CN111961193A - Resin composition, prepreg, insulating film, metal-clad laminate, and printed wiring board provided with same - Google Patents
Resin composition, prepreg, insulating film, metal-clad laminate, and printed wiring board provided with same Download PDFInfo
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- CN111961193A CN111961193A CN201910417793.XA CN201910417793A CN111961193A CN 111961193 A CN111961193 A CN 111961193A CN 201910417793 A CN201910417793 A CN 201910417793A CN 111961193 A CN111961193 A CN 111961193A
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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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
-
- 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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
-
- 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
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
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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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Abstract
The invention provides a resin composition which has higher glass transition temperature, high peel strength, low coarsening degree, low dielectric loss, high heat resistance, low water absorption and good dielectric property compared with the prior resin composition; the invention also provides a prepreg, an insulating film, a metal foil-clad laminate and a printed wiring board prepared by using the resin composition.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a resin composition with high cohesiveness, low coarsening degree, high heat resistance, low water absorption and good dielectric property, a prepreg, an insulating film, a metal foil-clad laminated board and a printed circuit board with the resin composition.
Background
In recent years, the printed circuit board market has been turning to communications from computers, particularly to mobile terminals such as smart phones and tablet computers. Therefore, the HDI board for the mobile terminal is a main point of the growth of the PCB. Mobile terminals represented by smart phones drive HDI boards to be higher density and thinner. According to the literature, the line width/line spacing L/S (line and space) of the PCB is required to be 10/10 μm or less in the future, so that the Ra value (coarsening degree average value) of the laminated insulating layer needs to be 300nm or less, and the adhesive property needs to be more than 0.6 kgf/cm. In addition, in the field of packaging technology, Flip chips (Flip chips) become the mainstream of future packaging, and thus, a Flip chip packaging substrate requires a lower coarsening degree and higher adhesiveness/peel strength for a build-up insulating layer, and satisfies an insulating material having excellent overall performance.
Prior art JP2010090238 discloses a resin composition wherein the problems of low coarsening and high adhesion are solved with an active ester and a triazine structure phenolic resin in an epoxy resin system. When the active ester curing agent reacts with the epoxy resin, polar hydroxyl is not generated, the high symmetry of a triazine structure in the phenolic resin further reduces the coarsening degree, and the phenolic resin containing the polar hydroxyl is matched to improve the peeling strength.
Furthermore, prior art JP2017019970 discloses a resin composition wherein triazine-hydroxyl group containing active ester compounds are used in epoxy resin systems to solve the problems of low coarsening and high adhesion.
However, these compounds contain hydroxyl groups, and the properties such as water absorption of the final cured product are affected.
In view of the above, it is desirable to provide a novel resin composition, and a prepreg, an insulating film, a metal-clad laminate, and a printed wiring board having the same to solve the above problems.
Disclosure of Invention
The invention aims to provide a resin composition with high adhesion, low coarsening degree, high heat resistance, low water absorption and good dielectric property, and a prepreg, an insulating film, a metal foil-clad laminate and a printed wiring board prepared by using the resin composition.
The term "comprising" or "containing" in the present specification means that other components capable of imparting different characteristics to the resin composition may be contained in addition to the components.
In order to achieve the purpose, the invention adopts the following technical scheme: a resin composition comprises 100 parts by weight of epoxy resin, 1-100 parts by weight of curing agent and 0.001-5 parts by weight of curing accelerator; the curing agent at least comprises an active ester compound shown as a structural formula (1):
wherein R is1Represents hydrogen or C1-C5 alkyl, m is an integer from 1 to 10, A is one of the following groups:
wherein R is10、R11、R12、R13Are respectively selected from hydrogen, alkyl of C1-C5, or aryl or aralkyl of C6-C10.
The active ester compound shown as the structural formula (1) in the curing agent is an active ester compound containing two reaction groups, wherein the active ester group does not generate hydroxyl with stronger polarity when reacting with epoxy resin, so that excellent dielectric property and low coarsening degree are obtained after reaction, and meanwhile, the aromatic amino group at the tail end reacts with the epoxy resin to obtain an insulating layer with high cohesiveness, so that two opposite properties of low coarsening degree and high peeling strength are solved; in addition, both the active ester group and the aromatic amino group in the active ester compound shown as the structural formula (1) and the epoxy resin are subjected to curing reaction, so that the crosslinking density of a cured product can be effectively improved, and more excellent heat resistance, low water absorption and high rigidity can be obtained.
