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CN111393594B - Active ester resin and resin composition thereof - Google Patents

Active ester resin and resin composition thereof Download PDF

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Publication number
CN111393594B
CN111393594B CN202010364287.1A CN202010364287A CN111393594B CN 111393594 B CN111393594 B CN 111393594B CN 202010364287 A CN202010364287 A CN 202010364287A CN 111393594 B CN111393594 B CN 111393594B
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resin
active ester
parts
resin composition
weight
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CN111393594A (en
Inventor
黄荣辉
崔春梅
戴善凯
谌香秀
陈诚
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Suzhou Shengyi Technology Co Ltd
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Suzhou Shengyi Technology Co Ltd
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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
    • 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
    • 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
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

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

Active ester resin and resin composition thereof
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 the curing process with the epoxy resins, and simultaneously, the cured products have lower water absorption rate, better dielectric constant and dielectric loss due to the low polarity of the structures of the cured products. 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):
Figure BDA0002476042370000021
Figure BDA0002476042370000022
wherein n = an integer of 1 to 10; r1 and R2 are the same or different and are respectively hydrogen, alkyl, alkoxy, aryl or aryloxy; x is
Figure BDA0002476042370000023
Figure BDA0002476042370000024
(m =0 or 1) or
Figure BDA0002476042370000025
Y 1 、Y 2 、Y 3 Same or different, -CH2-CH = CH respectively 2 Or
Figure BDA0002476042370000026
Wherein R3 is aryl or substituted aryl;
in the structural formula of the active ester resin, the resin takes-CH 2-CH = CH 2 And
Figure BDA0002476042370000027
is 1.0mol, -CH2-CH = CH 2 The molar amount of (b) is 0.05 to 0.95mol.
Preferably, said Y is 1 、Y 2 、Y 3 Same or different, -CH2-CH = CH respectively 2 Or
Figure BDA0002476042370000028
Wherein R3 is phenyl or naphthyl,
in the structural formula of the active ester resin, the resin is represented by-CH 2-CH = CH 2 And
Figure BDA0002476042370000029
is 1.0mol, -CH2-CH = CH 2 The molar amount of (b) is 0.2 to 0.8mol. More preferably, in the structural formula of the active ester resin, the resin has the structure of-CH 2-CH = CH 2 And
Figure BDA00024760423700000210
the total molar amount of (C) is 1.0mol, and-CH 2-CH＝CH 2 The 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 0.9mol.
The invention also claims a preparation method of the active ester resin, which is prepared by esterifying aromatic carboxylic acid or halide thereof and 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 formed 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 means that a part of phenolic hydroxyl groups in the phenolic resin are converted to allyl groups such that-CH 2-CH = CH 2 And the total molar amount of-OH is 1.0mol, -CH2-CH = CH 2 The molar amount of (b) is 0.05 to 0.95mol.
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 the molecular structure.
Still more preferably, the maleimide resin has the following structural formula (4):
Figure BDA0002476042370000031
wherein, R group is selected from at least one of the following structural formulas:
Figure BDA0002476042370000032
Figure BDA0002476042370000041
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 naphthalene ring type epoxy resin having a structural formula shown in formula (5), the biphenyl type epoxy resin having a structural formula shown in formula (6), the dicyclopentadiene type epoxy resin having a structural formula shown in formula (7):
Figure BDA0002476042370000042
wherein p is an integer of 1 to 10;
Figure BDA0002476042370000043
wherein n is an integer of 1 to 10;
Figure BDA0002476042370000051
wherein m is an integer of 1 to 10.
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 oxides, metal nitrides, non-metal nitrides, inorganic hydrates, inorganic salts, metal hydrates 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 used 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 in space and in the interest of brevity, and the invention is not intended to be exhaustive of the specific points included in the range. Preferably, the filler content is 10 to 100 parts by weight, more preferably, 30 to 70 parts by weight.
Preferably, the filler has a median particle size 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 filler has a median particle size value of from 1 to 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 of 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 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 of 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 benzoxazine (d).
As a further preferred of the present invention, a thermosetting resin composition comprises, by weight: 20 to 70 parts of 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; 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 the present invention, the final product may further comprise other additives in an amount of 0 to 5 parts by weight based on 100 parts by weight of the resin composition. The other auxiliary agents comprise a coupling agent, a dispersing agent, a defoaming agent, a flatting 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 aminosilane coupling agent; the dispersant is amino silane compound having amino group and having hydrolytic group or hydroxyl group such as gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, epoxy silane compound having epoxy group and having hydrolytic group or hydroxyl group such as 3-acryloxypropyltrimethoxysilane, vinyl silane compound having vinyl group and having hydrolytic group or hydroxyl group such as gamma-methacryloxypropyltrimethoxysilane, or cationic silane coupling agent, and the dispersant can be Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010, W903 (all product names) manufactured by BYK; the dye is a fluorescent dye and a black dye, wherein the fluorescent dye is pyrazoline and the like, and the black dye is carbon black (liquid or powder), a pyridine complex, an azo complex, aniline black, black talcum powder, cobalt chromium metal oxide, azine, phthalocyanine and the like.
