CN114230979B - Resin composition, prepreg, laminated board and printed wiring board - Google Patents

Resin composition, prepreg, laminated board and printed wiring board Download PDF

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CN114230979B
CN114230979B CN202010943038.8A CN202010943038A CN114230979B CN 114230979 B CN114230979 B CN 114230979B CN 202010943038 A CN202010943038 A CN 202010943038A CN 114230979 B CN114230979 B CN 114230979B
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resin composition
resin
prepreg
structural formula
parts
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CN114230979A (en
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崔春梅
何继亮
马建
任科秘
王宁
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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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/02—Coating on the layer surface on 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

Abstract

The invention discloses a resin composition, a prepreg, a laminated board and a printed wiring board, wherein the resin composition mainly comprises epoxy resin, maleimide compound and active ester compound containing carbon-carbon unsaturated groups. Experimental data demonstrates that: the resin composition of the invention can meet the current 5G products of prepregs, laminates and printed wiring boards prepared by the resin composition.

Description

Resin composition, prepreg, laminated board and printed wiring board
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a resin composition containing a modified active ester compound, a prepreg, a laminated board and a printed wiring board prepared from the resin composition.
Background
With the upgrade of technology, the consumer electronic market such as automobile market and smart phone has put forth new demands on PCB, and by 2018, with the commercial marketing of 5G, the requirements on dielectric properties of PCB substrate are higher, and the high-frequency high-speed copper-clad plate is one of the indispensable electronic substrates in the 5G age. In short, PCB substrate materials are required to have low dielectric constants and dielectric loss tangents to reduce delay, distortion and loss of signals and interference between signals at high speed transmission. Accordingly, it is desirable to provide a thermosetting resin composition with which a printed wiring board produced can exhibit a sufficiently low dielectric constant and low dielectric loss tangent during signal transmission at high speeds and high frequencies.
In the prior art, JP2002012650A, JP2003082063A, JP2004155990A, JP2009235165A and JP2012246367A disclose a series of active ester resins which are used as an epoxy resin curing agent to suitably reduce the dielectric constant and dielectric loss of an epoxy resin cured product.
However, when the resin system is used to prepare a high-performance substrate for high frequency and high speed, in order to improve heat resistance, thermal expansion coefficient or flame retardancy, it is necessary to add other components such as bismaleimide resin, benzoxazine resin or phosphorus-containing flame retardant to the resin composition, and therefore the dielectric constant of the substrate material finally obtained still fails to satisfy the requirements of the high-frequency and high-speed substrate.
In view of the above, there is a need to provide a novel resin composition, a prepreg, a laminate, and a printed wiring board prepared therefrom to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a resin composition containing a modified active ester compound, a prepreg, a laminated board and a printed wiring board prepared from the resin composition. The prepreg, the laminated board and the printed circuit board prepared from the resin composition have low dielectric constant, low dielectric loss and high toughness.
In order to achieve the aim of the invention, the invention adopts the following technical scheme: a resin composition comprising, by weight:
(A) Epoxy resin: 10-80 parts of a lubricant;
(B) Curing agent: 10-80 parts of a lubricant;
(C) Crosslinking agent containing unsaturated bond: 1-60 parts;
the curing agent comprises an active ester compound containing a structural formula (1) or/and a structural formula (2):
Figure BDA0002674297640000021
a structural formula (1),
Figure BDA0002674297640000022
A structural formula (2),
wherein X is C containing an unsaturated group 4 -C 15 An olefinic group of (a); r is hydrogen, vinyl, allyl, acrylate, methacrylate or C 1 -C 10 Alkyl of (a); n is an integer of 1 to 20.
Further, X in the structural formula (1) and the structural formula (2) is
Figure BDA0002674297640000023
Figure BDA0002674297640000024
Further, the curing agent further comprises at least one of an amine compound, an amide compound, an acid anhydride compound, a phenol compound, a cyanate compound, and an active ester compound different from the structural formulae (1) and (2).
Further, the cross-linking agent containing unsaturated bonds is polybutadiene or modified polybutadiene, styrene or modified styrene, triallyl isocyanate resin, double bond-containing polyphenyl ether resin, double bond-containing benzoxazine resin, double bond-containing epoxy resin or maleimide resin.
