CN111849122A - Resin composition and application thereof - Google Patents

Resin composition and application thereof Download PDF

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CN111849122A
CN111849122A CN201910339285.4A CN201910339285A CN111849122A CN 111849122 A CN111849122 A CN 111849122A CN 201910339285 A CN201910339285 A CN 201910339285A CN 111849122 A CN111849122 A CN 111849122A
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parts
active ester
weight
resin composition
compound
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CN111849122B (en
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崔春梅
焦锋
戴善凯
陈诚
何继亮
杨宋
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Changshu 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • 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
    • C08G59/66—Mercaptans
    • 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
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • 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
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention discloses a resin composition, which comprises the following components in percentage by weight of solid: (A) epoxy resin: 100 parts of (A); (B) curing agent: 1-100 parts; (C) filling: 0-200 parts of a solvent; (D) curing accelerator: 0.001-5 parts; the curing agent at least contains an active ester compound. The resin composition disclosed by the invention adopts an active ester compound containing two reactive groups, wherein the active ester group does not generate a hydroxyl group with stronger polarity when reacting with epoxy resin, so that the dielectric property and the coarsening degree are excellent, meanwhile, an aromatic thiol group at the tail end can react with the epoxy resin, and the thiol group has better cohesiveness, so that the cohesiveness is extremely high, and the problem of opposite properties of low coarsening degree and high peel strength is solved.

Description

Resin composition and application thereof
Technical Field
The invention relates to a resin composition, and a prepreg and a laminated board prepared from the resin composition, and belongs to the technical field of electronic materials.
Background
In recent years, the printed circuit board market is gradually shifted to the communication field from computers, and 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. It is reported that the line width/line distance L/S (Linear space) of PCB board will reach 10/10 μm or less in future, therefore, the Ra value (i.e. coarsening degree average value) of the laminated insulation layer needs to reach 300nm or less, and the adhesive property reaches above 0.6 kgf/cm.
In addition, in the field of packaging technology, Flip chips (Flip chips) are becoming the mainstream of future packaging, and therefore, a Flip chip packaging substrate requires a lower coarsening degree and higher adhesiveness for a build-up insulating layer and satisfies an insulating material excellent in overall performance.
In view of the above problems, japanese patent JP2010090238 discloses a resin composition in which 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, meanwhile, the coarsening degree is further reduced due to the high symmetry of a triazine structure in the phenolic resin, and the stripping strength is improved by matching with the phenolic resin containing the polar hydroxyl. Further, Japanese patent JP2017019970 discloses a resin composition in which problems of low coarsening and high adhesion are solved with a triazine-hydroxyl group-containing active ester compound in an epoxy resin system, but the compound contains a hydroxyl group, which affects properties such as water absorption of a final cured product.
Therefore, it is obvious that the development of a resin composition having high adhesion, low coarsening degree, high heat resistance, low water absorption rate and good dielectric properties, and a prepreg and a laminate using the same have positive practical significance.
Disclosure of Invention
The invention aims to provide a resin composition with high adhesion, low coarsening degree, high heat resistance, low water absorption and excellent dielectric property, and a prepreg and a laminated board prepared by using the same.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a resin composition comprises the following components in percentage by weight of solid:
(A) epoxy resin: 100 parts of (A);
(B) curing agent: 1-100 parts;
(C) filling: 0-200 parts of a solvent;
(D) curing accelerator: 0.001-5 parts;
the curing agent at least contains an active ester compound shown in the following structural formula (1):
Figure BDA0002040210820000021
wherein A is selected from one of the following structures:
Figure BDA0002040210820000022
Figure BDA0002040210820000031
Figure BDA0002040210820000032
wherein R is10、R11、R12、R13The same or different, respectively selected from hydrogen, alkyl of C1-C5, aryl of C6-C10 or aralkyl of C6-C10.
In the above, in order to satisfy the requirements of heat resistance, rigidity and high modulus of the cured product, A in the structural formula (1) is a group containing at least two benzene ring groups.
Preferably, in the above formula (1), R10、R11、R12、R13The same or different, each being selected from hydrogen, methyl, ethyl, propyl or tert-butyl, or phenyl, biphenyl or naphthyl, more preferably hydrogen, methyl or phenyl.
