CN109988298B - Modified polyphenyl ether resin, thermosetting resin composition and application thereof - Google Patents

Modified polyphenyl ether resin, thermosetting resin composition and application thereof Download PDF

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CN109988298B
CN109988298B CN201711470773.6A CN201711470773A CN109988298B CN 109988298 B CN109988298 B CN 109988298B CN 201711470773 A CN201711470773 A CN 201711470773A CN 109988298 B CN109988298 B CN 109988298B
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resin composition
polyphenylene ether
formula
resin
thermosetting resin
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CN109988298A (en
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林伟
范华勇
许永静
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Shengyi Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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

Abstract

The invention relates to a modified polyphenyl ether resin, a thermosetting resin composition and application thereof; the modified polyphenylene ether resin is a resin structure obtained by reacting low-molecular-weight hydroxyl-terminated polyphenylene ether of formula (1-1) with dicarboxylic acid halide or dicarboxylic acid containing a structural unit of formula (1-2), monofunctional aromatic phenol or monofunctional aromatic acid halide or monofunctional aromatic carboxylic acid; the thermosetting resin composition comprises an epoxy resin and the modified polyphenylene ether resin as essential components; the invention also provides application of the thermosetting resin composition in prepregs, circuit substrates and build-up films. The prepreg, the circuit board and the laminated film made of the thermosetting resin composition have low dielectric constant, low dielectric loss tangent, high glass transition temperature, excellent heat resistance, moist heat resistance, low hygroscopicity and good bonding force with metal.

Description

Modified polyphenyl ether resin, thermosetting resin composition and application thereof
Technical Field
The invention belongs to the technical field of macromolecules, and particularly relates to a modified polyphenyl ether resin, a thermosetting resin composition and application thereof, in particular to a modified polyphenyl ether resin containing active ester groups on a main chain, a thermosetting resin composition thereof, and a cured product, a prepreg, a circuit substrate and a lamination film prepared from the thermosetting resin composition.
Background
In recent years, with the development of electronic information technology, miniaturization and high density of electronic equipment mounting, large capacity and high frequency of information have been required, and further, overall performance such as dielectric properties, heat resistance, wet heat resistance, mechanical properties, dimensional stability, water absorption, chemical resistance and the like of a circuit board has been required.
Polyphenylene Oxide (PPO) resin contains a large number of benzene ring structures in a molecular structure, does not contain strong polar groups, and endows PPO with excellent performances, such as high glass transition temperature, good dimensional stability, small linear expansion coefficient, low water absorption rate, especially excellent low dielectric constant and low dielectric loss, so that the PPO is introduced into a circuit substrate to improve the electrical performance of the circuit substrate, so that the PPO can be used in a high-frequency substrate material. However, PPO is thermoplastic resin, has the defects of high melting point of the resin, poor processability, poor solvent resistance to halohydrocarbon, aromatic hydrocarbon and the like, and has large structural difference with epoxy resin due to large molecular weight and high symmetry of PPO resin, so that the PPO resin has poor compatibility with the epoxy resin, the phenomenon of serious phase separation of PPO and the epoxy resin occurs in a curing system, and the performance level, the stability and the uniformity of a cured resin are poor.
PPO attracts many companies and researchers to modify the PPO, such as converting PPO into small molecules and/or thermosetting resin, due to its excellent physical properties, heat resistance, mechanical properties, electrical properties, etc., and achieves certain results. The ASAHI company (EP382,312A1) uses a resin composition comprising allyl-modified PPO, curing agent TAIC and initiator PH25B to fabricate a substrate, but the reaction conditions and process control of the allylated PPE are severe, and the allylated PPE needs to be crosslinked at high temperature, and cannot be used as a curing agent for epoxy resin. US4,853,423A1 discloses that mixing PPO with epoxy resin and adding zinc acetylacetonate or zinc stearate can solve the compatibility problem to some extent, but the introduction of two metal salts results in poor electrical properties. US5,834,565A1 discloses that PPO is made into small molecules, the Mn molecular weight is less than 3000, the problem of phase separation with epoxy resin can be effectively solved, but the electrical performance is reduced, the Tg is reduced, and the significance of introducing PPO is greatly reduced.
CN103102484B provides a crosslinkable polyphenylene ether resin, which is mainly characterized in that maleimide groups are introduced into the polyphenylene ether resin, meanwhile, substituent groups on benzene rings or double terminal groups of PPO can be selected to be ester groups, olefin or bismaleimide structures, but not polyphenylene ether resin containing active ester groups is embedded in a main chain, the steric hindrance of the molecular structure is large, the reaction conditions of olefin and bismaleimide are harsh, the crosslinking reaction can be carried out only at high temperature, and the process of the reaction process is difficult to control.
