CN111393594A - Active ester resin and resin composition thereof - Google Patents
Active ester resin and resin composition thereof Download PDFInfo
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- CN111393594A CN111393594A CN202010364287.1A CN202010364287A CN111393594A CN 111393594 A CN111393594 A CN 111393594A CN 202010364287 A CN202010364287 A CN 202010364287A CN 111393594 A CN111393594 A CN 111393594A
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- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
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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
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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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
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
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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
- 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
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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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
Abstract
The invention discloses an active ester resin and a resin composition thereof, which mainly comprise an active ester resin, a maleimide resin and an epoxy resin. The active ester resin of the invention has both allyl and active ester groups, so that bismaleimide resin can be combined by allyl and epoxy resin can be combined by active ester group, thus having the advantages of bismaleimide resin and epoxy resin, and finally obtaining the resin composition with excellent heat resistance, dielectric property and low water absorption rate.
Description
Technical Field
The invention relates to an active ester resin and a resin composition thereof, belonging to the technical field of electronic materials.
Background
With the upgrading of technology, the consumer electronics markets such as automobile markets and smart phones have new requirements on PCBs, and after the 5G commercial market appears in 2018, the requirements on the dielectric property of PCB substrates are one step higher, and the high-frequency high-speed copper-clad plate is one of indispensable electronic substrates in the 5G era. In short, the PCB substrate material needs to have a low dielectric constant and dielectric loss tangent to reduce the delay, distortion and loss of signals during high-speed transmission and the interference between signals. Accordingly, it is desirable to provide a thermosetting resin composition which can exhibit a sufficiently low dielectric constant and a low dielectric loss tangent (that is, the lower the dielectric constant and the dielectric loss tangent, the better) in a printed circuit board material produced by using the thermosetting resin composition in a signal transmission process of a high speed and a high frequency.
In the prior art, Japanese patent laid-open Nos. JP2002012650A, JP2003082063A, JP2004155990A, JP2009235165A and JP2012246367A disclose a series of active ester resins, which are used as curing agents for epoxy resins, do not generate secondary hydroxyl groups during curing with epoxy resins, and at the same time, the cured products have low water absorption, good dielectric constant and dielectric loss due to the low polarity of their own structures. In addition, compared with other low dielectric curing agents, such as SMA, modified PPO and the like, the active ester resin also has the characteristics of relatively low melt viscosity, relatively low active group equivalent, relatively high crosslinking density and the like, thereby having better manufacturability and performance. However, due to the structural limitation of the active ester resin, the active ester resin still has disadvantages in terms of higher heat resistance, low thermal expansion coefficient, better electrical property requirements, and the like.
Therefore, it is obvious that developing a new active ester and a resin system matched with the active ester and enabling the prepreg, the insulating film, the metal foil clad laminate and the printed wiring board prepared by the active ester to have low dielectric constant and low dielectric loss, excellent heat resistance and low water absorption rate simultaneously have positive practical significance.
Disclosure of Invention
The invention aims to provide an active ester resin and a thermosetting resin composition thereof.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: an active ester resin, the chemical structural formula of which comprises at least one of the following structural formula (1) and structural formula (2):
wherein n is an integer of 1-10; r1 and R2 are the same or different and are respectively hydrogen, alkyl, alkoxy, aryl or aryloxy; x is
(m is 0 or 1) or
Y1、Y2、Y3The same or different are-CH 2-CH ═ CH2Or
Wherein R3 is aryl or substituted aryl;
in the structural formula of the active ester resin, the compound is represented by-CH 2-CH ═ CH2And
the total molar amount of-CH 2-CH ═ CH is 1.0mol2The molar amount of (b) is 0.05 to 0.95 mol.
Preferably, said Y is1、Y2、Y3Are the same or different and are respectively-CH2-CH＝CH2Or
Wherein R3 is phenyl or naphthyl,
in the structural formula of the active ester resin, the compound is represented by-CH 2-CH ═ CH2And
the total molar amount of-CH 2-CH ═ CH is 1.0mol2The molar amount of (b) is 0.2 to 0.8 mol. More preferably, in the structural formula of the active ester resin, the compound is represented by-CH 2-CH ═ CH2And
the total molar amount of-CH 2-CH ═ CH is 1.0mol2The molar weight of (a) is 0.2-0.5 mol; of course, the molecular weight may be 0.25mol, 0.3mol, 0.35mol, 0.4mol, 0.45mol, 0.6mol, 0.7mol, 0.8mol or 0.9 mol.
