CN110885428B - Halogen-free thermosetting resin composition, prepreg using same, laminated board and printed circuit board - Google Patents

Halogen-free thermosetting resin composition, prepreg using same, laminated board and printed circuit board Download PDF

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CN110885428B
CN110885428B CN201811042369.3A CN201811042369A CN110885428B CN 110885428 B CN110885428 B CN 110885428B CN 201811042369 A CN201811042369 A CN 201811042369A CN 110885428 B CN110885428 B CN 110885428B
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CN110885428A (en
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罗成
唐国坊
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Shengyi Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
    • 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
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • 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
    • 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
    • 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
    • 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
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

Abstract

The invention provides a halogen-free thermosetting resin composition, a prepreg, a laminated board and a printed circuit board using the same, wherein the halogen-free thermosetting resin composition comprises halogen-free epoxy resin and a curing agent, the curing agent comprises cyanate ester resin and phosphoric anhydride-containing resin, and the contents of the components are as follows: 5-50 parts of cyanate ester resin, 30-60 parts of halogen-free epoxy resin and 15-40 parts of phosphoric anhydride-containing resin. According to the invention, cyanate ester and phosphoric anhydride are jointly used as the curing agent of the halogen-free epoxy resin, the cyanate ester and the phosphoric anhydride are synergistic, the high heat resistance of the composition is enhanced, the low dielectric loss value is achieved, and the three resins are mixed and cured, so that the system has excellent peel strength, interlayer adhesion and flame retardance.

Description

Halogen-free thermosetting resin composition, prepreg using same, laminated board and printed circuit board
Technical Field
The invention belongs to the technical field of laminates, and relates to a halogen-free thermosetting resin composition, a prepreg using the halogen-free thermosetting resin composition, a laminate and a printed circuit board.
Background
Conventional laminates for printed circuits are usually made flame retardant with brominated flame retardants, particularly tetrabromobisphenol a type epoxy resins, which have good flame retardancy but generate hydrogen bromide gas when burned. In addition, in recent years, carcinogens such as dioxin and dibenzofuran have been detected in combustion products of electronic and electrical equipment waste containing halogen such as bromine and chlorine, and thus the use of brominated epoxy resins has been limited. In 2006, 7/1, two environmental protection instructions of the european union, namely an instruction about scrapping electrical and electronic equipment and an instruction about limiting the use of certain harmful substances in electrical and electronic equipment, are formally implemented, the development of a halogen-free flame-retardant copper-clad laminate becomes a hotspot in the industry, and various manufacturers of the copper-clad laminates have introduced their own halogen-free flame-retardant copper-clad laminates.
The introduction of the phosphorus-containing compound into the resin matrix of the copper-clad plate becomes a main technical route of halogen-free flame retardation of the copper-clad plate. The phosphorus-containing flame retardant widely adopted in the field of copper-clad plates at present is mainly divided into a reaction type flame retardant and an additive type flame retardant. The reaction type is mainly DOPO compound, mainly containing phosphorus epoxy resin and phosphorus phenolic resin, and the phosphorus content is between 2 and 10 percent. However, in practical application, it is found that such reactive phosphorus-containing flame retardant forms a secondary hydroxyl group with large polarity after curing, and has large water absorption rate, poor dielectric properties and poor wet heat resistance of the board. The additive type is mainly phosphazene and phosphonate compounds, the flame retardant efficiency of the additive type flame retardant is low, and the flame retardant requirement can be met by adding more flame retardant. Meanwhile, due to the low melting point (generally lower than 150 ℃), the high-melting-point aluminum alloy is easy to migrate to the surface of a plate in the processing process of the laminated plate, and the performance of the plate is influenced.
In addition, in order to satisfy the requirements of PCB processability and performance of terminal electronic products, the copper clad substrate material must have good dielectric properties, heat resistance and mechanical properties, and also have good process processability, high peel strength, excellent humidity resistance and halogen-free flame retardant rating of UL 94V-0.
The hydroxyl-terminated phenoxy hydrocarbyl phosphine oxide is a phosphorus-containing curing agent with reactivity and can perform a curing reaction with epoxy resin, but as the active group is phenolic hydroxyl, secondary hydroxyl with larger polarity can be generated after the reaction with the epoxy resin, so that the dielectric property of a cured product is poor. In CN103384674A, polyphosphonate and/or phosphonate-carbonate copolymer with hydroxyl and epoxy are selected to form a composition, and the active group is phenolic hydroxyl, which also has the problem of poor dielectric property; CN103694642A discloses that epoxy resin, cyanate ester compound and/or cyanate ester prepolymer, and polyphosphonate and/or phosphonate-carbonate copolymer are used to prepare halogen-free UL94V-0 flame retardant prepreg and copper clad laminate with good dielectric property and humidity resistance, but the peel strength, interlayer adhesion and bending strength are low. CN108117633A discloses that the anhydride-modified phosphonate ester, cyanate ester resin and epoxy resin are used for preparing halogen-free copper clad laminate, but the moisture and heat resistance is slightly insufficient due to excessive P-O bonds in the anhydride-modified phosphonate ester.
It is known that there are many materials with low dielectric constant and dielectric loss tangent, such as: polyolefin, fluororesin, polystyrene, polyphenylene ether, modified polyphenylene ether, bismaleimide-triazine resin, polyvinyl benzene resin. Although the above resins have good dielectric properties, all have the defects of difficult process processing, poor heat resistance and the like, and poor peel strength and interlayer adhesion, and cannot meet the requirements of high-frequency high-speed halogen-free flame-retardant copper-clad substrates.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a halogen-free thermosetting resin composition, and a prepreg, a laminated board and a printed circuit board using the same.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a halogen-free thermosetting resin composition, which comprises halogen-free epoxy resin and a curing agent, wherein the curing agent comprises cyanate ester resin and phosphoric anhydride-containing resin, and the contents of the components are as follows:
5-50 parts of cyanate ester resin
30-60 parts of halogen-free epoxy resin
15-40 parts of phosphoric anhydride resin;
the phosphoric anhydride resin is DOPO type phosphoric anhydride resin.
