CN109825039A - Cyanate resin composition and application thereof - Google Patents
Cyanate resin composition and application thereof Download PDFInfo
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- CN109825039A CN109825039A CN201811621233.8A CN201811621233A CN109825039A CN 109825039 A CN109825039 A CN 109825039A CN 201811621233 A CN201811621233 A CN 201811621233A CN 109825039 A CN109825039 A CN 109825039A
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Abstract
The present invention provides a kind of cyanate resin composition and the prepreg comprising it, laminate, metal-clad laminate and printed wiring board.The cyanate resin composition includes: the cyanate ester resin (A) indicated by following formula (I)；And epoxy resin (B).Cyanate resin composition according to the present invention and its prepreg, laminate and metal-clad laminate obtained of use are with good heat resistance, humidity resistance, mechanical property, anti-flammability and reliability, low in-plane thermal expansion coefficient, the baseplate material suitable for production high density printed circuit board.
Description
Technical field
The present invention relates to a kind of resin combination more particularly to a kind of cyanate resin composition and use its preparation
Prepreg, laminate, metal-clad laminate and printed wiring board.
Background technique
With computer, electronics and information communication device miniaturization, high performance, multifunction development, to track
Higher requirements are also raised for road plate: miniaturization, slimming, highly integrated and high reliability.This requires for making printing
The metal-clad laminate of wiring board has superior moisture-proof, heat resistance and reliability etc..
Simultaneously as the raising of semiconductor packages density, in order to reduce the warpage issues generated in encapsulation process, in recent years
It is strongly required to reduce the in-plane thermal expansion coefficient of laminate.
Cyanate ester resin has excellent dielectric properties, heat resistance, mechanical property and technique processability, high-end making
It is a kind of common matrix resin in printed wiring board metal-clad laminate.But cyanate ester resin due to its solidify after it is resistance to
Humid is poor, thus carried out again after being generally modified by epoxy resin etc. to it using.
In order to obtain better performance such as heat resistance, humidity resistance, mechanical property, anti-flammability and reliability, low is flat
Face direction thermal expansion coefficient etc. still it is expected to develop the new cyanate resin composition with excellent properties in this field.
Summary of the invention
From technical problem described above, the object of the present invention is to provide a kind of cyanate resin composition and packets
Containing its prepreg, laminate, metal-clad laminate and printed wiring board.Cyanate resin composition according to the present invention with
And there is good heat resistance, humidity resistance, mechanical property using its prepreg, laminate and metal-clad laminate obtained
Energy, anti-flammability and reliability, low in-plane thermal expansion coefficient, the substrate material suitable for production high density printed circuit board
Material.
The present inventor passes through thoroughgoing and painstaking research, completes the present invention.
According to an aspect of the invention, there is provided a kind of cyanate resin composition, the cyanate resin composition
Include:
The cyanate ester resin (A) indicated by following formula (I):
Wherein, R is the arlydene with 6-18 carbon atom, R1、R2It is each independently hydrogen atom, has 1-6 carbon former
The alkyl of son, the aryl with 6-18 carbon atom or the aralkyl with 7-19 carbon atom；And n is integer of 1 to 20；
And
Epoxy resin (B).
Certain embodiments according to the present invention, the integer that n is 1 to 15, and n is preferably integer of 1 to 10.
Certain embodiments according to the present invention, R are phenylene, naphthylene or biphenylene, preferably phenylene.
Certain embodiments according to the present invention, R1、R2It is each independently hydrogen atom or methyl, preferably hydrogen atom.
Certain embodiments according to the present invention, the cyanate ester resin (A) have structure shown in following formula (I '):
Wherein, R is the arlydene with 6-18 carbon atom；And n is integer of 1 to 20.
Certain embodiments according to the present invention, the cyanate ester resin (A) account for cyanate ester resin (A) and epoxy resin
(B) the 10-90 weight % of total weight, preferably 20-80 weight %, and more preferably 30-70 weight %.
Certain embodiments according to the present invention, the epoxy resin (B) are selected from the ring containing at least two epoxy groups
Oxygen resin.
Certain embodiments according to the present invention, the epoxy resin (B) account for cyanate ester resin (A) and epoxy resin (B)
Total weight 10-90 weight %, preferably 20-80 weight %, and more preferably 30-70 weight %.
Certain embodiments according to the present invention, the cyanate resin composition also include maleimide compound
(C)。
Certain embodiments according to the present invention, with the total of the cyanate ester resin (A) and maleimide compound (C)
Weight is 100 parts by weight meters, and the amount of the maleimide compound (C) is 5~80 parts by weight, preferably 10~70 parts by weight.
Certain embodiments according to the present invention, the cyanate resin composition also include inorganic filler (D).
Certain embodiments according to the present invention, the total weight with the cyanate ester resin (A) and epoxy resin (B) are
100 parts by weight or with the total weight of the cyanate ester resin (A), epoxy resin (B) and maleimide compound (C) be 100
Parts by weight meter, the amount of the inorganic filler (D) are 10~300 parts by weight, preferably 30~270 parts by weight, more preferable 50~250 weight
Measure part.
According to another aspect of the present invention, a kind of prepreg is provided, the prepreg includes substrate and passes through impregnation
Adhere to the cyanate resin composition as described above on substrate after drying.
According to a further aspect of the invention, a kind of laminate is provided, the laminate includes an at least institute as above
The prepreg stated.
According to a further aspect of the invention, a kind of metal-clad laminate, the metal-clad laminate packet are provided
The metal foil for including at least one prepreg as described above and being overlying on the prepreg one or both sides.
According to a further aspect of the invention, a kind of printed wiring board is provided, the printed wiring board includes at least one
Open prepreg as described above.
Compared with the prior art in this field, the present invention has the advantages that
By that will have the specific cyanate ester resin (A) of formula (I) structure as curing agent and epoxy resin (B) or and epoxy
Resin (B) is used together with maleimide compound (C), can be obtained a kind of with good heat resistance, humidity resistance, power
The resin combination of performance, anti-flammability and reliability and low in-plane thermal expansion coefficient is learned, which can use
There is prepreg, laminate, metal-clad laminate and the printed wiring board of expected performance in preparation.In other words, the present invention mentions
The cyanate resin composition of confession, has good heat resistance, humidity resistance, mechanical property, anti-flammability and reliability, and low is flat
Face direction thermal expansion coefficient.Using prepreg, laminate and metal-clad laminate made from the cyanate resin composition,
Also there is good heat resistance, humidity resistance, mechanical property, anti-flammability and reliability, low in-plane thermal expansion coefficient is fitted
It shares in the baseplate material of production high density printed circuit board.
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.
Unless otherwise specified, expression characteristic size, quantity and materialization used in specification and claims are special
All numbers of property be construed as to be modified by term " about " in all cases.Therefore, unless there are opposite
Illustrate, the numerical parameter otherwise listed in description above and the appended claims is approximation, those skilled in the art
Member can seek the required characteristic obtained using teachings disclosed herein, suitably change these approximations.With endpoint table
The use for the numberical range shown includes all numbers within the scope of this and any range within the scope of this, for example, 1 to 5 includes
1,1.1,1.3,1.5,2,2.75,3,3.80,4 and 5 etc..