Preferably, said R is1May be hydrogen, methyl, ethyl, propyl or tert-butyl, more preferably, said R1May be hydrogen or methyl.
Preferably, the value of m is an integer of 1 to 5.
Preferably, R10, R11, R12 and R13 are each independently selected from hydrogen, methyl, ethyl, propyl or tert-butyl, or phenyl, biphenyl or naphthyl, more preferably hydrogen, methyl or phenyl.
Preferably, A in the active ester compound shown in the structural formula (1) contains dicyclopentadienyl or tricyclopentadienyl.
For example, in said R1When the compound is hydrogen, m is 1, and A is dicyclopentadienyl, the active ester compound shown in the structural formula (1) is dicyclopentadiene active ester, and the structural formula is shown as follows:
the preparation method of the active ester compound shown as the structural formula (1) in the invention comprises the following steps: reacting aromatic phenol resin, aromatic dicarboxylic acid or halogen compound and p-aminophenol to obtain the active ester compound. The following is an example of the preparation of dicyclopentadiene active ester, the reaction mechanism of which is shown below:
the first step is as follows:
the second step is that:
alternatively, it is prepared by the following method: firstly, the aromatic phenol resin and the aromatic dicarboxylic acid or the halogen compound are subjected to esterification reaction, then the aromatic phenol resin and the aromatic dicarboxylic acid or the halogen compound are subjected to esterification reaction, and finally reduction reaction is performed on a tail end nitro group.
The first step is as follows:
the second step is that:
the third step:
of course, the method is not limited thereto, and other methods can be used to prepare the active ester compound shown in formula (1), that is, all methods capable of preparing the active ester compound shown in formula (1) are within the scope of the present invention.
As a further improvement of the invention, the content of the active ester compound shown in the structural formula (1) in the curing agent is 1-100 parts by weight based on 100 parts by weight of the epoxy resin. More preferably 5 to 50 parts by weight; for example, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight, 41 parts by weight, 42 parts by weight, 43 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight, 51 parts by, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight, 59 parts by weight, 60 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight, 81 parts by weight, 82 parts by weight, 83 parts by weight, 84 parts by weight, 85 parts by weight, 86 parts by weight, 87 parts by weight, 88 parts by weight, 89 parts by weight, 90 parts by weight, 91 parts by weight, 92 parts by weight, 93 parts by weight, 94 parts by weight, 95 parts by weight, 96 parts by weight, 97 parts by weight, 98 parts by weight, 99 parts by weight, or 100 parts by weight, and specific point values therebetween, the invention is not intended to be exhaustive or to list the specific point values included within the scope, for reasons of brevity and clarity.
In a further improvement of the present invention, the curing agent further contains at least one of an amine compound, an amide compound, an acid anhydride compound, a phenol compound, and an active ester compound different from the structural formula (1). The content is 0 to 99 parts by weight, preferably 5 to 60 parts by weight, for example, 0 part by weight, 5 parts by weight, 10 parts by weight, 25 parts by weight, 35 parts by weight, 60 parts by weight, 70 parts by weight, 85 parts by weight, 99 parts by weight, and specific points between the above values, which are limited by space and in the interest of brevity, the present invention is not exhaustive and the range of the specific points included is not limited.
Specifically, the amine compound may be diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, dicarboxyphthalimide, imidazole, or the like, and diaminodiphenylmethane and diaminodiphenylsulfone are preferable; the amide compound may be dicyandiamide, low molecular polyamide, or the like, and is preferably dicyandiamide; 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, biphenol naphthol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylolmethane resin, or the like; the active ester compound different from the structural formula (1) can be selected from compounds represented by the structural formula (2):
wherein, X is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; n represents a repeating unit and is 0.25 to 1.25.
Of course, it is understood that the active ester compound other than the active ester compound of formula (1) may be selected.
As a further improvement of the present invention, the resin composition further comprises 0 to 200 parts by weight of a filler per 100 parts by weight of the epoxy resin, and 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 preferably contained in an amount of 10 to 100 parts by weight, more preferably 30 to 70 parts by weight, 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, or 200 parts by weight, based on 100 parts by weight of the epoxy resin; and the particular points between the above numerical values, are not intended to be exhaustive or to be in a concise sense and the invention is not intended to be exhaustive of the particular points included in the range.