Further, the resin composition also comprises a curing accelerator, and/or an initiator, and/or a flame retardant, and/or an auxiliary agent, wherein the auxiliary agent comprises at least one of a coupling agent, a dispersing agent and a dye.
Further, 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.
Further, the filler is an inorganic filler surface-treated with a silane coupling agent containing carbon-carbon unsaturated double bonds.
In order to achieve the above object, the present invention also provides a prepreg comprising a reinforcing material, and the above resin composition attached to the surface of the reinforcing material.
In order to achieve the above object, the present invention also provides a laminated board, which is formed by hot-pressing at least one side of one prepreg or at least two prepregs stacked and arranged with metal foil.
In order to achieve the above object, the present invention also provides a printed wiring board comprising at least one prepreg as described above, or at least one laminate as described above.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
the curing agent disclosed by the invention comprises an active ester compound containing an olefin group in the middle section of a molecule, so that the active ester compound does not generate polar hydroxyl with epoxy resin in the curing reaction process, and meanwhile, the cross-linked network structure of an olefin nonpolar group is increased, so that the dielectric constant and dielectric loss value of an epoxy resin curing system are further reduced; meanwhile, the olefin free radical polymerization reaction of the molecular middle section of the active ester compound is carried out, and a cross-linking agent containing double bonds is further added into the active ester compound and epoxy resin solid system, so that the olefin double bonds in the active ester compound react with the cross-linking agent containing double bonds, the dielectric property is further improved, the cross-linking structure of the whole cured product is more compact, and the brittleness problem of the maleimide cured product is improved.
Detailed Description
The following description is given of specific embodiments of the present invention, and it should be noted that, for those skilled in the art, it is possible to make several improvements and modifications without departing from the principle of the embodiments of the present invention, and these improvements and modifications are also considered as the protection scope of the embodiments of the present invention.
The terms "comprising," "including," "containing," and "containing" in this specification mean that other components, which are capable of imparting different properties to the resin composition, may be included in addition to the components.
The term "based on 100 parts by weight of the resin composition" in the present specification means that the total amount of components excluding the filler, the curing accelerator, the initiator, the auxiliary agent, and the flame retardant is 100 parts by weight.
A resin composition comprising, by weight:
(A) Epoxy resin: 10-80 parts of a lubricant;
(B) Curing agent: 10-80 parts of a lubricant;
(C) Crosslinking agent containing unsaturated bond: 1-60 parts;
the curing agent comprises an active ester compound containing a structural formula (1) or/and a structural formula (2):
Figure BDA0002674297640000041
a structural formula (1),
Figure BDA0002674297640000042
A structural formula (2),
wherein X is C containing an unsaturated group 4 -C 15 An olefinic group of (a); r is hydrogen, vinyl, allyl, acrylate, methacrylate or C 1 -C 10 Alkyl of (a); n is an integer of 1 to 20.
On one hand, the curing agent comprises an active ester compound containing olefin groups in the middle section of the molecule, so that the active ester compound does not generate polar hydroxyl groups with epoxy resin in the curing reaction process, and meanwhile, the cross-linked network structure of olefin nonpolar groups is increased, so that the dielectric constant and dielectric loss value of an epoxy resin curing system are further reduced; on the other hand, the olefin free radical polymerization reaction of the molecular middle section of the active ester compound, and the double bond-containing cross-linking agent is further added into the active ester compound and epoxy resin solid system, so that the olefin double bond in the active ester compound reacts with the double bond-containing cross-linking agent, the dielectric property is further improved, the cross-linking structure of the whole cured product is more compact, and the heat resistance of the cured product, in particular the brittleness problem of the maleimide cured product, is improved.
The cured product of the present invention may be understood as a prepreg, an insulating film, a laminate, a printed wiring board, or the like.