In the invention, cyanate ester and phosphoric anhydride are jointly used as the curing agent of the halogen-free epoxy resin, and the cyanate ester and the phosphoric anhydride are synergistic to enhance the high heat resistance of the composition and have low dielectric loss value, and the phosphoric anhydride and the epoxy resin do not generate secondary hydroxyl with large polarity and poor dielectric property in reaction, thereby bringing excellent dielectric property. And the three resins are mixed and cured, and the combined action also brings excellent anti-stripping strength and interlayer adhesion of the system. In addition, the phosphoric anhydride contains a halogen-free flame-retardant DOPO structure, is used as a reactive flame-retardant component, has high flame-retardant efficiency, and can enable the system to have halogen-free flame-retardant characteristics, and under the addition of the additive, the flame retardance of a cured product of the composition can reach the halogen-free flame-retardant effect of UL 94V-0. And the combination use of the phosphoric anhydride, the cyanate ester resin and the halogen-free epoxy resin can ensure that the composition has higher heat resistance.
The invention utilizes the synergistic effect among cyanate ester, phosphoric anhydride and epoxy resin, can obviously improve the glass transition temperature and heat resistance of the prepreg and the laminated board for the printed circuit which are prepared by using the resin composition, and enables the prepreg and the laminated board to have excellent dielectric property, low water absorption rate, high peel strength, high interlayer adhesive force, good humidity resistance and good process processability, and realizes halogen-free flame retardance, thereby reaching UL 94V-0.
Preferably, the phosphoric anhydride-containing resin is a resin having the following structure:
Figure BDA0001792431990000041
in the present invention, the amount of the phosphoric anhydride-containing resin added to the halogen-free thermosetting resin composition may be 15 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 33 parts, 35 parts, 38 parts or 40 parts, and specific values therebetween, which are not exhaustive for reasons of space and simplicity, are included in the range.
In the present invention, the amount of the cyanate ester resin added in the halogen-free thermosetting resin composition may be 5 parts, 8 parts, 10 parts, 13 parts, 15 parts, 18 parts, 20 parts, 25 parts, 28 parts, 30 parts, 35 parts, 38 parts, 40 parts, 43 parts, 45 parts, 48 parts or 50 parts. And the particular values between the above, are not intended to be exhaustive or to limit the invention to the precise values encompassed within the scope, for reasons of brevity and clarity.
Preferably, the cyanate ester resin has the following structure:
Figure BDA0001792431990000042
wherein R is5is-CH2-、
Figure BDA0001792431990000043
Any one or a mixture of at least two of them; r1、R2、R3、R4、R6、R7、R8、R9Each independently selected from any one of a hydrogen atom, a substituted or unsubstituted linear alkyl or branched alkyl group having 1 to 4 carbon atoms (for example, 1, 2, 3 or 4 carbon atoms) (for example, any one of a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a tert-butyl group may be used).
Preferably, the cyanate ester resin is selected from the group consisting of 2, 2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, bis (3, 5-dimethyl-4-cyanatophenyl) methane, 2-bis (4-cyanatophenyl) -1,1,1,3,3, 3-hexafluoropropane, α' -bis (4-cyanatophenyl) -m-diisopropylbenzene, cyclopentadiene-type cyanate ester, phenol novolac-type cyanate ester, cresol novolac-type cyanate ester, 2-bis (4-cyanatophenyl) propane prepolymer, bis (4-cyanatophenyl) ethane prepolymer, bis (3, 5-dimethyl-4-cyanatophenyl) methane prepolymer, 2-bis (4-cyanatophenyl) -1,1,1,3,3, 3-hexafluoropropane prepolymer, α' -bis (4-cyanatophenyl) -m-diisopropylbenzene prepolymer, dicyclopentadiene type cyanate ester prepolymer, phenol novolac type cyanate ester prepolymer or cresol novolac type cyanate ester prepolymer, or a mixture of at least two thereof, preferably 2, 2-bis (4-cyanatophenyl) propane, any one or a mixture of at least two of α, α '-bis (4-cyanatophenyl) -m-diisopropylbenzene, bis (3, 5-dimethyl-4-cyanatophenyl) methane, 2-bis (4-cyanatophenyl) propane prepolymer, α' -bis (4-cyanatophenyl) -m-diisopropylbenzene prepolymer, or bis (3, 5-dimethyl-4-cyanatophenyl) methane prepolymer.
In the present invention, the halogen-free epoxy resin may be added to the halogen-free thermosetting resin composition in an amount of 30 parts, 33 parts, 35 parts, 38 parts, 40 parts, 43 parts, 45 parts, 48 parts, 50 parts, 53 parts, 55 parts, 58 parts or 60 parts, and specific values therebetween, which is included in the range not exhaustive for brevity and conciseness.
The halogen-free epoxy resin is preferably used in the present invention, and the halogen-free epoxy resin means an epoxy resin having two or more epoxy groups in 1 molecule.
Preferably, the halogen-free epoxy resin is any one of or a mixture of at least two of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, alicyclic epoxy resin, epoxidized olefin epoxy resin, hydantoin epoxy resin or imide epoxy resin, wherein a typical but non-limiting mixture is: a mixture of glycidyl ether type epoxy resin and glycidyl ester type epoxy resin, a mixture of alicyclic epoxy resin and epoxidized olefin type epoxy resin, and a mixture of glycidyl amine type epoxy resin and hydantoin type epoxy resin.
Preferably, the glycidyl ether type epoxy resin includes any one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, o-cresol novolac epoxy resin, bisphenol a type novolac epoxy resin, triphenol type novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl type novolac epoxy resin, alkylbenzene type novolac epoxy resin, or naphthol type novolac epoxy resin, or a mixture of at least two thereof.
Further preferably, the glycidyl ether epoxy resin is selected from epoxy resins having the following structure:
Figure BDA0001792431990000061
wherein, Z1、Z2And Z3Each independently selected from
Figure BDA0001792431990000062
R is selected from any one of hydrogen atom, substituted or unsubstituted straight-chain alkyl or branched-chain alkyl with 1-5 carbon atoms (such as 1, 2, 3, 4 or 5), and can be methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, tert-butyl or isopreneAny one of the above groups;
Y1and Y2Each independently selected from-CH2-、
Figure BDA0001792431990000063
Figure BDA0001792431990000064
Any one of the above; r10Any one selected from hydrogen atom, substituted or unsubstituted straight chain alkyl or branched chain alkyl with 1-5 carbon atoms (such as 1, 2, 3, 4 or 5); for example, it may be any of methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, tert-butyl or isopentyl;
n2Is any integer from 1 to 10, such as 1, 2, 3,4, 5, 6, 7, 8, 9 or 10.