It was found by the inventors of the present invention that the cyanate ester resin (A) with formula (I) structure is used as curing agent and epoxy resin
(B) or with epoxy resin (B) with maleimide compound (C) it is used together, cyanate resin composition can be significantly improved
Heat resistance, humidity resistance, mechanical property, anti-flammability and reliability, reduce in-plane thermal expansion coefficient.Based on above-mentioned hair
Existing, inventor completes the present invention.
According to an aspect of the invention, there is provided a kind of cyanate resin composition, the cyanate resin composition
Include:
The cyanate ester resin (A) indicated by following formula (I):
Wherein, R is the arlydene with 6-18 carbon atom, R1、R2It is each independently hydrogen atom, has 1-6 carbon former
The alkyl of son, the aryl with 6-18 carbon atom or the aralkyl with 7-19 carbon atom；And n is integer of 1 to 20；
And
Epoxy resin (B).
Cyanate ester resin (A) with formula (I) structure of the invention is not particularly limited, molecule knot can be selected from
Containing at least four cyanic acid ester groups and such as the cyanate ester resin or cyanate prepolymer of formula (I) structure in structure.The cyanate
Resin (A) can be used alone, and also can according to need and is used in mixed way at least two cyanate ester resins (A).
The position of cyanic acid ester group is not particularly limited, there are two cyanic acid for band on each naphthylene group in solemnity (I)
Ester group.It is preferred that two cyanic acid ester groups on naphthalene are located on different phenyl ring.For example, cyanate ester resin (A) can be with
With structure shown in following formula (I '):
Preferably, in the cyanate ester resin (A) indicated by formula (I), the integer that n is 1 to 15, and n is preferably 1 to 10
Integer.When molecular weight is excessive, it can cause to react too fast since cyanate group is excessive, so that gummosis window becomes smaller, lamination
Difficulty in process.
Preferably, in the cyanate ester resin (A) indicated by formula (I), R be phenylene, naphthylene or biphenylene, and
R is preferably phenylene.
Preferably, in the cyanate ester resin (A) indicated by formula (I), R1、R2It is each independently hydrogen atom or methyl, and
And R1、R2Preferably hydrogen atom.
The synthetic method of the cyanate ester resin (A) indicated by formula (I) is not particularly limited, the technology people of fields
Member can combine the professional knowledge of oneself to be selected according to prior art.Specifically, can for example obtain in the following way
The cyanate ester resin (A) indicated by formula (I): under conditions of there are alkali compounds, make the phenolic aldehyde of the structure as shown in formula (II)
Resin reacts in inert organic solvents with cyanogen halides, to obtain the cyanate ester resin (A) indicated by formula (I).
Wherein, R, R1、R2It is identical as above with respect to the definition in formula (I) with n.
According to the technique and scheme of the present invention, the dosage of the cyanate ester resin (A) is not particularly limited.In order to realize
Good result of the cyanate ester resin (A) in the cyanate resin composition, preferably accounts for the cyanate with formula (I) structure
The 10-90 weight % of resin (A) and epoxy resin (B) total weight, for example, 12%, 15%, 21%, 26%, 32%, 36%,
45%, 52%, 58%, 63%, 67%, 72%, 77%, 85%, 88%, further preferred 20-80 weight %, particularly preferably
30-70 weight %.
Epoxy resin of the present invention (B) is not particularly limited, is selected from and contains at least two epoxy groups
Epoxy resin, for example, bisphenol A type epoxy resin, bisphenol E-type epoxy resin, bisphenol f type epoxy resin, tetramethyl can be selected from
Base bisphenol f type epoxy resin, bis-phenol M type epoxy resin, bis-phenol p-type epoxy resin, bisphenol-s epoxy resin, novolac type
Epoxy resin, cresol novolak type epoxy resin, bisphenol-A phenolic type epoxy resin, trifunctional phenol-type epoxy resin, tetrafunctional phenolic
Epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol novolac type epoxy resin, anthracene type epoxy resin, phenolphthalein type ring
Oxygen resin, phenoxy group type epoxy resin, norbornene-type epoxy resin, adamantane type epoxy resin, Cong type epoxy resin, biphenyl
Type epoxy resin, dicyclopentadiene type epoxy resin, dicyclopentadiene phenolic aldehyde type ring oxygen resin, aralkyl-type epoxy resin, virtue
Epoxy resin containing arylene ether structure, cycloaliphatic epoxy resin, polyalcohol type ring in alkyl phenolic type epoxy resin, molecule
Oxygen resin contains epoxy silicone, nitrogen-containing epoxy thermoset, phosphorous epoxy resin, glycidyl amine epoxy resin, ethylene oxidic ester ring
Oxygen resin etc..In order to improve heat resistance, the anti-flammability of cyanate resin composition, epoxy resin (B) of the present invention is into one
Walk preferred novolac type epoxy resin, cresol novolak type epoxy resin, naphthol type epoxy resin, naphthol novolac type asphalt mixtures modified by epoxy resin
Rouge, anthracene type epoxy resin, phenolphthalein type epoxy resin, biphenyl type epoxy resin, aralkyl-type epoxy resin, aralkyl phenolic aldehyde type ring
In epoxy resin containing arylene ether structure in oxygen resin, molecule any one or at least two mixture, especially
It is preferred that novolac type epoxy resin, cresol novolak type epoxy resin, naphthol novolac type epoxy resin, anthracene type epoxy resin, phenol
It is phthalein type epoxy resin, aralkyl phenol aldehyde type epoxy resin, any one in the epoxy resin containing arylene ether structure in molecule
Kind or at least two mixture.Epoxy resin (B) can be used alone, and also can according to need at least two asphalt mixtures modified by epoxy resin
Rouge (B) is used in mixed way.
The dosage of the epoxy resin (B) is not particularly limited, and preferably accounts for the cyanate ester resin indicated by formula (I)
(A) and the 10-90 weight % of the total weight of epoxy resin (B), for example, 12%, 15%, 21%, 26%, 32%, 36%, 45%,
52%, 58%, 63%, 67%, 72%, 77%, 85%, 88%, further preferred 20-80 weight %, particularly preferred 30-70 weight
Measure %.