CN104761719B discloses a double-end-group multifunctional active ester resin containing a PPO main chain, wherein the crosslinking of PPO and epoxy is improved by introducing a plurality of active ester reaction groups at two ends of the resin, but the active ester groups are only at two ends of the PPO resin, so the crosslinkable point density is still lower, and a plurality of active ester groups are concentrated at two ends of the PPO resin, the steric hindrance is large, the reaction is difficult, part of the ester groups are difficult to effectively react, and the performances of a cured product are deteriorated if more unreacted ester groups remain.
Disclosure of Invention
In order to solve the problems of poor compatibility of PPO and epoxy resin, low density of functional groups capable of effectively performing a crosslinking reaction, harsh curing conditions, phase separation of a cured product, low bonding force with metal, poor processability and the like, one of the objects of the present invention is to provide a modified polyphenylene ether resin obtained by modifying low molecular weight dihydroxy polyphenylene ether.
According to the modified polyphenylene oxide resin obtained by modifying low-molecular-weight hydroxyl-terminated polyphenylene oxide, active ester groups are introduced into the main chain structure and two molecular ends of PPO, and the problem of poor compatibility of polyphenylene oxide and epoxy resin is effectively solved because the molecular weight of a PPO continuous section in the designed resin structure is small and the embedded active ester groups and epoxy groups have good reactivity and compatibility; meanwhile, active ester groups are arranged at the main chain and two ends of the modified PPO, so that the crosslinking density of a cured product can be effectively improved, and the problem that the Tg of the cured product is greatly reduced due to the reduction of the molecular weight of a PPO continuous section is solved.
On the other hand, the modified polyphenylene ether resin does not generate secondary hydroxyl after the active ester group and the epoxy group are cured, and a cured product of the modified polyphenylene ether resin has good dielectric property, excellent bonding property, good toughness, low water absorption, heat resistance and moist heat resistance, so that the modified polyphenylene ether resin has small influence on the inherent excellent performance of PPO, and overcomes the defects of poor bonding force of PPO and poor bonding force with metal.
Another object of the present invention is to provide a thermosetting resin composition containing the above-mentioned modified polyphenylene ether resin, which has a low dielectric constant, a low dielectric loss tangent, a high glass transition temperature, and excellent heat resistance, moist heat resistance, low hygroscopicity and good bonding force with metals after curing, and use thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a modified polyphenylene ether resin, which is a resin structure obtained by reacting low-molecular-weight hydroxyl-terminated polyphenylene ether of a formula (1-1) with dicarboxylic acid halide or dicarboxylic acid containing a structural unit of a formula (1-2), monofunctional aromatic phenol or monofunctional aromatic acid halide or monofunctional aromatic carboxylic acid:
Figure BDA0001531959970000031
wherein n is1、n2Is a positive integer greater than 0, and satisfies n is not less than 21+n2Less than or equal to 30, e.g. n1+n2Is 2,3, 5,8, 10, 12, 13, 15, 18, 20, 22, 25, 26, 28 or 30, preferably 2. ltoreq. n1+n2≤20。
The hydroxyl-terminated polyphenylene ether is a series of n1+n2Mixtures of resins of different values, low molecular weight hydroxy-terminated polyphenylene ethers selected according to the invention, n1+n2The value falls between 2 and n1+n2The mass ratio within the range of less than or equal to 30 is more than 90 percent; such as n1+n2>A ratio of 30 is too high, and the solubility of the modified polyphenylene ether resin and the compatibility with the epoxy resin are affected.
R1Same or different, selected from H, F, substituted or unsubstituted C1-C6 (e.g. C1, C2, C3, C4, C5 or C6) straight chain or branched chain alkyl.
X is selected from
Figure BDA0001531959970000041
Figure BDA0001531959970000042
Figure BDA0001531959970000043
Any one of them.
R2Same or different from H, F, substituted or unsubstituted C1-C6 (such as C1, C2, C3, C4, C5 or C6) straight chain or branched chain alkyl,
Figure BDA0001531959970000044
Any one of them.
Y is selected from any one of substituted or unsubstituted benzene ring and substituted or unsubstituted diphenyl ether.
In the present invention, the modified polyphenylene ether resin preferably has a structure represented by formula (I) or formula (II):
Figure BDA0001531959970000045
Figure BDA0001531959970000051
wherein n is1、n2Is a positive integer greater than 0, and satisfies n is not less than 21+n2Less than or equal to 30, e.g. n1+n2Is 2,3, 5,8, 10, 12, 13, 15, 18, 20, 22, 25, 26, 28 or 30, preferably 2. ltoreq. n1+n2≤20；n3Is a positive integer greater than 1, such as 2,3, 5,8, 10, etc.; n is4Is a positive integer greater than 0, such as 1,2, 3, 5,8, 10, and the like.
R1Same or different, selected from H, F, substituted or unsubstituted C1-C6 (e.g. C1, C2, C3, C4, C5 or C6) straight chain or branched chain alkyl.
X is selected from
Figure BDA0001531959970000052
Figure BDA0001531959970000053
Figure BDA0001531959970000054
Any one of them.
