CN116410594A - Resin composition, prepreg and metal foil-clad laminate - Google Patents

Resin composition, prepreg and metal foil-clad laminate Download PDF

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Publication number
CN116410594A
CN116410594A CN202111683505.9A CN202111683505A CN116410594A CN 116410594 A CN116410594 A CN 116410594A CN 202111683505 A CN202111683505 A CN 202111683505A CN 116410594 A CN116410594 A CN 116410594A
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China
Prior art keywords
parts
bis
compound
resin composition
maleimidophenoxy
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CN202111683505.9A
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Chinese (zh)
Inventor
李志光
唐军旗
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to CN202111683505.9A priority Critical patent/CN116410594A/en
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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
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • 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
    • 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
    • B32B5/22—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
    • B32B5/24—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 one layer being a fibrous or filamentary layer
    • B32B5/26—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 one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • 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
    • H05K1/036—Multilayers with layers of different types
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B32B2038/168—Removing solvent
    • 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
    • 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
    • B32B2307/70—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
    • 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
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • 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
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a resin composition, a prepreg and a metal foil-clad laminate, wherein the resin composition comprises the following components in parts by weight in terms of solid content: 10 to 70 parts of modified maleimide compound, 10 to 60 parts of polyphenyl ether containing unsaturated groups and 5 to 30 parts of polyfunctional vinyl aromatic polymer. The problems that the glass transition temperature of the resin composition shows double peaks after curing and the warpage of the resin composition, the laminated board and the metal foil-clad laminated board is large are solved by the synergistic compounding of polymer materials, particularly the introduction of the multifunctional vinyl aromatic polymer. Meanwhile, the resin composition, the laminated board comprising the resin composition, the metal foil-clad laminated board and the printed circuit board have low plane thermal expansion coefficient and low dielectric loss tangent, high glass transition temperature, excellent dielectric property and good peel strength, and are suitable for high-grade high-speed packaging.

Description

Resin composition, prepreg and metal foil-clad laminate
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to a resin composition, prepreg and metal foil-clad laminated plate.
Background
In recent years, the application of electronic products has entered the era of high-frequency and high-speed transmission, and the demand for information transmission in electronic communication technology has been increasing, so that the dielectric properties of related electronic materials should be also required to reach corresponding levels. Particularly, with the advent of the 5G age, high-frequency RF (PA, wiGig, wiHD/60GHz, etc.), large-size chips, DDR5 (3.2 to 6.4 Gbps), etc. are represented, and higher requirements are being put on the performance of package substrate materials: it has low planar thermal expansion coefficient and low dielectric loss tangent.
With the trend of high frequency and high speed of signal transmission, miniaturization of electronic components, and high density of circuit board wiring, it has been difficult to satisfy the performance requirement of low dielectric properties with conventional substrate materials prepared from resin systems mainly composed of epoxy resins, and instead, resin compositions mainly composed of polyphenylene ether resins have been used. The main chain of the polyphenyl ether resin contains a large amount of benzene rings, and has lower dielectric constant and dielectric loss tangent, and good physical and mechanical properties. However, the polyphenylene ether resin has a high melting point, poor flowability and poor processability, and thus the prepreg containing the polyphenylene ether resin has a high melt viscosity, and it is difficult to satisfy the process requirements of the multilayer circuit board. Therefore, in order to meet the requirements of actual production and processing, there is a need for performance improvement of polyphenylene ether resin systems by chemical grafting or blend modification.
Hydrocarbon resin is also called polyolefin resin, does not contain polar groups, has the characteristics of good dielectric property and good flexibility, and can ensure that the resin composition has good balance between processability and mechanical property when being combined with polyphenyl ether. For example, CN111253702a discloses a resin composition comprising an unsaturated polyphenylene ether resin, a polyolefin resin, a terpene resin and an initiator, and a prepreg and a circuit material using the same; wherein the polyolefin resin is selected from one or a combination of at least two of unsaturated polybutadiene resin, SBS resin or styrene-butadiene resin. The resin composition has good film forming property, cohesiveness and dielectric property through the mutual matching of resin components, and the circuit board adopting the resin composition has higher interlayer peeling strength; however, the resin composition has a low glass transition temperature and a high thermal expansion coefficient, so that the heat resistance and the dimensional stability of the circuit board are poor, and the performance requirement of high-frequency equipment on the packaging substrate is difficult to meet.
CN110831761a discloses a metal foil-clad laminate, a metal foil with a resin, and a wiring board, wherein an insulating layer material in the metal foil-clad laminate is a cured product of a resin composition comprising a polyphenylene ether copolymer having an unsaturated group at the end, a thermosetting curing agent having 2 or more carbon-carbon unsaturated double bonds at the molecular end, and a thermoplastic elastomer, wherein the thermoplastic elastomer is a styrene-based thermoplastic elastomer. The insulating layer and the metal foil in the metal foil-clad laminated plate have higher and more stable adhesive force, but the insulating layer has high thermal expansion coefficient, and the dimensional stability and reliability of the plate are lower.
The maleimide resin has higher monomer activity, and the cured product thereof has high glass transition temperature and good heat resistance, can keep stable performance in a wider temperature range, and is beneficial to improving the thermal expansibility of the material. CN111630076a discloses a resin composition, a prepreg, a film with a resin, a metal foil-clad laminate, and a wiring board, in which the resin composition includes a maleimide compound, a modified polyphenylene ether compound, and a crosslinking agent, wherein the crosslinking agent contains an allyl compound; the resin composition has higher glass transition temperature and heat resistance, but has higher dielectric loss tangent and thermal expansion coefficient, and insufficient dielectric property and reliability; moreover, the resin composition comprising the modified maleimide and polyphenylene ether may exhibit warpage problems after curing, affecting the application properties of the substrate.
Therefore, development of a resin material having a low planar thermal expansion coefficient, a low dielectric loss tangent, and a high glass transition temperature to satisfy the performance requirements of high-frequency high-speed electronic substrates is an important research point in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a resin composition, a prepreg and a metal foil-clad laminated board, which solve the problem of warping of a cured product through the cooperative compounding of different materials, so that the resin composition has high glass transition temperature, low dielectric loss tangent and low plane thermal expansion coefficient, and is suitable for a substrate material of high-level high-speed high-frequency packaging.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a resin composition comprising, in parts by weight of solid content:
10 to 70 parts of modified maleimide compound
10 to 60 parts of polyphenyl ether containing unsaturated groups
5-30 parts of multifunctional vinyl aromatic polymer.
The modified maleimide compound includes an addition reaction product of a maleimide compound a1 having at least 2 (e.g., 2, 3, 4, etc.) N-substituted maleimide groups in 1 molecule and an amine compound a2 having at least 2 (e.g., 2, 3, 4, etc.) primary amino groups in 1 molecule;
the modified maleimide compound is a glue solution of the compound, and the solvent of the glue solution comprises ketone solvents.
The "parts" and "parts by weight" according to the present invention are calculated as solid content, and do not include solvents, dispersants, and the like therein.
The resin composition provided by the invention comprises a modified maleimide compound, an unsaturated group-containing polyphenyl ether and a multifunctional vinyl aromatic polymer; the modified maleimide compound comprises an addition reactant of a maleimide compound a1 containing at least 2N-substituted maleimide groups in 1 molecule and an amine compound a2 containing at least 2 primary amino groups in 1 molecule, has high reactivity and low plane thermal expansion coefficient, and good solubility and excellent heat resistance, is used together with polyphenyl ether containing unsaturated groups, and has low dielectric loss tangent, small plane thermal expansion coefficient and high glass transition temperature.