Preferably, the glycidyl amine epoxy resin is selected from any one of triglycidyl para-aminophenol, triglycidyl isocyanurate, tetraglycidyl diaminoxylylene, tetraglycidyl-4, 4 ' -diaminodiphenylmethane, tetraglycidyl-3, 4 ' -diaminodiphenyl ether, tetraglycidyl-4, 4 ' -diaminodiphenyl ether, or tetraglycidyl-1, 3-diaminomethylcyclohexane, or a mixture of at least two thereof.
Preferably, the curing agent further comprises a SMA resin, and in the present invention, the SMA resin means a styrene-maleic anhydride resin, and can be obtained by copolymerizing styrene and maleic anhydride at a ratio of 1:1 to 8:1 (e.g., 1:1, 1.5:1, 1.8:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, or 8:1), for example.
In the present invention, the SMA resin is added in an amount of 0 to 40 parts by weight, for example, 1 part by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 33 parts by weight, 35 parts by weight, 38 parts by weight, or 40 parts by weight, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent, and specific points between the above values are not limited to space and for brevity, and the present invention is not exhaustive.
In the present invention, the curing agent further includes a phenolic resin, and the phenolic resin is a phenolic resin containing phosphorus or not containing phosphorus, which is a phenolic resin known in the art, and the present invention is not particularly limited.
According to the present invention, the phenolic resin is added in an amount of 0 to 20 parts by weight, for example, 0 part by weight, 2 parts by weight, 4 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 15 parts by weight, 17 parts by weight or 20 parts by weight, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent, and specific points between the above-mentioned values are not exhaustive for the invention, and are not limited to specific points included in the range for brevity and conciseness.
According to the present invention, the curing agent may further comprise a small-molecular polyphenylene ether resin; the small molecular polyphenylene ether resin is a small molecular polyphenylene ether resin known in the art, and the present invention is not particularly limited.
According to the present invention, the small molecular polyphenylene ether resin is added in an amount of 0 to 20 parts by weight, for example, 0 part by weight, 2 parts by weight, 4 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 15 parts by weight, 17 parts by weight, or 20 parts by weight, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent, and specific points between the above-mentioned values are not limited to space and for the sake of brevity, and the present invention is not exhaustive enumeration of specific points included in the range.
Preferably, the curing agent further comprises an active ester curing agent.
In the present invention, the active ester curing agent is added in an amount of 0 to 20 parts by weight, for example, 0 part by weight, 2 parts by weight, 4 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 15 parts by weight, 17 parts by weight or 20 parts by weight, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent, and specific points between the above-mentioned values are not exhaustive for the invention and for the sake of brevity.
Preferably, the curing agent further comprises a bismaleimide-triazine resin.
In the present invention, the bismaleimide-triazine resin is added in an amount of 0 to 50 parts by weight, for example, 0 part by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, or 50 parts by weight, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.
Preferably, in the present invention, the halogen-free thermosetting resin composition specifically comprises, based on 100 parts by weight of organic solids: 20-60 parts of phosphoric anhydride-containing resin, 30-60 parts of halogen-free epoxy resin, 5-50 parts of cyanate ester resin, 0-50 parts of bismaleimide-triazine resin, 0-40 parts of SMA resin, 0-20 parts of phenolic resin, 0-20 parts of polyphenyl ether resin and 0-20 parts of active ester resin.
The "total weight of the halogen-free epoxy resin and the curing agent in the thermosetting resin composition" referred to in the present invention refers to the total weight of the components participating in the cross-linking polymerization reaction, wherein the curing agent refers to a phosphoric anhydride and a cyanate ester resin which function to cure the epoxy resin and optionally a bismaleimide-triazine resin, an SMA resin, a phenolic resin or a polyphenylene ether resin, an active ester resin, which does not contain components such as a filler, an accelerator, and a flame retardant.
In the invention, the halogen-free thermosetting resin composition also comprises a halogen-free flame retardant, wherein the halogen-free flame retardant is an organic halogen-free flame retardant and/or an inorganic halogen-free flame retardant.
Preferably, the flame retardant is a phosphorus-containing flame retardant and/or a nitrogen-containing flame retardant.
According to the invention, the flame retardant is selected from any one or a mixture of at least two of tris (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphinobenzene, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenoxyphosphazene compound, phosphate ester, polyphosphate ester, polyphosphonate ester or phosphonate ester-carbonate copolymer, melamine polyphosphate, melamine cyanurate or ammonium polyphosphate.
In the present invention, the halogen-free flame retardant is added in an amount of 0 to 15 parts by weight, for example, 1 part by weight, 3 parts by weight, 5 parts by weight, 6 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 or 15 parts by weight, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent, and specific points between the above-mentioned values are not limited to the specific points included in the range for brevity and conciseness.
Preferably, the halogen-free thermosetting resin composition further comprises a curing accelerator.
Preferably, the curing accelerator comprises an organic metal salt and any one or a mixture of at least two selected from imidazole compounds, imidazole compound derivatives, piperidine compounds, pyridine compounds, lewis acids or triphenylphosphine.
Preferably, the organic metal salt comprises any one of or a mixture of at least two of a metal salt of caprylic acid, a metal salt of isooctanoic acid, a metal salt of acetylacetone, a metal salt of naphthenic acid, a metal salt of salicylic acid, or a metal salt of stearic acid;
preferably, the metal contained in the organic metal salt is selected from any one or a mixture of at least two of zinc, copper, iron, tin, cobalt or aluminum.
Preferably, the imidazole compound is any one or a mixture of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole.
Preferably, the piperidine compound is any one or a mixture of at least two of 2, 3-diaminopiperidine, 2, 5-diaminopiperidine, 2, 6-diaminopiperidine, 2-amino-3-methylpiperidine, 2-amino-4-methylpiperidine, 2-amino-3-nitropiperidine, 2-amino-5-nitropiperidine and 2-amino-4, 4-dimethylpiperidine.