The invention also claims the preparation method of the active ester resin, which is prepared by esterifying aromatic carboxylic acid or halide thereof with partially allylated phenolic resin, wherein the reaction molar ratio is more than or equal to 1, and the reaction is carried out under the condition of excessive aromatic carboxylic acid or halide thereof.
Preferably, the aromatic compound is selected from benzoic acid, isophthalic acid, terephthalic acid, trimellitic acid, naphthoic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-2, 3-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid or naphthalene-2, 7-dicarboxylic acid; or an acid halide selected from benzoic acid, isophthalic acid, terephthalic acid, trimellitic acid, naphthoic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-2, 3-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid or naphthalene-2, 7-dicarboxylic acid.
Preferably, the partially allylated phenolic resin is a phenolic resin in which a part of phenolic hydroxyl groups are converted to allyl groups to form-CH 2-CH ═ CH2And the total molar amount of-OH is 1.0mol, -CH2-CH ═ CH2The molar amount of (b) is 0.05 to 0.95 mol.
The invention also claims a thermosetting resin composition, which comprises: by weight:
(1) the above active ester resin: 20-70 parts of (by weight),
(2) maleimide resin: 10-40 parts of (by weight),
(3) epoxy resin: 10-60 parts.
Preferably, the thermosetting resin composition consists essentially of, by weight:
(1) the above active ester resin: 20-70 parts of (by weight),
(2) maleimide resin: 10-40 parts of (by weight),
(3) epoxy resin: 10-60 parts.
Preferably, the maleimide resin is a compound having two or more imide rings in its molecular structure.
Still more preferably, the maleimide resin has the following structural formula (4):
wherein, R group is selected from at least one of the following structural formulas:
preferably, the epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus epoxy resin, nitrogen epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl novolac epoxy resin, alicyclic epoxy resin, glycidylamine epoxy resin, glycidylether epoxy resin, and glycidylester epoxy resin.
More preferably, the epoxy resin may be a naphthalene ring type epoxy resin, a biphenyl type epoxy resin, or a dicyclopentadiene type epoxy resin, the structural formula of the naphthalene ring type epoxy resin is shown in structural formula (5), the structural formula of the biphenyl type epoxy resin is shown in structural formula (6), and the structural formula of the dicyclopentadiene type epoxy resin is shown in structural formula (7):
Preferably, the resin composition further comprises a filler in an amount of 0 to 200 parts by weight based on 100 parts by weight of the resin composition;
the filler is an organic filler or an inorganic filler, wherein the inorganic filler is selected from one or more of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
The inorganic filler is preferably at least one of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder. Preferably, the filler is silica, more preferably, surface-treated spherical silica. Specifically, the surface treatment agent for treating the silica is a silane coupling agent such as an epoxy silane coupling agent or an aminosilane coupling agent.
It is understood that the resin composition may or may not contain the filler. When a filler is contained in the resin composition, the filler is 0 to 200 parts by weight based on 100 parts by weight of the resin composition; for example, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight, and specific points between the above values are not intended to be limiting to the space and in the interest of brevity, and the invention is not intended to be exhaustive of the specific points included in the recited ranges. Preferably, the filler content is 10 to 100 parts by weight, more preferably 30 to 70 parts by weight.
Preferably, the filler has a particle size median value of 1 to 15 microns, such as 1.5 microns, 2 microns, 2.5 microns, 3 microns, 3.5 microns, 4 microns, 4.5 microns, 5 microns, 6 microns, 7 microns, 8 microns, 9 microns, 10 microns, 11 microns, 12 microns, 13 microns, 14 microns, and specific values therebetween, not to be limited by space and in the interest of brevity, the invention is not exhaustive of the specific values included in the ranges. More preferably, the median value of the particle size of the filler is 1-10 microns.
As a further improvement of the present invention, the resin composition further includes a cyanate ester resin, a polyphenylene ether resin, a benzoxazine resin or a hydrocarbon resin.
