CN114103314A - Preparation method of copper-clad plate with low dielectric loss, high Tg and high heat resistance - Google Patents

Preparation method of copper-clad plate with low dielectric loss, high Tg and high heat resistance Download PDF

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Publication number
CN114103314A
CN114103314A CN202111267822.2A CN202111267822A CN114103314A CN 114103314 A CN114103314 A CN 114103314A CN 202111267822 A CN202111267822 A CN 202111267822A CN 114103314 A CN114103314 A CN 114103314A
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China
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resin
portions
copper
clad plate
preparation
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Inventor
李凌云
秦伟峰
杨永亮
姜大鹏
刘政
姜晓亮
栾好帅
郑宝林
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SHANDONG JINBAO ELECTRONICS CO Ltd
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SHANDONG JINBAO ELECTRONICS CO Ltd
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Priority to CN202111267822.2A priority Critical patent/CN114103314A/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
    • 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
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    • 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
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    • B32B38/00—Ancillary operations in connection with laminating processes
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    • B32—LAYERED PRODUCTS
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    • 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
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • 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
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract

The invention belongs to the technical field of copper-clad plate production, and relates to a preparation method of a low-dielectric-loss, high-Tg and high-heat-resistance copper-clad plate, which comprises the following steps: (1) preparing resin glue solution: according to the weight portion, 20-80 portions of PPE resin, 5-40 portions of PPO modified BT resin, 1-20 portions of crosslinking curing agent, 0.1-1 portion of dispersing agent, 40-100 portions of solvent, 0.1-30 portions of flame retardant and 10-50 portions of filling material are mixed, emulsified and stirred uniformly; (2) preparing a prepreg; (3) and preparing the copper-clad plate with low dielectric loss, high Tg and high heat resistance. The copper-clad plate prepared by the invention has the advantages that the T288 can not be delaminated within 120min, the Tg is as high as 220 ℃, and the Df is less than 0.007, so that the high-frequency high-speed circuit board is suitable for high-level design of a high-frequency high-speed circuit board, and the packaging efficiency and the reliability of a PCB (printed circuit board) are greatly improved.