The reason why the glass transition temperature of the resin composition shows double peaks after curing is solved by introducing the multifunctional vinyl aromatic polymer into the resin composition provided by the invention, and the problem that the resin composition, the laminated board and the metal foil-clad laminated board are large in warping is not clear is presumed that the ketone solvent is contained in the glue solution of the modified maleimide compound, the ketone on the ketone solvent reacts with the modified maleimide compound under the catalysis of the amine compound and becomes a phase state independently on microcosmic scale, so that the resin composition mainly comprising the modified maleimide compound and the polyphenyl ether containing unsaturated groups shows double peaks after curing, and the laminated board and the metal foil-clad laminated board containing the resin composition have serious warping problem. According to the resin composition provided by the invention, the polyfunctional vinyl aromatic polymer is introduced, and due to the conjugation of vinyl and phenyl, the polyfunctional vinyl aromatic polymer preferentially reacts with the modified maleimide compound, and the residual double bonds on the reaction product can further react with components such as polyphenyl ether containing unsaturated groups, so that the generation of double peaks is avoided, the problem of warping of the resin composition, the laminated board and the metal foil-clad laminated board caused by double peaks of glass transition temperatures is effectively solved, and the dielectric loss tangent and the planar thermal expansion coefficient of the resin composition are further reduced. The resin composition has lower plane thermal expansion coefficient, dielectric loss tangent and warping degree and higher glass transition temperature through screening and synergistic compounding of three components, and fully meets the requirements of high-frequency and high-speed electronic substrates.
The ketone solvent of the present invention is not limited and may dissolve the modified maleimide compound, and preferably, the ketone solvent refers to a compound having a boiling point of not more than 170 ℃ at 1 atmosphere and a ketone group in a molecular structure, and includes any one or a combination of at least two of acetone, butanone, methyl isobutyl ketone, and cyclohexanone.
Preferably, the solvent of the glue solution also comprises propylene glycol monomethyl ether.
In the resin composition of the present invention, the modified maleimide compound may be 10 to 70 parts, for example, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, or the like.
The unsaturated group-containing polyphenylene ether may be 10 to 60 parts, for example, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, or the like.
The polyfunctional vinyl aromatic polymer is 5 to 30 parts, and may be 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, or the like, for example.
In the resin composition provided by the invention, the three components are combined in the content proportion, so that the resin composition is endowed with high glass transition temperature, low dielectric loss tangent, low plane thermal expansion coefficient and low warping degree.
In the resin composition provided by the invention, if the dosage of the modified maleimide compound is too low, the glass transition temperature of the resin composition is low; if the amount of the modified maleimide compound is too high, dielectric loss of the resin composition may be too high.
In the resin composition provided by the invention, if the content of the unsaturated group-containing polyphenyl ether is too small, the dielectric loss of the resin composition is increased, and the dielectric property cannot meet the requirement of high-speed application; if the amount of the unsaturated group-containing polyphenylene ether is too large, the glass transition temperature of the resin composition decreases, affecting the reliability of the resin composition, the laminate, the metal foil-clad laminate and the printed wiring board.
In the resin composition provided by the invention, the multifunctional vinyl aromatic polymer can effectively improve the double peak problem and warpage of the glass transition temperature of the resin composition, and enable the resin composition to have low dielectric loss and low plane thermal expansion coefficient, if the using amount of the multifunctional vinyl aromatic polymer is too low, the double peak problem and warpage of the glass transition temperature cannot be effectively improved, and the dielectric property is influenced; if the amount is too high, the glass transition temperature of the resin composition decreases, and the reliability decreases.
Preferably, the maleimide compound a1 contains 2N-substituted maleimide groups in 1 molecule, which can impart better fluidity and solubility to the modified maleimide compound.
Preferably, the maleimide compound a1 includes N, N '-ethylene bismaleimide, N' -hexamethylene bismaleimide, N '- (1, 3-phenylene) bismaleimide, N' - (1, 3- (2-methylphenyl)) bismaleimide, N '- (1, 3- (4-methylphenyl)) bismaleimide, N, N' - (1, 4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3-ethyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1, 4-bis (4-maleimidophenyl) cyclohexane, 1, 4-bis (maleimidomethyl) benzene, 1, 3-bis (4-maleimidophenoxy) benzene, 1, 3-bis (3-maleimidophenoxy) benzene, bis (4- (3-maleimidophenoxy) phenyl) methane, bis (4- (4-maleimidophenoxy) phenyl) methane, 1-bis (4- (3-maleimidophenoxy) phenyl) ethane, 1-bis (4- (4-maleimidophenoxy) phenyl) ethane, 1, 2-bis (4- (3-maleimidophenoxy) phenyl) ethane, 1, 2-bis (4- (4-maleimidophenoxy) phenyl) ethane 2, 2-bis (4- (3-maleimidophenoxy) phenyl) propane, 2-bis (4- (4-maleimidophenoxy) phenyl) propane, 2-bis (4- (3-maleimidophenoxy) phenyl) butane, 2-bis (4- (4-maleimidophenoxy) phenyl) butane, 4 '-bis (3-maleimidophenoxy) biphenyl, 4' -bis (4-maleimidophenoxy) biphenyl, bis (4- (3-maleimidophenoxy) phenyl) ketone, bis (4- (4-maleimidophenoxy) phenyl) ketone, any one or a combination of at least two of bis (4- (3-maleimidophenoxy) phenyl) ether or bis (4- (4-maleimidophenoxy) phenyl) ether, and more preferably any one or a combination of at least two of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (4-maleimidophenyl) methane, or 2, 2-bis (4- (4-maleimidophenoxy) phenyl) propane.
Preferably, the method comprises the steps of, the amine compound a2 includes a siloxane compound having at least 2 primary amino groups, diaminobenzidine, 3 '-dimethoxy-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-diethyl-4, 4' -diaminobiphenyl, diaminodiphenylmethane, and 3,3 '-dimethoxy-4, 4' -diaminodiphenylmethane, 3 '-dimethyl-5, 5' -dimethyl-4, 4 '-diaminodiphenylmethane, 3' -diethyl-5, 5 '-diethyl-4, 4' -diaminodiphenylmethane 3,3 '-dimethoxy-4, 4' -diaminodiphenylmethane, 3 '-dimethyl-5, 5' -dimethyl-4, 4 '-diaminodiphenylmethane 3,3' -diethyl-4, 4 '-diaminodiphenylmethane, 3' -diethyl-5, 5 '-diethyl-4, 4' -diaminodiphenylmethane, any one or a combination of at least two of 2, 2-bis (4- (4-aminophenoxy) phenyl) propane, 2-bis (4- (3-aminophenoxy) phenyl) propane, 4' -bis (4-aminophenoxy) biphenyl, 1, 4-bis (4-aminophenoxy) benzene, 2' -dimethyl-4, 4' -diaminobiphenyl or 4,4' -diamino-3, 3' -dihydroxybiphenyl; further preferred is any one or a combination of at least two of a siloxane compound having at least 2 primary amino groups, 3' -dimethyl-4, 4' -diaminodiphenylmethane, 3' -dimethyl-5, 5' -dimethyl-4, 4' -diaminodiphenylmethane, 3' -diethyl-5, 5' -diethyl-4, 4' -diaminodiphenylmethane, 3' -dimethyl-5, 5' -diethyl-4, 4' -diaminodiphenylmethane or 2, 2-bis (4- (4-aminophenoxy) phenyl) propane.
Preferably, the amine compound a2 includes a siloxane compound having 2 primary amino groups in 1 molecule, and more preferably includes a siloxane compound having 2 primary amino groups at the molecular terminals.
