CN112063113A - Glue solution for copper-clad plate applied to HDI (high Density interconnect) multilayer plate and preparation method and application thereof - Google Patents

Glue solution for copper-clad plate applied to HDI (high Density interconnect) multilayer plate and preparation method and application thereof Download PDF

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CN112063113A
CN112063113A CN202010983664.XA CN202010983664A CN112063113A CN 112063113 A CN112063113 A CN 112063113A CN 202010983664 A CN202010983664 A CN 202010983664A CN 112063113 A CN112063113 A CN 112063113A
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parts
copper
epoxy resin
glue solution
hdi
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Inventor
李广元
李永平
钟英雄
谢长乐
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Linzhou Zhiyuan Electronic Technology Co ltd
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Linzhou Zhiyuan Electronic Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
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    • 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
    • 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
    • H05K1/0296—Conductive pattern lay-out details not covered by sub groups H05K1/02 - H05K1/0295
    • H05K1/0298—Multilayer circuits
    • 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
    • H05K3/46—Manufacturing multilayer circuits
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • 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
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2461/04, C08J2461/18, and C08J2461/20
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    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract

The invention provides a glue solution for a copper-clad plate applied to an HDI (high Density interconnect) multilayer plate and a preparation method and application thereof. The glue solution for the copper-clad plate applied to the HDI multilayer plate comprises the following components in parts by weight: 15-35 parts of DOPO epoxy resin, 20-50 parts of DCPD epoxy resin, 2-10 parts of polyacrylate modified novolac epoxy resin, 20-50 parts of phenolic resin, 10-40 parts of diaminodiphenyl ether type benzoxazine resin, 0.01-0.05 part of curing accelerator, 5-12 parts of flame retardant, 25-65 parts of inorganic filler, 0.1-0.3 part of interface bonding agent and 30-70 parts of solvent. The copper-clad plate prepared by the glue solution for the copper-clad plate can be well applied to an HDI (high density interconnect) multilayer plate, has high toughness, reduces microcracking when the HDI multilayer plate is prepared, and simultaneously reduces hygroscopicity; in addition, the dielectric constant and the dielectric loss of the substrate are low, and the market requirements of high transmission and low loss can be met.

Description

Glue solution for copper-clad plate applied to HDI (high Density interconnect) multilayer plate and preparation method and application thereof
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a glue solution for a copper-clad plate applied to an HDI (high Density interconnection) multilayer plate and a preparation method and application thereof.
Background
Electronic products are continuously developing to high density and high precision, so called "high", which is to reduce the volume of the machine in addition to improving the performance of the machine. High Density Integration (HDI) technology can allow for more miniaturization of end product designs while meeting higher standards for electronic performance and efficiency. At present, many popular electronic products, such as mobile phones, digital (video) cameras, notebook computers, automotive electronics, and the like, use HDI boards; with the updating of electronic products and the demand of markets, the development of HDI boards will be very rapid.
An HDI board (High Density interconnect), i.e., a High Density interconnect board, is a circuit board with a relatively High line distribution Density using a micro-blind via-burying technique. The HDI board is provided with an inner layer circuit and an outer layer circuit, and the inside of each layer of circuit is connected by utilizing the processes of drilling, in-hole metallization and the like. The HDI board is generally manufactured by a lamination method, and the more times of lamination, the higher the technical grade of the board. The common HDI board is basically laminated for 1 time, the high-order HDI board adopts the lamination technology for 2 times or more, the highest HDI board has 6 times and 7 times of pressing, and advanced PCB technologies such as hole stacking, electroplating hole filling, laser direct punching and the like are adopted.
The HDI board is generally required to be a halogen-free medium Tg material, the conventional material has the problems of poor dimensional stability, line layer deviation caused by unstable expansion and contraction of an inner layer board after multiple times of pressing, high water absorption, insufficient heat resistance, poor laser processing performance, incomplete burning in a hole, resin residue and the like.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a glue solution for a copper-clad plate applied to an HDI (high density interconnect) multilayer plate, and a preparation method and application thereof.
