CN110204862A - Resin combination, prepreg, laminate, metal-clad laminate and printed wiring board - Google Patents
Resin combination, prepreg, laminate, metal-clad laminate and printed wiring board Download PDFInfo
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- CN110204862A CN110204862A CN201910475295.0A CN201910475295A CN110204862A CN 110204862 A CN110204862 A CN 110204862A CN 201910475295 A CN201910475295 A CN 201910475295A CN 110204862 A CN110204862 A CN 110204862A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising 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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
A kind of resin combination is provided, it includes a certain proportion of specific maleimide compound, styrene-maleic anhydride copolymer, epoxy resin and specific phosphonitrile fire retardants.Additionally provide prepreg, laminate, metal-clad laminate and the printed wiring board using its preparation.The resin combination has excellent dielectric properties, high flame retardant, good heat resistance, low water absorbable, low thermal coefficient of expansion and the high zygosity with conductor after solidifying.
Description
Technical field
The present invention relates to heat reactive resins, and in particular to a kind of resin combination and the prepreg using its preparation, lamination
Plate, metal-clad laminate and printed wiring board.
Background technique
As the miniaturization of electronic component, lightweight, multifunction direction are developed, LSI, chip part etc. are highly integrated
Development, form also rapidly change to diversification, miniaturization.Therefore multilayer printed-wiring board is in order to improve the installation of electronic component
Density is carrying out the exploitation of fine wiring.
As the manufacturing method for the multilayer printed-wiring board for adapting to these requirements, increasing layer (Buildup) method is proposed, and
And the method as adaptation lightweight, miniaturization, miniaturization is increasingly becoming mainstream.In addition, from environmental consciousness is improved, it is right
It is also increasingly severeer that there may be the management of the limitation of the material of harmful substance when being contained in burning in electronic component.Previous
In multilayer printed-wiring board, although being used for flame-retarded bromine compounds, due to being possible to have in burning
Harmful substance, so prediction can not use the bromine compounds in the near future.
In the usually used solder crossed in multilayer printed-wiring board for connecting electronic component, lead-free Pb-free coating
Material is also gradually practical.The lead-free solder is about 20 to 30 DEG C high using temperature compared with previous eutectic solder, so with previous
It compares, to material requirements high-fire resistance.
Meanwhile the high speed and multifunction, applying frequency handled with electronic product information is continuously improved, it is desirable that dielectric
Constant (Dk) and dielectric loss value (Df) are lower and lower, therefore reduce that Dk/Df has become substrate dealer chases hot spot.
In turn, due to the slimming of multilayer printed-wiring board, the insulating resin layer without glass fibre shows thermal expansion
Rate big tendency, so being generated significantly with the difference of fillingization, the stacked coefficient of thermal expansion of the copper of through-hole to the reliability of connection
It influences, so the material for requiring coefficient of thermal expansion small in insulating resin layer.
When reducing coefficient of thermal expansion in insulating resin layer, small inorganic of the common coefficient of thermal expansion of a large amount of fillings is used to fill out
Expect, make the method that the coefficient of thermal expansion of insulating layer entirety reduces.But such method is easy to cause mobility variation, insulation can
By more problems such as property declines.
In addition, passing through the selection or improvement of resin, attempt to realize low thermal expansion.For example, as modified bismaleimide
The example (see CN106103534_A) of resin, although there is the maleimide tree used with acid imide skeleton or benzene skeleton
Rouge come improve crosslink density and improve glass transition temperature (Tg), so that coefficient of thermal expansion be made to reduce.However, modified bismaleimide
With technologic resistance to control, resin varnish is also difficult to long-term preservation, and it is then right that highly polar amine groups are introduced in modifier
The dielectric properties (Dk/Df) of resin combination have greatly negative effect.
On the other hand, for reducing Dk/Df, there is the measure by introducing various low polarity curing agent such as acid anhydrides.However it is logical
Often the small molecules anhydride reaction speed such as seen acid anhydrides such as methyl hexahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, alicyclic acid anhydrides is too fast, waves
Hair property is too strong, and hydroscopicity is high, and dissolubility is poor, and heat resistance is low without being used.
On the other hand, to realize halogen-free flameproof, phosphorus-containing compound is usually introduced to improve the anti-flammability of resin combination.Contain
Phosphorus compound can be divided into response type and two kinds of addition type from reactivity to classify.In order to reach more excellent Dk/Df, usually
Using addition type phosphonium flame retardant.However, it is commercially available major part addition type phosphonium flame retardant because softening point too low (< 260 DEG C) and
In the presence of melting the risk of precipitation in PCB processing flow, and then affect the reliability of PCB.
For printed wire board industry, it is still necessary to find the resin combination for having comprehensive performance high.
Summary of the invention
The present invention provides a kind of resin combination, and it includes maleimide compounds shown in formula (I), styrene-horse
Carry out phosphonitrile fire retardant shown in acid anhydride copolymer, epoxy resin and formula (II)；
Wherein, R1For phenylene, biphenylene, naphthylene or dicyclopentadienyl, R2, R3Respectively
It independently is hydrogen atom, alkyl, aryl or aralkyl, n is integer of 1 to 20；
Wherein, in alkyl, hydroxyl or the allyl that Rp is hydrogen atom, carbon atom number is 1 to 5
It is a kind of；
Wherein with maleimide compound shown in formula (I), styrene-maleic anhydride copolymer, epoxy resin it is total
Weight is 100 parts by weight meters,
The maleimide compound is 10 parts by weight to 80 parts by weight；
The styrene-maleic anhydride copolymer is 5 parts by weight to 50 parts by weight, wherein styrene units and maleic acid
The molar ratio of acid anhydride unit is 0.5 to 10, and the acid value of the styrene-maleic anhydride copolymer is 80-800mgKOH/g；
The epoxy resin is 10 parts by weight to 60 parts by weight；
Phosphorus in the phosphonitrile fire retardant is total relative to the maleimide compound, the phenylethylene-maleic anhydride
The total weight of polymers, the epoxy resin and the phosphonitrile fire retardant is 0.1 weight % to 5 weight %.