As a preferred embodiment of the present invention, the amine compound a2 includes a siloxane compound having 2 primary amino groups in 1 molecule, and a resin composition having a low coefficient of planar expansion can be obtained. The siloxane compound having 2 primary amino groups may be used commercially, and exemplary include, but are not limited to: PAM-E (side chain methyl type, 130g/mol of functional group equivalent), KF-8010 (side chain methyl type, 430g/mol of functional group equivalent), X-22-161A (side chain methyl type, 800g/mol of functional group equivalent), X-22-161B (side chain methyl type, 1500g/mol of functional group equivalent), KF-8012 (side chain methyl type, 2200g/mol of functional group equivalent), KF-8008 (side chain methyl type, 5700g/mol of functional group equivalent), X-22-1660B-3 (side chain phenyl type, 2200g/mol of functional group equivalent) and/or X-22-9409 (side chain phenyl type, 670g/mol of functional group equivalent) and the like of the Xinyue chemical industry Co.
Preferably, the silicone compound is used in an amount of 1 to 30 parts by weight, for example, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, etc., more preferably 2 to 15 parts, based on 100 parts by weight of the total amount of the modified maleimide compound, the unsaturated group-containing polyphenylene ether and the polyfunctional vinyl aromatic polymer, and the resin composition can have a low planar thermal expansion coefficient and at the same time have good fluidity.
In the present invention, the addition reaction of the maleimide compound a1 having at least 2N-substituted maleimide groups in the 1 molecule and the amine compound a2 having at least 2 primary amino groups in the 1 molecule is carried out in an organic solvent, the kind of the organic solvent is not particularly limited, and propylene glycol monomethyl ether is more preferable; the product obtained by the addition reaction is a resin mixture in a varnish state, and is convenient to mix with other components of the resin composition. Wherein, the mixed solvent containing propylene glycol monomethyl ether and ketone solvent can improve the solubility of the modified maleimide compound in the resin mixture in the state of varnish; the ratio of the ketone solvent to propylene glycol monomethyl ether and the ratio of the modified maleimide compound to the ketone solvent to propylene glycol monomethyl ether are not particularly limited, as long as the modified maleimide compound is completely dissolved.
In the present invention, the temperature of the addition reaction between the maleimide compound a1 having at least 2N-substituted maleimide groups in the 1 molecule and the amine compound a2 having at least 2 primary amino groups in the 1 molecule is not particularly limited, and the temperature of the addition reaction may be, for example, 102 ℃, 105 ℃, 108 ℃, 110 ℃, 112 ℃, 115 ℃, 118 ℃, 120 ℃, 122 ℃, 125 ℃, 128 ℃ or the like from the viewpoints of the reaction rate and the boiling point of the solvent, as a preferable embodiment of the present invention.
In the present invention, the time for the addition reaction of the maleimide compound a1 having at least 2N-substituted maleimide groups in 1 molecule and the amine compound a2 having at least 2 primary amino groups in 1 molecule is not particularly limited, and the time for the addition reaction is preferably 2 to 10 hours, and may be, for example, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, etc., and more preferably 3 to 8 hours.
Preferably, the unsaturated group-containing polyphenylene ether has a structure as shown in formula I:
Figure BDA0003453718340000091
in the formula I, R 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, C1-C8 straight or branched alkyl; the C1-C8 linear or branched alkyl group may be a C1, C2, C3, C4, C5, C6, C7, or C8 linear or branched alkyl group, exemplary including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, and the like.
In the formula I, m and n represent the number of the repeating units and are respectively and independently selected from 0 to 100, such as 2, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 and the like; and m and n are not 0 at the same time.
In the formula I, A 1 、A 2 Each independently selected from
Figure BDA0003453718340000101
p and q are each independently selected from integers from 0 to 8, and may be, for example, 0, 1, 2, 3, 4, 5, 6, 7 or 8. When p is 0, it represents a benzene ring linked to the backbone of formula I by a single bond; when q is 0, it represents alkenyl linked to the backbone of formula I by a single bond.
In the present invention, a short straight line on one or both sides of the group (e.g
Figure BDA0003453718340000102
Short straight line on the right) represents an access bond of a group, not representing methyl; the same expressions are referred to hereinafter, all having the same meaning.
R 5 、R 6 、R 7 Each independently selected from hydrogen,C1-C8 (e.g., C1, C2, C3, C4, C5, C6, C7, or C8) straight or branched alkyl.
M is selected from carbonyl, C6-C18 arylene, C1-C10 straight chain or branched alkylene.
The C6-C18 arylene group may be a C6, C9, C10, C12, C14, C16, C18, etc., exemplary including but not limited to: phenylene, biphenylene, naphthylene, anthrylene, phenanthrylene, and the like.
The C1-C10 linear or branched alkylene may be a C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10 linear or branched alkylene, exemplary including but not limited to: methylene, ethylene, propylene, butylene, and the like.
In the formula I, Z is selected from
Figure BDA0003453718340000103
Figure BDA0003453718340000111
X is selected from C1-C20 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C14, C16, C18, or C19, etc.) linear or branched alkylene, C3-C20 (e.g., C3, C4, C5, C6, C7, C8, C9, C10, C12, C14, C16, C18, or C19, etc.) cycloalkylene, C2-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C14, C16, C18, or C19, etc.) heterocycloalkylene, or at least 2-CH that is not adjacent to 1-C20 linear or branched alkylene 2 -is interrupted by-O-, -S-, -CO-,
Figure BDA0003453718340000112
Figure BDA0003453718340000113
Substituted groups.
The hetero atom in the C2-C20 heterocycloalkylene group comprises O, S, N, P, si or the like.
R Z1 、R Z2 、R Z3 、R Z4 、R Z5 、R Z6 、R Z7 、R Z8 、R N 、R P 、R S1 、R S2 Each independently selected from hydrogen, C1-C8 (e.g., C1, C2, C3, C4, C5, C6, C7, or C8) straight or branched alkyl.
Preferably, the A 1 、A 2 Each independently selected from
Figure BDA0003453718340000114
Figure BDA0003453718340000115
Any one of the following.
Preferably, said R 7 Selected from hydrogen or methyl.
As a preferable technical scheme of the invention, the A 1 、A 2 Each independently selected from any one of vinylbenzyl, vinylphenyl, acrylate or methacrylate groups.
From the viewpoint of improving heat resistance and dielectric properties of the resin composition, the A is preferably 1 、A 2 At least 1 of them is
Figure BDA0003453718340000121
That is, the unsaturated group-containing polyphenylene ether is a polyphenylene ether having a vinylbenzyl group (e.g., p-vinylbenzyl or m-vinylbenzyl) at the terminal. Polyphenylene ether having a vinylbenzyl group at the terminal may be commercially available, and exemplary include, but are not limited to: OPE-2st1200 (number average molecular weight M) n 1200) and/or OPE-2st 2200 (number average molecular weight M) n 2200), etc.
Preferably, the number average molecular weight of the unsaturated group-containing polyphenylene ether is 500 to 3000, for example 600, 800, 1000, 1100, 1300, 1500, 1700, 1900, 2000, 2100, 2300, 2500, 2700 or 2900, etc.
In the present invention, the polymerizable monomer of the polyfunctional vinyl aromatic polymer is not particularly limited as long as it is an aromatic compound having at least 1 vinyl group, and as a preferable embodiment of the present invention, the polymerizable monomer of the polyfunctional vinyl aromatic polymer includes at least 1 (for example, 1,2, 3, 4 or the like) kind of a divinyl aromatic compound.
Preferably, the divinylaromatic compound comprises any one or a combination of at least two of divinylbenzene, divinylbiphenyl, divinylnaphthalene, diisopropenylbenzene, diisopropenylnaphthalene or diisopropenylbiphenyl.