R2Same or different from H, F, substituted or unsubstituted C1-C6 (such as C1, C2, C3, C4, C5 or C6) straight chain or branched chain alkyl,
Figure BDA0001531959970000055
Any one of them.
Y is any one of substituted or unsubstituted benzene ring and substituted or unsubstituted diphenyl ether.
Z is any one of a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring and a substituted or unsubstituted aromatic fused ring.
Preferably, the preparation method of the modified polyphenylene ether resin with the structure of the formula (I) comprises the following steps:
the low molecular weight hydroxyl-terminated polyphenylene ether of the formula (1-1), the dicarboxylic acid halide or dicarboxylic acid containing the structural unit of the formula (1-2) and the monofunctional aromatic phenol are used as raw materials, and 0.5 to 1.5 (for example, 0.5, 0.8, 0.9, 1.0, 1.2, 1.4 or 1.5) moles of the dicarboxylic acid halide or dicarboxylic acid containing the structural unit of the formula (1-2) are added to the low molecular weight hydroxyl-terminated polyphenylene ether based on 1 mole of the phenolic hydroxyl group, and then 0.05 to 0.6 (for example, 0.05, 0.08, 0.1, 0.12, 0.15, 0.2, 0.3, 0.4, 0.5 or 0.6) moles of the monofunctional aromatic phenol are added to the raw materials to react.
In the preparation method of the modified polyphenylene ether resin with the structure shown in the formula (I), the added dicarboxylic acid halide or dicarboxylic acid is in proper excess, and monofunctional aromatic phenol is required to be added to seal unreacted carboxylic acid halide or carboxylic acid; if the added dicarboxylic acid halide or dicarboxylic acid exceeds 1.5 mol, on one hand, raw materials are wasted, and on the other hand, the residual dicarboxylic acid halide or dicarboxylic acid with a large amount reacts with the monofunctional aromatic phenol to generate small-molecular active ester, which has a certain influence on the heat resistance of the final modified resin.
Preferably, the preparation method of the modified polyphenylene ether resin with the structure of the formula (II) comprises the following steps:
the low molecular weight hydroxyl-terminated polyphenylene ether of the formula (1-1), the dicarboxylic acid halide or dicarboxylic acid containing the structural unit of the formula (1-2) and the monofunctional aromatic acid halide or monofunctional aromatic carboxylic acid are used as raw materials, and 0.25 to 0.5 (for example, 0.25, 0.3, 0.32, 0.35, 0.4, 0.45 or 0.5) mole of the dicarboxylic acid halide or dicarboxylic acid containing the structural unit of the formula (1-2) is added to 1 mole of the phenolic hydroxyl group in the low molecular weight hydroxyl-terminated polyphenylene ether, and then 0.05 to 0.6 (for example, 0.05, 0.08, 0.1, 0.12, 0.15, 0.2, 0.3, 0.4, 0.5 or 0.6) mole of the monofunctional aromatic acid halide or monofunctional aromatic carboxylic acid is added to react.
In the preparation method of the modified polyphenyl ether resin with the structure shown in the formula (II), the added bis-hydroxyl polyphenyl ether is excessive, and monofunctional aromatic acyl halide or monofunctional aromatic carboxylic acid is required to be added to seal unreacted phenolic hydroxyl; if the added dicarboxylic acid halide or dicarboxylic acid is less than 0.25 mol, the residual amount of the double-end polyphenylene ether is more than that of the double-end polyphenylene ether, and the monofunctional aromatic acid halide or the monofunctional aromatic carboxylic acid directly react to generate the double-end modified polyphenylene ether resin only containing active ester groups at two ends, so that the crosslinkable density is reduced, and the glass transition temperature of a cured modified resin is influenced to a certain extent.
The present invention also provides a thermosetting resin composition comprising an epoxy resin and the modified polyphenylene ether resin as described above, that is, the thermosetting resin composition comprises the epoxy resin and the modified polyphenylene ether resin as essential components, preferably comprises the epoxy resin and the modified polyphenylene ether resin represented by the structural formula (I) and/or (II) as described above as essential components.
Preferably, the modified polyphenylene ether resin comprises 10% to 80% by weight of the total thermosetting resin composition, for example 10%, 12%, 15%, 17%, 18%, 20%, 25%, 28%, 30%, 32%, 35%, 38%, 41%, 43%, 45%, 50%, 55%, 60%, 65%, 70%, 72%, 75% or 80%, preferably 25% to 60%.
Preferably, the epoxy resin comprises 20% to 65% of the total weight of the thermosetting resin composition, such as 20%, 22%, 25%, 27%, 28%, 30%, 35%, 38%, 40%, 42%, 45%, 48%, 51%, 53%, 55%, 60% or 65%, preferably 30% to 55%.