The invention provides a glue solution for a copper-clad plate applied to an HDI (high Density interconnect) multilayer plate, which comprises the following components in parts by weight: 15-35 parts of DOPO epoxy resin, 20-50 parts of DCPD epoxy resin, 2-10 parts of polyacrylate modified novolac epoxy resin, 20-50 parts of phenolic resin, 10-40 parts of diaminodiphenyl ether type benzoxazine resin, 0.01-0.05 part of curing accelerator, 5-12 parts of flame retardant, 25-65 parts of inorganic filler, 0.1-0.3 part of interface bonding agent and 30-70 parts of solvent.
The invention does not strictly limit the auxiliary agent or additive used; for example, the curing accelerator may be 2-phenylimidazole; the flame retardant may be a phosphazene flame retardant; the interface bonding agent may be a silane coupling agent; the solvent may be propylene glycol methyl ether; the inorganic filler may include 20-55 parts of fine silica powder and 5-10 parts of aluminum hydroxide.
In the invention, the polyacrylate modified novolac epoxy resin is obtained by reacting novolac epoxy resin with polyacrylate in the presence of a catalyst.
Preferably, the glue solution for the copper-clad plate applied to the HDI multilayer plate comprises the following components in parts by weight: 25-35 parts of DOPO epoxy resin, 20-40 parts of DCPD epoxy resin, 2-6 parts of acrylate modified phenolic epoxy resin, 20-32 parts of phenolic resin, 15-35 parts of diaminodiphenyl ether type benzoxazine resin, 0.01-0.05 part of 2-phenylimidazole, 5-10 parts of phosphazene flame retardant, 20-30 parts of silica powder, 5-10 parts of aluminum hydroxide, 0.1-0.3 part of silane coupling agent and 30-50 parts of propylene glycol methyl ether.
The invention also provides a preparation method of the glue solution for the copper-clad plate, which comprises the following steps:
A) mixing a solvent and an interface bonding agent according to parts by weight, and stirring to obtain a first mixture;
B) adding inorganic filler into the first mixture according to the parts by weight, and stirring to obtain a second mixture;
C) adding DOPO epoxy resin, DCPD epoxy resin, polyacrylate modified novolac epoxy resin, phenolic resin, diaminodiphenyl ether type benzoxazine resin, curing accelerator and flame retardant into the second mixture according to the parts by weight, and stirring to obtain a glue solution.
Specifically, in the step A), the stirring speed is controlled to be 800-; in the step B), the stirring speed is controlled to be 1500-; in step C), the stirring comprises: stirring at 1800-.
In the present invention, the preparation method of the polyacrylate modified novolac epoxy resin may include: under the protection atmosphere, the novolac epoxy resin and the polyacrylate react in the presence of a catalyst.
Wherein, the catalyst can be selected from at least one of tetrabutylammonium chloride, tetramethylammonium chloride, tri-n-butylamine and triisopropylamine, and is preferably tetramethylammonium chloride. In addition, the mass ratio between the novolac epoxy resin, the polyacrylate and the catalyst may be 100: (15-25): (0.01-0.1); further, the reaction temperature can be 180-185 ℃, and the reaction time can be 4-6 h.
The invention also provides an application of the glue solution for the copper-clad plate in preparing the copper-clad plate applied to the HDI multi-layer plate.
The invention also provides a preparation method of the copper-clad plate applied to the HDI multilayer plate, which comprises the following steps:
soaking the electronic glass cloth in the glue solution for the copper-clad plate, and baking to obtain a prepreg;
and (3) overlapping the prepreg and the copper foil, and then carrying out hot pressing to obtain the copper-clad plate applied to the HDI multi-layer plate.
Specifically, when the prepreg is prepared, the glue content can be controlled to be 40-50%, the fluidity can be controlled to be 15-50%, and the gelling time can be controlled to be 120-180 s.