Further, X in the structural formula (1) and the structural formula (2) is
Figure BDA0002674297640000051
Figure BDA0002674297640000052
Further, X in the structural formulas (1) and (2) is an olefinic group containing a carbon-carbon unsaturated group in a side chain, such as
Figure BDA0002674297640000053
Figure BDA0002674297640000054
The vinyl-containing olefin group in the side chain is selected, so that the reactivity of the vinyl can be further improved, the curing crosslinking density is further improved, the crosslinking structure of the whole cured product is more compact, the dielectric constant and dielectric loss value of the epoxy resin curing system are reduced, and the heat resistance and toughness of the cured product are improved.
Further, n in the structural formula (1) and the structural formula (2) is an integer of 1-10, such as 1, 2, 3, 4, or 5, and is not limited thereto.
Further, R in the structural formula (1) and the structural formula (2) is hydrogen, vinyl, allyl, methyl, ethyl, propyl, tert-butyl or octyl.
More preferably, R in the structural formulae (1) and (2) is vinyl, allyl or propenyl, whereby the R group is coordinated to an unsaturated group-containing C in the middle 4 -C 15 Further reduces the dielectric constant and dielectric loss value of the cured product, and at the same time, obtains a more compact crosslinked network structure and improves the heat resistance of the cured product.
In one embodiment, R in the structural formula (1) and the structural formula (2) is allyl. Of course, this is not a limitation.
The preparation method of the active ester compound of the structural formula (1) or/and the structural formula (2) comprises the following steps: the following 3 reactants were reacted: the active ester compound is obtained by mixing (1) vinyl-containing aromatic bisphenol resin, (2) aromatic dicarboxylic acid or halogen compound, and (3) phenol or naphthol or modified phenol thereof, and performing chemical reaction.
The following is an example of the preparation of active ester compounds containing butadiene groups, the reaction mechanism of which is as follows:
Figure BDA0002674297640000061
of course, it is not limited thereto, and other methods may be used to prepare the active ester compounds represented by the structural formulas (1) and (2), that is, all the preparation methods capable of preparing the active ester compounds represented by the structural formulas (1) and (2) are within the scope of the present invention.
Further, the epoxy resin is at least one selected from bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S-type epoxy resin, bisphenol E-type epoxy resin, phosphorus-containing epoxy resin, nitrogen-containing epoxy resin, o-cresol formaldehyde 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 type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl novolac epoxy resin, alicyclic type epoxy resin, glycidylamine type epoxy resin, glycidylether type epoxy resin, and glycidylester type epoxy resin.
In one embodiment, the epoxy resin is naphthalene ring type epoxy resin, and the naphthalene ring type epoxy resin has better heat resistance and can enhance the heat resistance of a cured product.
The structural formula of the naphthalene ring type epoxy resin is shown as a structural formula (3),
Figure BDA0002674297640000071
structural formula (3); wherein p is an integer of 1 to 10;
in another embodiment, the epoxy resin may be selected from biphenyl type epoxy resins and dicyclopentadiene type epoxy resins, which have good dielectric properties and can further reduce the dielectric constant and dielectric loss value of the cured product.
The structural formula of the biphenyl type epoxy resin is shown as a structural formula (4), and the structural formula of the dicyclopentadiene type epoxy resin is shown as a structural formula (5):
Figure BDA0002674297640000072
structural formula (4); wherein n is an integer of 1 to 10;
Figure BDA0002674297640000081
structural formula (5), wherein m is an integer of 1-10.
Further, the cross-linking agent containing unsaturated bonds is polybutadiene or modified polybutadiene, styrene or modified styrene, triallyl isocyanate resin, double bond-containing polyphenyl ether resin, double bond-containing benzoxazine resin, double bond-containing epoxy resin or maleimide resin.
In one embodiment, the unsaturated bond-containing cross-linking agent is a maleimide resin; of course, this is not a limitation.
Further, the maleimide resin is a compound having a molecular structure containing at least an imide ring group represented by the structural formula (6):
Figure BDA0002674297640000082
formula (6), wherein R 1 H or alkyl with 1-5 carbon atoms.
The maleimide resin is further preferably a bismaleimide compound represented by the structural formula (7) or a modified prepolymer thereof:
Figure BDA0002674297640000083
structural formula (7), wherein, R group is selected from one of the following structural formulas:
Figure BDA0002674297640000091
the modified bismaleimide prepolymer is modified by allyl phenol, aromatic amine, aromatic phenol compound or benzoxazine.