Specifically, the filler is an organic filler or an inorganic filler, wherein 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; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
More preferably, the inorganic filler is at least one selected from the group consisting of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
Preferably, the filler is silica, more preferably, surface treated silica.
Preferably, the filler has a median particle size of 1 to 15 μm, such as 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, and specific values therebetween are not intended to be exhaustive, and for brevity, the invention is not intended to be limited to the specific values included in the ranges.
More preferably, the median value of the particle size of the filler is 1-10 μm.
Specifically, the surface treatment agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent.
As a further improvement of the present invention, 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 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 glycidylether 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 (3), the structural formula of the biphenyl type epoxy resin is shown in structural formula (4), and the structural formula of the dicyclopentadiene type epoxy resin is shown in structural formula (5):
in the present invention, the curing accelerator is at least one selected from the group consisting of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole and zinc isooctoate, 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 isooctoate, and a mixture of 2-methylimidazole, 2-methyl-4-ethylimidazole and 2-phenylimidazole, although not limited thereto.
The curing accelerator is included in an amount of 0.001 to 5 parts by weight, for example, 0.001 part by weight, 0.01 part by weight, 1 part by weight, 2.5 parts by weight, 5 parts by weight, and specific points between the above-mentioned values, based on 100 parts by weight of the epoxy resin, not to be limited by space and in the interest of brevity, and the present invention is not exhaustive.
More preferably, the curing accelerator is contained in an amount of 0.01 to 1 part by weight.
Furthermore, the phenolic resin or cyanate resin or the composition thereof is also added into the resin composition.
Preferably, in order to control the surface roughness of the insulating layer, the phenoxy resin is selected from the group consisting of phenoxy resins represented by structural formula (6), alicyclic modified phenoxy resins, and other modified phenoxy resins, and the alicyclic is a cyclopentadienyl group, a tricyclopentadienyl group, or a terpene group. The other modified phenolic-oxygen resin is phosphorus-containing phenolic-oxygen resin or fluorenyl phenolic-oxygen resin, etc.
Wherein R is20、R21Respectively is one of-H, -OH or epoxy group, and the molecular weight is 1.5-10 ten thousand.
Further, the content of the phenoxy resin is 1 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the epoxy resin, and the present invention is not exhaustive of the specific points included in the range, limited to space and in the interest of brevity.
Furthermore, in order to improve the dielectric property of the cured product, the cyanate ester resin is selected from one or more of bisphenol a cyanate ester, bisphenol F cyanate ester, dicyclopentadiene cyanate ester, phenolic cyanate ester, tetramethyl bisphenol F cyanate ester, bisphenol M cyanate ester, bisphenol E cyanate ester, phosphorus cyanate ester and prepolymers of the cyanate ester.
Further, the cyanate ester resin is included in an amount of 1 to 50 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the epoxy resin, for purposes of space and brevity, the present invention is not intended to be exhaustive of the specific points included in the ranges set forth.
In a preferred resin composition of the present invention, it specifically comprises the following components: 100 parts of epoxy resin, 20-60 parts of active ester compound shown in structural formula (1), 1-30 parts of other components except the active ester compound shown in structural formula (1) in a curing agent, 1-30 parts of phenoxy resin, 0-200 parts of filler and 0.001-5 parts of curing accelerator.
In another preferred resin composition of the present invention, it specifically comprises the following components: 100 parts of epoxy resin, 20-60 parts of active ester compound shown in a structural formula (1), 1-30 parts of other components except the active ester compound shown in the structural formula (1) in a curing agent, and cyanate ester: 5-20 parts of filler, 0-200 parts of filler and 0.001-5 parts of curing accelerator.
It is understood that the other components of the curing agent except the active ester compound represented by the structural formula (1) specifically refer to: the curing agent contains an amine compound, an amide compound, an acid anhydride compound, a phenol compound, and another active ester compound having a non-structural formula (1).
According to the present invention, the resin composition further comprises a flame retardant to improve the 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 points between the above values, which are limited by space and in the interest of conciseness, the present invention does not exhaustively enumerate the specific points included in the range.
Preferably, the content of the flame retardant is 5 to 50 parts by weight.