Preferably, in the thermosetting resin composition, the epoxy resin means an epoxy resin having two or more epoxy groups in 1 molecule, and more preferably a bifunctional bisphenol A-type epoxy resin, a bifunctional bisphenol F-type epoxy resin, a bifunctional bisphenol S-type epoxy resin, a phenol formaldehyde-type epoxy resin, a methylphenol novolac-type epoxy resin, a bisphenol A-type novolac epoxy resin, a dicyclopentadiene epoxy resin, a biphenyl epoxy resin, a resorcinol-type epoxy resin, a naphthalene-type epoxy resin, a phosphorus-containing epoxy resin, a silicon-containing epoxy resin, a glycidylamine-type epoxy resin, an alicyclic epoxy resin, a polyethylene glycol-type epoxy resin, a tetraphenol ethylene tetraglycidyl ether, a triphenol methane-type epoxy resin, a bifunctional cyanate ester or a condensate of a bifunctional isocyanate and an epoxy resin, and other types of epoxy resins, but not limited thereto, one or a mixture of at least two thereof, wherein a typical but non-limiting mixture is: bifunctional bisphenol a type epoxy resin and bifunctional bisphenol F type epoxy resin; bifunctional bisphenol S type epoxy resins and phenol formaldehyde type epoxy resins; resorcinol type epoxy resins and naphthalene type epoxy resins; alicyclic epoxy resins and polyethylene glycol type epoxy resins.
Preferably, the thermosetting resin composition may further comprise other epoxy resin curing agents in addition to the modified polyphenylene ether resin of the invention, and the other epoxy resin curing agents account for 0% to 30% of the total weight of the thermosetting resin composition, such as 1%, 3%, 5%, 10%, 12%, 15%, 20%, 25%, 28%, 30%; it may be selected from any one or a mixture of at least two of dicyandiamide, aromatic amine, phenolic resin, benzoxazine resin, active ester, cyanate ester resin, polystyrene-maleic anhydride resin (SMA), bis hydroxy polyphenylene ether resin or bis maleimide-triazine resin, wherein a typical but non-limiting mixture is: dicyandiamide and aromatic amines; aromatic amine and phenolic resin, preferably one of active ester, cyanate ester resin, polystyrene-maleic anhydride resin (SMA) or bismaleimide-triazine resin or a mixture of at least two of them.
Preferably, the active ester is an active ester shown in a structural formula (1-3) or a structural formula (1-4);
Figure BDA0001531959970000081
wherein j is an integer of 0 to 20, such as 0, 1,2, 3, 5,8, 10, 12, 14, 15, 16, 18 or 20; k is an integer of 0 to 20, such as 0, 1,2, 3, 5,8, 10, 12, 14, 15, 16, 18 or 20.
Ar1Is a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring.
Z is any one of methylene, divalent aliphatic cyclic hydrocarbon group, phenylene dimethylene and biphenylene-dimethylene.
Ar2Is selected from
Figure BDA0001531959970000091
Figure BDA0001531959970000092
Figure BDA0001531959970000093
Any one of them.
Preferably, the thermosetting resin composition of the present invention may further include a flame retardant selected from an organic flame retardant and/or an inorganic flame retardant.
Preferably, the organic flame retardant is selected from any one of or a mixture of at least two of a halogen-based organic flame retardant, a phosphorus-based organic flame retardant, a nitrogen-based organic flame retardant, a silicon-containing organic flame retardant, and a phosphorus-and/or nitrogen-and/or silicon-containing organic flame retardant.
Preferably, a curing accelerator may be further included in the thermosetting resin composition of the present invention.
Preferably, the curing accelerator is added in an amount of 0.01 to 2%, for example, 0.01%, 0.05%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, or 2% of the total mass of the epoxy resin, the modified polyphenylene ether resin, and the above-mentioned optional other thermosetting resin.
Preferably, the curing accelerator is selected from any one or a mixture of at least two of imidazole compounds, imidazole compound derivatives, piperidine compounds, pyridine compounds, organic metal salt Lewis acid or triphenylphosphine.
Preferably, the thermosetting resin composition of the present invention may further include a filler selected from an organic filler and/or an inorganic filler.
Preferably, the filler is added in an amount of 5 to 300 parts by weight, for example, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, 250 parts by weight, 280 parts by weight or 300 parts by weight, preferably 25 to 150 parts by weight, based on 100 parts by weight of the sum of the addition amounts of the modified polyphenylene ether, the epoxy resin and the above optional other components which may be added.
Preferably, the organic filler is selected from any one of polytetrafluoroethylene powder, polyphenylene sulfide or polyether sulfone powder or a mixture of at least two of the polytetrafluoroethylene powder, the polyphenylene sulfide or the polyether sulfone powder.
Preferably, the inorganic filler is selected from any one or a mixture of at least two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus, preferably any one or a mixture of at least two of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate or mica.
The term "comprising" as used herein means that it may include, in addition to the components, other components which impart different characteristics to the thermosetting resin composition. In addition, the term "comprising" as used herein may be replaced by "being" or "consisting of … …" as closed.
For example, the thermosetting resin composition may further include various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These various additives may be used alone or in combination of two or more.
The conventional preparation method of the thermosetting resin composition of the present invention is: firstly, adding the solid matter, then adding the liquid solvent, stirring until the solid matter is completely dissolved, then adding the liquid resin and the accelerator, and continuously stirring uniformly.
The solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol, and butanol; ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, butyl carbitol and the like; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and ethoxyethyl acetate; nitrogen-containing solvents such as N, N-dimethylformamide and N, N-dimethylacetamide. The above solvents may be used alone or in combination of two or more. Ketones such as acetone, methyl ethyl ketone, and cyclohexanone are preferable. The addition amount of the solvent is selected by the skilled person according to the experience of the person in the art, so that the resin glue solution can reach the viscosity suitable for use.
The present invention also provides a cured product obtained by curing the thermosetting resin composition described above.
The invention also provides a prepreg, which is prepared by the following method: and baking the reinforcing material and the thermosetting resin composition attached to the reinforcing material after impregnation and drying at the temperature of 100-250 ℃ for 1-15 minutes to obtain the prepreg. The reinforcing material used in the present invention is not particularly limited, and may be an organic fiber, an inorganic fiber woven fabric or a nonwoven fabric. The organic fiber can be aramid fiber non-woven fabric, and the inorganic fiber woven fabric can be E-glass fiber fabric, D-glass fiber fabric, S-glass fiber fabric, T-glass fiber fabric, NE-glass fiber fabric or quartz fabric. The thickness of the reinforcing material is not particularly limited, and the woven fabric and the non-woven fabric preferably have a thickness of 0.01 to 0.2mm in consideration of good dimensional stability of the laminate, and are preferably subjected to a fiber opening treatment and a surface treatment with a silane coupling agent, and the silane coupling agent is preferably one of an epoxy silane coupling agent, an amino silane coupling agent, or a vinyl silane coupling agent or a mixture of at least two thereof in order to provide good water resistance and heat resistance.
The invention also provides a circuit substrate, which is prepared by the following method: a laminate made by bonding one or more sheets of prepreg together by heating and pressing, and a metal foil bonded to one or both sides of the laminate. The laminated board is prepared by curing in a hot press, the curing temperature is 150-250 ℃, and the curing pressure is 10-60 kg/cm2. The metal foil is copper foil, nickel foil, aluminum foil, SUS foil, etc., and the material is not limited.
The invention also provides a laminated film, which is prepared by the following method: the above thermosetting resin composition is dissolved or dispersed in an organic solvent, and then coated on a base film or a metal foil, followed by drying to obtain the multilayer film.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) according to the modified polyphenylene oxide resin obtained by modifying low-molecular-weight hydroxyl-terminated polyphenylene oxide, active ester groups are introduced into the main chain structure and two molecular ends of PPO, and the problem of poor compatibility of polyphenylene oxide and epoxy resin is effectively solved because the molecular weight of a PPO continuous section in the designed resin structure is small and the embedded active ester groups and epoxy groups have good reactivity and compatibility; meanwhile, active ester groups exist in the main chain and two ends of the modified PPO, so that the crosslinking density of a cured product can be effectively improved, and the problem that the Tg of the cured product is greatly reduced due to the reduction of the molecular weight of a PPO continuous section is solved;
(2) the modified polyphenylene oxide resin provided by the invention does not generate secondary hydroxyl after the active ester group and the epoxy group are cured, and a cured product of the modified polyphenylene oxide resin has good dielectric property, excellent bonding property, good toughness, low water absorption, heat resistance and moist heat resistance, so that the modified polyphenylene oxide resin has little influence on the inherent excellent property of PPO, and overcomes the defects of poor bonding force of PPO and poor bonding force with metal;
(3) the thermosetting resin composition containing the modified polyphenylene ether resin has low dielectric constant, low dielectric loss tangent, high glass transition temperature, excellent heat resistance, moist heat resistance, low hygroscopicity and good bonding force with metal after being cured.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Examples
(1) Synthesis of modified polyphenylene ether resin having structure of formula (I)
A flask equipped with a thermometer, a dropping funnel and a stirrer was charged with 1mol (425g) of RPE-HL and 1500g of tetrahydrofuran, and nitrogen gas was introduced thereinto to stir until completely dissolved. Then, 0.7mol (142.1g) of isophthaloyl dichloride was added and dissolved by stirring, and then 1.4mol (141.4g) of triethylamine (prepared as a 20% triethylamine/tetrahydrofuran solution) was slowly added dropwise (more than 0.5 hour) while controlling the system temperature to 20 ℃ or lower. Then, the reaction is continued for 2.0 to 3.0 hours under stirring at a temperature of 20 ℃. Then, 0.4mol (37.6g) of phenol was charged, and the reaction was continued with stirring at 20 ℃ or lower for 2.0 hours. And standing after the reaction is finished, filtering to remove triethylamine hydrochloride solid, carrying out reduced pressure distillation concentration on the solution, then adding methanol to separate out a resin product, filtering, washing with water until the pH value of a final water layer is 7, then washing with methanol, and drying to obtain a product. The ester equivalent of the modified polyphenylene ether thus prepared was 396g/eq based on the charge ratio.