Total weight preferably, in the maleic acid anhydride group and the epoxy resin in the styrene-maleic anhydride copolymer
Epoxy group equivalent proportion be 0.5 to 1.5.
Preferably, with maleimide compound shown in formula (I), styrene-maleic anhydride copolymer, epoxy resin
Total weight is 100 parts by weight meters, and the styrene-maleic anhydride copolymer is 10 parts by weight to 40 parts by weight.
Preferably, the epoxy resin is phosphorous epoxy resin, novolac type epoxy resin, cresol novolak type epoxy tree
Rouge, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol novolac type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type
Epoxy resin, aralkyl-type epoxy resin, aralkyl phenol aldehyde type epoxy resin, contains dicyclopentadiene phenolic aldehyde type ring oxygen resin
The epoxy resin of arylene ether structure or their mixture.
Preferably, with maleimide compound shown in formula (I), styrene-maleic anhydride copolymer, epoxy resin
Total weight is 100 parts by weight meters, and the epoxy resin is 20 parts by weight to 50 parts by weight.
Preferably, the phosphorus in the phosphonitrile fire retardant is relative to the maleimide compound, the styrene-Malaysia
The total weight of acid anhydride copolymer, the epoxy resin and the phosphonitrile fire retardant is 0.5 weight % to 4 weight %.
Preferably, the resin combination also includes co-curing agent, filler, curing accelerator, silane coupling agent, demoulding
One of agent, pigment and emulsifier are a variety of.
The present invention also provides a kind of prepreg, the prepreg is by being impregnated or coated substrate according to above-mentioned resin
Composition is simultaneously solidified.
The present invention also provides a kind of laminate, the laminate includes at least one according to above-mentioned prepreg.
The present invention also provides a kind of metal-clad laminate, the metal-clad laminate includes at least one according to above-mentioned
Prepreg and be overlying on the metal foils of the prepreg one or both sides.
The present invention also provides a kind of printed wiring board, the printed wiring board includes at least one according to above-mentioned preimpregnation
Material.
Compositions of thermosetting resin of the invention has good compatibility, and has excellent dielectric properties, high resistant
Combustion property, good heat resistance, low water absorbable, low thermal coefficient of expansion and the high zygosity with conductor.
Specific embodiment
Below with reference to specific embodiment, present invention is further described in detail.It will be appreciated that, it is contemplated that other realities
Mode is applied, and does not depart from the scope or spirit of the invention, it is possible to implement these other embodiments.Therefore, below to retouch in detail
It states and is non-limiting.
The present invention provides a kind of resin combinations, and it includes maleimide compounds shown in formula (I), benzene second
Alkene-copolymer-maleic anhydride, epoxy resin；With phosphonitrile fire retardant shown in formula (II) etc., with maleimide shown in formula (I)
Amine compounds, styrene-maleic anhydride copolymer, epoxy resin total weight be 100 parts by weight meters, the maleimation
Conjunction object is 10 parts by weight to 80 parts by weight, and the styrene-maleic anhydride copolymer is 5 parts by weight to 50 parts by weight, the ring
Oxygen resin is 10 parts by weight to 60 parts by weight, and the phosphorus in the phosphonitrile fire retardant is relative to the maleimide compound, institute
The total weight for stating styrene-maleic anhydride copolymer, the epoxy resin and the phosphonitrile fire retardant is 0.1 weight % to 5 weights
Measure %.Inventor surprisingly it has been found that used containing with specific molecular structure maleimide compound, specific point
The resin combination of the phosphonitrile fire retardant of the styrene-maleic anhydride copolymer of minor structure, epoxy resin and specific molecular structure
Prepreg and plywood show excellent dielectric properties, high flame retardant, good heat resistance, low water absorbable, low thermal expansion
Coefficient and high zygosity with conductor.
Each component described in detail below:
Maleimide compound:
Maleimide compound used in the present invention with unsaturated maleimide base leads to formula (I) institute as follows
Show, the synthetic method of maleimide compound is not particularly limited, those skilled in the art can be according to existing
Technology combines the professional knowledge of oneself to be selected.Specifically, for example it can be by having at least in maleic anhydride and 1 molecule
The aminated compounds reaction of 2 primary amine groups obtains.The reaction preferably carries out in organic solvent.As product example, there is Japan
The MIR-3000 of chemical drug Co., Ltd. manufacture.The compound is a kind of multifunctional biphenyl methane type maleimide, in the present invention
System in compatibility it is good, reactivity is high, and heat resistance is high, good to the dissolubility of solvent, thus realize high dielectric properties,
Peel strength, heat resistance and anti-flammability.
Wherein, R1For phenylene, biphenylene, naphthylene or dicyclopentadienyl, R2, R3 be each independently hydrogen atom,
Alkyl, aryl or aralkyl, n are integer of 1 to 20.