Specifically, the flame retardant may be a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organosilicon flame retardant, an organic metal salt flame retardant, an inorganic flame retardant, or the like. Wherein the bromine flame retardant can be decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalimide. The phosphorus-containing flame retardant may be an inorganic phosphorus, a phosphate compound, a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, an organic phosphorus-containing compound such as 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2, 6-dimethylphenyl) phosphine, phosphazene, or the like. The nitrogen-based flame retardant may be a triazine compound, a cyanuric acid compound, an isocyanic acid compound, phenothiazine, or the like. The organic silicon flame retardant can be organic silicon oil, organic silicon rubber, organic silicon resin and the like. The organometallic flame retardant may be ferrocene, acetylacetone metal complexes, organometallic carbonyl compounds, and the like. 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, it being understood that the flame retardant to be added may be selected according to the particular application of the laminate, e.g. the application where halogen is required, preferably a non-halogen flame retardant, e.g. a phosphorus or nitrogen containing flame retardant.
Preferably, when the phosphorus-containing flame retardant is selected, nitrogen and phosphorus are formed to be used for realizing synergistic flame retardance with nitrogen elements of the active ester compound in the curing agent, so that the flame retardant efficiency is improved.
The preparation method of the resin composition is a conventional technical means in the field, and specifically comprises the following steps: taking a container, putting solid components in the container, adding a liquid organic solvent, stirring until the solid components are completely dissolved, adding liquid resin, a filler and a curing accelerator, continuously stirring uniformly, and finally adjusting the solid content of the liquid to 50-80% by using the solvent to prepare a glue solution, wherein the solid content is calculated by weight.
The organic solvent and the solvent used in the present invention are not particularly limited. For example, the organic solvent may be selected from one or a combination of any of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene and cyclohexane.
The amount of the solvent to be added is selected by a person skilled in the art according to his own experience, as long as the viscosity of the resulting glue solution is such that it is suitable for use.
In order to achieve the above object, the present invention further provides a prepreg, which includes a reinforcing material, and the above resin composition attached to a surface of the reinforcing material.
The reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric, and the inorganic fabric is preferably glass fiber cloth, and the glass fiber cloth is preferably open fiber cloth or flat 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 reinforcing material in the resin composition glue solution, then baking the soaked reinforcing material for 1-10min at the temperature of 50-170 ℃, and drying to obtain the prepreg.
In order to achieve the above object, the present invention further provides an insulation film comprising a carrier film and the above resin composition coated on the surface of the carrier 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 above-mentioned heating and drying conditions are baking at 50-170 deg.C for 1-10min, but not limited thereto.
Further, the side of the insulating resin layer facing away from the carrier film is covered with a protective film to protect the insulating resin layer.
Specifically, the material of the protective film is the same as that of the carrier film, but of course, the material is not limited thereto.
In order to achieve the above object, the present invention further provides a metal-clad laminate including at least one prepreg as described above and a metal foil formed on at least one side of the prepreg.
The metal foil-clad laminate is formed by bonding one or two prepregs by heating and pressing to form a laminate, and then bonding a metal foil on one side or both sides of the laminate by heating and pressing.
The preparation steps of the metal foil-clad laminate 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 metal foil and the laminated board are 0.2-2 MPa pressure and 180 ℃
Pressing for 2-4 hours at the temperature of 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 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.
In order to achieve the above object, the present invention further provides a printed wiring board, which includes at least one prepreg as described above, or at least one insulating film as described above.
The invention has the beneficial effects that: the invention adopts the active ester compound which contains two reactive groups and is shown in the structural formula (1), wherein the active ester group does not generate hydroxyl with stronger polarity when reacting with the epoxy resin, thereby obtaining the insulating layer with excellent dielectric property and low coarsening degree, and simultaneously, the aromatic amino group at the tail end reacts with the epoxy resin to obtain high cohesiveness, thereby solving the two opposite properties of low coarsening degree and high peeling strength, and being better applied to high-multilayer laminated circuit boards.
Meanwhile, the active ester group and the aromatic amino group in the active ester compound shown in the structural formula (1) in the invention are subjected to a curing reaction with the epoxy resin, so that the crosslinking density of a cured product is effectively improved, and more excellent heat resistance, low water absorption and high rigidity are obtained, so that the prepreg and the insulating film can better meet the heat resistance and rigidity requirements of an organic packaging substrate and a coreless substrate.