In the present invention, the above-listed divinylaromatic compounds include all isomers thereof. The divinylbenzene is any one or the combination of at least two of ortho-divinylbenzene, meta-divinylbenzene and para-divinylbenzene. The divinylbenzene includes any one or a combination of at least two of 4,4' -divinylbenzene, 4,3' -divinylbenzene, 4,2' -divinylbenzene, 3' -divinylbenzene, 2' -divinylbenzene or 2, 4-divinylbenzene. The divinyl naphthalene comprises any one or a combination of at least two of 1, 3-divinyl naphthalene, 1, 4-divinyl naphthalene, 1, 5-divinyl naphthalene, 1, 8-divinyl naphthalene, 2, 3-divinyl naphthalene, 2, 6-divinyl naphthalene and 2, 7-divinyl naphthalene. The diisopropenylbenzene is any one or a combination of at least two of 1, 2-diisopropenylbenzene, 1, 3-diisopropenylbenzene and 1, 4-diisopropenylbenzene. The diisopropenylnaphthalene includes any one or a combination of at least two of 1, 3-diisopropenylnaphthalene, 1, 4-diisopropenylnaphthalene, 1, 5-diisopropenylnaphthalene, 1, 8-diisopropenylnaphthalene, 2, 3-diisopropenylnaphthalene, 2, 6-diisopropenylnaphthalene or 2, 7-diisopropenylnaphthalene. The diisopropenylbiphenyl includes any one or a combination of at least two of 4,4' -diisopropenylbiphenyl, 4,3' -diisopropenylbiphenyl, 4,2' -diisopropenylbiphenyl, 3' -diisopropenylbiphenyl, 2' -diisopropenylbiphenyl or 2, 4-diisopropenylbiphenyl.
Preferably, at least 1 monovinylaromatic compound is also included in the polymerized monomers of the multifunctional vinylaromatic polymer.
The monovinylaromatic compound may be a vinylaromatic compound substituted with a nuclear alkyl group, a vinylaromatic compound substituted with an alpha-alkyl group, a vinylaromatic compound substituted with a beta-alkyl group, or a vinylaromatic compound substituted with an alkoxy group.
Preferably, the monovinylaromatic compound comprises a substituted or unsubstituted styrene, the substituted substituent being selected from C1 to C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) linear or branched alkyl.
Preferably, the multifunctional vinyl aromatic polymer comprises any one or a combination of at least two of the following structural units:
Figure BDA0003453718340000131
Figure BDA0003453718340000141
wherein R is 8 、R 9 Each independently selected from the group consisting of C6-C12 (e.g., C6, C7, C8, C9, C10, C12, etc.) arylene groups, exemplary include, but are not limited to: phenylene, biphenylene, naphthylene, indenylene, or methyl substituted phenylene, and the like.
R 10 Selected from hydrogen, C1-C12 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, or C11, etc.), straight or branched alkyl, C3-C12 (e.g., C3, C4, C5, C6, C7, C8, C9, C10, or C11, etc.), alicyclic hydrocarbon groups. The C3-C12 alicyclic hydrocarbon group may be a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group.
In the present invention, the multifunctional vinyl aromatic polymer may be commercially available, and exemplary include, but are not limited to: the vinyl equivalent of the ODV-XET series of New Hill iron chemical industry Co Ltd may be 200 to 300g/mol, for example 207g/mol, 240g/mol, 265g/mol or 293g/mol etc.
As a preferable embodiment of the present invention, the resin composition further includes 5 to 30 parts of a crosslinking agent, for example, 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, or the like. Thereby further increasing the crosslink density of the resin composition and improving the glass transition temperature and heat resistance. If the amount of the crosslinking agent is too high, the dielectric loss tangent of the resin composition is increased, and at the same time, the unreacted groups are excessive to cause insufficient heat curing reaction, which affects the reliability of the resin composition, the laminate, the metal foil-clad laminate and the printed wiring board.
In the present invention, the crosslinking agent is not particularly limited as long as the composition is subjected to a crosslinking reaction, and as a preferable embodiment of the present invention, the crosslinking agent includes a crosslinking agent having a carbon-carbon unsaturated double bond in a molecule and/or a cyanate ester.
Preferably, the crosslinking agent having a carbon-carbon unsaturated double bond in the molecule includes any one or a combination of at least two of a polyfunctional vinyl compound, an allyl compound, an acrylate compound, a trialkenyl isocyanurate compound, other maleimide compound, an acenaphthylene compound, or polybutadiene.
Preferably, the acrylic ester compound comprises tricyclodecane dimethanol methacrylate, and the structural formula is
Figure BDA0003453718340000151
Preferably, the trialkenyl isocyanurate compound includes triallyl isocyanurate.
Preferably, the multifunctional vinyl compound comprises a styrene-butadiene copolymer and/or a styrene-isoprene copolymer.
As a further preferable technical scheme of the invention, the cross-linking agent comprises an acrylic ester compound, wherein the acrylic ester compound is preferably tricyclodecane dimethanol methacrylate, and the volatility of the acrylic ester compound is lower in the heat treatment process, so that the stability of the performance of the resin composition is ensured; furthermore, tricyclodecane dimethanol methacrylate may also produce a synergistic effect with the modified maleimide compound, improving the peel strength of the resin composition from the metal foil.
Preferably, the acrylate compound (e.g., tricyclodecane dimethanol methacrylate) is used in an amount of 50 parts or more, for example, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 78 parts, 80 parts, 82 parts, 85 parts, 88 parts, 90 parts, 92 parts, 95 parts, 98 parts or 100 parts, etc., based on 100 parts by weight of the crosslinking agent, which is more useful for improving the peel strength of the resin composition and the metal foil.
Preferably, the modified maleimide compound is used in an amount of 10 to 70 parts by weight, for example, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, or the like, and more preferably 10 to 60 parts, based on 100 parts by weight of the total amount of the modified maleimide compound, the unsaturated group-containing polyphenylene ether, the polyfunctional vinyl aromatic polymer, and the crosslinking agent.
Preferably, the unsaturated group-containing polyphenylene ether is used in an amount of 10 to 60 parts by weight, for example, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts or the like, based on 100 parts by weight of the total amount of the modified maleimide compound, the unsaturated group-containing polyphenylene ether, the polyfunctional vinyl aromatic polymer and the crosslinking agent.
Preferably, the polyfunctional vinyl aromatic polymer is used in an amount of 5 to 30 parts by weight, for example, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, or the like, based on 100 parts by weight of the total amount of the modified maleimide compound, the unsaturated group-containing polyphenylene ether, the polyfunctional vinyl aromatic polymer, and the crosslinking agent.
Preferably, the crosslinking agent is used in an amount of 5 to 30 parts by weight, for example, 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, or the like, based on 100 parts by weight of the total amount of the modified maleimide compound, the unsaturated group-containing polyphenylene ether, the polyfunctional vinyl aromatic polymer, and the crosslinking agent.
Preferably, the resin composition further includes 0.01 to 5 parts by weight of a curing accelerator, for example, the curing accelerator may be 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 4.8 parts, etc., more preferably 0.3 to 3 parts.
Preferably, the curing accelerator includes any one or a combination of at least two of an acidic curing accelerator, an organic phosphorus curing accelerator, an imidazole curing accelerator, a pyridine curing accelerator, an amine curing accelerator, a peroxide or an organic metal salt.
Illustratively, the acidic curing accelerator includes p-toluenesulfonic acid and the like, the organophosphorus curing accelerator includes triphenylphosphine and the like, the imidazole curing accelerator includes imidazole and/or imidazole derivatives (e.g., 2-methylimidazole, 2-ethylimidazole, or 2-ethyl-4-methylimidazole and the like), the pyridine curing accelerator includes pyridine and/or pyridine derivatives (e.g., 4-dimethylaminopyridine), the amine curing accelerator includes secondary amine compounds, tertiary amine compounds, or quaternary ammonium salts, the peroxide includes dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyne-3, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, or α, α' -bis (t-butylperoxy) diisopropylbenzene and the like, and the organometal salt includes zinc naphthenate, cobalt naphthenate, tin octoate, or cobalt octoate and the like. The curing accelerator may be used alone or in combination of at least two thereof.