Cyanate resin composition of the invention can also include maleimide compound (C).In cyanate ester resin group
It closes in object and maleimide compound (C) is added, available mechanical property, heat resistance, in-plane thermal expansion coefficient are more
Excellent resin combination.To maleimide compound of the present invention (C), there is no particular limitation, is selected from molecular structure
In the compound containing at least one maleimide base group, at least two maleimide base groups are contained in preferred molecular structure
Compound.Specifically, maleimide compound (C) can be selected from N-phenylmaleimide, N- (2- aminomethyl phenyl) horse
Come acid imide, N- (4- aminomethyl phenyl) maleimide, N- (2,6- 3,5-dimethylphenyl) maleimide, two (4- maleimides
Aminocarbonyl phenyl) methane, two (4- maleimidophenyl) ethers, two (4- maleimidophenyl) sulfones, 4- methyl-1, the Asia 3-
Phenyl-bismaleimide, meta-phenylene bismaleimide, 1,3- bis- (3- maleimide phenoxyl) benzene, 1,3- bis-
(4- maleimide phenoxyl) benzene, 2,2- bis- (4- (4- maleimide phenoxyl)-phenyl) propane, two (3,5- bis-
Methyl -4- maleimidophenyl) methane, two (3- ethyl -5- methyl -4- maleimidophenyl) methane, two (3,5-
Diethyl -4- maleimidophenyl) methane, in molecule biphenyl contenting structure maleimide, polyphenyl methylmethane Malaysia acyl
Imines (Polyphenylmethane maleimide), N-phenylmaleimide prepolymer, N- (2- aminomethyl phenyl) Malaysia acyl
Imines prepolymer, N- (4- aminomethyl phenyl) maleimide prepolymer, N- (2,6- 3,5-dimethylphenyl) maleimide prepolymer,
Two (4- maleimidophenyl) methane prepolymers, two (4- maleimidophenyl) ether prepolymers, two (4- maleimides
Aminocarbonyl phenyl) sulfone prepolymer, 4- methyl-1,3- phenylene Bismaleimide prepolymer, meta-phenylene bismaleimide are pre-
Polymers, 1,3- bis- (3- maleimide phenoxyl) benzene prepolymer, 1,3- bis- (4- maleimide phenoxyl) benzene pre-polymerization
Object, 2,2- bis- (4- (4- maleimide phenoxyl)-phenyl) propane prepolymer, two (3,5- dimethyl -4- maleimides
Base phenyl) methane prepolymer, two (3- ethyl -5- methyl -4- maleimidophenyl) methane prepolymers, two (3,5- diethyls
Base -4- maleimidophenyl) methane prepolymer, the maleimide prepolymer of biphenyl contenting structure, polyphenylene first in molecule
Alkane maleimide prepolymer, the prepolymer of N-phenylmaleimide and aminated compounds, N- (2- aminomethyl phenyl) Malaysia acyl
Prepolymer, the N- (2,6- of the prepolymer of imines and aminated compounds, N- (4- aminomethyl phenyl) maleimide and aminated compounds
3,5-dimethylphenyl) maleimide and aminated compounds prepolymer, two (4- maleimidophenyl) methane and amine
Close the prepolymer of object, the prepolymer of two (4- maleimidophenyl) ethers and aminated compounds, two (4- dimaleoyl imino benzene
Base) sulfone and aminated compounds prepolymer, 4- methyl-1, the prepolymer of 3- phenylene bismaleimide and aminated compounds,
The prepolymer of meta-phenylene bismaleimide and aminated compounds, (3- maleimide phenoxyl) benzene of 1,3- bis- and amine
The prepolymer of compound, the prepolymer of (4- maleimide phenoxyl) benzene of 1,3- bis- and aminated compounds, bis- (4- of 2,2-
(4- maleimide phenoxyl)-phenyl) propane and aminated compounds prepolymer, two (3,5- dimethyl -4- maleimides
Aminocarbonyl phenyl) prepolymer of methane and aminated compounds, two (3- ethyl -5- methyl -4- maleimidophenyl) methane and
The prepolymer of aminated compounds, two (3,5- diethyl -4- maleimidophenyl) methane and aminated compounds prepolymer,
The maleimide of biphenyl contenting structure and the prepolymer of aminated compounds or polyphenyl methylmethane maleimide and amine in molecule
In the prepolymer of compound any one or at least two mixture, preferably two (4- maleimidophenyl) first
Alkane, meta-phenylene bismaleimide, two (3,5- dimethyl -4- maleimidophenyl) methane, two (3- ethyl -5- first
Base -4- maleimidophenyl) methane, two (3,5- diethyl -4- maleimidophenyl) methane, the (4- (4- of 2,2- bis-
Maleimide phenoxyl)-phenyl) propane, in molecule biphenyl contenting structure maleimide or polyphenyl methylmethane Malaysia acyl
Imines and its prepolymer or in the prepolymer of aminated compounds any one or at least two mixture.
Maleimide compound (C) can according to need exclusive use or multiple combinations use.The maleimide
The dosage of compound (C) is not particularly limited.Preferably, with the cyanate ester resin (A) and maleimide compound (C)
Total weight be 100 parts by weight meters, the amount of the maleimide compound (C) is 5~80 parts by weight, preferably 10~70 weight
Part.
Cyanate resin composition of the invention can also include inorganic filler (D).Add in cyanate resin composition
Enter inorganic filler (D), available mechanical property, humidity resistance, flame retardant property, in-plane thermal expansion coefficient are more excellent
The resin combination of halogen-free flameproof.Specifically, different types of inorganic fill out can be added in order to realize different technical purposes
Expect (D).Inorganic filler of the present invention (D) is not particularly limited, silica, metal hydrate, oxidation are selected from
Molybdenum, zinc molybdate, titanium oxide, zinc oxide, strontium titanates, barium titanate, barium sulfate, boron nitride, aluminium nitride, silicon carbide, aluminium oxide, boric acid
Zinc, zinc stannate, clay, kaolin, talcum, mica, compound silicon powder, E glass powder, D glass powder, L glass powder, M glass powder, S
In glass powder, T glass powder, NE glass powder, Q glass powder, fused silica powder, short glass fiber or hollow glass any one or
The mixture of person at least two, preferably crystalline sillica, fused silica, amorphous silica, spherical titanium dioxide
Silicon, hollow silicon dioxide, aluminium hydroxide, boehmite, magnesium hydroxide, molybdenum oxide, zinc molybdate, titanium oxide, zinc oxide, strontium titanates,
Barium titanate, barium sulfate, boron nitride, aluminium nitride, silicon carbide, aluminium oxide, zinc borate, zinc stannate, clay, kaolin, talcum, cloud
Female, compound silicon powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass powder, Q glass
In powder, fused silica powder, short glass fiber or hollow glass any one or at least two mixture, the mixture
Such as the mixture of crystalline sillica and fused silica, the mixing of amorphous silica and preparing spherical SiO 2
The mixture of the mixture of object, hollow silicon dioxide and aluminium hydroxide, boehmite and magnesium hydroxide, molybdenum oxide and zinc molybdate mix
Close object, titanium oxide, zinc oxide, strontium titanates and barium titanate mixture, the mixture of barium sulfate, boron nitride and aluminium nitride, carbonization
Silicon, aluminium oxide, zinc borate and zinc stannate mixture, compound silicon powder, E glass powder, D glass powder, L glass powder and M glass powder
Mixture, S glass powder, T glass powder, NE glass powder and fused silica powder mixture, clay, kaolin, talcum and mica
Mixture, the mixture of short glass fiber and hollow glass, further preferred fused silica or/and boehmite.Wherein,
Fused silica have low thermal coefficient of expansion characteristic, the anti-flammability and excellent heat resistance of boehmite, therefore it is preferred that it.It is inorganic to fill out
Material (D) is more preferably spherical fused silica, and spherical fused silica has low thermal coefficient of expansion and good dielectricity
Can etc. characteristics while, and have it is good dispersibility, mobility, therefore it is preferred that it.
To the average grain diameter (d of inorganic filler (D)50) there is no particular limitation, but considers from dispersed angle, average grain diameter
(d50) it 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 (D) of different average grain diameters.
The present invention is not particularly limited the dosage of inorganic filler (D).With the cyanate ester resin with formula (I) structure
(A) and the total weight of epoxy resin (B) is for 100 parts by weight or with the cyanate ester resin (A), epoxy resin (B) and Malaysia acyl
The total weight of group with imine moiety (C) is 100 parts by weight meters, and the amount of the inorganic filler (D) can be 10-300 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, 200 parts by weight, 220 parts by weight, 240 parts by weight, 260 parts by weight, 280 parts by weight, 290 parts by weight, preferably
30-270 parts by weight, further preferably 50-250 parts by weight.