In addition, experiments show that the resin composition disclosed by the invention has excellent low coarsening degree, high peel strength, dielectric property, heat resistance and low water absorption rate after being cured.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
While the following is a detailed description of the embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
The following examples are provided to further illustrate embodiments of the present invention. It is to be understood that the embodiments of the present invention are not limited to the following specific examples. The present invention can be modified as appropriate without changing the scope of the claims.
Synthesis example 1: synthesis of Dicyclopentadienyl active ester Compounds
Taking dicyclopentadiene phenol resin and benzene dicarboxylic acid, stirring and dissolving the dicyclopentadiene phenol resin and the benzene dicarboxylic acid uniformly in a toluene solvent, introducing nitrogen at the same time at the temperature of 60 ℃, adding a tetrabutylammonium bromide catalyst, then slowly dropping a 20% sodium hydroxide aqueous solution, reacting for 4 hours, then adding p-aminophenol, continuing to react for 2 hours, after the reaction is finished and is washed for a plurality of times, drying for 5 hours under the vacuum condition of 105 ℃, and obtaining the dicyclopentadiene active ester compound, which is marked as active ester A.
Synthesis example 2: synthesis of Tricyclopentadienyl active ester Compounds
Taking tricyclopentadienyl phenol resin and benzene dicarboxylic acid, stirring and dissolving uniformly in a toluene solvent, introducing nitrogen at the same time at the temperature of 60 ℃, adding a tetrabutylammonium bromide catalyst, then slowly dropping a 20% sodium hydroxide aqueous solution, reacting for 4 hours, then adding p-aminophenol, continuing to react for 2 hours, washing for a plurality of times after the reaction is finished, and drying for 5 hours under the vacuum condition of 105 ℃ to obtain the tricyclopentadienyl active ester compound, which is marked as active ester B.
Synthesis example 3: synthesis of naphthyl active ester Compound
Taking naphthol resin and benzenedicarboxylic acid, stirring and dissolving the naphthol resin and the benzenedicarboxylic acid uniformly in a toluene solvent, introducing nitrogen at the same time at the temperature of 60 ℃, adding a tetrabutylammonium bromide catalyst, slowly dropping a sodium hydroxide aqueous solution with the concentration of 20%, reacting for 4 hours, adding p-aminophenol, continuing to react for 2 hours, washing for several times after the reaction is finished, and drying for 5 hours at the vacuum condition of 105 ℃ to obtain the naphthyl active ester compound, which is marked as active ester C.
Synthesis example 4: synthesis of Dicyclopentadienyl active ester Compound
Taking dicyclopentadiene naphthol resin and benzene dicarboxylic acid, stirring and dissolving uniformly in a toluene solvent, introducing nitrogen at the same time at the temperature of 60 ℃, adding tetrabutylammonium bromide catalyst, slowly dropping a 20% sodium hydroxide aqueous solution, reacting for 4 hours, adding p-aminophenol, continuing to react for 2 hours, washing for several times after the reaction is finished, and drying for 5 hours under the vacuum condition of 105 ℃ to obtain the dicyclopentadiene naphthyl active ester compound, which is marked as active ester D.
Examples 1 to 9 and comparative examples 1 to 3:
the components and contents of the resin compositions of examples 1 to 9 and comparative examples 1 to 3 are shown in the following table 1:
TABLE 1
Wherein, the component information related to examples 1 to 9 and comparative examples 1 to 3 is shown in the following table 2:
TABLE 2
The resin compositions of examples 1 to 9 and comparative examples 1 to 3 were prepared by a conventional method, specifically: according to the component contents in table 1, epoxy resin, active ester compounds a to D shown in structural formula (1) obtained in synthesis examples 1 to 4, and active ester compound E (active ester compound in the prior art) were respectively stirred and mixed with curing agent (phenolic resin, DDS), phenoxy resin, cyanate ester resin, curing accelerator (imidazole), filler (silica), flame retardant, and a proper amount of butanone solvent to obtain a glue solution with a solid content of 65%, wherein the solid content of 65% is calculated by weight.
Prepregs were prepared using the prepared resin compositions of examples 1 to 9 and comparative examples 1 to 3, and the preparation methods thereof were: and (3) soaking the E glass fiber cloth (7628) in the glue solution, and drying the soaked E glass fiber cloth in a 160 ℃ drying oven for 5min to obtain a prepreg.