Preferably, the pyridine compound is any one or at least two mixtures of 4-dimethylamino pyridine, 2-amino pyridine, 3-amino pyridine or 4-amino pyridine.
Preferably, the curing accelerator is added in an amount of 0.01 to 1 part by weight, for example, 0.01 part by weight, 0.025 part by weight, 0.05 part by weight, 0.07 part by weight, 0.085 part by weight, 0.1 part by weight, 0.3 part by weight, 0.5 part by weight, 0.8 part by weight, 0.9 part by weight, or 1 part by weight, preferably 0.025 to 0.85 part by weight, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.
The halogen-free thermosetting resin composition of the present invention may further include a filler.
Preferably, the filler is selected from organic or inorganic fillers, preferably inorganic fillers, further preferably surface treated inorganic fillers, most preferably surface treated silica.
Preferably, the surface treatment agent for surface treatment is selected from any one of a silane coupling agent, an organosilicon oligomer or a titanate coupling agent or a mixture of at least two thereof.
Preferably, the surface treatment agent is added in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, more preferably 0.75 to 2 parts by weight, based on 100 parts by weight of the inorganic filler.
Preferably, the inorganic filler is selected from any one or a mixture of at least two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus, preferably any one or a mixture of at least two 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 or mica.
Preferably, the organic filler is selected from any one of polytetrafluoroethylene powder, polyphenylene sulfide or polyether sulfone powder or a mixture of at least two of the polytetrafluoroethylene powder, the polyphenylene sulfide or the polyether sulfone powder.
Preferably, the median particle diameter of the filler is 0.01 to 50 μm, preferably 0.01 to 20 μm, and more preferably 0.1 to 10 μm.
Preferably, the filler is added in an amount of 5 to 300 parts by weight, for example, 5 parts by weight, 10 parts by weight, 20 parts by weight, 50 parts by weight, 80 parts by weight, 100 parts by weight, 130 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, 230 parts by weight, 250 parts by weight, 280 parts by weight, or 300 parts by weight, preferably 5 to 200 parts by weight, and more preferably 5 to 150 parts by weight, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.
The term "comprising" as used herein means that it may include, in addition to the components, other components which impart different properties to the halogen-free thermosetting resin composition. In addition, the term "comprising" as used herein may be replaced by "being" or "consisting of … …" in the closed form.
For example, the halogen-free thermosetting resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These additives may be used alone or in combination of two or more.
In another aspect, the present invention provides a resin solution, wherein the resin solution is obtained by dissolving or dispersing the halogen-free resin composition in a solvent.
The preparation method of the resin glue solution is a conventional technical means in the field, and the specific method comprises the following steps: firstly, putting the solid substance, then adding the liquid solvent, stirring until the solid substance is completely dissolved, then adding the liquid resin and the accelerator, and continuously stirring uniformly.
The solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol and butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol and butyl carbitol, ketones such as acetone, methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and ethoxyethyl acetate; nitrogen-containing solvents such as N, N-dimethylformamide and N, N-dimethylacetamide. The above solvents may be used alone or in combination of two or more. Ketones such as acetone, methyl ethyl ketone, and cyclohexanone are preferable. The addition amount of the solvent is selected by a person skilled in the art according to his own experience, so that the resin glue solution has a viscosity suitable for use.
In another aspect, the present invention provides a prepreg comprising a reinforcing material and the above halogen-free thermosetting resin composition attached thereto by impregnation and drying.
In the present invention, the reinforcing material to be used is not particularly limited, and may be an organic fiber, an inorganic fiber woven fabric or a nonwoven fabric. The organic fiber can be aramid fiber non-woven fabric, and the inorganic fiber woven fabric can be E-glass fiber fabric, D-glass fiber fabric, S-glass fiber fabric, T-glass fiber fabric, NE-glass fiber fabric or quartz fabric. The thickness of the reinforcing material is not particularly limited, and the woven fabric and the non-woven fabric preferably have a thickness of 0.01 to 0.2mm in consideration of good dimensional stability of the laminate, and are preferably subjected to a fiber opening treatment and a surface treatment with a silane coupling agent, and the silane coupling agent is preferably one of an epoxy silane coupling agent, an amino silane coupling agent, or a vinyl silane coupling agent or a mixture of at least two thereof in order to provide good water resistance and heat resistance.
In the present invention, the prepreg is obtained by impregnating the halogen-free thermosetting resin composition with the reinforcing material and baking the impregnated reinforcing material for 1 to 15 minutes (for example, 1 minute, 3 minutes, 5 minutes, 7 minutes, 9 minutes, 10 minutes, 12 minutes or 15 minutes) at 100 to 250 ℃ (for example, 100 ℃, 130 ℃, 150 ℃, 180 ℃, 200 ℃, 220 ℃ or 250 ℃).
In another aspect, the present invention provides a laminate comprising at least one prepreg as described above.
In another aspect, the present invention provides a metal-clad laminate comprising at least one prepreg as described above and a metal foil clad on one or both sides of the stacked prepregs.
In the invention, the metal foil-clad laminate is cured in a hot press at a temperature of 150-250 ℃ (e.g., 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃), and curedThe chemical pressure is 10-60 kg/cm2(e.g., 10 kg/cm)2、13kg/cm2、15kg/cm2、18kg/cm2、20kg/cm2、22kg/cm2、25kg/cm2、28kg/cm2、30kg/cm2、35kg/cm2、40kg/cm2、45kg/cm2、50kg/cm2、55kg/cm2Or 60kg/cm2)。
In the present invention, the metal foil is a copper foil, a nickel foil, an aluminum foil, a stainless steel foil (SUS foil), or the like, and the material thereof is not limited.
In another aspect, the present invention provides a printed circuit board comprising one or at least two superimposed prepregs as described above.