Preferably, in the maleimide compound (A) with formula (I) structure, the integer that n is 1~15, more preferable n is 1
~10 integer；
To the content of maleimide compound, from the viewpoint of glass transition temperature and water absorption rate, relative to horse
Carry out imide compound, styrene-maleic anhydride copolymer and epoxy resin add up to 100 parts by weight, maleimide compound
For the range of 10~80 parts by weight, when too high levels, it may appear that solidify insufficient or condition of cure harshness situation, content is too low
When, its excellent heat resistance cannot be fully demonstrated；More preferably 20~60 parts by weight.
Styrene-maleic anhydride copolymer:
Styrene-maleic anhydride copolymer used in the present invention influences the solidification of resin combination very big.Styrene-horse
To include styrene units and maleic anhydride units in acid anhydride copolymer, and wherein styrene units and maleic anhydride units
Molar ratio is between 0.5: 1 to 10: 1, and acid value is 80-800mgKOH/g.Such styrene-maleic anhydride copolymer is at this
Compatibility is good in the system of invention, to realize high dielectric properties, peel strength, heat resistance and humidity resistance.When two kinds of lists
The molar ratio or acid value of member not within the above range when, obtained styrene-maleic anhydride copolymer and this system compatibility are not
It is good, it is difficult to obtain excellent dielectric strength, peel strength, heat resistance and humidity resistance.Relative to maleimide compound, benzene
Ethylene maleic acid anhydride copolymer and epoxy resin add up to 100 parts by weight, and the content of styrene-maleic anhydride copolymer is 5 weight
Part to 50 parts by weight.When too high levels, the anti-flammability of resin combination, humidity resistance are performed poor, when content is too low, resin group
The dielectric properties for closing object cannot be guaranteed.Preferably, the content of styrene-maleic anhydride copolymer is 10 parts by weight to 40 weight
Part.
Epoxy resin:
To epoxy resin of the present invention, there is no particular limitation, is selected from the epoxy containing at least two epoxy groups
Resin, for example, bisphenol A type epoxy resin, bisphenol E-type epoxy resin, bisphenol f type epoxy resin, tetramethyl Bisphenol F can be selected from
It is type epoxy resin, bis-phenol M type epoxy resin, bis-phenol p-type epoxy resin, bisphenol-s epoxy resin, bisphenol Z type epoxy resin, double
Phenol AP type epoxy resin, bis-phenol TMC type epoxy resin, novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol-A
Phenol aldehyde type epoxy resin, trifunctional phenol-type epoxy resin, tetrafunctional phenol-type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy
Resin, naphthol novolac type epoxy resin, anthracene type epoxy resin, phenolphthalein type epoxy resin, phenoxy group type epoxy resin, norbornene
Type epoxy resin, adamantane type epoxy resin, Cong type epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin,
Dicyclopentadiene type epoxy resin, dicyclopentadiene phenolic aldehyde type ring oxygen resin, aralkyl-type epoxy resin, aralkyl phenolic aldehyde type ring
It is epoxy resin, cycloaliphatic epoxy resin, polyol type epoxy resin containing arylene ether structure in oxygen resin, molecule, siliceous
Epoxy resin, nitrogen-containing epoxy thermoset, phosphorous epoxy resin, glycidyl amine epoxy resin, ethylene oxidic ester epoxy resin etc..From
With the compatibility of the system of composition of the invention, high-fire resistance, low relative dielectric constant, high adhesiveness, low heat expansion, height
From the perspective of glass transition temperature, preferably phosphorous epoxy resin, novolac type epoxy resin, cresol novolak type epoxy tree
Rouge, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol novolac type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type
Epoxy resin, aralkyl-type epoxy resin, aralkyl phenol aldehyde type epoxy resin, contains dicyclopentadiene phenolic aldehyde type ring oxygen resin
The epoxy resin of arylene ether structure or their mixture, further preferred novolac type epoxy resin, o-cresol phenolic aldehyde
Type epoxy resin, naphthol type epoxy resin, naphthol novolac type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy
Resin, dicyclopentadiene phenolic aldehyde type ring oxygen resin, aralkyl-type epoxy resin, aralkyl phenol aldehyde type epoxy resin.From low dielectric
From the perspective of constant, low cost, further preferably dicyclopentadiene type epoxy resin, dicyclopentadiene phenolic aldehyde type ring oxygen tree
Rouge.Epoxy resin can be used alone, and also can be used together two or more.
Relative to maleimide compound, styrene-maleic anhydride copolymer and epoxy resin add up to 100 parts by weight,
The content of epoxy resin is 10 parts by weight to 60 parts by weight.When too high levels, the dielectric properties of resin combination are insufficient, content mistake
When low, the adhesive strength of resin combination can decline again.Preferably, the content of epoxy resin is 20 parts by weight to 50 parts by weight.
In the present compositions, it is closed when styrene-maleic anhydride copolymer and epoxy resin meet certain ratio
When being, resin combination can be made to realize the balance of humidity resistance, dielectric properties and adhesive strength.Preferably, styrene-Malaysia
The equivalent proportion of maleic acid anhydride group in acid anhydride copolymer and the epoxy group in epoxy resin is 0.5 to 1.5, further preferred 0.80
To 1.20.
