CN111978684A - Glue solution for improving toughness of medium-loss halogen-free copper-clad plate and preparation method and application thereof - Google Patents

Glue solution for improving toughness of medium-loss halogen-free copper-clad plate and preparation method and application thereof Download PDF

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CN111978684A
CN111978684A CN202010983654.6A CN202010983654A CN111978684A CN 111978684 A CN111978684 A CN 111978684A CN 202010983654 A CN202010983654 A CN 202010983654A CN 111978684 A CN111978684 A CN 111978684A
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parts
epoxy resin
glue solution
loss
dimer acid
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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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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
    • 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
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
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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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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Abstract

The invention provides a glue solution for improving toughness of a medium-loss halogen-free copper-clad plate and a preparation method and application thereof. The glue solution comprises the following components in parts by weight: 90-120 parts of DOPO phenolic epoxy resin, 5-10 parts of dimer acid modified phenolic epoxy resin, 30-50 parts of bisphenol A phenolic resin, 20-40 parts of bisphenol F benzoxazine resin, 0.01-0.3 part of 2-methyl-4-ethylimidazole, 60-80 parts of silicon micropowder, 0.02-0.05 part of silane coupling agent and 70-100 parts of solvent. The copper-clad plate manufactured by the glue solution can prevent the occurrence of crack phenomenon, has excellent heat resistance and reliability, reduces the dielectric constant and dielectric loss of the substrate, and can well meet the market demands of high transmission and medium loss of information.

Description

Glue solution for improving toughness of medium-loss halogen-free copper-clad plate and preparation method and application thereof
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to glue solution for improving toughness of a medium-loss halogen-free copper-clad plate and a preparation method and application thereof.
Background
In recent years, rapid development of global information technology towards digitization and networking, ultra-large capacity information transmission, ultra-fast speed and ultra-high density information processing have become targets for the development of information and communication equipment (ICT) technology. At present, the 4G communication function gradually tends to fail to meet the social communication demand, and the 5G technology is mature; the early laying work of the 5G base station is started, and at this time, communication products such as radars, antennas, servers, switches and the like with higher performance are necessarily developed, which bring unprecedented opportunities and challenges to the high-speed copper-clad plate.
From the development process of the whole communication technology, advanced concepts such as high transmission, large capacity, big data, cloud computing and the like are continuously proposed and developed, the performance of hardware products is required to be continuously improved, and especially, the design of a PCB (printed circuit board) is continuously upgraded, such as high layer number, large size, high aspect ratio, high density, lead-free welding, application of high-speed materials and the like, the high-speed copper-clad plate has higher requirements on the overall processing performance, reliability and transmission loss performance.
The current society has entered a highly information-oriented society, and the IT industry has become a strong driving force for social informatization. The coming of the 5G era, the wide application of automatic driving, automobile anti-collision systems, high-speed large-capacity memories, positioning systems, internet of things and the like all require electronic materials, electronic components and the like to have the functions of high-frequency, high-speed and large-capacity storage and signal transmission.
High-frequency high-speed material PCB products are generally in a high-multilayer stacked structure, in order to ensure the low dielectric property of the materials, a plurality of resins, fillers, auxiliaries and the like are usually added into the material formula, the processability of a plate material is poorer than that of common FR4, and the reliability is correspondingly challenged. However, after the conventional high-frequency and high-speed board is subjected to dense hole processing of a PCB, cracks (Crack) and the like are easily generated after thermal shock of 288 ℃, thereby affecting the performance of an end product.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide glue solution for improving the toughness of a medium-loss halogen-free copper-clad plate and a preparation method and application thereof.
The invention provides a glue solution for improving toughness of a medium-loss halogen-free copper-clad plate, which comprises the following components in parts by weight: 90-120 parts of DOPO phenolic epoxy resin, 5-10 parts of dimer acid modified phenolic epoxy resin, 30-50 parts of bisphenol A phenolic resin, 20-40 parts of bisphenol F benzoxazine resin, 0.01-0.3 part of 2-methyl-4-ethylimidazole, 60-80 parts of silicon micropowder, 0.02-0.05 part of silane coupling agent and 70-100 parts of solvent.
Preferably, the glue solution comprises the following components in parts by weight: 100-110 parts of DOPO phenolic epoxy resin, 5-10 parts of dimer acid modified phenolic epoxy resin, 30-35 parts of bisphenol A phenolic resin, 25-40 parts of bisphenol F benzoxazine resin, 0.01-0.1 part of 2-methyl-4-ethylimidazole, 60-70 parts of silicon micropowder, 0.02-0.05 part of silane coupling agent and 70-90 parts of solvent.