Using the prepared resin compositions of examples 1 to 9 and comparative examples 1 to 3, insulating films were prepared by the following methods: coating the glue solution on a PET carrier, and drying in a 160 ℃ oven for 5min to obtain the insulating film.
Sample laminates a, b prepared for performance evaluation:
(1) preparation of Metal foil-clad laminate a
And (3) placing 18-micron metal copper foils on the prepreg respectively, and placing the prepreg in a vacuum hot press for hot pressing to obtain the metal foil-clad laminated board a.
Specifically, the hot pressing process is carried out under a pressure of 1.5MPa and a temperature of 220 ℃ for 2 hours.
(2) Preparation of laminate b
And (3) taking a core plate, respectively placing the prepared insulating films on the upper surface and the lower surface of the core plate, placing the core plate in a vacuum hot press for pressing, and stripping the PET carrier after pressing. The specific pressing process is pressing under 1.5Mpa and 220 deg.C for 2 hr.
Then, the surface insulation film layer is coarsened by a potassium permanganate method, and the steps are as follows:
(1) soaking the plate in swelling solution for 10min, and taking out; wherein the swelling solution is diethylene glycol monobutyl ether solution;
(2) soaking the taken out plate in oxidant solution for 20min and taking out; wherein the oxidant is a potassium permanganate solution;
(3) soaking the taken out plate in a neutralizing solution for 10min, and taking out; wherein the neutralization solution is hydroxylamine sulfate aqueous solution;
(4) drying at 80 ℃ for 30min to obtain laminate b to be tested for coarseness.
The properties of the metal foil-clad laminates a and b obtained from the resin compositions of examples 1 to 9 and comparative examples 1 to 3 are shown in Table 3.
TABLE 3
The test method for the above properties is as follows:
(1) glass transition temperature Tg (. degree. C.): according to differential scanning calorimetry, the measurement was carried out by the DSC method specified by IPC-TM-6502.4.25.
(2) Peel Strength (PS): the peel strength of the metal cap was tested with laminate a according to the "post thermal stress" experimental conditions in the IPC-TM-650 method.
(3) Coarsening degree: using the laminate b, 10 point values were measured with a non-contact surface coarseness tester, and an average coarseness (Ra) value was calculated.
(4) Dielectric constant: the dielectric constant at 1GHz was measured with the laminate a by the IPC-TM-6502.5.5.9 plate method.
(5) Dielectric loss tangent: the dielectric loss factor at 1GHz was measured with laminate a using the plate method according to IPC-TM-6502.5.5.9.
(6) Tin immersion heat resistance: A50X 50mm sample of copper on both sides was immersed in a solder at 288 ℃ using a laminate a, and the time for delamination and blistering of the sample was recorded, where Δ represents 30min or more and KHz represents 30min or less.
(7) Tin immersion heat resistance after moisture treatment: 3 pieces of 100X 100mm substrate samples were held in a pressure cooker at 121 ℃ and 105Kpa for 3 hours using a laminate a, and then immersed in a solder bath at 288 ℃ for 2 minutes to observe whether or not delamination and bubbling occurred in the samples, wherein 3 pieces were 3/3, 2 pieces were 2/3, 1 piece was 1/3, and 0 piece was 0/3.
(8) Water absorption: using laminate a, the measurement was carried out according to the standard method specified in IPC-TM-650 at D23 deg.C/24 hr.
As can be seen from table 1 and table 3:
comparing examples 1 to 4 with comparative example 1, it can be seen that the active ester compound represented by the structural formula (1) in the present invention has a higher glass transition temperature, a high peel strength, a low coarsening degree, a low dielectric loss, a high heat resistance, and the resin composition of example 3 has a low water absorption rate, compared to other active ester compounds of the prior art; comparing example 6 with comparative example 2, it can be seen that the resin composition of the present invention has a higher glass transition temperature, high peel strength, low coarsening degree, low dielectric constant, low dielectric loss, high heat resistance, and low water absorption; comparing example 5 with comparative example 1, it can be seen that the resin composition of the present invention has a higher glass transition temperature, high peel strength, low coarsening degree, low dielectric constant, and high heat resistance; further, as is clear from comparison of examples 1 to 9 with comparative example 1 using a conventional active ester compound and comparative example 3 using an aromatic amine curing agent, the resin compositions of the present invention have higher heat resistance.