(2) Synthesis of modified polyphenylene ether resin having the structure of formula (II)
A flask equipped with a thermometer, a dropping funnel and a stirrer was charged with 1mol (425g) of RPE-HL and 1500g of tetrahydrofuran, and nitrogen gas was introduced thereinto to stir until completely dissolved. Then, 0.4mol (81.2g) of isophthaloyl dichloride was added and dissolved by stirring, and then 1mol (101.2g) of triethylamine (prepared as a 20% triethylamine/tetrahydrofuran solution) was slowly added dropwise (more than 0.5 hour) while controlling the system temperature to 20 ℃ or less. Then, the reaction is continued for 2.0 to 3.0 hours under stirring at a temperature of 20 ℃. Then, 0.2mol (28.2g) of benzoyl chloride was charged, and the reaction was continued with stirring at 20 ℃ or lower for 2.0 hours. And standing after the reaction is finished, filtering to remove triethylamine hydrochloride solid, carrying out reduced pressure distillation concentration on the solution, then adding methanol to separate out a resin product, filtering, washing with water until the pH value of a final water layer is 7, then washing with methanol, and drying to obtain a product. The ester equivalent of the modified polyphenylene ether thus prepared was 498g/eq, based on the charge ratio.
By repeating the above operations (1) and (2) and changing the reactants and their ratios, different modified polyphenylene ether resins can be obtained, as shown in Table 1 below.
TABLE 1
Figure BDA0001531959970000141
The information of the related synthetic raw materials is as follows:
RPE-HL: yake Jiangsu, Mn 1233, phenolic hydroxyl equivalent about 425g/eq
SA 90: a saber base, Mn 2059, a phenolic hydroxyl equivalent of about 840g/eq
RPE-HHH: yake Jiangsu, Mn 7644, phenolic hydroxyl equivalent about 2650g/eq
M-benzoyl chloride: molecular weight 203
Benzoyl chloride: molecular weight 140.6
1,2,4, 5-pyromellitic acid tetrachloride: molecular weight 328
Phenol: molecular weight 94
Triethylamine: molecular weight 101.2
(3) Resin composition containing modified polyphenylene ether resin and epoxy resin
The invention relates to a resin composition containing modified polyphenyl ether resin and epoxy resin and a preparation method of a copper-clad plate thereof, and specifically comprises the following steps: uniformly mixing epoxy resin, modified polyphenyl ether resin or other active ester and a curing accelerator in a solvent according to a certain proportion, controlling the solid content of a glue solution to be 65%, impregnating the glue solution with 2116 glass fiber cloth, controlling the proper thickness, baking in an oven at 145-175 ℃ for 2-15 min to prepare a prepreg, stacking a plurality of prepregs, overlapping copper foils on the upper surface and the lower surface of the prepregs, and curing at 190-200 ℃ and at the curing pressure of 30-60 kg/cm2And the copper-clad plate is prepared under the condition that the curing time is 90-120 min, and the specific components, the content and the plate performance are shown in tables 2-1 and 2-2. TABLE 2-1
Figure BDA0001531959970000151
Tables 2 to 2
Figure BDA0001531959970000152
Figure BDA0001531959970000161
Performance analysis:
as can be seen from examples and comparative examples 1-1, 1-2, 1-3, the molecular weight of the bishydroxy-polyphenylene ether used for synthesizing the modified polyphenylene ether is not so large, and the performance is excellent with the molar ratio of phenolic hydroxyl groups to diacid chlorides in the bishydroxy-polyphenylene ether controlled within the range of 1 (0.25-1.5); from comparative examples 1 to 4, it can be seen that the two-terminal multifunctional active ester resin containing a PPO main chain related to patent CN104761719B has active ester groups concentrated at two ends of the resin, has large steric hindrance, has very strict requirements on the conditions for completely curing the resin, and is prone to cause that various properties cannot achieve the expected effects due to incomplete curing.
(4) Resin composition containing modified polyphenylene ether resin, epoxy resin and cyanate ester
The resin composition containing modified polyphenyl ether resin, epoxy resin and cyanate ester and the preparation of the copper-clad plate thereofThe method specifically comprises the following steps: uniformly mixing epoxy resin, modified polyphenyl ether resin, optional cyanate ester resin or other active ester, a curing accelerator and a filler in a solvent according to a certain proportion, controlling the solid content of a glue solution to be 65%, impregnating the glue solution with 2116 glass fiber cloth, controlling the proper thickness, baking in an oven at 145-175 ℃ for 2-15 min to prepare a prepreg, then stacking a plurality of prepregs, stacking copper foils on the upper surface and the lower surface of the prepregs, and curing at 190-210 ℃ and at the curing pressure of 30-60 kg/cm2And curing for 90-120 min to prepare the copper-clad plate. The specific composition, content and sheet properties are shown in table 3.