The active ester compound described by structural formula (1) can be prepared by, but is not limited to, the following method:
the aromatic phenol resin and phenol thiocyanic acid or chlorophenol are subjected to two-step reaction to obtain the active ester compound, taking dicyclopentadiene active ester as an example, the reaction mechanism is as follows:
the first step is as follows:
Figure BDA0002040210820000033
the second step is that:
Figure BDA0002040210820000034
in the above technical solution, the epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus epoxy resin, nitrogen epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl novolac epoxy resin, alicyclic epoxy resin, glycidylamine epoxy resin, glycidylether epoxy resin, and glycidylether epoxy resin. More preferably a naphthalene type epoxy resin, a biphenyl type epoxy resin or a dicyclopentadiene type epoxy resin, the structure of which is as follows:
Figure BDA0002040210820000041
Preferably, the content of the active ester compound in the curing agent is 1 to 100% by weight, more preferably 5 to 50% by weight, based on 100% by weight of the curing agent. The content of the active ester compound in the curing agent may be 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, 35% by weight, 36% by weight, 37% by weight, 38% by weight, 39% by weight, 40% by weight, 41% by weight, 42% by weight, 43% by weight, 44% by weight, 45% by weight, 46% by weight, 47% by weight, 48% by weight, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100% by weight.
In the above technical solution, the curing agent further contains an active ester compound, an amine compound, an amide compound, an acid anhydride compound, or a phenol compound other than the active ester compound of the structural formula (1). The contents are as follows: the curing agent is contained in an amount of 0 to 99 parts, preferably 5 to 60 parts, based on 100 parts of the total amount of the curing agent.
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, etc., and is preferably styrene-maleic anhydride;
the phenolic compound may be bisphenol A phenol formaldehyde resin, naphthol phenol resin, biphenol naphthol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylolmethane resin, etc.;
The active ester compound can be selected from compounds shown in the following structural formula:
Figure BDA0002040210820000051
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.
Preferably, in the active ester compound of formula (1), group a contains dicyclopentadienyl, naphthyl or tricyclopentadienyl.
Preferably, the resin composition is further added with a phenoxy resin or a cyanate resin or a composition thereof.
Preferably, in order to control the surface roughness of the insulating layer, the phenoxy resin may be an alicyclic modified phenoxy resin, other modified phenoxy resin, or a phenoxy resin represented by the following structure:
Figure BDA0002040210820000061
wherein R is20、R21Respectively is one of-H, -OH or epoxy group, and the molecular weight of the phenoxy resin is 1.5-10 ten thousand;
the alicyclic group is cyclopentadienyl, tricyclopentadienyl or terpenyl;
the other modified phenoxy resin may be, for example, a phosphorus-containing phenoxy resin or a fluorenyl phenoxy resin;
the content of the phenoxy resin is 1-30 parts by weight, calculated by 100 parts by weight of epoxy resin; preferably 5 to 20 parts by weight.
Preferably, in order to improve the dielectric property of the cured product, a cyanate resin may be added, wherein the cyanate resin is selected from one or more of bisphenol a cyanate, bisphenol F cyanate, dicyclopentadiene cyanate, phenol-formaldehyde cyanate, tetramethyl bisphenol F cyanate, bisphenol M cyanate, bisphenol E cyanate, phosphorus cyanate and prepolymers of the cyanate; the content of the cyanate ester resin is 1 to 50 parts by weight, preferably 5 to 20 parts by weight based on 100 parts by weight of the epoxy resin.
As a preferred embodiment of the present invention, the resin composition comprises, by solid weight:
(A) epoxy resin: 100 parts of (A);
(B) an active ester compound described by structural formula (1): 20-60 parts;
(C) curing agent: 1-30 parts;
(D) phenoxy resin: 1-30 parts;
(E) filling: 0-200 parts of a solvent;
(F) curing accelerator: 0.001-5 parts;
as a further preferred of the present invention, the resin composition comprises, by solid weight:
(A) epoxy resin: 100 parts of (A);
(B) an active ester compound described by structural formula (1): 20-60 parts;
(C) curing agent: 1-30 parts;
(D) cyanate ester: 5-20 parts of a solvent;
(E) filling: 0-200 parts of a solvent;
(F) curing accelerator: 0.001-5 parts;
in the 2 preferred resin composition embodiments described above, the curing agent of component (C) is a curing agent other than component (B) as described above: the compound may be an active ester compound, an amine compound, an amide compound, an acid anhydride compound or a phenol compound other than the active ester compound represented by the structural formula (1).