Further, the curing agent further comprises at least one of an amine compound, an amide compound, an acid anhydride compound, a phenol compound, a cyanate compound, and an active ester compound different from the structural formulae (1) and (2).
Specifically, the amine-based compound may be diaminodiphenylmethane, diaminodiphenyl sulfone, diethylenetriamine, dicarboxyphthalimide, imidazole, or the like, and preferably diaminodiphenylmethane and diaminodiphenyl sulfone.
The amide compound may be dicyandiamide, low molecular polyamide, or the like, and dicyandiamide is preferable.
The acid anhydride compound may be phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride, or the like, and is preferably styrene-maleic anhydride.
The phenolic compound may be bisphenol a phenol resin, phenol resin, naphthol phenol resin, biphenyl phenol type naphthol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, or the like.
The cyanate ester compound is bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, dicyclopentadiene type cyanate ester resin, naphthalene type cyanate ester resin, biphenyl type cyanate ester resin or a combination of the cyanate ester resins.
The active ester compounds different from the structural formulas (1) and (2) can be selected from compounds shown in the following structural formula (8):
Figure BDA0002674297640000101
structure (8)
Wherein X is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; n represents a repeating unit of 0.25 to 1.25.
Further, the resin composition further contains a curing accelerator for accelerating the reaction between the epoxy resin and the active ester compound.
Specifically, the curing accelerator is at least one selected from 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, and zinc isooctanoate, for example: a mixture of 4-dimethylaminopyridine and 2-methylimidazole, a mixture of 2-methylimidazole and 2-methyl 4-ethylimidazole, a mixture of 2-phenylimidazole and zinc isooctanoate, and a mixture of 2-methylimidazole, 2-methyl 4-ethylimidazole and 2-phenylimidazole, although not limited thereto.
Further, the resin composition further comprises an initiator for opening the double bond in the olefinic group in the active ester compound represented by the structural formula (1) and/or the structural formula (2) and the double bond in the unsaturated bond-containing crosslinking agent, so that the olefinic group in the active ester compound and the double bond in the crosslinking agent can react with each other to obtain a tighter crosslinked network structure, improving the heat resistance of the cured product.
Specifically, the initiator is selected from one or more of diacyl peroxide, peroxy ketal, peroxy carbonate, peroxy ester, ketone peroxide, dialkyl peroxide and hydroperoxide.
Wherein the diacyl peroxide is selected from one or more of isononyl peroxide, decanoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide and di (3, 5-trimethylhexanoyl) peroxide; the peroxyketal is selected from 2, 2-bis (4, 4-bis- (di-tert-butylperoxy) cyclohexyl) propane; the peroxycarbonate is selected from one or two of di-3-methoxybutyl peroxydicarbonate and dicyclohexyl peroxydicarbonate; the peroxy ester is selected from one or more of tertiary butyl peroxybenzoate, tertiary butyl peroxyacetate, tertiary butyl peroxy-2-ethylhexanoate, tertiary butyl peroxyisobutyrate, tertiary butyl peroxyvalerate, tertiary butyl diperoxy adipate, cumyl peroxyneodecanoate, tertiary butyl peroxybenzoate, 1, 3-tetramethyl peroxy-2-ethylhexanoate and 2, 5-dimethyl-2, 5-di (benzoyl peroxy) hexane; the ketone peroxide is selected from one or two of methyl ethyl ketone peroxide and cyclohexanone peroxide; the dialkyl peroxide is selected from one or more of di-tertiary butyl peroxide, diisopropylbenzene peroxide, tertiary butyl isopropylbenzene peroxide, 1-di (tertiary hexyl peroxy) -3, 5-trimethylcyclohexane, di-tertiary hexyl peroxide and di (2-tertiary butyl peroxy isopropyl) benzene; the hydroperoxide is selected from one or more of cumene hydroperoxide, tertiary butyl hydroperoxide and p-menthane hydroperoxide.
Further, the resin composition further includes a filler, and it is understood that the filler may or may not be contained in the resin composition.
In the embodiment in which the 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.