The invention also provides a copper-clad plate applied to the HDI multilayer plate, and the copper-clad plate is prepared according to the preparation method.
The invention also provides an application of the copper-clad plate applied to the HDI multilayer plate in preparation of the HDI multilayer plate.
The implementation of the invention has at least the following advantages:
1. the DCPD epoxy resin and the diaminodiphenyl ether type benzoxazine resin are introduced, so that the dielectric constant and the dielectric loss of the substrate are reduced, and the transmission speed and the integrity of signals are improved;
2. according to the invention, the polyacrylate modified novolac epoxy resin is introduced, so that the toughness of the substrate is improved, the Tg is not reduced, the microcrack in the preparation of the HDI substrate is reduced, the hygroscopicity is reduced, and the characteristics such as electrical insulation and mechanical strength are improved;
3. the copper-clad plate disclosed by the invention is a halogen-free product with Tg of more than 150 ℃, is suitable for an HDI (high Density interconnection) lead-free manufacturing procedure of a PCB (printed Circuit Board), meets the requirements of a terminal product on high transmission, low loss and the like of materials, and can be well applied to HDI multilayer plates.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of polyacrylate modified novolac epoxy resin
Adding 100 parts of novolac epoxy resin and 20 parts of polyacrylate into a four-neck flask with a stirrer and a thermometer, introducing nitrogen, adding 0.05g of tetramethylammonium chloride catalyst at 135 ℃, slowly heating to 180 ℃, and carrying out heat preservation reaction for 5 hours to obtain yellow polyacrylate modified novolac epoxy resin.
Secondly, preparing glue solution
The glue solution for the copper-clad plate comprises the following components in parts by weight:
Figure BDA0002688375620000051
the preparation steps of the glue solution are as follows:
cleaning a glue mixing tank by using acetone, adding solvents of propylene glycol methyl ether and a silane coupling agent according to parts by weight, starting stirring, and stirring at the rotating speed of 800r/min for 1.5 hours; then adding the silicon micropowder and the aluminum hydroxide according to the weight part, stirring at a high speed of 1500r/min for 2h, and simultaneously introducing cooling water to keep the temperature in the tank at about 30 ℃.
And adding the rest raw materials in parts by weight, stirring at a high speed of 1800r/min for 4h, stirring at a rotating speed of 600r/min for 2h, and testing the gel time of the glue to be qualified to obtain the glue solution.
Thirdly, preparing a prepreg
The prepared glue solution is injected into a stainless steel gluing basin, the electronic glass cloth is soaked by the glue solution and then enters a vertical gluing machine for baking, and a prepreg is prepared; wherein the content of the rubber is controlled to be 45 percent, the fluidity is controlled to be 30 percent, the gelling time is 150s, and the volatile matter is less than 0.5 percent.
Fourthly, preparing the medium-loss halogen-free copper-clad plate
Cutting 8 prepregs into a certain size, covering a copper foil on each prepreg to form a combined stack, putting the stack into a hot press, and pressing for 3 hours under the conditions that the temperature is 210 ℃ and the pressure is 400psi to obtain the copper-clad plate.
The copper-clad plate is detected by adopting the following method:
glass transition temperature (Tg): according to Differential Scanning Calorimetry (DSC)
Measured by the DSC method defined by IPC-TM-6502.4.25;
thermal stratification time T-288: measured according to the IPC-TM-6502.4.24.1 method;
thermal cracking temperature (Td): measured according to the method specified in IPC-TM-6502.4.25.6;
flame retardancy: measured according to the UL 94 vertical burning method;
PCT + wicking: and (3) steaming the PCT for 3h, and then placing the PCT into a tin furnace at 288 ℃ to test whether the substrate has white spots, delamination and blistering.
Example 2
Preparation of polyacrylate modified novolac epoxy resin
Adding 100 parts of novolac epoxy resin and 15 parts of polyacrylate into a four-neck flask with a stirrer and a thermometer, introducing nitrogen, adding 0.01g of tetrabutylammonium chloride serving as a catalyst at 135 ℃, slowly heating to 185 ℃, and carrying out heat preservation reaction for 6 hours to obtain yellow polyacrylate modified novolac epoxy resin.