As a preferred embodiment of the present invention, the resin composition further comprises 10 to 250 parts by weight of an inorganic filler, for example, 15 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, 180 parts, 190 parts, 200 parts, 210 parts, 220 parts, 230 parts, 240 parts, or the like. The inorganic filler can further reduce the thermal expansion coefficient of the resin composition and improve the heat resistance and the moist heat resistance. If the amount of the inorganic filler is too large, the dielectric loss tangent of the resin composition may be increased, which is disadvantageous for signal transmission.
The present invention is not particularly limited in the kind of the inorganic filler, and includes, as examples: any one or a combination of at least two of silicon dioxide, aluminum hydroxide, magnesium hydroxide, boehmite, molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, titanium dioxide, strontium titanate, barium sulfate, clay, kaolin, talc, mica, boron nitride, aluminum nitride, silicon carbide, aluminum oxide, composite silica micropowder, glass frit, short glass fibers or hollow glass. In order to impart higher heat resistance, moist heat resistance and dimensional stability to the resin composition, it is preferably any one or a combination of at least two of silica, aluminum hydroxide, magnesium hydroxide, boehmite, boron nitride, aluminum nitride, silicon carbide, alumina, composite fine silica powder, glass frit, short glass fibers or hollow glass. Among them, the silica may be crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica, or the like, and is more preferably spherical silica.
Average particle diameter (D) of inorganic filler 50 ) The average particle diameter (d 50) is not particularly limited, but is preferably 0.01 to 20 micrometers, for example 0.02 micrometers, 0.05 micrometers, 0.1 micrometers, 0.2 micrometers, 0.8 micrometers, 1.5 micrometers, 2.1 micrometers, 2.6 micrometers, 3.5 micrometers, 4.5 micrometers, 5.2 micrometers, 5.5 micrometers, 6 micrometers, 6.5 micrometers, 7 micrometers, 7.5 micrometers, 8 micrometers, 8.5 micrometers, 9 micrometers, 9.5 micrometers, 12 micrometers, 13.5 micrometers, 15 micrometers, 17.5 micrometers, 18 micrometers, 19.5 micrometers, more preferably 0.1 to 10 micrometers, from the viewpoint of dispersibility. Inorganic fillers of different types, different particle size distributions or different average particle diameters may be used alone or in combination of plural kinds as required.
Preferably, the resin composition further comprises 0.01 to 10 parts by weight of a coupling agent, for example, the coupling agent may be 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 or 9.8 parts, etc., more preferably 0.1 to 6 parts of the coupling agent; the coupling agent can improve the compatibility of the inorganic filler with the resin composition.
Preferably, the coupling agent comprises a silane coupling agent.
The kind of the silane coupling agent according to the present invention is not particularly limited, and exemplary ones include, but are not limited to: any one or a combination of at least two of an epoxy silane coupling agent, an amino silane coupling agent, a vinyl silane coupling agent, a styryl silane coupling agent, an isobutylene silane coupling agent, an acryl silane coupling agent, an ureido silane coupling agent, a mercapto silane coupling agent, a chloropropyl silane coupling agent, a sulfide silane coupling agent, or an isocyanate-based silane coupling agent.
Preferably, the resin composition further comprises a flame retardant. The flame retardant is not particularly limited, and may be selected from halogen-based or non-halogen-based flame retardants which are dissolved or not dissolved in an organic solvent. Illustratively, the non-halogen based flame retardant includes inorganic phosphorus based flame retardants, organic phosphorus based flame retardants, metal hydrates, and the like.
The flame retardant is preferably an organic phosphorus flame retardant in view of environmental problems and excellent dielectric characteristics. Illustratively, the organophosphorus flame retardant includes aromatic phosphoric acid esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, cyclic organophosphorus compounds, and the like.
Illustratively, the aromatic phosphoric acid esters include triphenyl phosphate, tricresyl phosphate, tris (xylene) phosphate, cresyl diphenyl phosphate, cresyl di-2, 6-xylenyl phosphate, resorcinol bis (diphenyl phosphate), 1,3 phenylene bis (di (2, 6-dimethylphenyl) phosphate), 4' -biphenylyl bis (di (2, 6-dimethylphenyl) phosphate), bisphenol a-bis (diphenyl phosphate), 1, 3-phenylene bis (diphenyl phosphate), and the like; the monosubstituted phosphonic acid diester includes divinyl phenylphosphonate, diallyl phenylphosphonate, bis (1-butenyl) phenylphosphonate, and the like; the disubstituted phosphinates include phenyl diphenylphosphinate, methyl diphenylphosphinate, and the like; the metal salts of the disubstituted phosphinic acid include metal salts of dialkylphosphinic acid, metal salts of diallyl phosphinic acid, metal salts of divinyl phosphinic acid, metal salts of diaryl phosphinic acid, and the like; the organic nitrogen-containing and phosphorus-containing compound includes phosphazene compound, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, etc.; the cyclic organophosphorus compound includes 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, and the like.
The flame retardant may be used alone or in combination of at least two.
The amount of the flame retardant is not particularly limited. Preferably, in the case of using a phosphorus-based flame retardant in the resin composition of the present invention, the amount of the flame retardant is preferably 0.2 to 5 parts by weight, more preferably 0.3 to 3 parts by weight, still more preferably 0.5 to 3 parts by weight, in terms of phosphorus atom conversion, based on 100 parts by weight of the total amount of the modified maleimide compound, the unsaturated group-containing polyphenylene ether, the polyfunctional vinyl aromatic polymer and the flame retardant. When the weight part of the phosphorus atom is within this range, flame retardancy, manufacturability and heat resistance can be well balanced.
In view of the preparation and processing requirements, the resin composition further includes a solvent, and the amount of the solvent is not limited as long as the components in the resin composition are dissolved, dispersed, and mixed without separation.
The type of the solvent is not particularly limited, and includes any one or a combination of at least two of an alcohol solvent, an ether solvent, an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent, and a nitrogen-containing solvent, and preferably any one or a combination of at least two of acetone, butanone, methyl isobutyl ketone, cyclohexanone, toluene, and xylene.
In another aspect, the present invention provides a prepreg comprising a substrate, and the resin composition of the first aspect attached to the substrate by dip drying.
Preferably, the substrate comprises any one of glass fiber cloth, organic fiber cloth or glass fiber paper.
Wherein the glass fiber cloth comprises Q-glass fiber cloth, E-glass fiber cloth, D-glass fiber cloth, L-glass fiber cloth, M-glass fiber cloth, S-glass fiber cloth, T-glass fiber cloth, NE-glass fiber cloth and the like.
The organic fiber cloth comprises polyimide fiber cloth, polyamide fiber cloth, polyester fiber cloth, polyphenyl ether fiber cloth, liquid crystal polymer fiber cloth and the like.
Illustratively, the method of preparing the prepreg comprises: and (3) soaking the base material with the resin glue solution of the resin composition, and then drying to obtain the prepreg.
The solvent of the resin dope is not particularly limited, and is preferably any one or a combination of at least two of acetone, butanone, methyl isobutyl ketone, cyclohexanone, toluene, and xylene.
Preferably, the drying temperature is 100 to 180 ℃, for example 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, or the like.
Preferably, the drying time is 1 to 10min, for example, 2min, 3min, 4min, 5min, 6min, 7min, 8min or 9min, etc.
In another aspect, the present invention provides a metal foil-clad laminate comprising at least 1 sheet of the prepreg described above, and a metal foil disposed on one or both sides of the prepreg.
The metal foil can be copper foil, aluminum foil, nickel foil or alloy foil; preferably, the metal foil is copper foil.
The prepreg in the metal foil-clad laminate is preferably 1 to 20 sheets, and may be 1 sheet, 3 sheets, 5 sheets, 7 sheets, 9 sheets, 10 sheets, 11 sheets, 13 sheets, 15 sheets, 17 sheets, 19 sheets, or the like, for example.