As a further preferred of the present invention, a thermosetting resin composition comprises, by weight: 20 to 70 parts by weight of the active ester compound (a), 10 to 40 parts by weight of the maleimide resin (b), 10 to 60 parts by weight of the epoxy resin (c), and 1 to 50 parts by weight of the cyanate ester (d).
As a further preferred of the present invention, a thermosetting resin composition comprises, by weight: 20 to 70 parts by weight of the active ester compound (a), 10 to 40 parts by weight of the maleimide resin (b), 10 to 60 parts by weight of the epoxy resin (c), and 1 to 50 parts by weight of the polyphenylene ether (d).
As a further preferred of the present invention, a thermosetting resin composition comprises, by weight: 20 to 70 parts by weight of the active ester compound (a), 10 to 40 parts by weight of the maleimide resin (b), 10 to 60 parts by weight of the epoxy resin (c) and 1 to 50 parts by weight of the benzoxazine (d).
As a further preferred of the present invention, a thermosetting resin composition comprises, by weight: 20 to 70 parts of the active ester compound (a), 10 to 40 parts of maleimide resin (b), 10 to 60 parts of epoxy resin (c) and 1 to 50 parts of hydrocarbon resin (d).
In the above technical scheme, the cyanate ester is selected from one or more of bisphenol a cyanate ester, biphenyl cyanate ester, naphthalene ring cyanate ester, bisphenol F cyanate ester, dicyclopentadiene cyanate ester, phenol-formaldehyde cyanate ester, tetramethyl bisphenol F cyanate ester, bisphenol M cyanate ester, bisphenol E cyanate ester, or prepolymers thereof.
In the above technical scheme, the polyphenylene ether resin is a thermosetting polyphenylene ether resin, which is selected from at least one of styrene-modified polyphenylene ether, acrylate-modified polyphenylene ether, polybutadiene-modified polyphenylene ether, allyl-modified polyphenylene ether, maleimide-modified polyphenylene ether, amino-modified polyphenylene ether, and phenol-modified polyphenylene ether.
In the above technical scheme, the benzoxazine is at least one of bisphenol a type benzoxazine resin, bisphenol F type benzoxazine resin, 4' diaminodiphenylmethane benzoxazine resin, diaminodiphenyl ether benzoxazine resin, diaminodiphenyl sulfone benzoxazine resin, dicyclopentadiene type benzoxazine resin, phenolphthalein type benzoxazine resin, allyl benzoxazine resin, cyanate ester group benzoxazine resin, epoxy modified benzoxazine resin and maleimide modified benzoxazine resin.
In the above technical solution, the hydrocarbon resin is at least one of polybutadiene or modified polybutadiene, polypentadiene or modified polypentadiene, polyisoprene or modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleic anhydride diene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleic anhydride styrene-butadiene copolymer, cyclopentadiene or modified cyclopentadiene thereof, dicyclopentadiene or modified dicyclopentadiene thereof, norbornene polymer or modified norbornene polymer.
As a further improvement of the present invention, the resin composition further comprises a flame retardant. The flame retardant is selected from one or more of brominated flame retardants, phosphorus-containing flame retardants, nitrogen-containing compounds and silicon-containing compounds; the brominated flame retardants such as tribromophenyl maleimide, tetrabromobisphenol a allyl ether, decabromodiphenylethane, brominated polystyrene, brominated polycarbonate, tetrabromobisphenol a, brominated epoxy resins, and the like; the phosphorus-containing flame retardant, such as phosphorus-containing epoxy resin, phosphorus-containing phenolic resin, phosphorus-containing active ester, bis-DOPO ethane, phosphazene compound, phosphate ester compound, phosphorus-containing cyanate ester, phosphorus-containing bismaleimide and the like; the nitrogen-containing compounds such as melamine cyanurate and the like; the silicon-containing compound, such as silsesquioxane (POSS), silicone resin powder, and the like. The content of the flame retardant is 1 to 60 parts by weight based on 100 parts by weight of the resin composition.