Phosphonitrile fire retardant:
Phosphonitrile fire retardant shown in formula (II) has high-melting-point, good with the compatibility of the system of composition of the invention, from
And make composition of the invention while with flame-retarding characteristic, still there is high peel strength, heat resistance, moisture-proof heat type and resistance to
Thermal mobility.The present invention has found after study, the maleimide compound and styrene-maleic anhydride copolymer of specific formula (I)
Object, epoxy composite provide excellent dielectric properties, good heat resistance, low water absorbable, low thermal coefficient of expansion and and conductor
High adhesiveness, but anti-flammability is still insufficient.In order to improve the anti-flammability of composition, fire retardant can be added, especially Halogen contains
Phosphorus fire retardant.However, the halogen-free phosphorus-containing fire retardant agent of low melting point is bad with resin system compatibility after being added, it is resistance to reduce resin system
It is hot, the problem of being precipitated is melted under PCB high temperature process, influences the heat resistance, dielectric properties and reliability of laminate.Inventor goes out
Find to people's will material, and the Miscibility of phosphonitrile fire retardant shown in formula (II) and invention resin composition is good, makes resin
Composition still has high peel strength, heat resistance, humidity resistance and good dielectric while with highly effective flame-retardant characteristic
Performance, and be not in the migration problem of phosphonium flame retardant.
Wherein, one of Rp is hydrogen atom, carbon atom number is 1 to 5 alkyl, hydroxyl or allyl.
From the viewpoint of phosphorus content, the phosphorus in the phosphonitrile fire retardant is relative to the maleimide compound, institute
The total weight for stating styrene-maleic anhydride copolymer, the epoxy resin and the phosphonitrile fire retardant is 0.1 weight % to 5 weights
% is measured, the weight of preferably phosphorus contained in phosphonitrile fire retardant accounts for 0.5 weight % of composition to 4 weight %, even more preferably from 1 weight
Measure % to 3 weight %.
The present invention can also include optional co-curing agent, filler, curing accelerator, silane coupling agent, release agent, face
One of material, emulsifier are a variety of.
Co-curing agent:
Composition of the invention can also contain co-curing agent.As co-curing agent comprising amine system curing agent, mercaptan system
In curing agent, cyanate system curing agent, isocyanates system curing agent, active ester system curing agent, phenol system curing agent and benzoxazine
It is one or more.Wherein, from the viewpoint of high adhesiveness, low heat expansion, preferably amine system curing agent, cyanate system solidify
Agent, active ester system curing agent, phenol system curing agent, further preferably amine system curing agent and phenol system curing agent.Co-curing agent adds
Dosage can according to need adjustment.
The example of amine system curing agent may include: dicyandiamide；Ethylenediamine, diethylenetriamines, trien, four Asias
The chain rouge in addition to dicyandiamide such as five amine of ethyl, hexamethylene diamine, diethyl amino propyl amine, tetramethylguanidine, triethanolamine
Fat race amine；Isophorone diamine, diamino-dicyclohexyl methane, bis- (amino methyl) hexamethylenes, bis- (4- amino -3- methyl two
Cyclohexyl) methane, N- aminoethylpiperazine, -2,4,8,10- tetra- oxaspiro [5.5] hendecane of 3,9- bis- (3- aminopropyls) etc.
Annular aliphatic amine；Benzene dimethylamine, phenylenediamine, diaminodiphenyl-methane, diamino diphenyl sulfone, diamino-diphenyl ether
(ODA) aromatic amines etc. such as.Wherein, from the viewpoint of low relative dielectric constant and low water absorbable, preferred diamino-diphenyl
Ether and dicyandiamide.
The example of phenol system curing agent may include: biphenyl type phenolic curing agent, naphthalene type phenolic curing agent, novolac
The phenol system curing agent of resin type curing agent, naphthylene ether type phenolic curing agent and the skeleton containing triazine.
Filler:
Resin combination of the invention can also contain inorganic filler.It is not special to inorganic filler of the present invention
It limits, inorganic filler can be prepreg, known inorganic filler in laminate field, as long as it does not make resin group of the invention
The performance for closing object substantially deteriorates.Be added inorganic filler in resin combination, available mechanical property, humidity resistance,
The more excellent resin combination of flame retardant property, dielectric properties, thermal expansion coefficient.Inorganic filler can be selected from silica, gold
Belong to hydrate, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanates, barium titanate, barium sulfate, boron nitride, aluminium nitride, carbonization
Silicon, aluminium oxide, zinc borate, zinc stannate, clay, kaolin, talcum, mica, compound silicon powder, E glass powder, D glass powder, L glass
Glass powder, M glass powder, S glass powder, T glass powder, NE glass powder, Q glass powder, fused silica powder, short glass fiber or hollow glass
In any one or at least two mixture, preferably crystalline sillica, fused silica, amorphous titanium dioxide
Silicon, preparing spherical SiO 2, hollow silicon dioxide, aluminium hydroxide, boehmite, magnesium hydroxide, molybdenum oxide, zinc molybdate, titanium oxide, oxygen
Change zinc, strontium titanates, barium titanate, barium sulfate, boron nitride, aluminium nitride, silicon carbide, aluminium oxide, zinc borate, zinc stannate, clay, kaolinite
Soil, talcum, mica, compound silicon powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass
In glass powder, Q glass powder, fused silica powder, short glass fiber or hollow glass any one or at least two mixture,
The mixture of the mixture such as crystalline sillica and fused silica, amorphous silica and spherical titanium dioxide
The mixture of the mixture of the mixture of silicon, hollow silicon dioxide and aluminium hydroxide, boehmite and magnesium hydroxide, molybdenum oxide and molybdenum
The mixture of sour zinc, titanium oxide, zinc oxide, strontium titanates and barium titanate mixture, the mixing of barium sulfate, boron nitride and aluminium nitride
Object, silicon carbide, aluminium oxide, zinc borate and zinc stannate mixture, compound silicon powder, E glass powder, D glass powder, L glass powder and M
The mixture of glass powder, S glass powder, T glass powder, NE glass powder and fused silica powder mixture, clay, kaolin, talcum
With the mixture of mica, the mixture of short glass fiber and hollow glass.From the side that can be more compounded inanimate matter packing material
Face is set out, preferably aforementioned melt silica.Aforementioned melt silica can be used comminution, spherical middle arbitrary shape it is molten
Melt silica, it is excellent in order to improve the rising of the compounding amount of fused silica and the melt viscosity of inhibition solidification compound
Choosing mainly uses the silica of ball-type.