Preferably, the filler content is 10 to 100 parts by weight, more preferably 30 to 70 parts by weight, such as 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, or 200 parts by weight, based on 100 parts by weight of the resin composition; and the particular values of points between the values recited above, are limited in space and are for brevity and the invention is not intended to provide an exhaustive list of the particular values of points within the range.
Specifically, the filler is an organic filler or an inorganic filler.
The inorganic filler is selected from one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus. Preferably, the inorganic filler is at least one selected from fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
Further, the inorganic filler is an inorganic filler subjected to surface treatment by using a silane coupling agent containing carbon-carbon unsaturated double bonds. For example, the surface-treated spherical silica is easier to disperse, can prevent agglomeration, and at the same time, the surface-treated spherical silica itself has a low coefficient of thermal expansion, and can prevent warping of the final product.
Specifically, the surface treatment agent is a silane coupling agent containing carbon-carbon unsaturated groups, such as a silane coupling agent containing vinyl, acrylate or allyl groups, and specifically KBM-503, KBE-503, KBM-502, KBM-575, KBE-502, KBM-5103, KBM-1083 and the like can be selected from the group consisting of Xinyue chemical systems.
Further, the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
In addition, the median particle size of the filler is 1 to 15. Mu.m, for example 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, and the specific values between the above values, are limited in space and in the interest of brevity, the invention is not intended to be exhaustive of the specific values included in the ranges.
More preferably, the particle size of the filler has a median value of 1-10 mu m, is easier to disperse and has better anti-agglomeration effect.
Further, the resin composition further includes a flame retardant to improve flame retardancy of a finally formed cured product, which can be understood as a prepreg, an insulating film, a metal foil-clad laminate, a printed wiring board, and the like.
Further, the content of the flame retardant is 1 to 80 parts by weight, for example, 1 part by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, 50 parts by weight, 70 parts by weight, 80 parts by weight, and specific point values between the above values, based on 100 parts by weight of the resin composition, is limited in terms of space and for brevity, and the present invention is not exhaustive of the specific point values included in the range.
Preferably, the content of the flame retardant is 5 to 50 parts by weight, in order to prevent the flame retardant content from being too large, affecting the performance of the prime resin composition, and too small, making the final cured product unable to meet the requirement for flame retardant performance.
Specifically, the flame retardant may be a brominated flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an organometallic salt flame retardant, an inorganic flame retardant, or the like.
Wherein the brominated flame retardant can be decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalic acid amide. The phosphorus flame retardant may be inorganic phosphorus, phosphate compound, phosphoric acid compound, hypophosphorous acid compound, phosphorus oxide compound, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ),
Figure BDA0002674297640000131
(m is an integer of 1 to 5),
Figure BDA0002674297640000132
Organic phosphorus-containing compounds such as 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2, 6-dimethylphenyl) phosphorus, phosphazene and modified phosphazene. The nitrogen-based flame retardant may be a triazine compound, cyanuric acid compound, isocyanic acid compound, phenothiazine, or the like. The silicone flame retardant may be silicone oil, silicone rubber, silicone resin, or the like. The organometallic flame retardant may beAnd ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, etc. The inorganic flame retardant may be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, or the like.
Of course, the type of flame retardant is not limited thereto, and it is understood that the flame retardant to be added may be selected according to the specific application area of the laminate, for example, application area where halogen is required, preferably a non-halogen flame retardant such as a phosphorus-containing or nitrogen-containing flame retardant, more preferably phosphazenes (such as the marks SPB-100), DOPO or DOPO-HQ, modified phosphazenes (such as the marks BP-PZ, PP-PZ, SPCN-100, SPV-100 and SPB-100L),
Figure BDA0002674297640000133
Preferably, the flame retardant is selected from high melting point phosphorus-containing flame retardants,
such as
Figure BDA0002674297640000134
Further, depending on the requirements of the final product, an auxiliary agent is further included in the resin composition, preferably, 0 to 5 parts by weight based on 100 parts by weight of the resin composition.