According to different requirements of final products, the resin composition further comprises 0-5 parts by weight of other auxiliary agents based on 100 parts by weight of the resin composition, wherein the other auxiliary agents comprise a coupling agent, a dispersing agent, a defoaming agent, a leveling agent, an anti-aging agent, an antioxidant and a dye, the coupling agent is a silane coupling agent such as an epoxy silane coupling agent or an amino silane coupling agent, the dispersing agent is an epoxy silane compound which has amino groups and hydrolytic groups or hydroxyl groups such as gamma-aminopropyltriethoxysilane, N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane and the like, an epoxy silane compound which has epoxy groups and hydrolytic groups or hydroxyl groups such as 3-acryloxypropyltrimethoxysilane and a vinyl silane compound which has vinyl groups and hydrolytic groups or hydroxyl groups such as gamma-methacryloxypropyltrimethoxysilane and the like, and a cationic silane coupling agent, the dispersing agent can be Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010 and W903 manufactured by BYK (all of which are known as fluorescent dyes and black dyes, and black phthalocyanine black dyes, and powdery metal oxide complexes such as black phthalocyanine, black lead oxide, and aniline black lead oxide, and/or cobalt complex, and/or aniline complex.
The invention also discloses a prepreg prepared by the resin composition, the resin composition is dissolved by a solvent to prepare a glue solution, then the reinforcing material is soaked in the glue solution, and the soaked reinforcing material is heated and dried to obtain the prepreg.
Wherein the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric; preferably, the reinforcing material is glass fiber cloth, and open fiber cloth or flat cloth is preferably used in the glass fiber cloth. In addition, when the reinforcing material is a glass cloth, the glass cloth generally needs to be chemically treated to improve the interface between the resin composition and the glass cloth. The main method of the chemical treatment is a coupling agent treatment. The coupling agent used is preferably an epoxy silane, an aminosilane or the like to provide good water resistance and heat resistance.
The preparation method of the prepreg comprises the following steps: and (2) soaking the reinforcing material in the resin composition glue solution, then baking the soaked reinforcing material for 1-10min at the temperature of 100-200 ℃, and drying to obtain the prepreg.
The invention also discloses an insulating film prepared by adopting the resin composition, the resin composition is dissolved by a solvent to prepare a glue solution, then the glue solution is coated on a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the insulating film.
The preparation method of the insulating film comprises the following steps: and adding the resin composition into a solvent, dissolving to prepare a glue solution, coating the glue solution on a carrier film, heating and drying the carrier film coated with the glue solution, and forming an insulating resin layer by using the glue solution to obtain the insulating film. The solvent is selected from one or more of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether and propylene glycol methyl ether. The carrier film may be a polyethylene terephthalate (PET) film, a release film, a copper foil, an aluminum foil, or the like, and is preferably a PET film. The heating and drying conditions are baking at 100-200 ℃ for 1-10 minutes.
Further, one side of the insulating film, which faces away from the carrier film, is covered with a protective film to protect the insulating resin layer. The material of the protective film is the same as that of the carrier film, but of course, the material is not limited thereto.
The invention also discloses a laminated board, wherein a metal foil is coated on one side or two sides of one prepreg, or after at least 2 prepregs are stacked, a metal foil is coated on one side or two sides of the prepreg, and the laminated board is obtained by hot press forming.
The preparation steps of the laminated board are as follows: and covering a metal foil on one or two sides of one prepreg, or covering a metal foil on one or two sides of at least 2 prepregs after laminating, and performing hot press forming to obtain the metal foil laminated board. The pressing conditions of the above laminate were: pressing for 2-4 hours under the pressure of 0.2-5 MPa and the temperature of 180-250 ℃.
Specifically, the number of prepregs may be determined according to the thickness of a desired laminate, and one or more prepregs may be used.
The metal foil can be copper foil or aluminum foil, and the material is not limited; the thickness of the metal foil is also not particularly limited, and may be, for example, 5 micrometers, 8 micrometers, 12 micrometers, 18 micrometers, 35 micrometers, or 70 micrometers.