In the present invention, the solvent may be selected from at least one of cyclohexanone and butanone; preferably, the solvent comprises 10-20 parts of cyclohexanone and 60-80 parts of butanone.
In the invention, the dimer acid modified novolac epoxy resin is a block structure formed by the reaction of carboxyl and epoxy of dimer acid, and the long carbon chain of dimer acid can improve the brittleness of epoxy resin, the impact strength and the shearing force of epoxy resin, and the fracture toughness, and the heat resistance and the mechanical property cannot be reduced by using a proper amount. More specifically, the acid value of the dimer acid modified epoxy resin is less than 2mgKOH/g, and the epoxy equivalent is 280-300; when in use, butanone can be added to prepare 50 percent solvent type epoxy resin.
The method for producing the dimer acid-modified novolac epoxy resin is not particularly limited, and may be, for example, a method in which a novolac epoxy resin is reacted with a dimer acid.
The invention also provides a preparation method of the glue solution, which comprises the following steps:
A) mixing a solvent and a silane coupling agent according to parts by weight, and stirring to obtain a first mixture;
B) adding silicon micro powder into the first mixture according to the parts by weight, and stirring to obtain a second mixture;
C) adding DOPO novolac epoxy resin, dimer acid modified novolac epoxy resin, bisphenol A type novolac resin, bisphenol F type benzoxazine resin and 2-methyl-4 ethyl imidazole 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 can be controlled to be 800-; in the step B), the stirring speed can be controlled to be 1500-; in step C), the stirring may include: stirring at 1800-.
In one embodiment, the method for preparing the dimer acid-modified novolac epoxy resin may include:
and under the protective atmosphere, reacting the novolac epoxy resin with dimer acid in the presence of a catalyst to obtain the dimer acid modified novolac epoxy resin.
In the above preparation method, the catalyst may be selected from at least one of tetrabutylammonium bromide, tetraethylammonium bromide, ethyltriphenylphosphine acetate, triphenylphosphine, and magnesium stearate, and is preferably magnesium stearate. In addition, the mass ratio between the novolac epoxy resin, the dimer acid, and the catalyst may be 100: (20-40): (0.01-0.05); further, the reaction temperature can be 160-170 ℃, and the reaction time can be 2-4 h.
The invention also provides application of the glue solution in preparation of the loss halogen-free copper-clad plate.
The invention also provides a preparation method of the medium-loss halogen-free copper-clad plate, which comprises the following steps:
soaking the electronic glass cloth in the glue solution, and baking to obtain a prepreg;
and (3) laminating the prepreg and the copper foil, and then carrying out hot pressing to obtain the medium-loss halogen-free copper-clad plate.
Specifically, 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.
The invention also provides a medium-loss halogen-free copper-clad plate, which is prepared according to the preparation method; the medium-loss halogen-free copper-clad plate is environment-friendly, has good impact resistance and low dielectric loss, and is beneficial to improving the accuracy of signal transmission.
The implementation of the invention has at least the following advantages:
1. the dimer acid modified novolac epoxy resin is used as a reinforcing material, and the toughness of the material is improved and the thermal shock performance of the material is improved through a composite resin system of DOPO novolac epoxy resin and dimer acid modified novolac epoxy resin;
2. the invention adopts a composite curing agent system of bisphenol A type phenolic resin and bisphenol F type benzoxazine resin, thereby ensuring that the material has excellent electrical property after being pressed;
3. the copper-clad plate manufactured by the glue solution can prevent the occurrence of crack phenomenon, has excellent heat resistance and reliability, reduces the dielectric constant and dielectric loss of the substrate, and can well meet the market demands of high transmission and medium loss of information.
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 dimer acid modified novolac epoxy resin
Adding 100 parts of novolac epoxy resin and 30 parts of dimer acid into a four-neck flask with a stirrer and a thermometer, introducing nitrogen, adding 0.03 part of catalyst magnesium stearate at 125 ℃, slowly heating to 160 ℃, and carrying out heat preservation reaction for 4 hours to obtain light yellow dimer acid modified novolac epoxy resin.
Secondly, preparing glue solution
The glue solution of the embodiment comprises the following components in parts by weight:
Figure BDA0002688373960000051
the preparation steps of the glue solution are as follows:
cleaning the glue mixing tank by using acetone, then adding butanone, cyclohexanone and a silane coupling agent in parts by weight, starting stirring, and stirring at the rotating speed of 800r/min for 1.5 h; then adding the silicon micropowder 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 20 ℃.