Secondly, preparing glue solution
The glue solution for the copper-clad plate comprises the following components in parts by weight:
Figure BDA0002688375620000061
Figure BDA0002688375620000071
the preparation steps of the glue solution are as follows:
cleaning a glue mixing tank by using acetone, adding solvents of propylene glycol methyl ether and a silane coupling agent according to parts by weight, starting stirring, and stirring at the rotating speed of 1200r/min for 0.5 h; then adding the silicon micropowder and the aluminum hydroxide according to the weight part, stirring at a high speed of 2000r/min for 1h, and simultaneously introducing cooling water to keep the temperature in the tank at about 40 ℃.
And adding the rest raw materials in parts by weight, stirring at a high speed of 2000r/min for 3h, stirring at a speed of 500r/min for 2.5h, and testing the gel time of the glue to be qualified to obtain the glue solution.
Thirdly, preparing a prepreg
The prepared glue solution is injected into a stainless steel gluing basin, the electronic glass cloth is soaked by the glue solution and then enters a vertical gluing machine for baking, and a prepreg is prepared; wherein, the content of the glue is controlled to be 40 percent, the fluidity is controlled to be 35 percent, the gelling time is 120s, and the volatile matter is less than 0.5 percent.
Fourthly, preparing the medium-loss halogen-free copper-clad plate
Cutting 8 prepregs into a certain size, covering a copper foil on each prepreg to form a combined stack, putting the stack into a hot press, and pressing for 3 hours under the conditions that the temperature is 210 ℃ and the pressure is 400psi to obtain the copper-clad plate.
The copper-clad plate is detected by the method of the embodiment 1, and the result is shown in the table 1.
Example 3
Preparation of polyacrylate modified novolac epoxy resin
Adding 100 parts of novolac epoxy resin and 18 parts of polyacrylate into a four-neck flask with a stirrer and a thermometer, introducing nitrogen, adding 0.03g of catalyst triisopropylamine at 135 ℃, slowly heating to 185 ℃, and reacting for 4 hours under the condition of heat preservation to obtain yellow polyacrylate modified novolac epoxy resin.
Secondly, preparing glue solution
The glue solution for the copper-clad plate comprises the following components in parts by weight:
Figure BDA0002688375620000081
the preparation steps of the glue solution are as follows:
cleaning a glue mixing tank by using acetone, adding solvents of propylene glycol methyl ether and a silane coupling agent according to parts by weight, starting stirring, and stirring for 1h at the rotating speed of 1000 r/min; then, adding the silicon micropowder and the aluminum hydroxide according to the weight part, stirring at a high speed of 2000r/min for 1h, and simultaneously introducing cooling water to keep the temperature in the tank at about 20 ℃.
And adding the rest raw materials in parts by weight, stirring at a high speed of 2200r/min for 2h, stirring at a speed of 700r/min for 2h, and testing the gelling time of the glue to be qualified to obtain the glue solution.
Thirdly, preparing a prepreg
The prepared glue solution is injected into a stainless steel gluing basin, the electronic glass cloth is soaked by the glue solution and then enters a vertical gluing machine for baking, and a prepreg is prepared; wherein the content of the rubber is controlled to be 50%, the fluidity is 40%, the gelling time is 180s, and the volatile matter is less than 0.5%.
Fourthly, preparing the medium-loss halogen-free copper-clad plate
Cutting 8 prepregs into a certain size, covering a copper foil on each prepreg to form a combined stack, putting the stack into a hot press, and pressing for 3 hours under the conditions that the temperature is 210 ℃ and the pressure is 400psi to obtain the copper-clad plate.
The copper-clad plate is detected by the method of the embodiment 1, and the result is shown in the table 1.