The invention also provides a printed wiring board which comprises at least one prepreg or laminated board or at least one insulating film.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention develops a new active ester resin which simultaneously has allyl and active ester groups, so that the active ester resin can be simultaneously combined with bismaleimide resin through the allyl and epoxy resin through the active ester group, thereby having the advantages of the bismaleimide resin and the active ester resin, and finally obtaining a resin composition with excellent heat resistance, dielectric property and low water absorption rate, and experiments prove that: the prepreg and the laminated board prepared from the composition have excellent heat resistance, damp and heat resistance, dielectric property, low water absorption and lower XY axis thermal expansion coefficient, can be applied to IC packaging and high-speed and high-frequency fields, and have wide application prospects;
2. the active ester resin can freely adjust the mol ratio of allyl and active ester in the resin, so that resin compositions and laminated plates with better performance can be explored and prepared, and a foundation is laid for better serving IC packaging and high-speed and high-frequency fields.
Detailed Description
The invention is further described below with reference to the following examples:
the first synthesis example:
putting 200g of diphenol aldehyde resin (shown as the following formula 3, wherein R1 is H, and X is 4- (4' -benzylidene) benzyl), a proper amount of sodium hydroxide and 200g of toluene in a flask under the protection of nitrogen, stirring to completely dissolve, heating to 80 ℃, gradually dripping 38g of allyl chloride, stopping reaction after 5 hours of reaction, cooling to room temperature, neutralizing with hydrochloric acid, filtering, distilling and the like to obtain partially allylated phenol aldehyde resin A1 (the hydroxyl equivalent is 440 g/mol);
440 parts by mass of partially allylated phenol resin A1 and 500 parts by mass of toluene were put into a flask in a nitrogen atmosphere and stirred to be dissolved; then, 140 parts by mass of benzoyl chloride is added and stirred to be dissolved; controlling the temperature of the system below 60 ℃, and dropwise adding 200g of 20% sodium hydroxide aqueous solution for 3 hours; after the dropwise addition, the mixture is kept in the state and is continuously stirred for 1 hour to react; after the reaction is finished, standing the reaction mixture, separating liquid, and removing a water layer; this operation was repeated until the pH of the aqueous layer became 7, and then toluene or the like was distilled off under heating and reduced pressure to obtain an allyl group-containing active ester resin B1 (the total molar ratio of allyl groups to the active ester groups was 0.5) having an active ester equivalent of 500 g/mol.
Synthesis example two:
adding 104g of phenol-formaldehyde resin (shown as formula 3, R1 is H, and X is methylene), a proper amount of sodium hydroxide and 200g of toluene into a flask under the protection of nitrogen, stirring to completely dissolve the phenol-formaldehyde resin, heating to 80 ℃, gradually adding 23g of allyl chloride dropwise, stopping the reaction after reacting for 5H, cooling to room temperature, and performing neutralization with hydrochloric acid, suction filtration, distillation and other operation processes to obtain partially allylated phenol-formaldehyde resin A2 (the hydroxyl equivalent is 170 g/mol);
170 parts by mass of partially allylated phenol resin A2 and 300 parts by mass of toluene were put into a flask in a nitrogen atmosphere and stirred to be dissolved; then, 140 parts by mass of benzoyl chloride is added and stirred to be dissolved; controlling the temperature of the system below 60 ℃, and dropwise adding 200g of 20% sodium hydroxide aqueous solution for 3 hours; after the dropwise addition, the mixture is kept in the state and is continuously stirred for 1 hour to react; after the reaction is finished, standing the reaction mixture, separating liquid, and removing a water layer; this operation was repeated until the pH of the aqueous layer became 7, and then toluene or the like was distilled off under heating and reduced pressure to obtain an active ester equivalent of 270g/mol of an allyl group-containing active ester resin B2 (the molar ratio of allyl groups to the total of allyl groups and active ester groups: 0.3).
Synthesis example three:
in a flask, 200g of diphenol aldehyde resin (formula 3, R1 is H, X is 4- (4' -benzylidene) benzyl) and 300 parts by mass of toluene are added under nitrogen atmosphere, and stirred to be dissolved; then, 70 parts by mass of benzoyl chloride is added and stirred to be dissolved; controlling the temperature of the system below 60 ℃, and dropwise adding 200g of 20% sodium hydroxide aqueous solution for 3 hours; after the dropwise addition, the mixture is kept in the state and is continuously stirred for 1 hour to react; after the reaction is finished, standing the reaction mixture, separating liquid, and removing a water layer; this operation was repeated until the pH of the aqueous layer became 7, and then toluene or the like was distilled off under heating and reduced pressure to obtain an active ester resin B3 (the total molar ratio of allyl groups to the active ester groups was 0, that is, no allyl groups) having an active ester equivalent of 210 g/mol.