TABLE 3
Figure BDA0001531959970000162
Figure BDA0001531959970000171
Performance analysis:
as can be seen from the results of comparison between examples and comparative examples, the copper clad laminates obtained by using comparative examples 2-1 and 2-2 in an amount lower than the content of the modified polyphenylene ether resin in the thermosetting resin composition of the present invention or comparative examples 2-3 in an amount higher than the content of the modified polyphenylene ether resin in the thermosetting resin composition of the present invention are inferior to the present invention in dielectric properties, wet heat resistance and water absorption; in comparative examples 2 to 4 in which only DCPD active ester was used without the modified polyphenylene ether resin of the present invention, the heat resistance, dielectric properties, water absorption and the like were inferior to those of the present invention.
It can be seen that the thermosetting resin composition of the modified polyphenylene ether resin provided by the invention has low dielectric constant, low dielectric loss tangent, high glass transition temperature, excellent heat resistance, moist heat resistance, low hygroscopicity and good bonding force with copper foil after being cured.
The examples and comparative examples relate to the materials and the brand information as follows:
(A) modified polyphenylene ether resin
S1-S5: synthesis of modified polyphenylene ether resins obtained in examples 1 to 5
S6-S8: synthesis of modified polyphenylene ether resin prepared in comparative examples 6 to 8
S9: double-ended multifunctional active ester resin containing PPO main chain disclosed in patent CN103221442B
(B) Other resins and accelerators
HP-7200 HHH: DIC, DCPD type epoxy resin, epoxy equivalent 286
HP-7200H-75M: DIC, DCPD type epoxy resin, epoxy equivalent 278
HP-9900: DIC, naphthol type epoxy resin, epoxy equivalent 274
NC-2000-L: japanese chemical, aralkyl epoxy resin, epoxy equivalent 238
SKE-1: colt, Special epoxy resin, epoxy equivalent 120
BA-3000S: LONZA, bisphenol-type cyanate ester
CY-40: DCPD type cyanate ester of Wuqiao resin factory
HPC-8000-65T: DIC, DCPD active ester, ester equivalent 223
DMAP: 4-dimethylaminopyridine
BICATZ: zinc isooctanoate, The Shepherd Chemical Company
(C) Filler material
Fused silica (average particle diameter of 1 to 10 μm, purity 99% or more)
The test method of the above characteristics is as follows:
(1) glass transition temperature (Δ Tg): the measurement was carried out by using DSC measurement in accordance with the DSC measurement method specified by IPC-TM-6502.4.24.
(2) Glass transition temperature (Tg): the DMA test was used and the measurement was carried out according to the DMA test method specified in IPC-TM-6502.4.24.
(3) Dielectric constant and dielectric dissipation factor: testing according to the SPDR method.
(4) Evaluation of Wet Heat resistance (PCT): after etching the copper foil on the surface of the copper clad laminate, evaluating the substrate; placing the substrate in a pressure cooker, processing for several hours under the conditions of 120 ℃ and 105KPa, immersing in a tin furnace at 288 ℃, and recording corresponding time when the substrate is layered and exploded; the evaluation was concluded when the substrate had not blistered or delaminated in the tin oven for more than 5 minutes.
(5) T288, T300: the measurement was carried out by using a TMA meter according to the T288 or T300 test method specified in IPC-TM-6502.4.24.1.
(6) Water absorption: the measurement was carried out according to the water absorption test method specified in IPC-TM-6502.6.2.1.
(7) Thermal decomposition temperature (Td/5%): the temperature rise range is room temperature to 800 ℃, the temperature rise rate is 10 ℃/min, the protection of N2 is carried out by adopting a TG 209F3 type thermogravimetric analyzer produced by Germany NETZSHC company, and the temperature when the weight loss of a sample reaches 5% is recorded as Td 5%.
(8) Peel Strength (PS): the peel strength of the metal cap was tested according to the "as received" experimental conditions in the IPC-TM-6502.4.8 method.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (18)

1. A modified polyphenylene ether resin having a resin structure obtained by reacting a low-molecular weight bishydroxypolyphenylene ether of the formula (1-1) with a dicarboxylic acid halide or dicarboxylic acid, a monofunctional aromatic phenol or a monofunctional aromatic acid halide or a monofunctional aromatic carboxylic acid containing a structural unit of the formula (1-2):
Figure FDA0003149411500000011
Figure FDA0003149411500000012
wherein n is1、n2Is a positive integer greater than 0, and satisfies n is not less than 21+n2≤30；
R1Same or different, selected from H, F, substituted or unsubstituted C1-C6 straight or branched chain alkyl;
x is selected from
Figure FDA0003149411500000013
Figure FDA0003149411500000014
Or
Figure FDA0003149411500000015
Any one of the above;
R2same or different and selected from H, F, substituted or unsubstituted C1-C6 straight-chain alkyl or branched-chain alkyl,
Figure FDA0003149411500000016
Any one of the above;
y is selected from any one of substituted or unsubstituted benzene ring and substituted or unsubstituted diphenyl ether;
the modified polyphenylene ether resin has a structure represented by formula (I) or formula (II):
Figure FDA0003149411500000021
wherein n is1、n2、n4Is a positive integer greater than 0, and satisfies n is not less than 21+n2≤30；n3Is a positive integer greater than 1;
R1same or different, selected from H, F, substituted or unsubstituted C1-C6 straight or branched chain alkyl;
x is selected from
Figure FDA0003149411500000022
Figure FDA0003149411500000023
Or
Figure FDA0003149411500000024
Any one of the above;
R2same or different and selected from H, F, substituted or unsubstituted C1-C6 straight-chain alkyl or branched-chain alkyl,
Figure FDA0003149411500000025
Or
Figure FDA0003149411500000026
Any one of the above;
y is any one of substituted or unsubstituted benzene ring and substituted or unsubstituted diphenyl ether;
z is any one of a substituted or unsubstituted benzene ring and a substituted or unsubstituted aromatic fused ring.