Example 4
Preparation of polyacrylate modified novolac epoxy resin
Adding 100 parts of novolac epoxy resin and 25 parts of polyacrylate into a four-neck flask with a stirrer and a thermometer, introducing nitrogen, adding 0.1g of tetramethylammonium chloride catalyst at 135 ℃, slowly heating to 180 ℃, and carrying out heat preservation reaction for 5 hours to obtain yellow polyacrylate modified novolac epoxy resin.
Secondly, preparing glue solution
The glue solution for the copper-clad plate comprises the following components in parts by weight:
Figure BDA0002688375620000091
the preparation steps of the glue solution are as follows:
cleaning a glue mixing tank by using acetone, adding solvents of propylene glycol methyl ether and a silane coupling agent according to parts by weight, starting stirring, and stirring for 1h at the rotating speed of 1000 r/min; then, adding the silicon micropowder and the aluminum hydroxide according to the weight part, stirring at a high speed of 1800r/min for 1.5h, and simultaneously introducing cooling water to keep the temperature in the tank at about 30 ℃.
And adding the rest raw materials in parts by weight, stirring at a high speed of 2000r/min for 3h, stirring at a speed of 800r/min for 1.5h, and testing the gel time of the glue to be qualified to obtain the glue solution.
Thirdly, preparing a prepreg
The prepared glue solution is injected into a stainless steel gluing basin, the electronic glass cloth is soaked by the glue solution and then enters a vertical gluing machine for baking, and a prepreg is prepared; wherein, the content of the glue is controlled to be 40 percent, the fluidity is controlled to be 38 percent, the gelling time is 160s, and the volatile matter is less than 0.5 percent.
Fourthly, preparing the medium-loss halogen-free copper-clad plate
Cutting 8 prepregs into a certain size, covering a copper foil on each prepreg to form a combined stack, putting the stack into a hot press, and pressing for 3 hours under the conditions that the temperature is 210 ℃ and the pressure is 400psi to obtain the copper-clad plate.
The copper-clad plate is detected by the method of the embodiment 1, and the result is shown in the table 1.
Example 5
Preparation of polyacrylate modified novolac epoxy resin
Adding 100 parts of novolac epoxy resin and 22 parts of polyacrylate into a four-neck flask with a stirrer and a thermometer, introducing nitrogen, adding 0.08g of tetramethylammonium chloride catalyst at 135 ℃, slowly heating to 185 ℃, and carrying out heat preservation reaction for 5 hours to obtain yellow polyacrylate modified novolac epoxy resin.
Secondly, preparing glue solution
The glue solution for the copper-clad plate comprises the following components in parts by weight:
Figure BDA0002688375620000101
Figure BDA0002688375620000111
the preparation steps of the glue solution are as follows:
cleaning a glue mixing tank by using acetone, adding solvents of propylene glycol methyl ether and a silane coupling agent according to parts by weight, starting stirring, and stirring for 1h at the rotating speed of 1200 r/min; then, adding the silicon micropowder and the aluminum hydroxide according to the weight part, stirring at a high speed of 2000r/min for 2h, and simultaneously introducing cooling water to keep the temperature in the tank at about 30 ℃.
And adding the rest raw materials in parts by weight, stirring at a high speed of 2000r/min for 3h, stirring at a rotating speed of 750r/min for 2h, and testing the gel time of the glue to be qualified to obtain the glue solution.
Thirdly, preparing a prepreg
The prepared glue solution is injected into a stainless steel gluing basin, the electronic glass cloth is soaked by the glue solution and then enters a vertical gluing machine for baking, and a prepreg is prepared; wherein the content of the rubber is controlled to be 45 percent, the fluidity is controlled to be 35 percent, the gelling time is 150s, and the volatile matter is less than 0.5 percent.
Fourthly, preparing the medium-loss halogen-free copper-clad plate
Cutting 8 prepregs into a certain size, covering a copper foil on each prepreg to form a combined stack, putting the stack into a hot press, and pressing for 3 hours under the conditions that the temperature is 210 ℃ and the pressure is 400psi to obtain the copper-clad plate.