Compared with the prior art, the invention has the following beneficial effects:
the halogen-free thermosetting resin composition provided by the invention uses cyanate ester and phosphoric anhydride as the curing agent of halogen-free epoxy resin together, the cyanate ester and the phosphoric anhydride cooperate with each other to enhance the high heat resistance of the composition and have a low dielectric loss value, and the three resins are mixed and cured to bring about the excellent peeling strength, interlayer adhesion and excellent flame resistance of the system. The prepreg and the laminated board for the printed circuit, which are prepared from the halogen-free thermosetting resin composition, have the glass transition temperature as high as 248 ℃, excellent dielectric property, water absorption controlled within the range of 0.05-0.11%, high heat resistance, excellent wet heat resistance, good process processability and excellent flame retardant efficiency, and the flame retardance with the phosphorus content of 1.97 percent can reach the UL94V-0 level.
Drawings
FIG. 1 is an infrared spectrum of the phosphoric anhydride DOPO-MAH of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
Synthesis of phosphoric anhydride DOPO-MAH
49g of maleic anhydride and 108g of DOPO were stirred in a four-necked flask equipped with a stirrer and a thermometer while introducing nitrogen, and then the temperature was raised to 125 ℃ and reacted at this temperature for 3 hours to obtain a product, numbered DOPO-MAH. The structure is as follows:
Figure BDA0001792431990000141
the characterization was performed by using an infrared spectrometer Nicolet TR-460, as shown in FIG. 1, which is an infrared spectrogram of DOPO-MAH, and it can be seen that P-H in the DOPO structure is 2361cm-1、2342cm-1Disappearance of characteristic absorption indicating complete reaction; 1865cm-1And 1787cm-1The characteristic absorption of the five-membered cyclic anhydride indicates that the newly generated structure contains the five-membered anhydride, and indicates that the phosphoric anhydride with the structure is synthesized.
Examples 1 to 9
As shown in tables 1 and 2 (the component usage amounts are calculated by weight parts), phosphoric anhydride, halogen-free epoxy resin, a curing accelerator, a halogen-free flame retardant and a filler are uniformly mixed in a solvent according to a certain proportion, the solid content of the glue solution is controlled to be 65%, the glue solution is soaked by 2116 glass fiber cloth, the proper thickness is controlled, then the glue solution is baked for 2-15 min in an oven at the temperature of 115-175 ℃ to prepare a prepreg, then a plurality of prepregs are stacked together, 18 mu RTF copper foils are stacked on two sides of the prepregs, the curing temperature is 170-250 ℃, and the curing pressure is 25-60 kg/cm 2The copper-clad plate is prepared under the condition that the curing time is 60-300 min, and the composition of the resin composition and the performance test standard of the copper-clad plate are shown in tables 1 and 2.
Comparative examples 1 to 10
The preparation method of the copper clad laminate was the same as in examples 1 to 10 except that the composition of the resin composition is shown in tables 3 and 4 (the amounts of the components are in parts by weight).
Examples 1-9 and comparative examples 1-10 relate to materials and brand information as follows:
(A) cyanate ester
CY-40: DCPD type cyanate ester resin of Wuqiao resin factory
PT-60S: LONCZ, phenolic cyanate ester resin
CE01 PS: jiangsu Tianqi, bisphenol A type cyanate resin
CE01 MO: jiangsu Tianqi, bisphenol A type cyanate resin
(B) Epoxy resin
HP-7200 HHH: DIC, DCPD type epoxy resin, epoxy equivalent 288
HP-7200H-75M: DIC, DCPD type epoxy resin, epoxy equivalent 280
HP-6000: DIC, epoxy resin, epoxy equivalent 250
HP-9900: DIC, naphthol type epoxy resin, epoxy equivalent 274
NC-3000H: japanese chemical, Biphenyl epoxy, epoxy equivalent 294
SKE-1: colt, Special epoxy resin, epoxy equivalent 120
SKE-3: colt, Special epoxy resin, epoxy equivalent 120
(C) Phosphoric acid anhydride
DOPO-MAH：
Figure BDA0001792431990000161
DOPO-MAH-1：
Figure BDA0001792431990000162
P-A1：
Figure BDA0001792431990000163
(D) SMA resin
EF 60: clevix, styrene-maleic anhydride copolymer
(E) Phenolic resin
DOW 92741: phosphorus-containing phenolic aldehyde, Dow chemical
(F) Small molecule polyphenyl ether resin
SA90 Saboryl hydroxyl-terminated small molecular polyphenylene ether resin
(G) Active ester resin
Active ester resin of HPC-8000-65T DIC, DCPD type
(H) Accelerator
2E4 MZ: 2-ethyl-4-methylimidazole, four kingdoms of chemical origin
DMAP: 4-dimethylaminopyridine, Guangrong chemistry
BICAT Z: zinc isooctanoate, The Shepherd Chemical Company
(I) Filler material
DQ-1028L: spherical silicon micropowder of Jiangsu Liaorui
(J) Flame retardant
SPB-100: otsuka chemical, phosphazene fire retardant, phosphorus content 13.4%
MC-15: shouguepu chemical, MCA flame retardant.
Tables 1-2 show examples 1-10, and tables 3-4 show formulation compositions and physical property data of comparative examples 1-10.