Specifically, the auxiliary agent comprises a coupling agent, a dispersing agent 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 dispersant is an amino silane compound having an amino group and having a hydrolyzable group or a hydroxyl group, such as γ -aminopropyl triethoxysilane, N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, an epoxy silane compound having an epoxy group and having a hydrolyzable group or a hydroxyl group, such as 3-acryloxypropyl trimethoxysilane, a vinyl silane compound having a vinyl group and having a hydrolyzable group or a hydroxyl group, such as γ -methacryloxypropyl trimethoxysilane, a cationic silane coupling agent, and the dispersant may be Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010, W903 (all are product names) manufactured by BYK; the dye is fluorescent dye and black dye, wherein the fluorescent dye is pyrazoline and the like, and the black dye is liquid or powder carbon black, pyridine complex, azo complex, nigrosine, black talcum powder, cobalt chromium metal oxide, azine, phthalocyanine and the like.
Furthermore, the invention also provides a prepreg, which is formed by soaking the reinforcing material in the glue solution of the resin composition and then heating and drying.
Specifically, the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric; preferably, the reinforcing material is a glass fiber cloth, and a split cloth or a flat cloth is preferably used in the glass fiber cloth.
In addition, when the reinforcing material is a glass fiber cloth, the glass fiber cloth generally needs to be chemically treated to improve the bonding force between the resin composition and the interface of the glass fiber cloth. The main method of the chemical treatment is coupling agent treatment. The coupling agent used is preferably epoxy silane or amino silane or the like to provide good water resistance and heat resistance.
The preparation method of the prepreg comprises the following steps: adding a solvent into the resin composition to dissolve the resin composition to prepare a resin composition glue solution, and dipping the reinforcing material into the resin composition glue solution; and then heating and drying the impregnated reinforcing material to obtain the prepreg.
In one embodiment, the impregnated reinforcing material is baked for 1min to 10min at the temperature of 50 ℃ to 170 ℃ and dried to obtain the prepreg.
The organic solvent used for dissolving the resin composition in the present invention is not particularly limited. For example, the organic solvent may be one or a combination of several selected from acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.
The amount of the solvent to be added is selected by one skilled in the art according to his own experience, as long as the resulting resin composition dope can be brought to a viscosity suitable for use.
Further, the invention also provides a laminated board which comprises at least one prepreg and a metal foil formed on at least one surface of the prepreg.
In an embodiment in which the laminate comprises at least two prepregs as described above, the at least two prepregs are stacked and bonded together by heat and pressure, and then metal copper foil is bonded on one or both sides of the bonded prepregs by heat and pressure to form the laminate.
Specifically, the laminate was prepared as follows: and (3) coating metal foil on one side or both sides of one piece of the prepreg, or coating metal foil on one side or both sides of at least 2 pieces of the prepreg after overlapping, and performing hot press forming to obtain the metal foil laminated plate.
The pressing conditions of the laminated board are as follows: pressing for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃.
In particular, the number of prepregs may be determined according to the thickness of the laminate as desired, and one or more prepregs may be used.
The metal foil can be copper foil or aluminum foil, and the material of the metal foil 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.
Furthermore, the invention also provides a printed circuit board which comprises at least one prepreg or/and laminated board.
The preparation method of the printed wiring board can adopt the existing technology, and is not repeated here.
The following describes the present invention in detail with reference to specific examples; and the embodiments of the present invention are not limited to these embodiments.