From the above results, it can be seen that when the curing agent of the resin composition of the present invention is added with the active ester compound represented by the structural formula (1), the obtained resin composition satisfies a low coarsening degree, the peel strength of the insulating layer can be improved, and a cured product having high heat resistance and low water absorption can be obtained.
As described above, for example, a laminate prepared from the resin composition of the present invention has a higher glass transition temperature, a higher peel strength, a lower coarsening degree, a lower dielectric loss, a higher heat resistance, a lower water absorption rate, and a better dielectric property than a cured product prepared from a general resin composition.
It should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description is for clarity only, and those skilled in the art should make the description as a whole, and the technical solutions in the embodiments can also be combined appropriately to form other embodiments understood by those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. A resin composition characterized by: comprises 100 weight portions of epoxy resin, 1 to 100 weight portions of curing agent and 0.001 to 5 weight portions of curing accelerator; the curing agent at least comprises an active ester compound shown as a structural formula (1):
wherein R is1Represents hydrogen or C1-C5 alkyl, m is an integer from 1 to 10, A is one of the following groups:
wherein R is10、R11、R12、R13Are respectively selected from hydrogen, alkyl of C1-C5, or aryl or aralkyl of C6-C10.
2. The resin composition of claim 1, wherein: a in the active ester compound shown in the structural formula (1) contains dicyclopentadienyl, naphthyl or tricyclopentadienyl.
3. The resin composition according to claim 1 or 2, wherein: the content of the active ester compound shown as the structural formula (1) in the curing agent is 1-100 parts by weight based on 100 parts by weight of the epoxy resin.
4. The resin composition of claim 1, wherein: the curing agent further contains at least one of an amine compound, an amide compound, an acid anhydride compound, a phenol compound, and an active ester compound different from the structural formula (1).
5. The resin composition of claim 1, wherein: the epoxy resin composition further comprises 0-200 parts by weight of a filler based on 100 parts by weight, wherein the filler is an organic filler or an inorganic filler, and the inorganic filler is at least one selected from fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talcum powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica and glass fiber powder; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
6. The resin composition of claim 1, wherein: 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-containing epoxy resin, nitrogen-containing 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.
7. A prepreg characterized in that: the prepreg comprises a reinforcing material and a resin composition attached to the surface of the reinforcing material, wherein the resin composition is the resin composition in any one of claims 1 to 6.
8. An insulating film characterized in that: the insulation film comprises a carrier film and a resin composition coated on the surface of the carrier film, wherein the resin composition is the resin composition as claimed in any one of claims 1 to 6.
9. A metal-clad laminate characterized by: the metal-foil-clad laminate includes at least one prepreg according to claim 7, and a metal foil formed on at least one side of the prepreg.
10. A printed wiring board characterized in that: the printed wiring board comprises at least one prepreg according to claim 7, or at least one insulating film according to claim 8.
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| CN116102712A (en) * | 2022-12-28 | 2023-05-12 | 厦门大学 | Epoxy resin toughening agent and preparation method and application thereof |
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| US5026872A (en) * | 1984-02-01 | 1991-06-25 | American Cyanamid | Aromatic ether-ketone polyamines, intermediates and products, and methods for preparing same |
| CN106243626A (en) * | 2016-08-29 | 2016-12-21 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and use its prepreg made and laminate |
| CN106349442A (en) * | 2016-08-29 | 2017-01-25 | 苏州生益科技有限公司 | Thermosetting resin composition and prepregs and laminates produced by using the same |
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| US3968085A (en) * | 1973-08-29 | 1976-07-06 | Institut Francais Du Petrole, Des Carburants Et Lubrifiants | Polyamine compositions useful as hardening agents for epoxy resins |
| US5026872A (en) * | 1984-02-01 | 1991-06-25 | American Cyanamid | Aromatic ether-ketone polyamines, intermediates and products, and methods for preparing same |
| CN106243626A (en) * | 2016-08-29 | 2016-12-21 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and use its prepreg made and laminate |
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| CN116102712A (en) * | 2022-12-28 | 2023-05-12 | 厦门大学 | Epoxy resin toughening agent and preparation method and application thereof |
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