To the average grain diameter (d50) of inorganic filler, there is no particular limitation, but considers from dispersed angle, average grain diameter
It (d50) is preferably 0.1-10 microns, such as 0.2 micron, 0.8 micron, 1.5 microns, 2.1 microns, 2.6 microns, 3.5 microns, 4.5
Micron, 5.2 microns, 5.5 microns, 6 microns, 6.5 microns, 7 microns, 7.5 microns, 8 microns, 8.5 microns, 9 microns, 9.5 microns,
More preferably 0.2-5 microns.It can according to need exclusive use or multiple combinations and use different type, variable grain size distribution
Or the inorganic filler of different average grain diameters.
The present invention is not particularly limited the dosage of inorganic filler.With the maleimide compound, styrene-horse
To carry out acid anhydride copolymer and epoxy resin adds up to 100 parts by weight meters, the amount of the inorganic filler can be 10-200 parts by weight, such as
20 parts by weight, 40 parts by weight, 60 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 140 parts by weight, 160 parts by weight,
180 parts by weight, preferably 20-150 parts by weight, further preferably 30-100 parts by weight.
Inorganic filler of the invention can be used together with mating surface inorganic agent or wetting agent, dispersing agent.To surface treatment
There is no particular limitation for agent, can handle common surface treating agent selected from mineral surfaces.It is specially ethyl orthosilicate
Class compound, organic acid compound, aluminate compound, titanate ester compound, silicone oligomer, macromolecular processing
Agent, silane coupling agent etc..Silane coupling agent is not particularly limited, it is common silane coupled selected from mineral surfaces processing
Agent is specially amino silicane coupling agent, epoxy silane coupling, vinyl silicane coupling agent, phenyl silane coupling agent, sun
Ion silane coupling agent, mercaptosilane coupling agents etc., preferably amino silicane coupling agent, epoxy silane coupling, phenyl silane
Coupling agent, further preferred amino silicane coupling agent.Wetting agent, dispersing agent are not particularly limited, is selected from and is usually used in applying
Wetting agent, the dispersing agent of material.The present invention can according to need exclusive use or the different types of surface treatment of appropriately combined use
Agent or wetting agent, dispersing agent.
Resin combination of the invention can also include organic filler.To organic filler, there is no particular limitation, Ke Yixuan
From any one in organosilicon, liquid crystal polymer, thermosetting resin, thermoplastic resin, rubber or core shell rubbers or at least
Two kinds of mixture.The organic filler can be powder or particle.The additive amount of organic filler can according to need adjustment.
Curing accelerator:
Resin combination of the invention can also include curing accelerator, and resin cure temperature drops in the curing accelerator
It is low and accelerate resin solidification speed.The example of curing accelerator may include: phosphorus system promotor, tertiary amine, imidazoles, organic acid metal
Salt, lewis acid, amine complex salt etc..
Preferably, the curing accelerator is imidazoles curing accelerator or pyridines curing accelerator, wherein the miaow
Azole curing accelerator can be enumerated for example: 2-methylimidazole, 2- undecyl imidazole, 2- heptadecyl imidazole, 1,2- dimethyl
Imidazoles, 2-ethyl-4-methylimidazole, 1,2- methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole, 2- phenyl -4-
Methylimidazole, 1 benzyl 2 methyl imidazole, 1- benzyl -2- phenylimidazole, 1- cyano ethyl -2-methylimidazole, 1- cyano second
Base -2- undecyl imidazole, 1- cyano ethyl -2-ethyl-4-methylimidazole, 1- cyano ethyl -2- phenylimidazole, 1- cyano second
Base -2- undecyl imidazole trimellitic acid salt, 1- cyano ethyl -2- phenylimidazole trimellitic acid salt, 2,4- diamino -6-
[2 '-methylimidazolyls-(1 ')]-ethyl-s-triazine, 2,4- diamino -6- [2 '-undecyl imidazole base-(1 ')]-ethyl -
S-triazine, 2,4- diamino -6- [2 '--4 '-methylimidazolyl-(1 ') of ethyl]-ethyl-s-triazine, 2,4- diamino -6-
[2 '-methylimidazolyls-(1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2- phenylimidazole isocyanuric acid adduct, 2- benzene
Base -4,5- bishydroxymethyl imidazoles, -5 hydroxymethylimidazole of 2- phenyl -4- methyl, 2,3- dihydro -1H- pyrrolo- [1,2-a] benzene
And the imidazoles such as imidazoles, 1- dodecyl -2- methyl-3-benzyl imidazole chloride, 2-methylimidazole quinoline, 2- benzylimidazoline
Close the adduct of object and imidazolium compounds and epoxy resin.The pyridines curing accelerator is selected from triethylamine, benzyl diformazan
Amine and dimethylamino naphthyridine.Cooperate in resin combination of the invention curing accelerator (in addition to metal system curing accelerator)
In the case of, with the maleimide compound, styrene-maleic anhydride copolymer and epoxy resin add up to 100 parts by weight meters,
Curing accelerator is preferably the range of 0.005 to 5 mass parts, the range of more preferably 0.01 to 3 mass parts.If in the range
It is interior, then it can more efficiently heat cure, the also storage stability of raising resin varnish.