Inorganic filler (D) of the invention can be used together with mating surface inorganic agent or wetting agent, dispersing agent.At surface
Managing agent, there is no particular limitation, can handle common surface treating agent selected from mineral surfaces.Its silicic acid second that is specifically positive
Ester type compound, organic acid compound, aluminate compound, titanate ester compound, silicone oligomer, at macromolecular
Manage agent, silane coupling agent etc..Silane coupling agent is not particularly limited, it is even to handle common silane selected from mineral surfaces
Join agent, be specially amino silicane coupling agent, epoxy silane coupling, vinyl silicane coupling agent, phenyl silane coupling agent,
Cationic silane coupling agent, mercaptosilane coupling agents etc..Wetting agent, dispersing agent are not particularly limited, is selected from and is usually used in
Wetting agent, the dispersing agent of coating.The present invention can according to need at exclusive use or the different types of surface of appropriately combined use
Manage agent or wetting agent, dispersing agent.
Cyanate resin composition of the invention can also include organic filler (E).To organic filler (E) without special
It limits, it can be selected from any one in organosilicon, liquid crystal polymer, thermosetting resin, thermoplastic resin, rubber or core shell rubbers
Kind or at least two mixture, further preferred organosilicon powder or/and core shell rubbers.The organic filler (E) can be with
For powder or particle.Wherein, organosilicon powder has good flame-retarding characteristic, and core shell rubbers have good toughening effect, therefore
It is preferred that it.
The dosage of organic filler (E) is not particularly limited.With the cyanate ester resin (A) and epoxy resin (B)
Total weight is for 100 parts by weight or with the gross weight of the cyanate ester resin (A), epoxy resin (B) and maleimide compound (C)
Amount is 100 parts by weight meters, and the amount of the organic filler (E) can be 1-30 parts by weight, such as 2 parts by weight, 5 parts by weight, 7 weight
Part, 9 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 21 parts by weight, 24 parts by weight, 27 parts by weight, 29 parts by weight are excellent
It is selected as 3-25 parts by weight, further preferably 5-20 parts by weight.
" 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 ".
Cyanate resin composition of the invention can be combined with other than the cyanate ester resin (A) with formula (I) structure
Cyanate ester resin is used together, as long as its proper property for not damaging cyanate resin composition, can be selected from bisphenol A-type
Cyanate ester resin, bisphenol E-type cyanate resin, bisphenol-f type cyanate ester resin, tetramethyl bisphenol F cyanate resin, bis-phenol M
Type cyanate ester resin, bis-phenol p-type cyanate ester resin, bisphenol S type cyanate ester resin, novolac type cyanate ester resin, cresols phenol
Aldehyde type cyanate ester resin, naphthol type cyanate ester resin, Naphthol phenolic cyanate ester resin, bisphenol-A phenolic type cyanate ester resin, three
Function phenolic cyanate ester resin, tetrafunctional phenolic cyanate ester resin, anthracene type cyanate ester resin, Cong type cyanate ester resin, bicyclic penta
Diene type cyanate ester resin, biphenyl type cyanate ester resin, contains arlydene in molecule at dicyclopentadiene phenolic aldehyde type cyanate ester resin
The cyanate ester resin of ether structure, phenolphthalein type cyanate ester resin, aralkyl-type cyanate ester resin, aralkyl Novolac Cyanate Eater Resin tree
Rouge, bisphenol A cyanate ester prepolymer, bisphenol E-type cyanate prepolymer, bisphenol-f type cyanate prepolymer, tetramethyl bisphenol-f type
It is cyanate prepolymer, bis-phenol M type cyanate prepolymer, bis-phenol p-type cyanate prepolymer, bisphenol S type cyanate prepolymer, linear
Novolac Cyanate Eater Resin prepolymer, cresol novolak type cyanate prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate
Prepolymer, bisphenol-A phenolic type cyanate prepolymer, trifunctional phenolic cyanate prepolymer, tetrafunctional phenolic cyanate prepolymer,
Anthracene type cyanate prepolymer, Cong type cyanate prepolymer, dicyclopentadiene type ethylene rhodanate prepolymer, dicyclopentadiene phenolic aldehyde type cyanogen
Acid esters prepolymer, biphenyl type cyanate prepolymer, the cyanate prepolymer containing arylene ether structure, phenolphthalein type cyanic acid in molecule
Any one in ester prepolymer, aralkyl-type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer or at least two
The mixture of kind, the mixture of the mixture such as bisphenol A cyanate ester resin and bisphenol-f type cyanate ester resin, tetramethyl
The mixture of bisphenol-f type cyanate ester resin and bis-phenol M type cyanate ester resin, bisphenol S type cyanate ester resin and bisphenol E-type cyanate
The mixture of resin, the mixture of bis-phenol p-type cyanate ester resin and novolac type cyanate ester resin, cresol novolak type cyanate
The mixture of resin and Naphthol phenolic cyanate ester resin, bisphenol-A phenolic type cyanate ester resin and trifunctional phenolic cyanate resin
The mixture of rouge, the mixture of tetrafunctional phenolic cyanate ester resin and anthracene type cyanate ester resin, Cong type cyanate ester resin and bicyclic
The mixture of pentadiene Novolac Cyanate Ester Resins, the cyanic acid containing arylene ether structure in biphenyl type cyanate ester resin and molecule
The mixture of ester resin, the mixture of dicyclopentadiene type ethylene rhodanate resin and phenolphthalein type cyanate ester resin, aralkyl-type cyanic acid
The mixture of ester resin and aralkyl Novolac Cyanate Ester Resins, novolac type cyanate ester resin and bisphenol A cyanate ester are pre-
The mixture of polymers, the mixture of bisphenol A cyanate ester prepolymer and bisphenol-f type cyanate prepolymer, tetramethyl bisphenol-f type cyanogen
The mixture of acid esters prepolymer and bis-phenol M type cyanate prepolymer, bisphenol S type cyanate prepolymer and bisphenol E-type cyanate are pre-
The mixture of polymers, the mixture of bis-phenol p-type cyanate prepolymer and novolac type cyanate prepolymer, cresol novolak type cyanogen
The mixture of acid esters prepolymer and naphthol novolac type cyanate prepolymer, bisphenol-A phenolic type cyanate prepolymer and tri-functional phenols
The mixture of type cyanate prepolymer, the mixture of tetrafunctional phenolic cyanate prepolymer and anthracene type cyanate prepolymer, Cong type
The mixture of cyanate prepolymer and dicyclopentadiene phenolic aldehyde type cyanate prepolymer, in biphenyl type cyanate prepolymer and molecule
The mixture of cyanate prepolymer containing arylene ether structure, dicyclopentadiene type ethylene rhodanate prepolymer, phenolphthalein type cyanate
The mixture of prepolymer, aralkyl-type cyanate prepolymer and aralkyl Novolac Cyanate Eater Resin prepolymer, in order to improve cyanate
Heat resistance, the anti-flammability of resin combination, further preferred novolac type cyanate ester resin, cresol novolak type cyanate resin
Rouge, naphthol type cyanate ester resin, Naphthol phenolic cyanate ester resin, phenolphthalein type cyanate ester resin, anthracene type cyanate ester resin, biphenyl
Cyanate ester resin, aralkyl-type cyanate ester resin, aralkyl phenolic aldehyde containing arylene ether structure in type cyanate ester resin, molecule
Type cyanate ester resin, novolac type cyanate prepolymer, cresol novolak type cyanate prepolymer, naphthol type cyanate pre-polymerization
Object, naphthol novolac type cyanate prepolymer, phenolphthalein type cyanate prepolymer, anthracene type cyanate prepolymer, biphenyl type cyanate are pre-
Cyanate prepolymer, aralkyl-type cyanate prepolymer or aralkyl phenol aldehyde type containing arylene ether structure in polymers, molecule
In cyanate prepolymer any one or at least two mixture, particularly preferred novolac type cyanate ester resin, naphthalene
Cyanate ester resin, aralkyl Novolac Cyanate Ester Resins containing arylene ether structure in phenol Novolac Cyanate Ester Resins, molecule,
Novolac type cyanate prepolymer, naphthol novolac type cyanate prepolymer, the cyanate containing arylene ether structure in molecule
In prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer any one or at least two mixture.These cyanate resins
Rouge can according to need exclusive use or multiple combinations use.