Synthesis example 1:
taking butadiene-containing bisphenol resin and benzene dicarboxylic acid, uniformly stirring and dissolving in a toluene solvent, simultaneously introducing nitrogen at the temperature of 50 ℃, adding a tetrabutylammonium bromide catalyst, slowly dripping a sodium hydroxide aqueous solution with the concentration of 20%, reacting for 2.5 hours, adding phenol, continuing reacting for 1 hour, and drying for 3 hours under the vacuum condition of 80 ℃ after the reaction is finished and washing for several times to obtain the active ester compound A, wherein the chemical structural formula is as follows:
Figure BDA0002674297640000161
synthesis example 2:
taking pentadienyl phenol resin and benzene dicarboxylic acid, stirring and dissolving uniformly in toluene solvent, introducing nitrogen at the temperature of 50 ℃, adding tetrabutylammonium bromide catalyst, slowly dripping sodium hydroxide aqueous solution with the concentration of 20%, reacting for 2.5 hours, adding p-vinylphenol, continuing reacting for 0.5 hour, and drying for 3 hours under the vacuum condition of 80 ℃ after the reaction is finished and washing for several times to obtain the active ester compound B, wherein the chemical structural formula is as follows:
Figure BDA0002674297640000162
examples 1-5 and comparative examples 1-3:
the components and contents of the resin compositions of examples 1 to 5 and comparative examples 1 to 3 are shown in Table 1 below:
TABLE 1
Figure BDA0002674297640000163
Figure BDA0002674297640000171
Wherein the component information involved in examples 1-5 and comparative examples 1-3 is shown in Table 2 below:
TABLE 2
Figure BDA0002674297640000172
The preparation methods of the resin compositions of examples 1 to 5 and comparative examples 1 to 3 employ conventional preparation methods, specifically: the epoxy resin A, the epoxy resin B, the active ester compounds A-B obtained in Synthesis examples 1-2, the active ester C in the prior art, the active ester D in the prior art, the bismaleimide compound, the curing agent, the filler, the catalyst, the initiator and a proper amount of butanone solvent were stirred and mixed uniformly according to the components and the corresponding contents in Table 1 to obtain a resin composition glue solution with a solid content of 65%, wherein the solid content is 65% by weight.
The obtained resin composition glue solutions of examples 1 to 5 and comparative examples 1 to 3 were respectively impregnated and coated on E glass fiber cloth (7628), and baked in an oven at 160℃for 5 minutes to prepare prepregs of examples 1 to 5 and comparative examples 1 to 3, respectively.
Preparation for performance evaluation sample laminates were evaluated:
(1) Preparation of laminates
The prepregs obtained in examples 1 to 5 and comparative examples 1 to 3 were each placed with 18 μm metal copper foil on top of each other, and were placed in a vacuum hot press to be pressed to obtain laminated boards, respectively. The specific pressing process is to press for 2 hours at the temperature of 180-220 ℃ under the pressure of 1.5 MPa.
The performance evaluation method comprises the following steps:
(1) Glass transition temperature Tg (c): the measurement was performed according to the DSC method defined in IPC-TM-6502.4.25 by differential scanning calorimetry.
(2) Dielectric constant: the dielectric constant at 10GHz was measured using the plate method according to IPC-TM-650.2.5.5.9 using laminate a.
(3) Dielectric loss tangent: the dielectric loss factor at 1GHz was measured using the plate method according to IPC-TM-650 2.5.5.9 with laminate a.
(4) Tin immersion heat resistance: the time for delamination of the bubbles of the sample was recorded using a 50X 50mm double sided copper sample immersed in 288℃solder.
(5) Impact toughness testing using a 5512 impactor, impact hammer height: 45cm, the weight of the dropping weight was 1kg. Evaluation of good and poor toughness: the cross is clear and slender, and the better the toughness of the product is, the marking number is O; in contrast, the cross is fuzzy or is not provided, so that the product has poor toughness and large brittleness, and the mark number is ≡; the cross is between clear and simulated, and the toughness is still good, and the mark is +.
The properties of the laminates obtained using the prepregs in examples 1 to 5 and comparative examples 1 to 3, respectively, are shown in Table 3 below.
TABLE 3 Table 3
Figure BDA0002674297640000191
As is clear from the above table, the laminate obtained by using the resin composition of the present invention has a lower dielectric constant and low dielectric loss, and at the same time, a higher glass transition temperature and better toughness.
In particular, it is evident from the parallel comparison of example 1 and comparative example 2 that example 1 has a higher glass transition temperature, a lower dielectric constant, a dielectric loss value, and a better toughness than comparative example 2, and that example 2 has a higher glass transition temperature, a lower dielectric constant, a dielectric loss value, and a better toughness than comparative example 3, as is evident from the parallel comparison of example 2 and comparative example 3.
Meanwhile, other curing agents are added into the resin system, so that a cured product with excellent comprehensive performance can be obtained.
It should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is for clarity only, and that the skilled artisan should recognize that the embodiments may be combined as appropriate to form other embodiments that will be understood by those skilled in the art.
The above list of detailed descriptions is only specific to practical embodiments of the present invention, and they are not intended to limit the scope of the present invention, and all equivalent embodiments or modifications that do not depart from the spirit of the present invention should be included in the scope of the present invention.