Description

Preparation method of copper-clad plate with low dielectric loss, high Tg and high heat resistance
Technical Field
The invention belongs to the technical field of copper-clad plate production, and particularly relates to a preparation method of a low-dielectric-loss, high-Tg and high-heat-resistance copper-clad plate.
Background
With the widespread popularization of 5G communication technology, electronic products are changing day by day, faster data transmission speed is required, higher system operation frequency is also required, and meanwhile, lead-free welding requires materials to resist higher temperature, so that higher requirements are provided for printed circuit boards, and high-frequency, high-speed, low-loss and high-Tg copper-clad plates become basic conditions for realizing the requirements. The epoxy phenolic resin system which is generally applied to the copper-clad plate originally has large dielectric loss, so that the application of the epoxy phenolic resin system in the high-frequency high-speed field is limited. Many advanced countries abroad develop various high-performance resin materials such as BT resin, PPE, SMA, PI, PTFE and the like so as to meet the development requirements of electronic communication technology, and the reasonable application of the resins has important significance in the research and development of copper-clad plates.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the copper-clad plate with low dielectric loss, high Tg and high heat resistance, the T288 of the prepared copper-clad plate can not be layered for 120min, the Tg is as high as 220 ℃, and the Df is less than 0.007, so that the preparation method is suitable for the high-rise design of a high-frequency high-speed circuit board, and the packaging efficiency and the reliability of a PCB (printed circuit board) are greatly improved.
The specific technical scheme is as follows:
a preparation method of a copper-clad plate with low dielectric loss, high Tg and high heat resistance comprises the following steps:
(1) preparing resin glue solution: according to the weight portion, 20-80 portions of PPE resin, 5-40 portions of PPO modified BT resin, 1-20 portions of crosslinking curing agent, 0.1-1 portion of dispersing agent, 40-100 portions of solvent, 0.1-30 portions of flame retardant and 10-50 portions of filling material are mixed, emulsified and stirred uniformly;
(2) after the low dielectric electronic grade glass fiber cloth is soaked in the resin prepared in the step (1), the resin is processed by a sizing machine at the temperature of 100-200 ℃ to prepare a prepreg;
(3) stacking a plurality of prepregs prepared in the step (2) together, and covering a copper foil on each of two sides to obtain a plate; the plate and the stainless steel plate are overlapped up and down correspondingly and sent into a vacuum press at the temperature of 100 ℃ and 250 ℃ and the temperature of 70-15 DEG C0kgf/cm2And hot pressing for 150-.
Further, in step (1), the PPE resin is a low molecular weight difunctional acrylic-capped polyphenylene ether oligomer of the formula:
Figure BDA0003327517460000021
wherein m is more than or equal to 20 and less than or equal to 100, and n is more than or equal to 10 and less than or equal to 100.
The beneficial effect of adopting the further scheme is that: the PPE resins described above also have excellent solubility in toluene and butanone and low viscosity, designed for ultra-low dielectric and low water absorption applications.
Further, in the step (1), the PPO-modified BT resin is a B-stage prepolymer of bisphenol a dicyanate (Arocy B-10) and 4, 4' -diaminodiphenylmethane bismaleimide, and the PPO resin is prepared by mixing a mixture of 1: 9, and dissolving in the solvent in advance.
Further, in the step (1), the crosslinking curing agent is one or more of dicyandiamide, 2-methyl-4-ethylimidazole, a silane coupling agent KH-560, dicumyl peroxide and triallyl isocyanurate (TAIC).
Further, in the step (1), the dispersant is a BYK-W903 type wetting dispersant.
Further, in the step (1), the solvent is one or more than two of toluene, acetone, butanone and xylene.
Further, in the step (1), the flame retardant is one or two of decabromodiphenyl ether and decabromodiphenyl ethane, and the bromine content of the flame retardant is 81-83%.
Further, in the step (1), the filling material is one or two of high-purity superfine spherical nano amorphous silicon micro powder and aluminum hydroxide.
Preferably, SiO in the silicon micropowder2The content is up to 99.9%, the average particle size is 3-5 μm, the maximum particle size is not more than 20 μm, and the final addition is carried out.
Further, in the step (2), the gelling time of the prepreg is controlled to be 80-100 seconds.
Further, in the step (3), the number of prepregs can be adjusted according to different thickness requirements, and after the plate and the stainless steel plate are correspondingly overlapped up and down, the heat-resistant felt is firstly paved, and then the plate is sent into a vacuum compressor.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention soaks the E-GLASS GLASS fiber cloth of low dielectric type into the purpose-made resin glue solution, the polyphenyl ether resin (PPE) in the resin glue solution has good performance in the aspects of reducing dielectric loss, improving GLASS transition temperature, increasing toughness, reducing hygroscopicity, and the like, and is very suitable for free radical polymerization reaction with other unsaturated monomers or resins;
(2) the PPO modified BT resin not only retains the original excellent heat resistance and low metal ion migration resistance of the BT resin, but also has good dimensional stability, greatly improves the dielectric property, reduces the dielectric loss and the dielectric constant, and greatly improves the machining performance;