Preferably, the resin composition may further include 1 to 80 parts by weight of a flame retardant per 100 parts by weight of the epoxy resin in order to improve flame retardancy of the cured product. The flame retardant can be a bromine flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, an organic silicon flame retardant, an organic metal salt flame retardant, an inorganic flame retardant and 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. The flame retardant to be added may be chosen according to the specific application of the laminate, and halogen-demanding applications, preferably non-halogen flame retardants, such as phosphorus-or nitrogen-containing flame retardants. Preferably, when the phosphorus-containing flame retardant is selected, nitrogen and phosphorus are formed to be cooperated with nitrogen elements of the active ester in the technical scheme for flame retardance, so that the flame retardance efficiency is improved. Preferably, the amount of the flame retardant added to the resin composition is 5 to 50 parts by weight.
In the above technical scheme, the filler is selected from organic fillers or inorganic fillers,
wherein the inorganic filler is selected from one or a mixture of several of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus;
the organic filler is one or a mixture of several of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyether sulfone powder.
The inorganic filler is preferably any one or a mixture of more of 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 or glass fiber powder.
Preferably, the filler is silica, more preferably surface treated silica. The filler has a particle size median value of 1 to 15 microns, for example 1 micron, 2 microns, 5 microns, 8 microns, 10 microns, 11 microns, 12 microns, 13 microns, 14 microns or 15 microns, preferably 1 to 10 microns. The surface treatment agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent.
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.
In the above technical solution, the curing accelerator is selected from any one or a mixture of several of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole and zinc isooctoate, wherein a typical but non-limiting mixture is: 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, a mixture of 2-methylimidazole, 2-methyl-4-ethylimidazole and 2-phenylimidazole. Preferably, the curing accelerator is contained in an amount of 0.01 to 1 part.
The invention also discloses a prepreg prepared by the resin composition, the resin composition is dissolved by a solvent to prepare a glue solution, then the reinforcing material is soaked in the glue solution, and the soaked reinforcing material is heated and dried to obtain the prepreg.
The conventional production method of the resin composition of the present invention is: taking a container, putting the solid component in the container, adding a liquid organic solvent, stirring until the solid component is 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 the glue solution.
The preparation method of the prepreg comprises the following steps: and (3) soaking the reinforcing material in the resin composition glue solution, and then baking the soaked reinforcing material at the temperature of 50-170 ℃ for 1-10min to dry to obtain the prepreg.
Among them, the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric, and the inorganic fabric is particularly preferably glass fiber cloth, and the glass fiber cloth is preferably open fiber cloth or flat cloth. In addition, in order to improve the interfacial bonding between the resin and the glass cloth, the glass cloth generally needs to be chemically treated, mainly by a coupling agent such as epoxy silane, amino silane, etc. The organic solvent is selected from one or the combination of any more 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 invention also discloses a laminated board, wherein a metal foil is coated on one side or both sides of one prepreg, or at least 2 prepregs are stacked, then the metal foil is coated on one side or both sides of the prepreg, and hot press forming is carried out, so that the laminated board can be obtained.
The number of prepregs may be determined according to the thickness of the laminate desired, and one or more prepregs may be used. The metal foil may be a copper foil or an aluminum foil, and the thickness thereof is not particularly limited, such as 5 micrometers, 8 micrometers, 12 micrometers, 18 micrometers, 35 micrometers or 70 micrometers.
The pressing condition of the laminated board is that the laminated board is pressed for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃.
The invention also discloses an insulating film, which is obtained by coating any one of the resin compositions on a carrier and heating and drying the resin composition. Specifically, a resin composition is added with a solvent to be dissolved to prepare a glue solution, the glue solution is coated on a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the interlayer insulating film. The solvent is selected from one or more of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether and propylene glycol methyl ether. The carrier film may be a polyethylene terephthalate (PET) film, a release film, a copper foil, an aluminum foil, or the like, and is preferably a PET film. The heating and drying condition is baking for 1-10 minutes at 50-170 ℃. In the above technical solution, in order to protect the insulating thin film layer, the other surface of the resin layer is covered with a protective film, and the protective film may be made of the same material as the carrier film.