Claims (9)

1. A resin composition comprising, by weight:
(A) Epoxy resin: 10-80 parts of a lubricant;
(B) Curing agent: 10-80 parts of a lubricant;
(C) Crosslinking agent containing unsaturated bond: 1-60 parts;
the curing agent comprises an active ester compound containing a structural formula (1) or/and a structural formula (2):
Figure QLYQS_1
a structural formula (1),
Figure QLYQS_2
A structural formula (2),
wherein R is hydrogen, vinyl, allyl, acrylate, methacrylate or C 1 -C 10 Alkyl of (a); n is an integer of 1 to 20; x in the structural formula (1) and the structural formula (2) is
Figure QLYQS_4
Or->
Figure QLYQS_7
Or (b)
Figure QLYQS_10
Or->
Figure QLYQS_5
Or->
Figure QLYQS_8
Or->
Figure QLYQS_11
Or->
Figure QLYQS_12
Or->
Figure QLYQS_3
Or (b)
Figure QLYQS_6
Or->
Figure QLYQS_9
。
2. The resin composition according to claim 1, wherein the curing agent further comprises at least one of an amine-based compound, an amide-based compound, an acid anhydride-based compound, a phenol-based compound, a cyanate-based compound, and an active ester-based compound different from the structural formulae (1) and (2).
3. The resin composition according to claim 1, wherein: the cross-linking agent containing unsaturated bonds is polybutadiene or modified polybutadiene, styrene or modified styrene, triallyl isocyanate resin, double-bond-containing polyphenyl ether resin, double-bond-containing benzoxazine resin, double-bond-containing epoxy resin or maleimide resin.
4. The resin composition according to claim 1, wherein: the resin composition also comprises a curing accelerator, and/or an initiator, and/or a flame retardant, and/or an auxiliary agent, wherein the auxiliary agent comprises at least one of a coupling agent, a dispersing agent and a dye.
5. The resin composition according to claim 1, wherein: 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.
6. The resin composition according to claim 5, wherein: the filler is an inorganic filler subjected to surface treatment by using a silane coupling agent containing carbon-carbon unsaturated double bonds.
7. A prepreg, characterized in that: a prepreg is formed by impregnating a reinforcing material with a glue solution of the resin composition according to any one of claims 1 to 6 and then drying by heating.
8. A laminate, characterized in that: a laminated board is formed by coating at least one surface of a prepreg or at least two prepregs which are laminated with metal foil in a hot pressing mode, wherein the prepreg is the prepreg in claim 7.
9. A printed wiring board, characterized in that: the printed wiring board comprises at least one prepreg according to claim 7 or at least one laminate according to claim 8.
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CN109810468A (en) * 2019-01-25 2019-05-28 常熟生益科技有限公司 A kind of compositions of thermosetting resin and prepreg and laminate using its preparation
CN109810467A (en) * 2019-01-25 2019-05-28 苏州生益科技有限公司 A kind of compositions of thermosetting resin and prepreg and laminate using its preparation
CN109867912A (en) * 2019-01-25 2019-06-11 苏州生益科技有限公司 A kind of compositions of thermosetting resin and prepreg and laminate using its preparation
CN109943047A (en) * 2019-01-25 2019-06-28 苏州生益科技有限公司 A kind of compositions of thermosetting resin and prepreg and laminate using its preparation
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018044040A (en) * 2016-09-12 2018-03-22 味の素株式会社 Resin composition
KR20190125765A (en) * 2018-04-30 2019-11-07 삼성에스디아이 주식회사 Organic layer composition, and method of forming patterns
CN109810468A (en) * 2019-01-25 2019-05-28 常熟生益科技有限公司 A kind of compositions of thermosetting resin and prepreg and laminate using its preparation
CN109810467A (en) * 2019-01-25 2019-05-28 苏州生益科技有限公司 A kind of compositions of thermosetting resin and prepreg and laminate using its preparation
CN109867912A (en) * 2019-01-25 2019-06-11 苏州生益科技有限公司 A kind of compositions of thermosetting resin and prepreg and laminate using its preparation
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