In addition, resin combination of the invention can according to need addition silane coupling agent, release agent, pigment, emulsifier
Match mixture etc. various.
Resin combination of the invention embodies excellent solvent solubility.Therefore, the resin combination is in addition to above-mentioned each
Organic solvent can also be compounded except ingredient.Such as can enumerate aromatic hydrocarbon, aprotic polar solvent, alcohols, ketone,
Gylcol ether etc..It is preferred that aprotic polar solvent, alcohols, ketone, acid amides series solvent.Aromatic hydrocarbon can there are
Benzene,toluene,xylene etc..Alcohols can there are methanol, ethyl alcohol, propyl alcohol, butanol etc..Ketone can there are acetone, butanone
(MEK), hexone (MIBK), diisopropyl ketone, di-t-butyl ketone, 2-HEPTANONE, 4- heptanone, methyln-hexyl ketone, ring
Pentanone, cyclohexanone, cyclohexyl methyl ketone, acetophenone, acetylacetone,2,4-pentanedione, dioxane etc..Aprotic polar solvent
Concrete example can enumerate dimethyl sulfoxide (DMSO), formamide, N-METHYLFORMAMIDE, n,N-Dimethylformamide, acetamide, N-
Methylacetamide, n,N-dimethylacetamide, 2-Pyrrolidone, N-Methyl pyrrolidone etc..The concrete example of gylcol ether can
To enumerate, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol list n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol list
Monoethyl ether acetate, double ethylene glycol single methyl ethers, double ethylene glycol monomethyl ethers, double ethylene glycol list n-butyl ethers, double ethylene glycol two
Methyl ether, double ethylene glycol monomethyl ether acetates, propylene glycol monomethyl ether, propylene glycol list n-butyl ether, propylene glycol monomethyl ether
Acetic acid esters etc..
Resin combination of the invention can be combined with the maleimide other than the specific maleimide resin
Resin is used together, as long as its proper property for not damaging resin combination.The maleimide resin that can choose can
To be two (4- maleimidophenyl) methane, two (4- maleimidophenyl) ethers, two (4- dimaleoyl imino benzene
Base) sulfone, two (4- maleimidophenyl) thioethers, two (4- maleimidophenyl) ketone, 4- methyl-1,3- phenylene pair
Maleimide, meta-phenylene bismaleimide, 1,3- bis- (3- maleimide phenoxyl) benzene, (Malaysia 4- 1,3- bis-
Imide phenoxy group) benzene, 2,2- bis- (4- (4- maleimide phenoxyl)-phenyl) propane, two (4- (4- maleimides
Amido phenoxy group)-phenyl) sulfone, two (3,5- dimethyl -4- maleimidophenyl) methane, two (3- ethyl -5- methyl -4-
Maleimidophenyl) methane, two (3,5- diethyl -4- maleimidophenyl) methane, polyphenyl methylmethane Malaysia acyl
In imines (Polyphenylmethane maleimide) any one or at least two mixture.These Malaysia acyls
Imide resin can according to need exclusive use or multiple combinations use, or these maleimide resins are used allylation
Close object or the modified use of aminated compounds.
Resin combination of the invention can be combined with various high polymers, rubber, elastomer and be used together, as long as it is not damaged
The proper property of evil resin combination.It can be for example specifically liquid crystal polymer, thermosetting resin, thermoplastic resin, different
Flame-retardant compound or additive etc..Thermosetting resin can be selected from phenolic resin, cyanate ester resin, benzoxazine resin, polyphenyl
Ether resin, silicone resin, allyl resin, aminated compounds and dcpd resin.They, which can according to need, individually makes
With or multiple combinations use.
" comprising " of the present invention, it is intended that it can also include other components, these other components especially except described group
Assign the resin combination different characteristics.In addition to this, " comprising " of the present invention may be replaced by enclosed
" for " or " by ... form ".
Resin combination of the invention can be used for various electronic material purposes, and can be for example by using extrusion
Various one-components are sufficiently mixed by machine, kneader, roller etc. until uniform method is modulated.
When manufacturing printed circuit board using compositions of thermosetting resin of the invention, following method can be enumerated: will be wrapped
The compositions of thermosetting resin of varnish shape containing resin of the invention, curing agent, organic solvent, other additives etc. is infiltrated in increasing
Strong basis material is overlapped copper foil and carries out heating crimping.The enhancing base materials being able to use herein can be enumerated: paper, glass cloth, glass without
Woven fabric, aramid paper, aramid fabric, glass felt, roving fabric etc..If the above method is described in further detail, firstly, by will before
The compositions of thermosetting resin of varnish shape is stated with the heating temperature adaptable with used solvent type, preferably 50 to 170 DEG C
3~15min is heated, to obtain the prepreg as solidfied material.As the compositions of thermosetting resin and enhancing used at this time
The mass ratio of substrate, is not particularly limited, generally, it is preferred to reach the side of 30 to 90 quality % with the resin component in prepreg
Formula modulation.Then, the prepreg obtained as described above is laminated by conventional method, suitably overlapping copper foil, 1 to 10MPa
Pressurization under crimped 10 minutes~3 hours with 170 to 250 DEG C of heating, so as to obtain target print circuit substrate.