(3) the spherical silicon added into the glue solution has small particle size and good dispersibility, so that the PCB has lower molding shrinkage and good dimensional stability, and the glass fiber cloth used for dipping is also low-dielectric E-glass fiber cloth;
(4) the copper-clad plate prepared by the invention has the advantages that the T288 can not be delaminated within 120min, the Tg is as high as 220 ℃, and the Df is less than 0.007, so that the high-frequency high-speed circuit board is suitable for high-level design of a high-frequency high-speed circuit board, and the packaging efficiency and the reliability of a PCB (printed circuit board) are greatly improved.
Detailed Description
The principles and features of this invention are described in conjunction with the following examples, which are intended to illustrate the invention, but not to limit the scope of the invention, in which the amounts are in parts by weight.
Example 1
A preparation method of a copper-clad plate with low dielectric loss, high Tg and high heat resistance comprises the following steps:
(1) preparing resin glue solution: according to the weight parts, 70 parts of PPE resin (bifunctional acrylic acid end-capped polyphenyl ether oligomer), 20 parts of PPO modified BT resin (a B-stage prepolymer of Arocy B-10 and 4, 4' -dicyanodiphenylmethane bismaleimide and PPO resin are blended in a mass ratio of 1: 9), 10 parts of crosslinking curing agent TAIC, 1 part of dispersant BYK-W903, 100 parts of solvent butanone, 20 parts of flame retardant decabromodiphenylethane and 40 parts of filling material high-purity superfine spherical nano amorphous silicon micro powder are mixed, emulsified and stirred uniformly;
(2) dipping low-dielectric electronic-grade glass fiber cloth into the resin glue solution prepared in the step (1), and controlling the gelling time to be 90 seconds through a gluing machine at 170 ℃ to prepare a prepreg;
(3) taking 6 prepregs obtained in the step (2) to be overlaid together, and covering 18-micrometer copper foils on two sides of each prepreg to obtain a plate; laminating the plate and stainless steel plate, spreading high heat-resistant felt, feeding into vacuum press, heating at 225 deg.C and 120kgf/cm2And hot pressing for 180min under the condition to obtain the copper-clad plate with low dielectric loss and high Tg.
Example 2
A preparation method of a copper-clad plate with low dielectric loss, high Tg and high heat resistance comprises the following steps:
(1) preparing resin glue solution: according to the weight parts, 65 parts of PPE resin (bifunctional acrylic acid end-capped polyphenyl ether oligomer), 25 parts of PPO modified BT resin (a B-stage prepolymer of Arocy B-10 and 4, 4' -dicyanodiphenylmethane bismaleimide and PPO resin are blended in a mass ratio of 1: 9), 10 parts of crosslinking curing agent TAIC, 0.5 part of dispersant BYK-W903, 50 parts of solvent butanone and 50 parts of toluene, 25 parts of flame retardant decabromodiphenyl ether, 20 parts of high-purity superfine spherical nano amorphous silicon micro powder and 15 parts of aluminum hydroxide are mixed, emulsified and stirred uniformly;
(2) dipping low-dielectric electronic-grade glass fiber cloth into the resin glue solution prepared in the step (1), and controlling the gelling time to be 90 seconds through a gluing machine at 180 ℃ to prepare a prepreg;
(3) taking 6 prepregs obtained in the step (2) to be overlaid together, and covering 18-micrometer copper foils on two sides of each prepreg to obtain a plate; laminating the plate and stainless steel plate, spreading high heat-resistant felt, feeding into vacuum press, heating at 225 deg.C and 120kgf/cm2ConditionAnd (5) carrying out hot pressing for 200min to obtain the copper-clad plate with low dielectric loss and high Tg.
Example 3
A preparation method of a copper-clad plate with low dielectric loss, high Tg and high heat resistance comprises the following steps:
(1) preparing resin glue solution: according to parts by weight, 80 parts of PPE resin (bifunctional acrylic acid end-capped polyphenyl ether oligomer), 20 parts of PPO modified BT resin (prepared by blending a B-stage prepolymer of Arocy B-10 and 4, 4' -dicyanodiphenylmethane bismaleimide and PPO resin in a mass ratio of 1: 9), 0.1 part of 2-methyl-4-ethylimidazole, 1 part of silane coupling agent KH-560, 0.5 part of dispersant BYK-W903, 50 parts of butanone and 50 parts of xylene, 25 parts of flame retardant decabromodiphenyl ether and 40 parts of high-purity superfine spherical nano amorphous silicon micro powder serving as a filling material are mixed, emulsified and stirred uniformly;
(2) dipping low-dielectric electronic-grade glass fiber cloth into the resin glue solution prepared in the step (1), and controlling the gelling time to be 90 seconds through a gluing machine at 180 ℃ to prepare a prepreg;
(3) taking 4 prepregs prepared in the step (2) to be overlapped together, and covering 18-micrometer copper foils on two sides of each prepreg to obtain a plate; laminating the plate and stainless steel plate, spreading high heat-resistant felt, feeding into vacuum press, heating at 225 deg.C and 130kgf/cm2And hot pressing for 200min under the condition to obtain the copper-clad plate with low dielectric loss and high Tg.
Comparative example
A preparation method of a copper-clad plate comprises the following steps:
(1) preparing resin glue solution: according to the weight parts, 40 parts of PPE resin (dihydroxy-terminated polyphenyl ether oligomer), 140 parts of dicyclopentadiene epoxy resin, 10 parts of DDS resin, 0.3 part of crosslinking curing agent 2-methyl-4-ethylimidazole, 0.5 part of dispersant BYK-W903, 100 parts of solvent acetone, 20 parts of flame retardant tetrabromobisphenol A and 40 parts of filling material high-purity superfine spherical nano amorphous silicon micro powder are mixed, emulsified and stirred uniformly;