The invention also claims a printed wiring board which comprises at least one prepreg as described above or/and an insulating film as described above.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the resin composition disclosed by the invention adopts an active ester compound containing two reaction groups, wherein the active ester group does not generate a hydroxyl group with stronger polarity when reacting with epoxy resin, so that the resin composition has excellent dielectric property and low coarsening degree, meanwhile, an aromatic thiol group at the tail end can react with the epoxy resin, and the thiol group has better cohesiveness, so that the cohesiveness is extremely high, and the problem of two opposite properties of low coarsening degree and high peel strength is solved;
2. experiments show that the active ester group and the thiol group in the active ester compound can be subjected to curing reaction with the epoxy resin, so that the crosslinking density of a cured product is effectively improved, and more excellent heat resistance and high rigidity are obtained, and therefore, the prepreg and the insulating film can better meet the heat resistance and rigidity requirements of an organic packaging substrate and a coreless substrate.
3. When the cyanate ester resin is added into the resin composition, the matching of the active ester and the cyanate ester can obtain lower dielectric constant and dielectric loss value, and further improve the heat resistance of the plate.
4. When the phenoxy resin is added to the resin composition, the thiol group in the active ester and the phenoxy group or hydroxyl group in the phenoxy resin are matched to obtain higher peel strength value, so that a better balance between coarsening degree and peel strength is obtained.
Detailed Description
The invention is further described below with reference to the following examples:
synthesis example 1: synthesis of Dicyclopentadienyl active ester Compounds
The first step is as follows: 1mol of dicyclopentadiene phenol resin and 2mol of p-isothiocyanatobenzoic acid are taken, stirred and dissolved uniformly in a toluene solvent, nitrogen is simultaneously introduced at the temperature of 60 ℃, a catalyst (tetrabutylammonium bromide) is added, and the reaction is carried out for 4 hours;
Figure BDA0002040210820000101
the second step is that: under the protection of nitrogen, sodium hydroxide solution is dropped in, and the reaction is continued to obtain the active ester compound A with the terminal thiol group.
Figure BDA0002040210820000102
Synthesis example 2: synthesis of Tricyclopentadienyl active ester Compounds
The dicyclopentadiene naphthol resin in synthesis example 1 was replaced with a tricyclopentadienol resin, and the other steps were the same as in synthesis example 1 to obtain a tricyclopentadienyl active ester compound B.
Synthesis example 3: synthesis of naphthyl active ester Compound
The procedure of Synthesis example 1 was repeated except that a naphthol resin was used in place of the dicyclopentadiene naphthol resin in Synthesis example 1 to obtain a naphthyl active ester compound C.
Synthesis example 4: synthesis of Dicyclopentadienyl active ester Compound
Dicyclopentadienyl naphthol resin was used instead of dicyclopentadiene naphthol resin in Synthesis example 1, and the other steps were the same as in Synthesis example 1 to obtain dicyclopentadiene naphthyl active ester Compound D.
Examples and comparative examples:
according to the component contents in table 1, epoxy resin, the active ester compound obtained in the synthesis example, curing agent, phenoxy resin, cyanate ester resin, curing accelerator, filler, flame retardant and a proper amount of butanone solvent were uniformly stirred and mixed to obtain a glue solution with a solid content of 65 wt%.
The glue solution is soaked and coated on E glass fiber cloth (7628), and is dried in an oven at 160 ℃ for 5min to prepare a prepreg.
And coating the glue solution on a PET carrier, and drying in a 160 ℃ oven for 5min to obtain the insulating film.
Preparation of performance evaluation sample laminates:
(1) preparation of laminate a
And (3) placing 18-micron metal copper foils on the prepregs respectively from top to bottom, and placing the prepregs in a vacuum hot press for pressing to obtain the laminated board a. The specific pressing process is pressing for 2 hours under the pressure of 1.5Mpa and the temperature of 220 ℃.
(2) Preparation of laminate b
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. The specific pressing process is pressing for 2 hours under the pressure of 1.5Mpa and the temperature of 220 ℃.
Then, the surface insulation film layer is coarsened by a potassium permanganate method, and the steps are as follows:
(1) soaking the plate in a swelling solution (diethylene glycol monobutyl ether solution), and taking out after 10 min;
(2) the taken out plate is dipped in an oxidant (potassium permanganate solution) solution again and taken out after 20 min;
(3) the taken out plate is dipped in a neutralization solution (hydroxylamine sulfate aqueous solution) again and taken out after 10 min;
(4) drying at 80 ℃ for 30min to obtain laminate b to be tested for coarseness.