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 (3) soaking the reinforced material in the resin composition glue solution, then baking the soaked reinforced material for 1-10min at the temperature of 100-200 ℃, and drying to obtain the prepreg.
The invention also discloses an insulating film prepared from 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-dimethylformamide, 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 above heating and drying conditions are baking at 100-200 deg.C for 1-10 min.
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 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, such as 5 microns, 8 microns, 12 microns, 18 microns, 35 microns, or 70 microns.
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 boards 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 biphenyl phenolic resin (as shown in the following formula 3, 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 5H of reaction, cooling to room temperature, neutralizing with hydrochloric acid, filtering, distilling and the like to obtain partially allylated phenolic resin A1 (the hydroxyl equivalent is 440 g/mol);
Figure BDA0002476042370000101
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-containing active ester resin B1 (the total molar ratio of allyl groups to allyl groups and active ester groups was 0.5) having an active ester equivalent of 500g/mol.
Synthesis example two:
adding 104g of phenol-phenolic resin (shown as formula 3, R1 is H, and X is methylene), a proper amount of sodium hydroxide and 200g of toluene in a flask under the protection of nitrogen, stirring to completely dissolve the phenol-phenolic resin, heating to 80 ℃, gradually dripping 23g of allyl chloride, stopping the reaction after reacting for 5 hours, cooling to room temperature, and performing neutralization with hydrochloric acid, suction filtration, distillation and other operation processes to obtain partially allylated phenolic 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 water 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 total molar ratio of allyl groups to active ester groups was 0.3).
Synthesis example three:
in a flask, under the atmosphere of nitrogen, 200g of biphenyl phenol formaldehyde resin (shown as a formula 3, R1 is H, and X is 4- (4' -benzylidene) benzyl) and 300 parts by mass of toluene are added, 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 under reduced pressure to obtain an active ester resin B3 (the total molar ratio of allyl groups to active ester groups was 0, that is, no allyl groups) having an active ester equivalent of 210g/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) soaking the glue solution in 2116E glass fiber cloth, and drying in a 160 ℃ drying oven 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 of synthesis example 3, the diphenol epoxy resin 43 parts, 2-bis {4- (4-maleimide phenoxy) -phenyl } propane 22 parts, 2-ethyl-4-methylimidazole 0.2 part, bis-DOPO ethane 10 parts, the spherical silicon powder 150 parts and a proper amount of butanone are dissolved and stirred and mixed uniformly to obtain a 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.
Comparative example two:
50 parts of allyl phenolic resin, 25 parts of diphenol 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 powder and a proper amount of butanone are adopted for dissolving, and a glue solution with 70 percent of solid content is obtained by stirring and mixing uniformly.
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
Figure BDA0002476042370000121
Note:
1) The glass transition temperature adopts DMA, the type is TA.. The heating rate is 10 ℃/min, and the frequency is 10Hz;
2) PCT 5hrs water absorption: taking 3 samples with the thickness of 10cm multiplied by 10cm and the thickness of 0.40mm and with metal foils removed on two sides, drying at 100 ℃ for 2 hours, weighing, and recording the weight as W1, then processing at 121 ℃ and 2 atmospheric pressures in a Pressure Cooker test machine for 5 hours, weighing, recording the weight as W2, and recording the water absorption rate as (W2-W1)/W1 x 100%;
3) X-axis CTE: TMA is adopted, the heating rate is increased, and the test temperature range is 30-100 ℃;
4) Dielectric constant, dielectric loss: the dielectric constant at 10GHz was measured using a Keysight network analyser.
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):
Figure FDA0003882293600000011
structural formula (1),
Figure FDA0003882293600000012
In the structural formula (2),
wherein n = an integer of 1 to 10; r1 and R2 are the same or different and are respectively hydrogen, alkyl, alkoxy, aryl or aryloxy; x is
Figure FDA0003882293600000013
Figure FDA0003882293600000014
m =0 or 1, or
Figure FDA0003882293600000015
Y 1 、Y 2 、Y 3 Are the same or different and are each-CH 2 -CH＝CH 2 Or
Figure FDA0003882293600000016
Wherein R3 is aryl or substituted aryl;
in the structural formula of the active ester resin, the active ester resin is represented by-CH 2 -CH＝CH 2 And
Figure FDA0003882293600000017
the total molar amount of (b) is 1.0mol 2 -CH＝CH 2 The molar amount of (b) is 0.05 to 0.95mol.
2. The active ester resin of claim 1, wherein: said Y is 1 、Y 2 、Y 3 Are the same or different and are each-CH 2 -CH＝CH 2 Or
Figure FDA0003882293600000018
Wherein R3 is phenyl or naphthyl,
in the structural formula of the active ester resin, the active ester resin is represented by-CH 2 -CH＝CH 2 And
Figure FDA0003882293600000019
the total molar amount of (C) is 1.0mol 2 -CH＝CH 2 The molar amount of (B) is 0.2 to 0.8mol.
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 oxides, metal nitrides, non-metal nitrides, inorganic hydrates, inorganic salts, metal hydrates or inorganic phosphorus; the organic filler is selected from at least one of 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: and dissolving the resin composition by using 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 sheet of the prepreg according to claim 7 or the laminate according to claim 8 or at least one insulating film according to claim 9.
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