Cyanate resin composition of the invention can be combined with various high polymers, rubber, elastomer and be used together, as long as
Its proper property for not damaging cyanate resin composition.It for example can be specifically liquid crystal polymer, thermosetting resin, thermoplasticity
Resin, different flame-retardant compounds or additive etc..They can according to need exclusive use or multiple combinations use.
Cyanate resin composition of the invention can also be used together in conjunction with curing accelerator as needed, solid to control
Change reaction rate.The curing accelerator is not particularly limited, and can be selected from being conventionally used to facilitate solidification cyanate ester resin, epoxy
The curing accelerator of resin is specially the organic salt, imidazole and its derivants, tertiary amine of the metal of copper, zinc, cobalt, nickel, manganese etc
Deng, such as zinc octoate.
In addition, the cyanate resin composition can also contain various additives, as concrete example, can enumerate anti-
Oxygen agent, heat stabilizer, antistatic agent, ultraviolet absorbing agent, pigment, colorant, lubricant etc..
The preparation method of invention resin composition does not limit specifically, the system as one of invention resin composition
Preparation Method, can be by having the cyanic acid of formula (I) structure described in well known method cooperation, pre-polymerization, pre-reaction, stirring, mixing
It is prepared by ester resin (A) and epoxy resin (B) etc..
It is a further object to provide a kind of prepregs prepared using above-mentioned cyanate resin composition, lamination
Plate, metal-clad laminate and printed wiring board, the laminate made using the prepreg and metal-clad laminate tool
There are good heat resistance, humidity resistance, mechanical property, anti-flammability and reliability, low in-plane thermal expansion coefficient is suitble to use
In the baseplate material for preparing high density printed circuit board.
The present invention provides a kind of prepreg prepared using above-mentioned cyanate resin composition, the prepreg includes base
Material and pass through impregnation it is dry after adhere to the cyanate resin composition as described above on substrate.Substrate of the present invention does not have
Special limitation, can be selected from known for making the substrate of various printed wire plate materials.Specially inorfil (example
Such as E glass, D glass, L glass, M glass, S glass, T glass, NE glass, Q glass, quartz glass fibre), organic fiber
(such as polyimides, polyamide, polyester, polyphenylene oxide, liquid crystal polymer etc.).Substrate be typically in the form of textile fabric, non-woven fabrics,
Rove, staple fiber, fibrous paper etc..In above-mentioned substrate, the preferred glass fabric of substrate of the present invention.
The preparation method of prepreg of the present invention is not limited specifically, as long as it is by will be of the present invention
The method that cyanate resin composition prepares prepreg in conjunction with substrate.
It can according to need in the above-mentioned cyanate resin composition for preparing prepreg using organic solvent.To organic molten
There is no particular limitation for agent, as long as the mixture phase with cyanate ester resin (A) and epoxy resin (B) with formula (I) structure
The solvent of appearance, the solvent can be enumerated as concrete example: the alcohols such as methanol, ethyl alcohol, butanol, ethyl cellosolve, butyl are molten
The ethers such as fine agent, ethylene glycol-methyl ether, diethylene glycol ether, butyl, acetone, butanone, methyl ethyl ketone, methyl
The ketones such as isobutyl ketone, cyclohexanone, toluene, dimethylbenzene, mesitylene etc. are aromatic hydrocarbon, ethoxyethyl acetate, vinegar
The esters such as acetoacetic ester, the nitrogen-containing solvents such as n,N-Dimethylformamide, n,N-dimethylacetamide, n-methyl-2-pyrrolidone.
Above-mentioned solvent can be used alone, and also can according to need and is used in mixed way two or more.
The laminate and metal-clad laminate that the present invention also provides a kind of to be prepared using above-mentioned prepreg.The lamination
Plate includes an at least prepreg as described above, obtains laminate for the prepreg after overlapping is cured.It is described to cover gold
Belonging to foil laminate includes that an at least prepreg as described above, the one or both sides of the prepreg after overlapping are covered with metal
Foil, lamination solidification obtain metal-clad laminate.The laminate prepared using the prepreg is had with metal-clad laminate
Good heat resistance, humidity resistance, mechanical property, anti-flammability and reliability, low in-plane thermal expansion coefficient, therefore be suitble to
It is used to prepare the baseplate material of high density printed circuit board.
The preparation method of laminate of the invention does not limit specifically, can be prepared by well known method, such as:
One above-mentioned prepreg is placed or stacks two or two or more prepregs, as needed, in prepreg or is stacked pre-
Metal foil is placed in the side or two sides for soaking material, and is laminated solidification and obtains laminate or metal-clad laminate.The metal foil
It is not particularly limited, can be selected from the metal foil for printed wire plate material.Lamination can select printed wiring board
Laminate and multiple-plate general lamination.
The present invention also provides a kind of printed wiring board, the printed wiring board includes at least one preimpregnation as described above
Material.The preparation method of printed wiring board of the present invention does not limit specifically, can be prepared by well known method.
The present invention is described in more detail below with reference to embodiment.It may be noted that these descriptions and embodiment are all
In order to be easy to understand the present invention, rather than limitation of the present invention.Protection scope of the present invention is with appended claims
It is quasi-.
Embodiment
In the present invention, unless otherwise noted, used reagent is commercial products, is directly used without further
Purification process.In addition, mentioned " % " is " weight % ", and mentioned " part " is " parts by weight ".
Test method
According to the specific method being listed below, to the various copper-clad laminates prepared in embodiment and comparative example about
Glass transition temperature (Tg: DEG C), resistance to dip solderability (S), humidity resistance, bending modulus (GPa), in-plane thermal expansion coefficient
(CTE:ppm/ DEG C) and anti-flammability are tested.