And then adding DOPO novolac epoxy resin, dimer acid modified novolac epoxy resin, bisphenol A type novolac resin, bisphenol F type benzoxazine resin and 2-methyl-4 ethyl imidazole according to the parts by weight, stirring at a high speed of 1800r/min for 4 hours, then stirring at a rotating speed of 500r/min for 2.5 hours, and testing the qualified gelling time of the glue to obtain the glue solution.
Thirdly, preparing a prepreg
The prepared glue solution is injected into a stainless steel gluing basin, the machine speed of a gluing machine is set to be 10m/min, electronic glass cloth passes through the glue solution and enters a vertical gluing machine to be baked for 1-2min, and a prepreg is prepared; wherein, the content of the glue is controlled to be 40 percent, the fluidity is controlled to be 20 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 2.5 hours under the conditions that the temperature is 210 ℃ and the pressure is 400psi to obtain the medium-loss halogen-free copper-clad plate.
The IPC-650 method is adopted to detect the medium loss halogen-free copper-clad plate, and the result is shown in Table 1.
Example 2
Preparation of dimer acid modified novolac epoxy resin
Adding 100 parts of novolac epoxy resin and 30 parts of dimer acid into a four-neck flask with a stirrer and a thermometer, introducing nitrogen, adding 0.03 part of tetrabutylammonium bromide as a catalyst at 125 ℃, slowly heating to 170 ℃, and carrying out heat preservation reaction for 2 hours to obtain light yellow dimer acid modified novolac epoxy resin.
Secondly, preparing glue solution
The glue solution of the embodiment comprises the following components in parts by weight:
Figure BDA0002688373960000061
Figure BDA0002688373960000071
the preparation steps of the glue solution are as follows:
cleaning the glue mixing tank by using acetone, then adding butanone, cyclohexanone and a silane coupling agent in parts by weight, starting stirring, and stirring at the rotating speed of 1200r/min for 0.5 h; then adding the silicon micropowder 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 then adding DOPO novolac epoxy resin, dimer acid modified novolac epoxy resin, bisphenol A type novolac resin, bisphenol F type benzoxazine resin and 2-methyl-4 ethyl imidazole according to the parts by weight, stirring at a high speed of 2200r/min for 2 hours, then stirring at a speed of 800r/min for 1.5 hours, 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 machine speed of a gluing machine is set to be 15m/min, electronic glass cloth passes through the glue solution and enters a vertical gluing machine to be baked for 1-2min, 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 2 hours under the conditions that the temperature is 210 ℃ and the pressure is 400psi to obtain the medium-loss halogen-free copper-clad plate.
The IPC-650 method is adopted to detect the medium loss halogen-free copper-clad plate, and the result is shown in Table 1.
Example 3
Preparation of dimer acid modified novolac epoxy resin
Adding 100 parts of novolac epoxy resin and 30 parts of dimer acid into a four-neck flask with a stirrer and a thermometer, introducing nitrogen, adding 0.03 part of catalyst triphenylphosphine at 125 ℃, slowly heating to 165 ℃, and carrying out heat preservation reaction for 3 hours to obtain light yellow dimer acid modified novolac epoxy resin.
Secondly, preparing glue solution
The glue solution of the embodiment comprises the following components in parts by weight:
Figure BDA0002688373960000081
the preparation steps of the glue solution are as follows:
cleaning the glue mixing tank by using acetone, then adding butanone, cyclohexanone and a silane coupling agent in parts by weight, starting stirring, and stirring for 1h at the rotating speed of 1000 r/min; then adding the silicon micropowder 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 then adding DOPO novolac epoxy resin, dimer acid modified novolac epoxy resin, bisphenol A type novolac resin, bisphenol F type benzoxazine resin and 2-methyl-4 ethyl imidazole according to the parts by weight, stirring at a high speed of 2000r/min for 3 hours, then stirring at a rotating speed of 600r/min for 2 hours, and testing the gel time of the glue to be qualified to obtain the glue.
Thirdly, preparing a prepreg
The prepared glue solution is injected into a stainless steel gluing basin, the machine speed of a gluing machine is set to be 12m/min, electronic glass cloth passes through the glue solution and enters a vertical gluing machine to be baked for 1-2min, 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 medium-loss halogen-free copper-clad plate.
The IPC-650 method is adopted to detect the medium loss halogen-free copper-clad plate, and the result is shown in Table 1.
Comparative example 1
The glue solution of the comparative example consists of the following components in parts by weight:
Figure BDA0002688373960000091
the preparation method of the copper-clad plate of the comparative example is basically the same as that of the embodiment 3; the prepared copper-clad plate is detected by IPC-650 method, and the result is shown in Table 1.