The copper-clad plate is detected by the method of the embodiment 1, and the result is shown in the table 1.
Comparative example 1
The process is substantially the same as in example 1 except that 55 parts of DOPO epoxy resin and 2 parts of polyacrylate modified novolac epoxy resin are adopted as the epoxy resin system, namely, the DCPD epoxy resin is replaced by the same amount of DOPO epoxy resin.
The copper-clad plate prepared by the method of example 1 was tested, and the results are shown in table 1.
Comparative example 2
The process was substantially the same as in example 1 except that 37 parts of DOPO epoxy resin and 20 parts of DCPD epoxy resin were used as the epoxy resin system, that is, the polyacrylate-modified novolak epoxy resin was replaced with the same amount of DOPO epoxy resin.
The copper-clad plate prepared by the method of example 1 was tested, and the results are shown in table 1.
Comparative example 3
The procedure of example 1 was repeated, except that the curing agent system was 35 parts of a phenol resin, that is, an equivalent amount of a phenol resin was used instead of the diaminodiphenyl ether type benzoxazine resin.
The copper-clad plate prepared by the method of example 1 was tested, and the results are shown in table 1.
Table 1 performance test results of each copper-clad plate
Figure BDA0002688375620000121
Figure BDA0002688375620000131
Table 1 the results show that:
compared with the epoxy resin system and the immobilization system of the comparative example, in the embodiments 1 to 5 of the present invention, by using the composite resin system of the DOPO epoxy resin, the DCPD epoxy resin, and the polyacrylate modified novolac epoxy resin and the composite curing agent system of the diaminodiphenyl ether type benzoxazine resin and the phenolic resin, the dielectric constant and the dielectric loss of the substrate are reduced, the transmission speed and the integrity of the signal are improved, the toughness of the substrate is improved, the Tg is not reduced, the microcracking during the HDI substrate preparation is reduced, the moisture absorption is reduced, and the electrical insulation property, the mechanical strength and other properties are improved.
The copper-clad plate prepared by the invention is a halogen-free product with Tg of more than 150 ℃, is suitable for the HDI lead-free manufacturing procedure of PCB, meets the requirements of high transmission, low loss and the like of the terminal product on the material, and can be well applied to HDI multilayer plates.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. The glue solution for the copper-clad plate applied to the HDI multilayer plate is characterized by comprising the following components in parts by weight: 15-35 parts of DOPO epoxy resin, 20-50 parts of DCPD epoxy resin, 2-10 parts of polyacrylate modified novolac epoxy resin, 20-50 parts of phenolic resin, 10-40 parts of diaminodiphenyl ether type benzoxazine resin, 0.01-0.05 part of curing accelerator, 5-12 parts of flame retardant, 25-65 parts of inorganic filler, 0.1-0.3 part of interface bonding agent and 30-70 parts of solvent.
2. The glue solution for copper-clad plates according to claim 1, wherein the curing accelerator is 2-phenylimidazole; the flame retardant is a phosphazene flame retardant; the interface bonding agent is a silane coupling agent; the solvent is propylene glycol methyl ether.
3. The glue solution for copper-clad plates according to claim 1, wherein the inorganic filler comprises 20-55 parts of silica micropowder and 5-10 parts of aluminum hydroxide.
4. The glue solution for copper-clad plates according to claim 1, wherein the polyacrylate modified novolac epoxy resin is obtained by reacting novolac epoxy resin with polyacrylate in the presence of a catalyst.
5. The preparation method of the glue solution for the copper-clad plate according to any one of claims 1 to 4, which is characterized by comprising the following steps:
A) mixing a solvent and an interface bonding agent according to parts by weight, and stirring to obtain a first mixture;
B) adding inorganic filler into the first mixture according to the parts by weight, and stirring to obtain a second mixture;
C) adding DOPO epoxy resin, DCPD epoxy resin, polyacrylate modified novolac epoxy resin, phenolic resin, diaminodiphenyl ether type benzoxazine resin, curing accelerator and flame retardant into the second mixture according to the parts by weight, and stirring to prepare a glue solution;
preferably, in the step A), the stirring speed is controlled to be 800-; in the step B), the stirring speed is controlled to be 1500-; in step C), the stirring comprises: stirring at 1800-.