Glass transition temperature (Tg: DEG C)
The copper-clad laminate sample prepared in embodiment and comparative example is etched away into copper foil, is produced as 60mm × 12mm
Size will be in heating rate using the glass transition temperature (Tg: DEG C) of dynamic thermomechanical analysis (DMA) measurement sample
The peak temperature of tan δ when under conditions of being 10 DEG C/min from room temperature to 350 DEG C is denoted as Tg, test sample with a thickness of
0.8mm。
Resistance to dip solderability (S)
The size for being 50mm × 50mm by the copper-clad laminate sample producing prepared in embodiment and comparative example, by sample
Product immerse in 288 DEG C of tin furnace, and observation layering blister formation simultaneously records the corresponding time, and test sample is with a thickness of 0.4mm.
Humidity resistance
The copper-clad laminate sample prepared in embodiment and comparative example is etched away into copper foil, produce for 100mm ×
The size of 100mm.The sample is 2 hours dry at 105 DEG C.Then, by sample with steam pressure pot machine in 121 DEG C and two
It is handled under atmospheric pressure 2 hours, then by sample wicking 60 seconds in 260 DEG C of tin furnace, whether observing samples are layered, and are not layered such as
Bubbling is determined as " OK ", and such as layering, which is bubbled, is determined as "×", and test sample is with a thickness of 0.4mm.
Bending modulus (GPa)
By the copper-clad laminate sample prepared in embodiment and comparative example according to the test method of ASTM D882 standard
It is required that the bending modulus of test sample at room temperature, test sample is with a thickness of 0.8mm.
In-plane thermal expansion coefficient (CTE:ppm/ DEG C)
The copper-clad laminate sample prepared in embodiment and comparative example is etched away into copper foil, is produced as 4mm × 60mm
Size, using thermomechanical analysis (TMA) measurement sample in-plane thermal expansion coefficient, wherein measurement direction be along glass
Cloth warp thread direction is warming up to 300 DEG C from 25 DEG C of room temperature with the heating rate of 10 DEG C/min, measurement from 50 DEG C to 130 DEG C at it is flat
Face direction thermal expansion coefficient, test sample is with a thickness of 0.1mm.
Anti-flammability
The copper-clad laminate sample prepared in embodiment and comparative example is etched away into copper foil, according to UL94 vertical combustion
The test method requirement of testing standard, test sample anti-flammability, test sample is with a thickness of 0.1,0.4mm.
Preparation example 1
Phenyl aralkyl Naphthol phenolic cyanate ester resin A1
Phenyl aralkyl naphthol novolac resin (SN-395 is provided by Co., Ltd., Nippon Steel) is reacted with cyanogen chloride and is made
Phenyl aralkyl Naphthol phenolic cyanate ester resin A1.The phenyl aralkyl naphthol novolac resin has following formula (III) represented
Structure, wherein R be phenylene；The integer that n is 1~10.The phenyl aralkyl Naphthol phenolic cyanate ester resin A1 has
Structure represented by following formula (I '), wherein R is phenylene；The integer that n is 1~10.
Preparation example 2
Xenyl aralkyl Naphthol phenolic cyanate ester resin A2
In the flask for being equipped with thermometer, condenser pipe, blender, 1,6- dihydroxy naphthlene 533g, 4,4 '-bis- chloromethanes are added
Base biphenyl 167g and chlorobenzene 700g, slowly rising temperature for dissolving while stirring, reacts 2 hours at about 80 DEG C under nitrogen protection.So
Afterwards, it is warming up to 180 DEG C when distilling chlorobenzene, is reacted 1 hour at 180 DEG C.After reaction, by being evaporated under reduced pressure solvent and not
The monomer removing of reaction, later using deionized water washing until washing water to be neutral, obtains xenyl aralkyl naphthalene after dry
Phenol phenolic resin.Xenyl aralkyl naphthol novolac resin obtained is reacted with cyanogen chloride later, xenyl aralkyl naphthalene is made
Phenol Novolac Cyanate Ester Resins A2.The xenyl aralkyl naphthol novolac resin has structure represented by following formula (III),
Middle R is biphenylene；The integer that n is 1~10.The xenyl aralkyl Naphthol phenolic cyanate ester resin A2 has following formula
Structure represented by (I '), wherein R is biphenylene；The integer that n is 1~10.
Preparation example 3
Phenyl aralkyl Novolac Cyanate Ester Resins A3
In the flask for being equipped with thermometer, condenser pipe, blender, resorcinol 720g, Isosorbide-5-Nitrae-dichloride methyl benzene is added
175g reacts material temperature control 3 hours at 110-130 DEG C under stream of nitrogen gas.Then, it is small that 160 DEG C are warming up to the reaction was continued 3
When.After reaction, unreacted monomer removed by being evaporated under reduced pressure, later using deionized water washing until during washing water is
Property, phenyl aralkyl phenolic resin is obtained after dry.Later by phenyl aralkyl phenolic resin obtained with cyanogen chloride the system of reacting
Obtain phenyl aralkyl Novolac Cyanate Ester Resins A3.The phenyl aralkyl phenolic resin has knot represented by following formula (IV)
Structure, wherein R is phenylene；The integer that n is 1~10.The phenyl aralkyl Novolac Cyanate Ester Resins A3 has following formula (V)
Represented structure, wherein R is phenylene；The integer that n is 1~10.
Embodiment 1
By 30 parts by weight phenyl aralkyl Naphthol phenolic cyanate ester resin A1,70 parts by weight Biphenyl aralkyl type phenols
Epoxy resin (NC-3000FH is provided by Nippon Kayaku K. K), 0.02 parts by weight of octanoic acid zinc are dissolved in butanone and mix equal
It is even, it is adjusted to appropriate viscosity with butanone, is uniformly mixed, glue is made.With the E glass fabric dipping with a thickness of 0.1mm
The above glue, then prepreg is made after removing solvent in drying.1,4,8 above-mentioned prepregs are superimposed respectively, and
Respectively two sides cover the electrolytic copper foils of 18 μ m thicks for its, carry out solidifying for 2 hours in press, solidifying pressure 45Kg/cm2Gu
Changing temperature is 220 DEG C, obtains the copper-clad laminate with a thickness of 0.1,0.4,0.8mm.
Embodiment 2
By 50 parts by weight phenyl aralkyl Naphthol phenolic cyanate ester resin A1,50 parts by weight Biphenyl aralkyl type phenols
Epoxy resin (NC-3000H is provided by Nippon Kayaku K. K), 0.02 parts by weight of octanoic acid zinc are dissolved in butanone and are uniformly mixed,
It is adjusted to appropriate viscosity with butanone, is uniformly mixed, glue is made.According to manufacture craft same as Example 1, obtain thick
Degree is the copper-clad laminate of 0.1,0.4,0.8mm.
Embodiment 3
By 70 parts by weight phenyl aralkyl Naphthol phenolic cyanate ester resin A1,30 parts by weight Biphenyl aralkyl type phenols
Epoxy resin (NC-3000H is provided by Nippon Kayaku K. K), 0.02 parts by weight of octanoic acid zinc are dissolved in butanone and are uniformly mixed,
It is adjusted to appropriate viscosity with butanone, is uniformly mixed, glue is made.According to manufacture craft same as Example 1, obtain thick
Degree is the copper-clad laminate of 0.1,0.4,0.8mm.
Comparative example 1
With 50 parts by weight phenyl aralkyl-type cyanate ester resins (by 1 side of Chinese patent application CN101240111A synthesis example
Method be made) replace embodiment 2 used in 50 parts by weight phenyl aralkyl Naphthol phenolic cyanate ester resin A1, other according to
The copper-clad laminate that the identical method of embodiment 2 obtains with a thickness of 0.1,0.4,0.8mm.