Comparative example 2
The glue solution of the comparative example consists of the following components in parts by weight:
Figure BDA0002688373960000092
Figure BDA0002688373960000101
the preparation method of the copper-clad plate of the comparative example is basically the same as that of the embodiment 3; the prepared copper-clad plate is detected by IPC-650 method, and the result is shown in Table 1.
Comparative example 3
The glue solution of the comparative example consists of the following components in parts by weight:
Figure BDA0002688373960000102
the preparation method of the copper-clad plate of the comparative example is basically the same as that of the embodiment 3; the prepared copper-clad plate is detected by IPC-650 method, and the result is shown in Table 1.
Table 1 performance test results of each copper-clad plate
Figure BDA0002688373960000103
Figure BDA0002688373960000111
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 3 of the present invention, the dimer acid modified novolac epoxy resin is used as the reinforcing material, and the toughness of the material is increased and the thermal shock performance of the material is improved through the composite resin system of the DOPO novolac epoxy resin and the dimer acid modified novolac epoxy resin; meanwhile, the composite curing agent system of the bisphenol A type phenolic resin and the bisphenol F type benzoxazine resin ensures that the material has excellent electrical property after being pressed.
The copper-clad plate manufactured by the glue solution of the embodiments 1 to 3 can prevent the occurrence of crack phenomenon, has excellent heat resistance and reliability, reduces the dielectric constant and dielectric loss of the substrate, and can well meet the market demands of high transmission and medium loss of information.
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 improving the toughness of the medium-loss halogen-free copper-clad plate is characterized by comprising the following components in parts by weight: 90-120 parts of DOPO phenolic epoxy resin, 5-10 parts of dimer acid modified phenolic epoxy resin, 30-50 parts of bisphenol A phenolic resin, 20-40 parts of bisphenol F benzoxazine resin, 0.01-0.3 part of 2-methyl-4-ethylimidazole, 60-80 parts of silicon micropowder, 0.02-0.05 part of silane coupling agent and 70-100 parts of solvent.
2. The glue solution according to claim 1, wherein the solvent is at least one selected from cyclohexanone and butanone;
preferably, the solvent comprises 10-20 parts of cyclohexanone and 60-80 parts of butanone.
3. The glue solution of claim 1, wherein the dimer acid-modified novolac epoxy resin is obtained by reacting a novolac epoxy resin with a dimer acid.
4. A process for the preparation of a dope according to any one of claims 1 to 3, comprising:
A) mixing a solvent and a silane coupling agent according to parts by weight, and stirring to obtain a first mixture;
B) adding silicon micro powder into the first mixture according to the parts by weight, and stirring to obtain a second mixture;
C) adding DOPO novolac epoxy resin, dimer acid modified novolac epoxy resin, bisphenol A type novolac resin, bisphenol F type benzoxazine resin and 2-methyl-4 ethyl imidazole into the second mixture according to the parts by weight, and stirring to obtain a glue solution.
5. The preparation method as claimed in claim 4, wherein in the step A), the stirring speed is controlled to be 800-1200r/min, and the stirring time is controlled to be 0.5-1.5 h; 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 4, wherein the dimer acid-modified novolac epoxy resin is prepared by a method comprising:
and under the protective atmosphere, reacting the novolac epoxy resin with dimer acid in the presence of a catalyst to obtain the dimer acid modified novolac epoxy resin.
7. The method according to claim 6, wherein the catalyst is at least one selected from the group consisting of tetrabutylammonium bromide, tetraethylammonium bromide, ethyltriphenylphosphonium acetate, triphenylphosphine, and magnesium stearate, preferably magnesium stearate;
preferably, the mass ratio of the novolac epoxy resin to the dimer acid to the catalyst is 100: (20-40): (0.01-0.05);
preferably, the reaction temperature is 160-170 ℃, and the reaction time is 2-4 h.
8. The application of the glue solution of any one of claims 1 to 3 in preparing a loss halogen-free copper-clad plate.
9. The preparation method of the medium-loss halogen-free copper-clad plate is characterized by comprising the following steps:
soaking the electronic glass cloth in the glue solution of any one of claims 1 to 3, and baking to obtain a prepreg;
laminating the prepreg and the copper foil and then carrying out hot pressing to obtain a medium-loss halogen-free copper-clad 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.
10. The medium-loss halogen-free copper-clad plate is characterized by being prepared according to the preparation method of claim 9.
CN202010983654.6A 2020-09-18 2020-09-18 Glue solution for improving toughness of medium-loss halogen-free copper-clad plate and preparation method and application thereof Pending CN111978684A (en)

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