The first embodiment is as follows:
adopting 150 parts of active ester resin B, 25 parts of diphenol aldehyde epoxy resin, 25 parts of biphenyl type multifunctional bismaleimide resin, 0.2 part of 2-ethyl-4-methylimidazole, 10 parts of bis-DOPO ethane, 150 parts of spherical silicon micro powder and a proper amount of butanone for dissolving, and uniformly stirring and mixing to obtain glue solution with 70% of solid content;
and (3) dipping the glue solution by using 2116E glass fiber cloth, and drying in an oven at 160 ℃ for 5min to obtain a prepreg.
The 4 prepregs are stacked in order, a 12-micron low-profile electrolytic copper foil is placed on each prepreg, and the prepregs are placed in a vacuum hot press to be pressed to obtain a copper-clad plate; the specific pressing process is pressing for 1.5 hours under the pressure of 2.5Mpa and the temperature of 220 ℃. The properties of the copper-clad laminate obtained are shown in Table 1.
Example two:
adopting 140 parts of active ester resin B, 20 parts of diphenol epoxy resin, 20 parts of bis (3-ethyl-5-methyl-4-maleimide phenyl) methane, 20 parts of bisphenol A cyanate ester, 0.2 part of 2-ethyl-4-methylimidazole, 10 parts of bis DOPO ethane, 150 parts of spherical silica micropowder and a proper amount of butanone for dissolving, and stirring and mixing uniformly to obtain a glue solution with 70 percent of solid content; the preparation methods of the prepreg and the copper-clad laminate are the same as those of the first embodiment. The properties of the copper-clad laminate obtained are shown in Table 1.
Example three:
the active ester resin B240 parts, the diphenol epoxy resin 40 parts, the 2, 2-bis {4- (4-maleimide phenoxy) -phenyl } propane 20 parts, the 2-ethyl-4-methylimidazole 0.2 part, the bis-DOPO ethane 10 parts, the spherical silicon micropowder 150 parts and a proper amount of butanone are adopted for dissolving, and the solution is stirred and mixed uniformly to obtain a glue solution with the solid content of 70%. The preparation methods of the prepreg and the copper-clad laminate are the same as those of the first embodiment. The properties of the copper-clad laminate obtained are shown in Table 1.
Example four:
240 parts of active ester resin B, 30 parts of epoxidized polybutadiene epoxy resin, 15 parts of polyfunctional bismaleimide resin, 15 parts of bisphenol A cyanate ester, 0.2 part of 2-ethyl-4-methylimidazole, 0.5 part of DCP, 10 parts of bis-DOPO ethane, 150 parts of spherical silica micropowder and a proper amount of butanone are adopted for dissolving, and the mixture is stirred and mixed uniformly to obtain glue solution with 70 percent of solid content.
The preparation methods of the prepreg and the copper-clad laminate are the same as those of the first embodiment. The properties of the copper-clad laminate obtained are shown in Table 1.
Comparative example one:
the active ester resin B335 parts, the diphenol epoxy resin 43 parts, the 2, 2-bis {4- (4-maleimide phenoxy) -phenyl } propane 22 parts, the 2-ethyl-4-methylimidazole 0.2 part, the bis-DOPO ethane 10 parts, the spherical silica powder 150 parts and a proper amount of butanone are adopted for dissolving, and the mixture is stirred and mixed uniformly to obtain a glue solution with the solid content of 70%.
The preparation methods of the prepreg and the copper-clad laminate are the same as those of the first embodiment. The properties of the copper-clad laminate obtained are shown in Table 1.
Comparative example two:
50 parts of allyl phenolic resin, 25 parts of diphenol aldehyde epoxy resin, 25 parts of biphenyl type multifunctional bismaleimide resin, 0.2 part of 2-ethyl-4-methylimidazole, 10 parts of bis-DOPO ethane, 150 parts of spherical silicon micropowder and a proper amount of butanone are adopted for dissolving, and the components are stirred and mixed uniformly to obtain glue solution with 70% of solid content.