Comparative example 2
50 parts by weight phenyl used in embodiment 2 is replaced with 50 parts by weight phenyl aralkyl Novolac Cyanate Ester Resins A3
Aralkyl Naphthol phenolic cyanate ester resin A1, other obtain according to method same as Example 2 with a thickness of 0.1,0.4,
The copper-clad laminate of 0.8mm.
According to measurement method described in detail above to copper foil covered pressure made from above-described embodiment 1-3 and comparative example 1-2
Plate is tested about glass transition temperature (Tg: DEG C), resistance to dip solderability (S) and humidity resistance, and concrete outcome is shown below
In table 1.
The physical property measurement data of prepared copper-clad laminate in table 1 embodiment 1-3 and comparative example 1-2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Tg, DEG C | 240 | 270 | 300 | 240 | 255 |
| It is resistance to dip solderability, S | > 120 | > 120 | > 120 | > 120 | > 120 |
| Humidity resistance | OK | OK | OK | OK | × |
Embodiment 4
By 30 parts by weight phenyl aralkyl Naphthol phenolic cyanate ester resin A1,65 parts by weight Biphenyl aralkyl type phenols
Epoxy resin (NC-3000-FH is provided by Nippon Kayaku K. K), 5 parts by weight of bisphenol A type epoxy resin (1055, provided by Dainippon Ink Chemicals), 0.02 parts by weight of octanoic acid zinc be dissolved in butanone and be uniformly mixed, Zhi Houjia
Enter 200 parts by weight spherical fused silicas (SC2050 is provided by Admatechs), 2 parts by weight epoxy base silane coupling agents
(Z-6040 is provided by DOW CORNING), and it is adjusted to appropriate viscosity with butanone, it is stirred and is uniformly dispersed, glue is made.Use thickness
The above glue is impregnated for the E glass fabric of 0.1mm, then prepreg is made after removing solvent in drying.Respectively by 1,4,8
Above-mentioned prepreg be superimposed, and at its, respectively two sides cover the electrolytic copper foils of 18 μ m thicks, carry out consolidating for 2 hours in press
Change, solidifying pressure 45Kg/cm2, solidification temperature is 220 DEG C, obtains the copper-clad laminate with a thickness of 0.1,0.4,0.8mm.
Embodiment 5
By 50 parts by weight phenyl aralkyl Naphthol phenolic cyanate ester resin A1,50 parts by weight Biphenyl aralkyl type phenols
Epoxy resin (NC-3000H is provided by Nippon Kayaku K. K), 0.02 parts by weight of octanoic acid zinc are dissolved in butanone and are uniformly mixed,
110 parts by weight boehmites (APYRAL AOH 30, provided by Nabaltec), 1 parts by weight epoxy base silane coupling agent are provided later
(Z-6040 is provided by DOW CORNING), 1 parts per weight dispersing agent (BYK-W903 is provided by BYK), and suitable glue is adjusted to butanone
Degree, is stirred and is uniformly dispersed, and glue is made.According to manufacture craft same as Example 4, obtain with a thickness of 0.1,0.4,
The copper-clad laminate of 0.8mm.
Embodiment 6
By 70 parts by weight phenyl aralkyl Naphthol phenolic cyanate ester resin A1,30 parts by weight naphthylene ether type naphthols epoxies
Resin (EXA-7311 is provided by Dainippon Ink Chemicals), 0.02 parts by weight of octanoic acid zinc are dissolved in butanone and are uniformly mixed, and are added later
The organosilicon powder of 170 parts by weight spherical fused silicas (SC2050 is provided by Admatechs), 5 parts by weight core-shell structures
(KMP-605 is provided by SHIN-ETSU HANTOTAI's chemistry), 1.5 parts by weight epoxy base silane coupling agents (Z-6040 is provided by DOW CORNING), are used in combination
Butanone is adjusted to appropriate viscosity, is stirred and is uniformly dispersed, and glue is made.According to manufacture craft same as Example 4, obtain
With a thickness of the copper-clad laminate of 0.1,0.4,0.8mm.
Embodiment 7
By 30 parts by weight phenyl aralkyl Naphthol phenolic cyanate ester resin A1,20 parts by weight, two (3- ethyl -5- methyl -
4- maleimidophenyl) methane (BMI-70 is provided by KIChemical Industry Co., Ltd.), 50 parts by weight connection
Phenyl aralkyl type phenol epoxy resin (NC-3000H is provided by Nippon Kayaku K. K), 0.02 parts by weight of octanoic acid zinc are molten
It in DMF, butanone and is uniformly mixed, 170 parts by weight spherical fused silicas are added later, and (SC2050 is mentioned by Admatechs
For), the organosilicon powder (KMP-605 is provided by SHIN-ETSU HANTOTAI's chemistry) of 5 parts by weight core-shell structures, 1 parts by weight epoxy base silane coupling
Agent (Z-6040 is provided by DOW CORNING), and it is adjusted to appropriate viscosity with butanone, it is stirred and is uniformly dispersed, glue is made.According to
Manufacture craft same as Example 4 obtains the copper-clad laminate with a thickness of 0.1,0.4,0.8mm.
Embodiment 8
By 40 parts by weight phenyl aralkyl Naphthol phenolic cyanate ester resin A1,5 parts by weight novolac type cyanate resins
Rouge (PT-30 is provided by LONZA), 5 parts by weight 2,2- bis- (4- (4- maleimide phenoxyl)-phenyl) propane (BMI-
80, by KIChemical Industry Co., Ltd. provide), 25 parts by weight phenyl aralkyl-type naphthol novolac epoxy resins
(ESN-385 is provided by Nippon Steel), 25 parts by weight Biphenyl aralkyl type phenol epoxy resin (NC-3000-FH, by Japanization
Medicine Co., Ltd. provide), 0.02 parts by weight of octanoic acid zinc be dissolved in DMF, butanone and be uniformly mixed, be added later 150 parts by weight spherical shape
Fused silica (SC2050 is provided by Admatechs), 1 parts by weight epoxy base silane coupling agent (Z-6040, by DOW CORNING
There is provided), 1 parts per weight dispersing agent (BYK-W903 is provided by BYK) and be adjusted to appropriate viscosity with butanone, it is equal to be stirred dispersion
It is even, glue is made.According to manufacture craft same as Example 4, the copper foil covered pressure with a thickness of 0.1,0.4,0.8mm is obtained
Plate.
Embodiment 9
30 weight used in embodiment 4 are replaced with 30 parts by weight Biphenyl aralkyl Naphthol phenolic cyanate ester resin A2
Part phenyl aralkyl Naphthol phenolic cyanate ester resin A1, other obtain according to method same as Example 4 with a thickness of 0.1,
0.4, the copper-clad laminate of 0.8mm.
Comparative example 3
With 50 parts by weight phenyl aralkyl-type cyanate ester resins (by 1 side of Chinese patent application CN101240111A synthesis example
Method be made) replace embodiment 5 used in 50 parts by weight phenyl aralkyl Naphthol phenolic cyanate ester resin A1, other according to
The copper-clad laminate that the identical method of embodiment 5 obtains with a thickness of 0.1,0.4,0.8mm.