6. The method according to claim 5, wherein the method for preparing the polyacrylate-modified novolac epoxy resin comprises:
reacting phenolic epoxy resin with polyacrylate in the presence of a catalyst in a protective atmosphere;
preferably, the catalyst may be selected from at least one of tetrabutylammonium chloride, tetramethylammonium chloride, tri-n-butylamine, and triisopropylamine, more preferably tetramethylammonium chloride;
preferably, the mass ratio of the novolac epoxy resin, the polyacrylate and the catalyst is 100: (15-25): (0.01-0.1);
preferably, the reaction temperature is 170-180 ℃, and the reaction time is 4-6 h.
7. The application of the glue solution of any one of claims 1 to 4 in preparing a copper-clad plate applied to an HDI multilayer plate.
8. The preparation method of the copper-clad plate applied to the HDI multilayer plate is characterized by comprising the following steps of:
soaking electronic glass cloth in the glue solution for the copper-clad plate according to any one of claims 1 to 4, and baking to obtain a prepreg;
laminating the prepreg and the copper foil and then carrying out hot pressing to obtain a copper-clad plate applied to the HDI multi-layer plate;
preferably, when the prepreg is prepared, the gel content is controlled to be 40-50%, the fluidity is controlled to be 15-50%, and the gelling time is controlled to be 120-180 s.
9. A copper-clad plate applied to an HDI multilayer plate, which is characterized by being prepared according to the preparation method of claim 8.
10. The use of the copper clad laminate applied to an HDI multilayer board according to claim 9 in the preparation of an HDI multilayer board.
CN202010983664.XA 2020-09-18 2020-09-18 Glue solution for copper-clad plate applied to HDI (high Density interconnect) multilayer plate and preparation method and application thereof Pending CN112063113A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114953646A (en) * 2022-06-09 2022-08-30 山东金宝电子股份有限公司 Preparation method of copper-clad plate for mini LED backboard and copper-clad plate

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103724936A (en) * 2012-10-10 2014-04-16 慧智科技（中国）有限公司 Low-dielectric halogen-free epoxy resin composite with improved impact resistance property
CN103992622A (en) * 2014-06-10 2014-08-20 广东生益科技股份有限公司 Halogen-free resin composition, prepreg prepared from halogen-free resin composition and laminated board prepared from halogen-free resin composition and used for printed circuit
CN105542394A (en) * 2015-12-23 2016-05-04 陕西生益科技有限公司 Halogen-free resin composition and application thereof
CN105542396A (en) * 2016-01-26 2016-05-04 广东汕头超声电子股份有限公司覆铜板厂 High-modulus epoxy resin composition, preparation method thereof, prepreg and laminated board manufactured from same and preparation method of prepreg and laminated board

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103724936A (en) * 2012-10-10 2014-04-16 慧智科技（中国）有限公司 Low-dielectric halogen-free epoxy resin composite with improved impact resistance property
CN103992622A (en) * 2014-06-10 2014-08-20 广东生益科技股份有限公司 Halogen-free resin composition, prepreg prepared from halogen-free resin composition and laminated board prepared from halogen-free resin composition and used for printed circuit
CN105542394A (en) * 2015-12-23 2016-05-04 陕西生益科技有限公司 Halogen-free resin composition and application thereof
CN105542396A (en) * 2016-01-26 2016-05-04 广东汕头超声电子股份有限公司覆铜板厂 High-modulus epoxy resin composition, preparation method thereof, prepreg and laminated board manufactured from same and preparation method of prepreg and laminated board

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114953646A (en) * 2022-06-09 2022-08-30 山东金宝电子股份有限公司 Preparation method of copper-clad plate for mini LED backboard and copper-clad plate

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