The preparation methods of the prepreg and the copper-clad laminate are the same as those of the first embodiment.
The properties of the copper-clad laminate obtained are shown in Table 1.
TABLE 1 Properties of copper-clad laminates obtained by Using various examples and comparative examples
Note:
1) the glass transition temperature adopts DMA, the model is TA., the heating rate is 10 ℃/min, and the frequency is 10 Hz;
2) PCT 5hrs water absorption, 3 samples with thickness of 10cm × 10cm and thickness of 0.40mm and metal foil removed on both sides are dried at 100 deg.C for 2 hours, weighed, and the weight is recorded as W1, and then treated in autoclave cooking test (Pressure Cooker test) machine at 121 deg.C and 2 atmospheric Pressure for 5 hours, and weighed, and the weight is recorded as W2, and the water absorption is (W2-W1)/W1 100%;
3) x-axis CTE: adopting TMA (three-dimensional model), raising the temperature rate, and testing the temperature range to be 30-100 ℃;
4) dielectric constant, dielectric loss: the dielectric constant at 10GHz was measured using a Keysight network analyzer.
As seen from Table 1, in comparative example 1, which employs an active ester containing no allyl group, heat resistance and electrical properties are deteriorated; in comparative example 2, the dielectric properties were deteriorated and the water absorption rate was increased by using the allylphenol resin. The prepreg and the laminated board prepared from the thermosetting resin composition have excellent dielectric property, heat resistance, low water absorption and XY axis thermal expansion coefficient.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. An active ester resin characterized by: the chemical structural formula of the compound comprises at least one of the following structural formula (1) and structural formula (2):
wherein n is an integer of 1-10; r1 and R2 are the same or different and are respectively hydrogen, alkyl, alkoxy, aryl or aryloxy; x is
(m is 0 or 1) or
Y1、Y2、Y3The same or different are-CH 2-CH ═ CH2Or
Wherein R3 is aryl or substituted aryl;
in the structural formula of the active ester resin, the compound is represented by-CH 2-CH ═ CH2And
the total molar amount of-CH 2-CH ═ CH is 1.0mol2The molar amount of (b) is 0.05 to 0.95 mol.
2. The active ester resin of claim 1, wherein: said Y is1、Y2、Y3The same or different are-CH 2-CH ═ CH2Or
Wherein R3 is phenyl or naphthyl,
in the structural formula of the active ester resin, the compound is represented by-CH 2-CH ═ CH2And
the total molar amount of-CH 2-CH ═ CH is 1.0mol2The molar amount of (b) is 0.2 to 0.8 mol.
3. A method of preparing the active ester resin of claim 1, wherein: is prepared by esterifying aromatic carboxylic acid or its halide with partially allylated phenolic resin.
4. A thermosetting resin composition, comprising: by weight:
(1) the active ester resin of claim 1: 20-70 parts of (by weight),
(2) maleimide resin: 10-40 parts of (by weight),
(3) epoxy resin: 10-60 parts.
5. The resin composition according to claim 4, characterized in that: the maleimide resin is a compound containing two or more imide rings in the molecular structure.
6. The resin composition according to claim 4, further comprising a filler in an amount of 0 to 200 parts by weight based on 100 parts by weight of the resin composition;
the filler is an organic filler or an inorganic filler, wherein the inorganic filler is selected from one or more of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
7. A prepreg produced using the resin composition according to any one of claims 4 to 6, characterized in that: dissolving the resin composition with a solvent to prepare a glue solution, then soaking the reinforcing material in the glue solution, and heating and drying the soaked reinforcing material to obtain the prepreg.
8. A laminate, characterized by: the laminate can be obtained by coating a metal foil on one side or both sides of a prepreg according to claim 7, or by laminating at least 2 prepregs according to claim 7, coating a metal foil on one side or both sides, and hot press forming.
9. An insulating film produced from the resin composition according to any one of claims 4 to 6, wherein the resin composition is dissolved in a solvent to prepare a glue solution, the glue solution is applied to a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the insulating film.
10. A printed wiring board comprising at least one prepreg or laminate according to claim 7 or at least one insulating film according to claim 9.
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