(2) dipping low-dielectric electronic-grade glass fiber cloth into the resin glue solution prepared in the step (1), and controlling the gelling time to be 90 seconds through a gluing machine at 170 ℃ to prepare a prepreg;
(3) taking 6 prepregs obtained in the step (2) to be overlaid together, and covering 18-micrometer copper foils on two sides of each prepreg to obtain a plate; laminating the plate and stainless steel plate, spreading high heat-resistant felt, feeding into vacuum press, heating at 225 deg.C and 120kgf/cm2And hot pressing for 180min under the condition to obtain the copper-clad plate.
Description of the test methods:
1) dielectric loss: split column dielectric resonator measurements, IPC TM-6502.5.5.13;
2) tg: differential scanning calorimetry (DSC method), IPC TM-650;
3) t288 (min): thermomechanical analysis (TMA), IPC TM-650.
The experimental data for the performance tests of the samples obtained in examples 1-3 and comparative example are shown in table 1.
TABLE 1 comparison of the data from the various performance tests of the samples from examples 1-3 and comparative examples
Figure BDA0003327517460000061
As can be seen from Table 1, the copper-clad plate prepared in examples 1-3 has a T288 of 120min without delamination, a Tg of 220 ℃ and a Df of less than 0.007. Compared with a comparative example, the copper-clad plates prepared in examples 1 to 3 have excellent dielectric loss, Tg and T288 test effects, and the copper-clad plates prepared in the invention are proved to have low dielectric loss, high Tg and heat resistance.
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A preparation method of a copper-clad plate with low dielectric loss, high Tg and high heat resistance is characterized by comprising the following steps:
(1) preparing resin glue solution: according to the weight portion, 20-80 portions of PPE resin, 5-40 portions of PPO modified BT resin, 1-20 portions of crosslinking curing agent, 0.1-1 portion of dispersing agent, 40-100 portions of solvent, 0.1-30 portions of flame retardant and 10-50 portions of filling material are mixed, emulsified and stirred uniformly;
(2) after the low dielectric electronic grade glass fiber cloth is soaked in the resin prepared in the step (1), the resin is processed by a sizing machine at the temperature of 100-200 ℃ to prepare a prepreg;
(3) stacking a plurality of prepregs prepared in the step (2) together, and covering a copper foil on each of two sides to obtain a plate; the plate and the stainless steel plate are overlapped up and down correspondingly, and then sent into a vacuum press, and the temperature is controlled at 100 ℃ and 250 ℃ and 70-150kgf/cm2And hot pressing for 150-.
2. The method of claim 1, wherein in step (1), the PPE resin is a low molecular weight difunctional acrylic-capped polyphenylene ether oligomer of the formula:
Figure FDA0003327517450000011
wherein m is more than or equal to 20 and less than or equal to 100, and n is more than or equal to 10 and less than or equal to 100.
3. The method according to claim 1, wherein in the step (1), the PPO-modified BT resin is a B-stage prepolymer of Arocy B-10 and 4, 4' -diaminodiphenylmethane bismaleimide and the PPO resin are mixed in a ratio of 1: 9 by mass ratio.
4. The method according to claim 1, wherein in the step (1), the crosslinking/curing agent is one or more selected from dicyandiamide, 2-methyl-4-ethylimidazole, a silane coupling agent KH-560, dicumyl peroxide, and triallyl isocyanurate.
5. The method according to claim 1, wherein in the step (1), the dispersant is a BYK-W903 type wetting dispersant.
6. The method according to claim 1, wherein in the step (1), the solvent is one or more of toluene, acetone, methyl ethyl ketone, and xylene.
7. The preparation method according to claim 1, wherein in the step (1), the flame retardant is one or two of decabromodiphenyl ether and decabromodiphenyl ethane, and the bromine content is 81-83%.
8. The preparation method according to claim 1, wherein in the step (1), the filling material is one or two of high-purity ultrafine spherical nano amorphous silica micropowder and aluminum hydroxide.
9. The method according to claim 8, wherein SiO is contained in the fine silica powder2The content is 99.9%, the average particle size is 3-5 μm, and the maximum particle size is not more than 20 μm.
10. The manufacturing method according to claim 1, wherein in the step (2), the prepreg gel time is controlled to 80 to 100 seconds.
CN202111267822.2A 2021-10-29 2021-10-29 Preparation method of copper-clad plate with low dielectric loss, high Tg and high heat resistance Pending CN114103314A (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
US4492730A (en) * 1982-03-26 1985-01-08 Showa Denko Kabushiki Kaisha Substrate of printed circuit
US20050042466A1 (en) * 2003-08-20 2005-02-24 Daisuke Ohno Resin composition and prepreg for laminate and metal-clad laminate
WO2015088245A1 (en) * 2013-12-11 2015-06-18 주식회사 두산 Thermosetting resin composition for high frequency having low dielectric loss, prepreg using same, and copper clad laminate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4492730A (en) * 1982-03-26 1985-01-08 Showa Denko Kabushiki Kaisha Substrate of printed circuit
US20050042466A1 (en) * 2003-08-20 2005-02-24 Daisuke Ohno Resin composition and prepreg for laminate and metal-clad laminate
WO2015088245A1 (en) * 2013-12-11 2015-06-18 주식회사 두산 Thermosetting resin composition for high frequency having low dielectric loss, prepreg using same, and copper clad laminate

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Title
刘辉等: "聚苯醚改性双马来酰亚胺三嗪树脂及其复合材料性能研究", 《塑料工业》 *

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