 pieces with the same size, overlapping the prepreg with the copper foil, and pressing to obtain the copper-clad laminated paper.
3. The method for preparing a high heat resistant FR-4 material according to claim 2, wherein in step S1, the stirring duration in step (1) is 1.5-2.5 hours, and the stirring speed is 500-1000 rpm.
4. The method for preparing a high heat resistant FR-4 material according to claim 2, wherein the time for the high efficiency shearing and emulsifying of step (2) in step S1 is 1-3 hours.
5. The method for preparing a highly heat-resistant FR-4 material according to claim 2, wherein in step S1, the stirring duration in step (3) is 4-12 hours, and the stirring speed is 1000-1500 rpm.
6. The method for preparing a high heat resistant FR-4 material according to claim 2, wherein the sizing linear speed in step S2 is controlled to be 5-25 m/min.
7. The method for preparing a high heat resistant FR-4 material according to claim 2, wherein the parameters of the pressing in step S3 are controlled as follows:
a. pressure: 100-550 psi;
b. temperature of the hot plate: 80-200 ℃;
c. vacuum degree: 0.030-0.080 Mpa;
d. pressing time: 140-180 minutes;
e. curing time: keeping the temperature of more than 190 ℃ for 40-100 minutes.
CN202010240622.7A 2020-03-31 2020-03-31 High-heat-resistance FR-4 material and preparation method thereof Withdrawn CN111531985A (en)

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Application publication date: 20200814