Illustratively, the method of making the metal foil-clad laminate includes: pressing metal foil on one side or two sides of 1 piece of prepreg, and curing to obtain the metal foil-clad laminated board; or, laminating at least 2 prepregs, then laminating metal foils on one side or two sides of the laminated prepregs, and curing to obtain the metal-clad laminate.
Preferably, the curing is performed in a press.
Preferably, the curing temperature is 200 to 250 ℃, for example 205 ℃, 210 ℃, 212 ℃, 215 ℃, 218 ℃, 220 ℃, 223 ℃, 225 ℃, 228 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, or 245 ℃, etc., more preferably 210 to 230 ℃.
Preferably, the curing pressure is 10 to 60kg/cm 2 For example 15kg/cm 2 、20kg/cm 2 、25kg/cm 2 、30kg/cm 2 、35kg/cm 2 、40kg/cm 2 、45kg/cm 2 、50kg/cm 2 Or 55kg/cm 2 Etc.
Preferably, the curing time is 30-180 min, for example, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min or 175min, etc.
In another aspect, the invention provides a printed circuit board comprising at least 1 prepreg as described above or a metal foil-clad laminate as described above.
Compared with the prior art, the invention has the following beneficial effects:
(1) The resin composition provided by the invention comprises a modified maleimide compound, polyphenyl ether containing unsaturated groups and a multifunctional vinyl aromatic polymer, and solves the problems that the glass transition temperature of the resin composition shows double peaks after solidification and the resin composition, a laminated board and a metal foil-clad laminated board have large warping through screening and compounding of three components, particularly the introduction of the multifunctional vinyl aromatic polymer; meanwhile, the resin composition has a low planar thermal expansion coefficient and dielectric loss tangent, and has a high glass transition temperature, and is suitable for high-level high-speed packaging.
(2) The resin composition enables the glass transition temperature of the prepared prepreg, laminated board and metal foil-clad laminated board to reach 201-298 ℃, the plane thermal expansion coefficient to be 7-14 ppm/DEG C, the dielectric constant to be 3.71-4.25 at 10GHz, the dielectric loss tangent to be 0.0045-0.0057, the maximum warping to be as low as 112-251 mu m, the peeling strength to reach 0.47-0.62N/mm, and the resin composition has the advantages of low plane thermal expansion coefficient, low dielectric loss tangent and low warping degree, excellent dielectric property and dimensional stability, high board reliability and fully meets the application requirements of high-frequency high-speed electronic materials.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The preparation method of the modified maleimide compound comprises the following steps:
the experimental materials involved in the following preparation examples of the modified maleimide compound of the present invention include:
(1) Amine compound:
kayahard A-A,3 '-diethyl-4, 4' -diaminodiphenylmethane, japanese chemical Co., ltd;
BAPP, 2-bis (4- (4-aminophenoxy) phenyl) propane, and singer refinement industries, inc;
X-22-161A, a siloxane compound having 2 primary amino groups at the molecular terminal, believed to be available from Xinyue chemical industries, inc.;
X-22-161B, a siloxane compound having 2 primary amino groups at the molecular terminals, believed to be available from Kagaku Kogyo Co., ltd.
(2) Maleimide compound:
BMI-1000, bis (4-maleimidophenyl) methane, daghe chemical Co., ltd;
BMI-4000,2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, large and chemical industry Co.
(3) Solvent:
propylene glycol monomethyl ether, cyclohexanone.
Preparation examples 1 to 3
The preparation method of the modified maleimide compound comprises the following steps:
adding an amine compound and a maleimide compound into a three-mouth bottle with a thermometer, a stirring paddle and a reflux condenser, and carrying out thermal insulation reaction in a solvent system to obtain the modified maleimide compound; specific components and reaction conditions (temperature and time) are shown in Table 1, and the unit of the amount of each component is "part".
TABLE 1
Figure BDA0003453718340000231
Figure BDA0003453718340000241
The experimental materials referred to in the following examples and comparative examples of the present invention include:
(1) Modified maleimide compound
BMI A1, preparation 1;
BMI A2, preparation 2;
BMI A3, preparation 3.
(2) Polyphenylene ether containing unsaturated group
OPE-2st 2200, polyphenylene ether containing vinylbenzyl group at the terminal, mitsubishi chemical Co., ltd;
SA-9000, polyphenylene ether with methacrylate at the end, M n About 1900-2300, sand foundation industry company.
(3) Vinyl aromatic polymers
a) Multifunctional vinyl aromatic polymers
ODV-XET (X05), polydivinylbenzene, new Nissan chemical Co., ltd;
ODV-XET (X04), polydivinylbenzene, new Nissan chemical Co., ltd;
b) Monofunctional vinyl aromatic polymers
Styrene monomer, jun xin chemical industry.
(4) Crosslinking agent
NK ESTER DCP tricyclodecane dimethanol methacrylate, new Zhongcun chemical industry Co., ltd;
FARIDA TAIC-A, triallyl isocyanurate, ruida technologies Co., ltd. In the south of the lake.
(5) Curing accelerator
Triginox 311,3,3,5,7,7-pentamethyl-1, 2, 4-trioxypropane, acciaierie, arkesinobell, USA.
(6) Inorganic filler
SC2300-SVJ spherical silica surface-treated with a vinyl silane coupling agent, median particle diameter D 50 0.5 μm, from adematechs, japan.
(7) Coupling agent
KBM-573, N-phenyl-3-aminopropyl trimethoxysilane, japanese Xinyue Co.
Example 1
The embodiment provides a resin composition which comprises the following components in parts by weight based on the solid content:
Figure BDA0003453718340000251
wherein the modified maleimide compound BMI A1 is a compound glue solution, and the solvent of the glue solution is a mixture of cyclohexanone and propylene glycol monomethyl ether.
The embodiment also provides a metal foil-clad laminated board, and the specific preparation method comprises the following steps:
(1) Mixing the resin composition provided by the embodiment, toluene and butanone, fully dissolving and uniformly dispersing to obtain a resin glue solution with the solid content of 60%;
(2) Soaking glass fiber cloth (3313 manufactured by huber of taiwan) with the resin glue solution obtained in the step (1), heating and drying for 4min in a blast oven at 140 ℃ to convert the resin composition in a varnish state into the resin composition in a semi-curing state, and controlling the average thickness to be 100 mu m to obtain the prepreg;
(3) Laminating 2 (or 8) prepregs obtained in step (2), pressing 18 μm thick electrolytic copper foil on upper and lower sides, and placing at 220deg.C in a press at 45kg/cm 2 Curing for 2 hours to obtain the copper-clad laminate with the core plate thickness of 0.20mm (or 0.80 mm).
After the gold copper foil of the copper clad laminate is etched, a laminate having a thickness of 0.20mm (or 0.80 mm) is obtained.
Examples 2 to 10, comparative examples 1 to 6
A resin composition having the components and contents shown in tables 2 and 3; the amount units of each component in tables 2 and 3 are parts.