Embodiment
Then, using following embodiments, the present invention will be described in more detail, and still, these embodiments are in any feelings
The present invention is not limited under shape.In each case, resin varnish, prepreg and copper-clad laminated board are made, and to made
Copper-clad laminated board evaluated.Evaluation method is as follows shown.
Evaluation method
(A) glass transition temperature (Tg)
Use determination of viscoelasticity device (solid determination of viscoelasticity device RSAII, the square of DMA:Rheometric company manufacture
Shape stretches (Rectangular Tension) method；5 DEG C/min of frequency 1Hz, heating rate), to aforementioned evaluation sample, measure bullet
Property modulus change reach maximum (tan δ change rate is maximum) temperature, evaluated as glass transition temperature.
(B) thermal expansion coefficient (CTE)
It is measured according to IPC-TM-650 2.4.24 method.
(C) dielectric constant (Dk) and dielectric loss factors (Df)
The dielectric constant and dielectric loss factors under 1GHz are tested according to capacity plate antenna method.
(D) peel strength
It is measured according to IPC-TM-650 2.4.8 method.
(E) humidity resistance is evaluated
After the copper foil on copper-clad plate surface is etched, substrate is evaluated；By in substrate placement force pot, in 120 DEG C, 105KPa item
It handles 3 hours, is then immersed in 288 DEG C of tin furnace under part, record the corresponding time when substrate de-lamination plate bursting；When substrate is in tin
It can terminate to evaluate when also not occurring blistering or being layered more than 5min in furnace.It is not blistering and it is not stratified be denoted as O, blistering or layering note
For ×.
(F) anti-flammability
It is measured according to 94 vertical combustion of UL.
(G) resistance to thermal mobility
By copper-clad plate after 5 reflow soldering processing procedures (material temperature > 260 DEG C), section sample is made, in electron microscope
Lower its resin form of observation.Resin layer is denoted as O without generation migration or lamination, there is generation migration or lamination in resin layer
Be denoted as ×.
The raw material used in embodiment includes:
Maleimide compound:
(A1) biphenyl aralkyl-type maleimide resin " MIR-3000-70MT " (Nippon Kayaku K. K's system), tool
There is structure shown in formula (I)
(A2) two (3- ethyl -5- methyl -4- maleimidophenyl) methane " KI-70 " (Japanese KI Co., Ltd.),
Without structure shown in formula (I)
Styrene-maleic anhydride copolymer (B):
(B1) " SMA EF30 " (phenylethylene/maleic anhydride=3, SARTOMER corporation), acid value 280mgKOH/g
(B2) " SMA EF40 " (phenylethylene/maleic anhydride=4, SARTOMER corporation), acid value 215mgKOH/g
Epoxy resin (C):
(C1) dicyclopentadiene type epoxy resin " HP-7200H " (Dainippon Ink Chemicals's system)
(C2) biphenyl aralkyl-type epoxy resin " NC-3000-H " (Nippon Kayaku K. K's system)
Fire retardant (D):
(D1) high-melting-point phosphazene compound (Otsuka Kagaku K.K.), chemical formula is as follows
(D2) phosphazene compound " SPB-100 " (Otsuka Kagaku K.K.)
(D3) phosphate compound " PX-200 " (big eight Chemical Co., Ltd.)
Co-curing agent (E):
(E1) 4,4- diaminodiphenyl ether " DDE " (Shandong Wanda's chemical industry system)
(E2) dicyandiamide " Dicy " (Ningxia Daiei system)
(E3) biphenyl aralkyl-type phenol resin " MEH-7851 " (bright and chemical conversion Co. Ltd. system)
Inorganic filler (F): preparing spherical SiO 2 " DQ1028L " (Jiangsu joins auspicious corporation)
Curing accelerator (G): 2- phenylimidazole " 2PZ " (four countries are melted into corporation)
Compare curing agent:
(B3) methyl hexahydrophthalic anhydride " MHHPA " (the Guangdong flourishing age reaches system)
(B4) methylnadic anhydride " MNA " (Taiwan Changchun system)
Each embodiment is prepared with forming of enumerating in following table 1-5 and the above-mentioned various neccessary compositions etc. referred to and is compared
The resin varnish of example.
Make the glass cloth (0.1mm) of resulting each resin varnish infiltration 2116, it is 5 minutes dry at 155 DEG C, obtain pre-preg
Body.8 prepregs are overlapped again, 18 μm of Double-side laminated of reversion copper foil (Mitsui Metal Co., Ltd.'s Co. Ltd. system), in temperature 200
DEG C, heat press molding 90 minutes under pressure 25kgf/cm2 (2.45MPa), thickness 1.0mm copper-clad plate is made, according to above-mentioned side
Method surveys relative dielectric constant, metal foil cementability, glass transition temperature, thermal expansivity, anti-flammability and craftsmanship
Fixed and evaluation.
As a result as shown in tables 1 to 5.
1 embodiment 1-6 of table
2 embodiment 7-12 of table
3 comparative example 1-6 of table
4 comparative example 7-12 of table
5 comparative example 13-14 of table
It can be seen that in embodiment 1-12 from table 1-2, change the dosage of each independent component and part in resin combination and plant
Class, the performance of composition are excellent.