TABLE 1
Example 1 Example 2 Example 3 Example 4 Example 5
DOPO-MAH 15 20 30 35 40
CE01MO 50
CEO1PS 40
CY-40 10
PT-60S 5 5
HP-7200HHH 60
NC-3000H 40 60 55
SKE-3 35
SPB-100 4
Zinc iso-octoate 0.0125 0.04 0.02 0.025 0.025
2-PZ 1 0.8 0.6 0.4 0.2
DQ-1028L 0 50 150 300 300
P％ 2.02％ 1.97％ 2.96％ 3.45％ 3.95％
Tg(DMA)/℃ 248 230 210 182 188
Dk(10GHz) 3.72 3.80 4.00 4.20 4.20
Df(10GHz) 0.0068 0.0065 0.0070 0.0068 0.0063
PS thermal stress/N/mm 1.2 1.15 0.9 0.8 0.8
Interlayer bonding force/N/mm 0.82-1.25 0.76-1.13 0.56-0.93 0.54-0.88 0.52-0.83
Water absorption/% 0.11 0.08 0.065 0.052 0.055
PCT/6h OOO OOO OOO OOO OOO
T288/min ＞60 ＞60 ＞60 ＞60 ＞60
Fire resistance property V-0 V-0 V-0 V-0 V-0
TABLE 2
Figure BDA0001792431990000171
Figure BDA0001792431990000181
TABLE 3
Figure BDA0001792431990000182
Figure BDA0001792431990000191
TABLE 4
Comparative example 6 Comparative example 7 Comparative example 8 Comparative example 9 Comparative example 10
DOPO-MAH 20 20 20 20
PA-1 15
CE01MO 20 10 10 20 50
DOW92741 25
EF60 45
SA90 25
HPC-8000-65T 25
HP-6000 45
HP-9900 35
NC-3000H 35
SKE-3 25 35
SPB100 5 2 4
MC-15 10 6
Zinc iso-octoate 0.04 0.01 0.01 0.02 0.0125
2E4MZ 0 0.2 0.4 0.8
2-PZ 1
DQ-1028L 50 50 50 50 0
P％ 4.47％ 2.64％ 1.97％ 2.24％ 1.28％
Tg(DMA)/℃ 125 200 205 145 252
Dk(10GHz) 3.9 3.8 3.9 3.8 3.72
Df(10GHz) 0.0085 0.006 0.007 0.006 0.0068
PS thermal stress/N/mm 0.65 1.1 0.98 1.23 1.2
Interlayer bonding force/N/mm 0.32-0.45 0.76-1.03 0.71-1.00 0.95-1.24 0.82-1.25
Water absorption/%) 0.15 0.055 0.072 0.07 0.14
PCT/6h xxx OOO OOO xxx xxx
T288/min Delamination at 243 deg.C ＞60 ＞60 Delamination at 276 ℃ ＞60
Flame retardancy V-0 V-1 V-1 V-1 V-1
Supplementary notes on the PCT/6h Performance icon: and x is a layered explosion plate, and O is a non-layered explosion plate.
The test method of the above characteristics is as follows:
(1) Glass transition temperature (Tg): the DMA test was used and the measurement was carried out according to the DMA test method specified in IPC-TM-6502.4.24.
(2) Dielectric constant and dielectric dissipation factor: testing according to the SPDR method.
(3) Evaluation of Wet Heat resistance (PCT): after etching the copper foil on the surface of the copper clad laminate, evaluating the substrate; placing the substrate in a pressure cooker, processing for 6 hours under the conditions of 120 ℃ and 105KPa, immersing in a tin furnace at 288 ℃, and recording corresponding time when the substrate is layered and exploded; the evaluation was concluded when the substrate had not blistered or delaminated in the tin oven for more than 5 minutes.
(4) T288: the measurement was carried out by using a TMA meter according to the T300 test method specified in IPC-TM-6502.4.24.1.
(5) Water absorption: the measurement was carried out according to the water absorption test method specified in IPC-TM-6502.6.2.1.
(6) Flame retardancy: the method is carried out according to the UL 94 standard method.
(7) PS thermal stress: the procedure was carried out according to the IPC-TM-6502.4.8 (12/94 version C) standard method.
(8) Interlayer bonding force: Q/GDSY 6052-2016P01 standard method.
From a comparison of the data in tables 1-4, it can be seen that:
compared with the example 1, the copper-clad plate prepared by using the cyanate ester in the comparative example 1 with the addition amount exceeding the upper limit and the phosphoric anhydride containing with the upper limit has poor humidity resistance and poor flame retardance due to PCT board explosion, and does not reach V0 grade; comparative example 2 compared with example 2, in comparative example 2, the use of the epoxy resin is insufficient, so that the addition amount of the phosphoric anhydride is too large, the plate cannot be completely cured, and the heat resistance, the wet heat resistance, the interlayer bonding force and the peeling strength are poor; comparative example 3 compared to example 3, comparative example 3 had more epoxy resin, relatively less curing agent, and the board did not cure well, resulting in low Tg and poor electrical properties; compared with the embodiment 4, the comparative example 4 does not use cyanate ester resin, and the copper-clad plate prepared by the comparative example 4 has poor dielectric property and low Tg; comparative example 5 and example 2 compare, and the phosphorus-containing acid anhydride of DOPO-MAH-1 in comparative example 5 has low Tg and poor flame retardancy due to the fact that the DOPO structure is connected with one more flexible methine group.
Further, when comparative example 6 and example 6 were compared, it was found that the epoxy resin content of the plate material was insufficient due to a large amount of the phosphorus-containing phenol aldehyde in comparative example 6, the plate material was not cured well due to an excessive amount of the curing agent, and the heat resistance, the moist heat resistance and the dielectric property were inferior. Comparing comparative example 7 with example 7, it can be seen that the use of more SMA resin in comparative example 7 results in a copper clad laminate with low Tg and poor flame retardancy. Comparing comparative example 8 with example 8, it can be seen that the use of more PPO resin in comparative example 8 results in a low Tg and poor flame retardancy of the resulting copper clad laminate. Comparing comparative example 9 with example 9, it is clear that the epoxy resin content of the plate is insufficient due to the large amount of active ester contained in comparative example 9, the curing agent content is excessive, and the plate is not cured well, resulting in low Tg and poor heat resistance and moist heat resistance. Comparative example 10 comparing with example 1, the phosphorus-containing anhydride with PA-1 structure has higher water absorption than that of the phosphorus-containing anhydride with DOPO structure, the PCT is easy to delaminate and burst, and the total phosphorus content is lower due to the lower phosphorus content and the same addition amount, and the flame retardance is difficult to reach V0 level.
From the above results, it can be seen that the prepreg and the laminate for printed circuits, which are prepared by compounding the phosphoric anhydride, halogen-free epoxy resin and cyanate ester resin according to the present invention, and other possible epoxy curing agents, have glass transition temperatures as high as 248 ℃; excellent dielectric property, and the water absorption is controlled within the range of 0.05-0.11%; high heat resistance; excellent moist heat resistance and good process processability; excellent flame retardant efficiency, and the phosphorus content of 1.97 percent can reach UL 94V-0.