The laminate properties obtained are shown in table 3.
TABLE 1
Figure BDA0002040210820000121
The detailed specification of the components is as follows:
TABLE 2
Figure BDA0002040210820000122
TABLE 3
Figure BDA0002040210820000131
As can be seen from the above examples and comparative examples, the examples using the active ester of the present invention achieve a higher glass transition temperature, a high peel strength, a low coarsening degree, a low dielectric constant, a low dielectric loss, a high heat resistance, and a balance of properties in all respects. Among them, example 1 had more excellent glass transition temperature and high peel strength than comparative example 1 (prior art active ester), and the coarsening degree was not greatly changed; furthermore, examples 1 to 9 have higher heat resistance than comparative example 1 using a conventional active ester and comparative example 3 using an aromatic amine curing agent.
The performance evaluation method comprises the following steps:
(1) 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.
(2) 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.
(3) 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.
(4) 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.
(5) Dielectric constant: the dielectric constant at 1GHz was measured with the laminate a by the IPC-TM-6502.5.5.9 plate method.
(6) 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.
(7) Tg (. degree. C.): according to differential scanning calorimetry, the measurement was carried out by the DSC method specified by IPC-TM-6502.4.25.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A resin composition is characterized by comprising the following components in percentage by weight of solid:
(A) epoxy resin: 100 parts of (A);
(B) curing agent: 1-100 parts;
(C) filling: 0-200 parts of a solvent;
(D) curing accelerator: 0.001-5 parts;
the curing agent at least contains an active ester compound shown in the following structural formula (1):
Figure FDA0002040210810000011
structural formula (1), wherein A is selected from one of the following structures:
Figure FDA0002040210810000012
Figure FDA0002040210810000021
wherein R is10、R11、R12、R13The same or different, respectively selected from hydrogen, alkyl of C1-C5, aryl of C6-C10 or aralkyl of C6-C10.
2. The resin composition according to claim 1, characterized in that: the solid weight ratio of the components is as follows:
(A) epoxy resin: 100 parts of (A);
(B) an active ester compound described by structural formula (1): 20-60 parts;
(C) curing agent: 1-30 parts;
(D) cyanate ester: 5-20 parts of a solvent;
(E) filling: 0-200 parts of a solvent;
(F) curing accelerator: 0.001-5 parts;
the curing agent of the component (C) is an active ester compound, an amine compound, an amide compound, an acid anhydride compound or a phenol compound other than the active ester compound of the structural formula (1).
3. The resin composition according to claim 1, characterized in that: the solid weight ratio of the components is as follows:
(A) epoxy resin: 100 parts of (A);
(B) an active ester compound described by structural formula (1): 20-60 parts;
(C) curing agent: 1-30 parts;
(D) phenoxy resin: 1-30 parts;
(E) filling: 0-200 parts of a solvent;
(F) curing accelerator: 0.001-5 parts;
the curing agent of the component (C) is an active ester compound, an amine compound, an amide compound, an acid anhydride compound or a phenol compound other than the active ester compound of the structural formula (1).
4. The resin composition according to claim 2 or 3, characterized in that: the active ester compounds except the active ester compound shown in the structural formula (1) have the following structural formula:
Figure FDA0002040210810000031
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.
5. The resin composition according to claim 1, characterized in that: the content of the active ester compound shown in the structural formula (1) in the curing agent is 1-100% by weight based on 100% by weight of the curing agent.
6. The resin composition according to any one of claims 1 to 3, wherein: in the active ester compound of the structural formula (1), the group A contains dicyclopentadienyl, naphthyl or tricyclopentadienyl.
7. A prepreg produced using the resin composition according to any one of claims 1 to 6, characterized in that: dissolving the resin composition with a solvent to prepare a glue solution, then soaking the reinforcing material in the glue solution, and heating and drying the soaked reinforcing material to obtain the prepreg.
8. A laminate, characterized by: the laminate can be obtained by coating a metal foil on one side or both sides of a prepreg according to claim 7, or by laminating at least 2 prepregs according to claim 7, coating a metal foil on one side or both sides, and hot press forming.
9. An insulating film, wherein the insulating film is obtained by coating the resin composition according to any one of claims 1 to 6 on a support and drying it by heating.
10. Printed wiring board, characterized in that it comprises at least one prepreg according to claim 7 or/and a laminate according to claim 8 or/and an insulating film according to claim 9.
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