Comparative example 4
With 40 parts by weight phenyl aralkyl-type cyanate ester resins (by 1 side of Chinese patent application CN101240111A synthesis example
Method be made) replace embodiment 8 used in 40 parts by weight phenyl aralkyl Naphthol phenolic cyanate ester resin A1, other according to
The copper-clad laminate that the identical method of embodiment 8 obtains with a thickness of 0.1,0.4,0.8mm.
Comparative example 5
50 parts by weight phenyl used in embodiment 5 is replaced with 50 parts by weight phenyl aralkyl Novolac Cyanate Ester Resins A3
Aralkyl Naphthol phenolic cyanate ester resin A1, other obtain according to method same as Example 5 with a thickness of 0.1,0.4,
The copper-clad laminate of 0.8mm.
Comparative example 6
40 parts by weight phenyl used in embodiment 8 is replaced with 40 parts by weight phenyl aralkyl Novolac Cyanate Ester Resins A3
Aralkyl Naphthol phenolic cyanate ester resin A1, other obtain according to method same as Example 8 with a thickness of 0.1,0.4,
The copper-clad laminate of 0.8mm.
According to measurement method described in detail above to copper foil covered pressure made from above-described embodiment 4-9 and comparative example 3-6
Plate is about resistance to dip solderability (S), humidity resistance, bending modulus (GPa), in-plane thermal expansion coefficient (CTE:ppm/ DEG C) and fire-retardant
Property is tested, and concrete outcome is shown below in table 2.
The physical property measurement data of prepared copper-clad laminate in 2 embodiment 4-9 of table
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| It is resistance to dip solderability, S | > 120 | > 120 | > 120 | > 120 | > 120 | > 120 |
| Humidity resistance | OK | OK | OK | OK | OK | OK |
| Bending modulus, GPa | 32 | 29 | 32 | 32 | 31 | 32 |
| CTE, ppm/ DEG C | 6 | 12 | 6 | 6 | 8 | 6 |
| Anti-flammability | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
Table 2 continues the physical property measurement data of copper-clad laminate prepared in comparative example 3-6
| Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| It is resistance to dip solderability, S | > 120 | > 120 | > 120 | > 120 |
| Humidity resistance | OK | OK | OK | × |
| Bending modulus, GPa | 27 | 28 | 28 | 29 |
| CTE, ppm/ DEG C | 15 | 10.5 | 15 | 10.5 |
| Anti-flammability | V-0 | V-0 | V-0 | V-1 |
The result as shown in Tables 1 and 2 compares it is found that epoxy resin (B) and tool ought be chosen within the scope of the invention
When having cyanate ester resin (A) of formula (I) structure, the available cyanate resin composition with excellent properties uses the cyanogen
Metal-clad laminate made from acid ester resin composition have good heat resistance, humidity resistance, mechanical property, anti-flammability and
Reliability, low in-plane thermal expansion coefficient, the baseplate material suitable for production high density printed circuit board.
In conclusion cyanate resin composition of the present invention and using its prepreg obtained, laminate with
Metal-clad laminate has good heat resistance, humidity resistance, mechanical property (for example, bending modulus), anti-flammability and reliable
Property, low in-plane thermal expansion coefficient, the baseplate material suitable for production high density printed circuit board.
Embodiment of the present invention is only the description carried out to the preferred embodiment of the present invention, not to the present invention
Conception and scope be defined, under the premise of not departing from design philosophy of the present invention, in this field engineers and technicians to this
The all variations and modifications that the technical solution of invention is made, should all fall into protection scope of the present invention, and the present invention is claimed
Technology contents are all described in the claims.
Claims (14)
1. a kind of cyanate resin composition, the cyanate resin composition includes:
The cyanate ester resin (A) indicated by following formula (I):
Wherein, R is the arlydene with 6-18 carbon atom, R1、R2It is each independently hydrogen atom, with 1-6 carbon atom
Alkyl, the aryl with 6-18 carbon atom or the aralkyl with 7-19 carbon atom；And n is integer of 1 to 20；And
Epoxy resin (B).
2. cyanate resin composition according to claim 1, the integer that wherein n is 1 to 15, and n is preferably 1 to 10
Integer.
3. cyanate resin composition according to claim 1, wherein R is phenylene, naphthylene or biphenylene, and
R is preferably phenylene；R1、R2It is each independently hydrogen atom or methyl, and R1、R2Preferably hydrogen atom.
4. cyanate resin composition according to claim 1, wherein the cyanate ester resin (A) has following formula (I ')
Shown in structure:
Wherein defined in R and n such as claim 1.
5. cyanate resin composition according to claim 1, wherein the cyanate ester resin (A) accounts for cyanate ester resin
, and more preferably 30-70 weight % (A) and the 10-90 weight % of the total weight of epoxy resin (B), preferably 20-80 weight %.
6. cyanate resin composition according to claim 1, wherein the epoxy resin (B), which is selected from, contains at least two
The epoxy resin of epoxy group.
7. cyanate resin composition according to claim 1, wherein the cyanate resin composition also includes Malaysia
Imide compound (C).
8. cyanate resin composition according to claim 7, wherein with the cyanate ester resin (A) and maleimide
The total weight of compound (C) is 100 parts by weight meters, and the amount of the maleimide compound (C) is 5~80 parts by weight, preferably
10~70 parts by weight.
9. cyanate resin composition according to claim 1 or claim 7, wherein the cyanate resin composition also includes nothing
Machine filler (D).
10. cyanate resin composition according to claim 9, wherein with the cyanate ester resin (A) and epoxy resin
(B) total weight is for 100 parts by weight or with the cyanate ester resin (A), epoxy resin (B) and maleimide compound (C)
Total weight be 100 parts by weight meters, the amount of the inorganic filler (D) is 10~300 parts by weight, preferably 30~270 parts by weight, more
It is preferred that 50~250 parts by weight.
11. a kind of prepreg, the prepreg include substrate and by impregnation adhere to after dry on substrate according to claim
Cyanate resin composition described in any one of 1-10.
12. a kind of laminate, the laminate includes an at least prepreg according to claim 11.
13. a kind of metal-clad laminate, the metal-clad laminate includes at least one according to claim 11
Prepreg and the metal foil for being overlying on the prepreg one or both sides.
14. a kind of printed wiring board, the printed wiring board includes an at least prepreg according to claim 11.
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| JP2014012763A (en) * | 2012-07-04 | 2014-01-23 | Ajinomoto Co Inc | Resin composition |
| CN107207855A (en) * | 2015-03-31 | 2017-09-26 | 三菱瓦斯化学株式会社 | Resin composition for printed circuit board, prepreg, resin compounded piece and clad with metal foil plywood |
| CN107406582A (en) * | 2015-03-31 | 2017-11-28 | 三菱瓦斯化学株式会社 | Cyanate esters, include the hardening resin composition of the compound and its solidfied material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014012763A (en) * | 2012-07-04 | 2014-01-23 | Ajinomoto Co Inc | Resin composition |
| CN107207855A (en) * | 2015-03-31 | 2017-09-26 | 三菱瓦斯化学株式会社 | Resin composition for printed circuit board, prepreg, resin compounded piece and clad with metal foil plywood |
| CN107406582A (en) * | 2015-03-31 | 2017-11-28 | 三菱瓦斯化学株式会社 | Cyanate esters, include the hardening resin composition of the compound and its solidfied material |
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