In conclusion, compared with the common laminated board, the prepreg and the laminated board for the printed circuit, which are prepared from the halogen-free thermosetting resin composition, have the advantages of high glass transition temperature, excellent dielectric property, low water absorption rate, high heat resistance, excellent humidity resistance and good process processability, and can realize halogen-free flame retardance, so that the halogen-free flame retardance of UL94V-0 is achieved.
The applicant states that the present invention is described by the above examples of the halogen-free thermosetting resin composition, the prepreg, the laminate and the printed circuit board using the same, but the present invention is not limited to the above examples, that is, the present invention is not limited to the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (50)

1. The halogen-free thermosetting resin composition is characterized by comprising halogen-free epoxy resin and a curing agent, wherein the curing agent comprises cyanate ester resin and phosphoric anhydride resin and does not comprise SMA resin, and the contents of the components are as follows:
5-50 parts of cyanate ester resin
30-60 parts of halogen-free epoxy resin
15-40 parts of phosphoric anhydride resin;
the phosphoric anhydride resin is DOPO type phosphoric anhydride resin;
the phosphoric anhydride-containing resin is a resin with the following structure:
Figure FDA0003587464350000011
2. the halogen-free thermosetting resin composition according to claim 1, wherein the cyanate ester resin has the following structure:
Figure FDA0003587464350000012
wherein R is5is-CH2-、
Figure FDA0003587464350000013
Any one or a mixture of at least two of them; r1、R2、R3、R4、R6、R7、R8、R9Each independently selected from any one of hydrogen atom, substituted or unsubstituted straight-chain alkyl or branched-chain alkyl with 1-4 carbon atoms.
3. The halogen-free thermosetting resin composition according to claim 1, wherein the cyanate ester resin is selected from the group consisting of 2, 2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, bis (3, 5-dimethyl-4-cyanatophenyl) methane, 2-bis (4-cyanatophenyl) -1,1,1,3,3, 3-hexafluoropropane, α' -bis (4-cyanatophenyl) -m-diisopropylbenzene, cyclopentadiene-type cyanate ester, phenol novolac-type cyanate ester, cresol novolac-type cyanate ester, 2-bis (4-cyanatophenyl) propane prepolymer, bis (4-cyanatophenyl) ethane prepolymer, bis (3, 5-dimethyl-4-cyanatophenyl) methane prepolymer, 2, 2-bis (4-cyanatophenyl) -1,1,1,3,3, 3-hexafluoropropane prepolymer, α' -bis (4-cyanatophenyl) -m-diisopropylbenzene prepolymer, dicyclopentadiene type cyanate prepolymer, phenol novolac type cyanate prepolymer or cresol novolac type cyanate prepolymer, or a mixture of at least two thereof.
4. The halogen-free thermosetting resin composition according to claim 3, wherein the cyanate ester resin is selected from any one of 2, 2-bis (4-cyanatophenyl) propane, α '-bis (4-cyanatophenyl) -m-diisopropylbenzene, bis (3, 5-dimethyl-4-cyanatophenyl) methane, 2-bis (4-cyanatophenyl) propane prepolymer, α' -bis (4-cyanatophenyl) -m-diisopropylbenzene prepolymer, or bis (3, 5-dimethyl-4-cyanatophenyl) methane prepolymer, or a mixture of at least two thereof.
5. The halogen-free thermosetting resin composition according to claim 1, wherein the halogen-free epoxy resin is any one or a mixture of at least two of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, alicyclic epoxy resin, epoxidized olefin epoxy resin, hydantoin epoxy resin or imide epoxy resin.
6. The halogen-free thermosetting resin composition according to claim 5, wherein the glycidyl ether type epoxy resin comprises any one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, o-cresol novolac epoxy resin, bisphenol A type novolac epoxy resin, triphenol type novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl type novolac epoxy resin, alkylbenzene type novolac epoxy resin or naphthol type novolac epoxy resin or a mixture of at least two thereof.
7. Halogen-free thermosetting resin composition according to claim 5, characterized in that the glycidyl ether based epoxy resin is selected from epoxy resins having the following structure:
Figure FDA0003587464350000031
wherein Z is1、Z2And Z3Each independently selected from
Figure FDA0003587464350000032
R is selected from any one of hydrogen atoms, substituted or unsubstituted linear alkyl or branched alkyl containing 1-5 carbon atoms; y is1And Y2Each independently selected from-CH2-、
Figure FDA0003587464350000033
Figure FDA0003587464350000034
Any one of the above; r10Selected from any one of hydrogen atom, substituted or unsubstituted linear alkyl or branched alkyl containing 1-5 carbon atoms, n2Is an arbitrary integer of 1 to 10.
8. Halogen-free thermosetting resin composition according to claim 5, characterized in that the glycidyl amine based epoxy resin is selected from any one or a mixture of at least two of triglycidyl p-aminophenol, triglycidyl isocyanurate, tetraglycidyl diaminodimethylene benzene, tetraglycidyl-4, 4 ' -diaminodiphenylmethane, tetraglycidyl-3, 4 ' -diaminodiphenyl ether, tetraglycidyl-4, 4 ' -diaminodiphenyl ether or tetraglycidyl-1, 3-diaminomethylcyclohexane.
9. The halogen-free thermosetting resin composition according to claim 1, wherein the curing agent further comprises a phenolic resin, and the phenolic resin is a phenolic resin containing phosphorus or not containing phosphorus.
10. The halogen-free thermosetting resin composition according to claim 9, wherein the phenolic resin is added in an amount of 0 to 20 parts by weight, excluding 0, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.
11. The halogen-free thermosetting resin composition as claimed in claim 1, wherein the curing agent further comprises a small molecular polyphenylene ether resin.
12. The halogen-free thermosetting resin composition according to claim 11, wherein the small molecular polyphenylene ether resin is added in an amount of 0 to 20 parts by weight excluding 0, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.
13. The halogen-free thermosetting resin composition according to claim 1, wherein the curing agent further comprises an active ester curing agent.
14. The halogen-free thermosetting resin composition according to claim 13, wherein the active ester curing agent is added in an amount of 0 to 20 parts by weight excluding 0, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.
15. The halogen-free thermosetting resin composition according to claim 1, further comprising a halogen-free flame retardant, wherein the halogen-free flame retardant is an organic halogen-free flame retardant and/or an inorganic halogen-free flame retardant.