TABLE 2
Figure BDA0003453718340000261
Figure BDA0003453718340000271
TABLE 3 Table 3
Figure BDA0003453718340000272
The above resin composition was prepared into a metal foil-clad laminate according to the method in example 1, and the properties of the laminate and the test methods of the test materials were as follows:
(1) Glass transition temperature T g : taking a laminated board with the length of 60mm, the width of 10mm and the thickness of 0.80mm as a sample, measuring by using a dynamic mechanical thermal analyzer (DMA), and heating at a speed of 10 ℃/min, wherein the unit is that the temperature of a transition peak of tan delta is obtained;
(2) Coefficient of planar thermal expansion (XY-CTE): taking a laminated board with the length of 60mm, the width of 4mm and the thickness of 0.20mm as a sample, taking the warp direction of glass fiber as the Y direction and the weft direction of glass fiber as the X direction, drying the sample in a drying oven at 105 ℃ for 1h, and cooling to room temperature in a dryer. Measuring by using a thermal analysis mechanical method (TMA), heating from room temperature to 300 ℃ at a heating rate of 10 ℃/min, heating twice, cooling to room temperature after the first heating is finished, and then lofting again to perform the second heating, wherein the unit of the thermal expansion coefficient in the plane direction at 50 ℃ to 130 ℃ is ppm/°c;
(3) Dielectric constant (D) k ) And dielectric loss tangent (D) f ): a laminate having a length of 100mm, a width of 100mm and a thickness of 0.20mm was used as the laminateAfter the sample is ultrasonically cleaned of impurities on the surface in deionized water, the sample is dried in a drying oven at 105 ℃ for 1h and then cooled to room temperature in a dryer; measurement of dielectric constant at frequency 10GHz (D using cavity resonator device k ) And dielectric loss tangent (D) f )；
(4) Maximum warpage: a laminate having a length of 240mm, a width of 70mm and a thickness of 0.20mm was taken as a sample, and the amount of warpage change during the reflow process was tested, and reflow parameters were set as follows: heating from 30 ℃ to 260 ℃, cooling from 260 ℃ to 30 ℃ at a rate of 3 ℃/min, and measuring the maximum warpage in mu m by using a warpage tester;
(7) Number average molecular weight: the test method is GB/T21863-2008, and is measured by gel permeation chromatography based on polystyrene calibration;
(8) Peel Strength (PS): taking a metal foil-clad laminated plate with the length of 50mm and the width of 50mm as a sample, and preparing a test strip with the metal foil width of 3.0mm on the sample by using a tape method and an etching method; the metal foil is peeled off from the laminate by applying pressure in the vertical direction at a rate of 50mm/min using a peeling resistance gauge, and the peel strength of the metal foil-clad laminate is obtained in N/mm.
The test results are shown in table 4:
TABLE 4 Table 4
Figure BDA0003453718340000281
Figure BDA0003453718340000291
From the performance test data in Table 4, it is understood that the resin compositions provided in examples 1 to 10 of the present invention are used for producing laminated boards and metal foil-clad laminated boards, and have a glass transition temperature of 201 to 298 ℃, a planar thermal expansion coefficient of 7 to 14ppm/°c, a dielectric constant of 3.71 to 4.25 at 10GHz, a dielectric loss tangent of 0.0045 to 0.0057, a maximum warpage as low as 112 to 251 μm, and a peel strength of 0.47 to 0.62N/mm, and have a low planar thermal expansion coefficient, a low dielectric loss tangent and a low warpage, excellent dielectric properties and dimensional stability, and a high board reliability, and sufficiently meet the application requirements of high-frequency high-speed electronic materials.
If the polyfunctional vinyl aromatic polymer (comparative example 1) is not used or is replaced with an equal part by weight of the monofunctional vinyl aromatic polymer (comparative example 2), the glass transition temperature after curing of the resin composition exhibits a bimodal problem (i.e., two T's in Table 4 g ) Further, the degree of warpage of the laminate increases, and the application performance decreases; if the content of the polyfunctional vinyl aromatic polymer is too high (comparative example 3), the glass transition temperature of the cured product does not have a double peak, but the glass transition temperature of the resin composition is drastically reduced, the planar thermal expansion coefficient of the laminate is increased, and the maximum degree of warpage is drastically increased, failing to meet the performance requirements of the high-speed high-frequency package substrate.
If the amount of the modified maleimide compound in the resin composition is too high (comparative example 4), the dielectric loss of the laminate increases, while the glass transition temperature after curing of the resin composition exhibits a double-peak problem (having a double peak at 155 ℃ C., 320 ℃ C.), and the degree of warpage of the laminate increases; if the amount of the modified maleimide compound in the resin composition is too low (comparative example 5), the glass transition temperature of the laminate decreases, the planar thermal expansion coefficient of the laminate increases, and the degree of warpage increases. If the amount of the unsaturated group-containing polyphenylene ether in the resin composition is too low (comparative example 6), the dielectric constant and dielectric loss tangent of the laminate are increased, and the requirements of the high-speed high-frequency package carrier are not satisfied.
The applicant states that the present invention is described by way of the above examples as a resin composition, prepreg and metal foil clad laminate of the present invention, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. A resin composition, characterized in that the resin composition comprises the following components in parts by weight of solid content:
10 to 70 parts of modified maleimide compound
10 to 60 parts of polyphenyl ether containing unsaturated groups
5-30 parts of a multifunctional vinyl aromatic polymer;
the modified maleimide compound includes an addition reactant of a maleimide compound a1 containing at least 2N-substituted maleimide groups in the molecule and an amine compound a2 containing at least 2 primary amino groups in the molecule;
the modified maleimide compound is a glue solution of the compound, and the solvent of the glue solution comprises ketone solvents.
2. The resin composition according to claim 1, wherein the ketone solvent comprises any one or a combination of at least two of acetone, butanone, methyl isobutyl ketone, or cyclohexanone;
preferably, the solvent of the glue solution also comprises propylene glycol monomethyl ether.
3. The resin composition according to claim 1 or 2, wherein the maleimide compound a1 contains 2N-substituted maleimide groups in 1 molecule;
preferably, the maleimide compound a1 includes N, N '-ethylene bismaleimide, N' -hexamethylene bismaleimide, N '- (1, 3-phenylene) bismaleimide, N' - (1, 3- (2-methylphenyl)) bismaleimide, N '- (1, 3- (4-methylphenyl)) bismaleimide, N, N' - (1, 4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3-ethyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1, 4-bis (4-maleimidophenyl) cyclohexane, 1, 4-bis (maleimidomethyl) benzene, 1, 3-bis (4-maleimidophenoxy) benzene, 1, 3-bis (3-maleimidophenoxy) benzene, bis (4- (3-maleimidophenoxy) phenyl) methane, bis (4- (4-maleimidophenoxy) phenyl) methane, 1-bis (4- (3-maleimidophenoxy) phenyl) ethane, 1-bis (4- (4-maleimidophenoxy) phenyl) ethane, 1, 2-bis (4- (3-maleimidophenoxy) phenyl) ethane, 1, 2-bis (4- (4-maleimidophenoxy) phenyl) ethane 2, 2-bis (4- (3-maleimidophenoxy) phenyl) propane, 2-bis (4- (4-maleimidophenoxy) phenyl) propane, 2-bis (4- (3-maleimidophenoxy) phenyl) butane, 2-bis (4- (4-maleimidophenoxy) phenyl) butane, 4 '-bis (3-maleimidophenoxy) biphenyl, 4' -bis (4-maleimidophenoxy) biphenyl, bis (4- (3-maleimidophenoxy) phenyl) ketone, bis (4- (4-maleimidophenoxy) phenyl) ketone, any one or a combination of at least two of bis (4- (3-maleimidophenoxy) phenyl) ether or bis (4- (4-maleimidophenoxy) phenyl) ether, and more preferably any one or a combination of at least two of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (4-maleimidophenyl) methane, or 2, 2-bis (4- (4-maleimidophenoxy) phenyl) propane;
Preferably, the method comprises the steps of, the amine compound a2 includes a siloxane compound having at least 2 primary amino groups, diaminobenzidine, 3 '-dimethoxy-4, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-diethyl-4, 4' -diaminobiphenyl, diaminodiphenylmethane, and 3,3 '-dimethoxy-4, 4' -diaminodiphenylmethane, 3 '-dimethyl-5, 5' -dimethyl-4, 4 '-diaminodiphenylmethane, 3' -diethyl-5, 5 '-diethyl-4, 4' -diaminodiphenylmethane 3,3 '-dimethoxy-4, 4' -diaminodiphenylmethane, 3 '-dimethyl-5, 5' -dimethyl-4, 4 '-diaminodiphenylmethane 3,3' -diethyl-4, 4 '-diaminodiphenylmethane, 3' -diethyl-5, 5 '-diethyl-4, 4' -diaminodiphenylmethane, any one or a combination of at least two of 2, 2-bis (4- (4-aminophenoxy) phenyl) propane, 2-bis (4- (3-aminophenoxy) phenyl) propane, 4' -bis (4-aminophenoxy) biphenyl, 1, 4-bis (4-aminophenoxy) benzene, 2' -dimethyl-4, 4' -diaminobiphenyl or 4,4' -diamino-3, 3' -dihydroxybiphenyl; further preferred is any one or a combination of at least two of a siloxane compound containing at least 2 primary amino groups, 3' -dimethyl-4, 4' -diaminodiphenylmethane, 3' -dimethyl-5, 5' -dimethyl-4, 4' -diaminodiphenylmethane, 3' -diethyl-5, 5' -diethyl-4, 4' -diaminodiphenylmethane, 3' -dimethyl-5, 5' -diethyl-4, 4' -diaminodiphenylmethane or 2, 2-bis (4- (4-aminophenoxy) phenyl) propane;
Preferably, the amine compound a2 includes a siloxane compound having 2 primary amino groups in 1 molecule, and further preferably includes a siloxane compound having 2 primary amino groups at the molecular terminals;
preferably, the siloxane compound is used in an amount of 1 to 30 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the total amount of the modified maleimide compound, the unsaturated group-containing polyphenylene ether and the polyfunctional vinyl aromatic polymer.