2. The modified polyphenylene ether resin according to claim 1, wherein Z in the formula (I) or the formula (II) is a substituted or unsubstituted naphthalene ring.
3. The modified polyphenylene ether resin according to claim 1, wherein the modified polyphenylene ether resin having a structure of the formula (I) is prepared by a method comprising:
the low molecular weight hydroxyl-terminated polyphenylene ether of the formula (1-1), the dicarboxylic halide or dicarboxylic acid containing the structural unit of the formula (1-2) and the monofunctional aromatic phenol are used as raw materials, and 0.5-1.5 mol of the dicarboxylic halide or dicarboxylic acid containing the structural unit of the formula (1-2) is added and then 0.05-0.6 mol of the monofunctional aromatic phenol is added for reaction, wherein the phenolic hydroxyl group in the low molecular weight hydroxyl-terminated polyphenylene ether of the formula (1-1) is calculated as 1 mol.
4. The modified polyphenylene ether resin according to claim 1, wherein the modified polyphenylene ether resin having a structure of the formula (II) is prepared by a method comprising:
the low molecular weight hydroxyl-terminated polyphenylene ether of the formula (1-1), the dicarboxylic acid halide or dicarboxylic acid containing the structural unit of the formula (1-2) and the monofunctional aromatic acid halide or monofunctional aromatic carboxylic acid are used as raw materials, and 0.25 to 0.5 mol of the dicarboxylic acid halide or dicarboxylic acid containing the structural unit of the formula (1-2) is added and then 0.05 to 0.6 mol of the monofunctional aromatic acid halide or monofunctional aromatic carboxylic acid is added to react, calculated by taking 1mol of phenolic hydroxyl in the low molecular weight hydroxyl-terminated polyphenylene ether of the formula (1-1).
5. A thermosetting resin composition characterized by comprising an epoxy resin and the modified polyphenylene ether resin according to any one of claims 1 to 4.
6. The thermosetting resin composition claimed in claim 5, wherein the modified polyphenylene ether resin is present in an amount of 10 to 80% by weight based on the total weight of the thermosetting resin composition.
7. The thermosetting resin composition claimed in claim 6, wherein the modified polyphenylene ether resin is present in an amount of 25 to 60% by weight based on the total weight of the thermosetting resin composition.
8. The thermosetting resin composition claimed in claim 5, wherein the epoxy resin is 20 to 65% by weight based on the total weight of the thermosetting resin composition.
9. The thermosetting resin composition of claim 8, wherein the epoxy resin comprises 30% to 55% by weight of the total thermosetting resin composition.
10. The thermosetting resin composition claimed in claim 5, further comprising an additional epoxy resin curing agent.
11. The thermosetting resin composition of claim 10, wherein the other epoxy resin curing agent is any one of or a mixture of at least two of dicyandiamide, aromatic amine, phenol resin, benzoxazine resin, active ester, cyanate ester resin, polystyrene-maleic anhydride resin, bis-hydroxy-p-phenylene ether resin, or bis-maleimide-triazine resin.
12. The thermosetting resin composition claimed in claim 5, further comprising a flame retardant.
13. The thermosetting resin composition according to claim 12, wherein the flame retardant is an organic flame retardant and/or an inorganic flame retardant.
14. The thermosetting resin composition claimed in claim 5, further comprising a filler and/or a curing accelerator.
15. A cured product obtained by curing the thermosetting resin composition according to any one of claims 5 to 14.
16. A prepreg is characterized by being prepared by the following method: the prepreg is produced by dissolving or dispersing the thermosetting resin composition according to any one of claims 5 to 14 in an organic solvent, impregnating it into a reinforcing material, and semi-curing the resulting impregnated substrate.
17. A circuit substrate, wherein the circuit substrate is prepared by hot-pressing at least one prepreg according to claim 16 and a metal foil.
18. A laminated film is characterized by being prepared by the following method: the heat-curable resin composition according to any one of claims 5 to 14 is dissolved or dispersed in an organic solvent, and then coated on a substrate film or a metal foil, and dried to obtain the laminate film.
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