In comparative example 1, compared with Example 7, by multifunctional biphenyl aralkyl-type maleimide resin shown in formula (I)
Replace with bifunctional maleimides' resin shown in non-formula (I), the dielectric properties of resin combination, peel strength, heat resistance
It all declines to a great extent with anti-flammability.
In comparative example 2,3, compared with Example 7, styrene-maleic anhydride copolymer is replaced with into common small molecule acid
Acid anhydride, the dielectric properties of resin combination, peel strength, heat resistance, wet-hot aging performance all decline to a great extent.
In comparative example 4,5,6, compared with Example 7, phosphonitrile fire retardant is replaced with into other phosphonium flame retardants, resin combination
The peel strength of object, heat resistance, humidity resistance, heat-resisting migration performance all decline to a great extent.
In comparative example 7-14, after each component exceeds the scope of the claims, the performance of resin combination has in various degree
Deterioration performance.
Compositions of thermosetting resin of the invention has good compatibility, and has excellent dielectric properties, high resistant
Combustion property, good heat resistance, low water absorbable, low thermal coefficient of expansion and the high zygosity with conductor.
Obviously, those skilled in the art can carry out various modification and variations without departing from this hair to the embodiment of the present invention
Bright spirit and scope.In this way, if these modifications and changes of the present invention belongs to the claims in the present invention and its equivalent technologies
Within the scope of, then the present invention is also intended to include these modifications and variations.
Claims (11)
1. a kind of resin combination, it includes:
Shown in maleimide compound shown in formula (I), styrene-maleic anhydride copolymer, epoxy resin and formula (II)
Phosphonitrile fire retardant；
Wherein, R1For phenylene, biphenylene, naphthylene or dicyclopentadienyl, R2、R3It is each independently hydrogen atom, alkane
Base, aryl or aralkyl, n are integer of 1 to 20；
Wherein, one of Rp is hydrogen atom, carbon atom number is 1 to 5 alkyl, hydroxyl or allyl；
Wherein with the total weight of maleimide compound shown in formula (I), styrene-maleic anhydride copolymer, epoxy resin
For 100 parts by weight meters,
The maleimide compound is 10 parts by weight to 80 parts by weight；
The styrene-maleic anhydride copolymer is 5 parts by weight to 50 parts by weight, wherein styrene units and maleic anhydride list
The molar ratio of member is 0.5 to 10, and the acid value of the styrene-maleic anhydride copolymer is 80-800mgKOH/g；
The epoxy resin is 10 parts by weight to 60 parts by weight；
Phosphorus in the phosphonitrile fire retardant relative to the maleimide compound, the styrene-maleic anhydride copolymer,
The total weight of the epoxy resin and the phosphonitrile fire retardant is 0.1 weight % to 5 weight %.
2. resin combination according to claim 1, wherein the maleic acid in the styrene-maleic anhydride copolymer
The equivalent proportion of anhydride group and the epoxy group in the epoxy resin is 0.5 to 1.5.
3. resin combination according to claim 1 or 2, wherein with maleimide compound, benzene shown in formula (I)
Ethylene maleic acid anhydride copolymer, the total weight of epoxy resin are 100 parts by weight meters, and the styrene-maleic anhydride copolymer is
10 parts by weight to 40 parts by weight.
4. resin combination according to claim 1 or 2, wherein the epoxy resin is phosphorous epoxy resin, linear phenol
Aldehyde type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol novolac type asphalt mixtures modified by epoxy resin
Rouge, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, dicyclopentadiene phenolic aldehyde type ring oxygen resin, aralkyl type epoxy
Resin, aralkyl phenol aldehyde type epoxy resin, the epoxy resin containing arylene ether structure or their mixture.
5. resin combination according to claim 1 or 2, wherein with maleimide compound, benzene shown in formula (I)
Ethylene maleic acid anhydride copolymer, the total weight of epoxy resin are 100 parts by weight meters, and the epoxy resin is 20 parts by weight to 50
Parts by weight.
6. resin combination according to claim 1 or 2, wherein the phosphorus in the phosphonitrile fire retardant is relative to the horse
Carry out the total weight of imide compound, the styrene-maleic anhydride copolymer, the epoxy resin and the phosphonitrile fire retardant
For 0.5 weight % to 4 weight %.
7. resin combination according to claim 1 or 2, wherein the resin combination also includes co-curing agent, fills out
One of material, curing accelerator, silane coupling agent, release agent, pigment and emulsifier are a variety of.
8. a kind of prepreg, the prepreg is by being impregnated or coated according to claim 1 described in any one of -7 to substrate
Resin combination and solidified.
9. a kind of laminate, the laminate includes an at least prepreg as claimed in claim 8.
10. a kind of metal-clad laminate, the metal-clad laminate includes at least one preimpregnation as claimed in claim 8
Expect and be overlying on the metal foil of the prepreg one or both sides.
11. a kind of printed wiring board, the printed wiring board includes an at least prepreg as claimed in claim 8.
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| TW108129019A TWI716967B (en) | 2019-05-31 | 2019-08-14 | Resin composition, prepreg, laminate, metal-clad laminate and printed circuit board |
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| TWI716967B (en) | 2021-01-21 |
| TW201940589A (en) | 2019-10-16 |
| CN110204862B (en) | 2021-11-30 |
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