4. A resin composition according to any one of claims 1 to 3, wherein the unsaturated group-containing polyphenylene ether has a structure as shown in formula I:
Figure FDA0003453718330000031
wherein R is 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, C1-C8 straight or branched alkyl;
m and n are each independently selected from 0 to 100, and m and n are not 0 at the same time;
A 1 、A 2 each independently selected from
Figure FDA0003453718330000041
p and q are each independently selected from integers from 0 to 8;
R 5 、R 6 、R 7 each independently selected from hydrogen, C1-C8 straight or branched alkyl;
m is selected from carbonyl, C6-C18 arylene, C1-C10 straight chain or branched alkylene;
z is selected from
Figure FDA0003453718330000042
X is selected from C1-C20 straight-chain or branched-chain alkylene, C3-C20 cycloalkylene, C2-C20 heterocycloalkylene, or at least 2-CH of 1 or non-adjacent C1-C20 straight-chain or branched-chain alkylene 2 -is interrupted by-O-, -S-, -CO-,
Figure FDA0003453718330000043
An alternative group;
R Z1 、R Z2 、R Z3 、R Z4 、R Z5 、R Z6 、R Z7 、R Z8 、R N 、R P 、R S1 、R S2 each independently selected from hydrogen, C1-C8 straight or branched alkyl;
preferably, the A 1 、A 2 Each independently selected from
Figure FDA0003453718330000044
Figure FDA0003453718330000045
Any one of them;
preferably, the A 1 、A 2 At least one of them is
Figure FDA0003453718330000046
Preferably, the number average molecular weight of the unsaturated group-containing polyphenylene ether is 500 to 3000.
5. The resin composition according to any one of claims 1 to 4, wherein the polymerized monomer of the multifunctional vinyl aromatic polymer comprises at least 1 kind of a divinyl aromatic compound-containing;
preferably, the divinylaromatic compound comprises any one or a combination of at least two of divinylbenzene, divinylbiphenyl, divinylnaphthalene, diisopropenylbenzene, diisopropenylnaphthalene or diisopropenylbiphenyl;
preferably, the polymerized monomer of the multifunctional vinyl aromatic polymer further comprises at least 1 monovinyl aromatic compound;
preferably, the monovinylaromatic compound comprises a substituted or unsubstituted styrene, the substituted substituent being selected from C1 to C10 linear or branched alkyl groups;
preferably, the multifunctional vinyl aromatic polymer comprises any one or a combination of at least two of the following structural units:
Figure FDA0003453718330000051
Wherein R is 8 、R 9 Each independently selected from C6-C12 arylene groups;
R 10 selected from hydrogen, C1-C12 straight chain or branched alkyl, and C3-C12 alicyclic hydrocarbon.
6. The resin composition according to any one of claims 1 to 5, further comprising 5 to 30 parts by weight of a crosslinking agent;
preferably, the crosslinking agent includes a crosslinking agent having a carbon-carbon unsaturated double bond in a molecule and/or a cyanate;
preferably, the crosslinking agent having a carbon-carbon unsaturated double bond in the molecule includes any one or a combination of at least two of a polyfunctional vinyl compound, an allyl compound, an acrylate compound, a trialkenyl isocyanurate compound, other maleimide compound, acenaphthylene compound, or polybutadiene;
preferably, the acrylic acid ester compound comprises tricyclodecane dimethanol methacrylate;
preferably, the trialkenyl isocyanurate compound comprises triallyl isocyanurate;
preferably, the multifunctional vinyl compound comprises a styrene-butadiene copolymer and/or a styrene-isoprene copolymer;
preferably, the modified maleimide compound is used in an amount of 10 to 70 parts, preferably 10 to 60 parts, based on 100 parts by weight of the total amount of the modified maleimide compound, the unsaturated group-containing polyphenylene ether, the polyfunctional vinyl aromatic polymer and the crosslinking agent;
Preferably, the unsaturated group-containing polyphenylene ether is used in an amount of 10 to 60 parts by weight based on 100 parts by weight of the total amount of the modified maleimide compound, the unsaturated group-containing polyphenylene ether, the multifunctional vinyl aromatic polymer and the crosslinking agent;
preferably, the polyfunctional vinyl aromatic polymer is used in an amount of 5 to 30 parts by weight based on 100 parts by weight of the total amount of the modified maleimide compound, the unsaturated group-containing polyphenylene ether, the polyfunctional vinyl aromatic polymer and the crosslinking agent;
preferably, the crosslinking agent is used in an amount of 5 to 30 parts by weight based on 100 parts by weight of the total amount of the modified maleimide compound, the unsaturated group-containing polyphenylene ether, the polyfunctional vinyl aromatic polymer and the crosslinking agent.
7. The resin composition according to any one of claims 1 to 6, further comprising 0.01 to 5 parts by weight of a curing accelerator;
preferably, the curing accelerator comprises any one or a combination of at least two of an acidic curing accelerator, an organic phosphorus curing accelerator, an imidazole curing accelerator, a pyridine curing accelerator, an amine curing accelerator, a peroxide or an organic metal salt;
Preferably, the resin composition further comprises 10 to 250 parts by weight of an inorganic filler;
preferably, the resin composition further comprises 0.01 to 10 parts by weight of a coupling agent;
preferably, the coupling agent comprises a silane coupling agent.
8. A prepreg comprising a substrate, and the resin composition according to any one of claims 1 to 7 attached to the substrate by impregnation drying;
preferably, the substrate comprises any one of glass fiber cloth, organic fiber cloth or glass fiber paper.
9. A metal foil-clad laminate comprising at least 1 prepreg according to claim 8, and a metal foil disposed on one or both sides of the prepreg;
preferably, the metal foil is copper foil.
10. A printed circuit board comprising at least 1 prepreg according to claim 8 or a metal foil-clad laminate according to claim 9.
CN202111683505.9A 2021-12-31 2021-12-31 Resin composition, prepreg and metal foil-clad laminate Pending CN116410594A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116970169A (en) * 2023-09-20 2023-10-31 苏州生益科技有限公司 Amine compound modified maleimide prepolymer, resin composition and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116970169A (en) * 2023-09-20 2023-10-31 苏州生益科技有限公司 Amine compound modified maleimide prepolymer, resin composition and application thereof

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