16. The halogen-free thermosetting resin composition according to claim 15, wherein the halogen-free flame retardant is a phosphorus-containing flame retardant and/or a nitrogen-containing flame retardant.
17. The halogen-free thermosetting resin composition according to claim 16, the halogen-free flame retardant is selected from any one or a mixture of at least two of tris (2, 6-dimethylphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphinobenzene, 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, a phenoxyphosphazene compound, phosphate ester, polyphosphate ester, polyphosphonate or phosphonate-carbonate copolymer, melamine polyphosphate, melamine cyanurate and ammonium polyphosphate.
18. The halogen-free thermosetting resin composition according to claim 15, wherein the halogen-free flame retardant is added in an amount of 0 to 15 parts by weight excluding 0, based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.
19. The halogen-free thermosetting resin composition according to claim 18, further comprising a curing accelerator.
20. The halogen-free thermosetting resin composition according to claim 19, wherein the curing accelerator comprises an organic metal salt and any one or a mixture of at least two selected from imidazole compounds, derivatives of imidazole compounds, piperidine compounds, pyridine compounds, lewis acids or triphenylphosphine.
21. The halogen-free thermosetting resin composition according to claim 20, wherein the organic metal salt comprises any one or a mixture of at least two of a metal salt of caprylic acid, a metal salt of isooctanoic acid, a metal salt of acetylacetone, a metal salt of naphthenic acid, a metal salt of salicylic acid, or a metal salt of stearic acid.
22. The halogen-free thermosetting resin composition according to claim 20, wherein the metal contained in the organic metal salt is selected from any one or a mixture of at least two of zinc, copper, iron, tin, cobalt or aluminum.
23. The halogen-free thermosetting resin composition according to claim 20, wherein the imidazole based compound is any one or a mixture of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-undecylimidazole.
24. The halogen-free thermosetting resin composition according to claim 20, wherein the piperidine compound is any one or a mixture of at least two of 2, 3-diaminopiperidine, 2, 5-diaminopiperidine, 2, 6-diaminopiperidine, 2-amino-3-methylpiperidine, 2-amino-4-methylpiperidine, 2-amino-3-nitropiperidine, 2-amino-5-nitropiperidine, or 2-amino-4, 4-dimethylpiperidine.
25. The halogen-free thermosetting resin composition according to claim 20, wherein the pyridine compound is any one or a mixture of at least two of 4-dimethylaminopyridine, 2-aminopyridine, 3-aminopyridine and 4-aminopyridine.
26. The halogen-free thermosetting resin composition according to claim 20, wherein the curing accelerator is added in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.
27. The halogen-free thermosetting resin composition according to claim 26, wherein the curing accelerator is added in an amount of 0.025 to 0.85 parts by weight.
28. The halogen-free thermosetting resin composition according to claim 1, wherein the halogen-free thermosetting resin composition further comprises a filler.
29. Halogen-free thermosetting resin composition according to claim 28, characterised in that the filler is selected from organic or inorganic fillers.
30. The halogen-free thermosetting resin composition according to claim 29, wherein the filler is an inorganic filler.
31. The halogen-free thermosetting resin composition according to claim 30, wherein the filler is an inorganic filler subjected to surface treatment.
32. The halogen-free thermosetting resin composition according to claim 31, wherein the filler is surface-treated silica.
33. The halogen-free thermosetting resin composition according to claim 32, wherein the surface treatment agent is selected from any one or a mixture of at least two of silane coupling agent, silicone oligomer or titanate coupling agent.
34. The halogen-free thermosetting resin composition according to claim 32, wherein the surface treatment agent is added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the inorganic filler.
35. The halogen-free thermosetting resin composition according to claim 34, wherein the surface treatment agent is added in an amount of 0.5 to 3 parts by weight based on 100 parts by weight of the inorganic filler.
36. The halogen-free thermosetting resin composition according to claim 35, wherein the surface treatment agent is added in an amount of 0.75 to 2 parts by weight based on 100 parts by weight of the inorganic filler.
37. The halogen-free thermosetting resin composition according to claim 29, wherein the inorganic filler is selected from any one or a mixture of at least two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus.
38. The halogen-free thermosetting resin composition according to claim 37, wherein the inorganic filler is selected from any one or a mixture of at least two 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 or mica.
39. The halogen-free thermosetting resin composition according to claim 29, wherein the organic filler is selected from any one of polytetrafluoroethylene powder, polyphenylene sulfide or polyether sulfone powder or a mixture of at least two of the polytetrafluoroethylene powder, the polyphenylene sulfide and the polyether sulfone powder.
40. The halogen-free thermosetting resin composition according to claim 29, wherein the filler has a median particle diameter of 0.01 to 50 μm.
41. The halogen-free thermosetting resin composition according to claim 40, wherein the filler has a median particle diameter of 0.01 to 20 μm.
42. The halogen-free thermosetting resin composition according to claim 41, wherein the filler has a median particle diameter of 0.1 to 10 μm.
43. The halogen-free thermosetting resin composition according to claim 29, wherein the filler is added in an amount of 5 to 300 parts by weight based on 100 parts by weight of the total amount of the halogen-free epoxy resin and the curing agent.
44. The halogen-free thermosetting resin composition according to claim 43, wherein the filler is added in an amount of 5 to 200 parts by weight.
45. The halogen-free thermosetting resin composition according to claim 44, wherein the filler is added in an amount of 5 to 150 parts by weight.
46. A resin cement, which is obtained by dissolving or dispersing the halogen-free thermosetting resin composition according to any one of claims 1 to 45 in a solvent.
47. A prepreg comprising a reinforcing material and the halogen-free thermosetting resin composition of any one of claims 1-45 attached thereto by drying by impregnation.
48. A laminate comprising at least one prepreg according to claim 47.
49. A metal-clad laminate comprising at least one prepreg according to claim 47 and a metal foil clad on one or both sides of the laminated prepreg.
50. A printed circuit board comprising one or at least two superimposed prepregs according to claim 47.
CN201811042369.3A 2018-09-07 2018-09-07 Halogen-free thermosetting resin composition, prepreg using same, laminated board and printed circuit board Active CN110885428B (en)

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