CN101643572B - Thermosetting resin composition and prepreg and laminate for printed circuits thereby - Google Patents
Thermosetting resin composition and prepreg and laminate for printed circuits thereby Download PDFInfo
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- CN101643572B CN101643572B CN2009101897314A CN200910189731A CN101643572B CN 101643572 B CN101643572 B CN 101643572B CN 2009101897314 A CN2009101897314 A CN 2009101897314A CN 200910189731 A CN200910189731 A CN 200910189731A CN 101643572 B CN101643572 B CN 101643572B
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Abstract
The invention relates to a thermosetting resin composition and a prepreg and a laminate for printed circuits thereby. The thermosetting resin composition comprises at least an epoxy resin of the structural formula (I) and a cyanate resin. The thermosetting resin composition of the invention has high heat resistance, low dielectric constant and low dielectric dissipation factors, thus being used for manufacturing the resin sheets, resin composition copper foils, the prepregs, the laminate and the printed circuit boards. R is: n and m are natural numbers.
Description
Technical field
The present invention relates to a kind of resin combination, relate in particular to and contain a kind of compositions of thermosetting resin and with its prepreg of making and laminate for printed circuits.
Background technology
The existing material that is used for tellite, the Resins, epoxy of widely-used adhesion properties excellence.Resins, epoxy is to contain two or more epoxide groups in the general reference molecule, with organic compound such as aliphatics, alicyclic or aromatic series is skeleton, and can react the general name of the compound that generates three-dimensional netted cured article by epoxide group in the presence of suitable chemical reagent (solidifying agent).It is one of kind important in the thermoset macromolecule material.Resins, epoxy is owing to have good chemical stability, electrical insulating property, erosion resistance, cohesiveness and physical strength thereby be widely used in fields such as tackiness agent, coating, veneer sheet, moulding material, cast material, tellite.
In recent years, along with the development of computer and information communication device high performance, multifunction and networking, for high-speed transfer and processing large vol information, operation signal trends towards high frequencyization, thereby the material of circuit substrate has been proposed requirement.These requirements comprise: 1, excellent dielectric properties (promptly low specific inductivity and low medium consumption factor), and can under the temperature of relative broad range and frequency condition, keep stable; 2, can anti-PCB course of processing soda acid, high temperature and high humidity environment impact and the moisture absorption does not take place expand so that the layering explosion; 3, processing and the mounting process requirement under the adaptation high temperature.More than requiring needs Resins, epoxy to guarantee lower water-intake rate, lower polarity in high humidity environment.
Yet, general specific inductivity of common Resins, epoxy circuit substrate (FR-4 copper-clad plate) and dielectric loss angle tangent higher (specific inductivity 4.4, dielectric loss angle tangent about 0.02), high frequency characteristics is insufficient, requirement that can not the adaptation signal high frequencyization.Can satisfy service requirements as much as possible after making epoxy resin cure, the researchist in present technique field adopts low polar solidifying agent such as Zelan 338 (SMA) or adopts the low resin (as cyanate) of polarity that Resins, epoxy is carried out modification and promotes its high-frequency dielectric performance thermotolerance.Below further inquire into regard to these achievements in research.
Belgian patent has disclosed a composition epoxy resin that uses styrene-maleic anhydride copolymer (SMA, the structural formula of See Figure) as epoxy resin cross-linking agent for No. 627887.The shortcoming of this composition epoxy resin is the low and poor heat stability of their second-order transition temperature, makes in its base material copper-clad plate that is not suitable for being applied in printed circuit board (pcb) to use.
United States Patent (USP) uses for No. 6509414 phenylethylene/maleic anhydride copolymer, Resins, epoxy and tetrabromo-bisphenol to make copper-clad plate.Though this patent cooperates with phenylethylene/maleic anhydride copolymer by adopting dihydroxyphenyl propane or tetrabromo-bisphenol, form mixed curing agent and overcome single low and poor heat stability shortcoming of second-order transition temperature of making the epoxy curing agent existence of phenylethylene/maleic anhydride copolymer.But because there are two hydroxyls that polarity is very big in the tetrabromo-bisphenol molecular structure, the introducing of tetrabromo-bisphenol but to a certain extent deterioration the dielectric properties of system; Simultaneously the tetrabromo-bisphenol monomer easily in system crystallization separate out make veneer sheet make and application process in have hidden danger.
The copper-clad plate composition that United States Patent (USP) uses bifunctional cyanate and autopolymer, styrene-maleic anhydride and derivative, Resins, epoxy etc. to make a kind of low-k and the low-dielectric loss factor No. 6667107.Though this copper-clad plate composition adopts cyanate ester resin and styrene-maleic anhydride and the shared second-order transition temperature that improves epoxy-resin systems of derivative thereof, and has good high-frequency dielectric performance, but exist anhydride group in the molecular structure of the Zelan 338 that uses in this system, this anhydride group can generate thermostability and the bad carboxylic group of humidity resistance; Be used with the bad cyanate of original humidity resistance again, can make humidity resistance deterioration more.Though improved wet-hot aging performance to a certain extent by adding Resins, epoxy, improve limitedly, can not fundamentally eliminate, in PCB making processes, sheet material is subjected to the etch of moisture easily and the layering plate bursting takes place like this, and product percent of pass is very low.
In addition, in above technical scheme, all be to adopt styrene-maleic anhydride and derivative thereof to come composition epoxy resin is improved as solidifying agent, make to diminish, also make to be subjected to limitation in the modification that promotes aspect dielectric properties and the humidity resistance as the Resins, epoxy of main ingredient in the system choice to solidifying agent.
Summary of the invention
The object of the present invention is to provide a kind of novel composition epoxy resin that contains low polarity vinylbenzene structure, this resin combination is compared with the maleic anhydride styrol copolymer that tradition adopts, and has better thermostability and humidity resistance.
Another object of the present invention is to provide a kind of prepreg made from compositions of thermosetting resin, it has low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder, wet fastness, and good characteristics of humidity resistance.。
Another purpose of the present invention is to provide a kind of laminate for printed circuits made from compositions of thermosetting resin, and it has low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder, wet fastness, and good characteristics of humidity resistance.
To achieve these goals, the invention provides a kind of compositions of thermosetting resin, it comprises, and to have a kind of component at least be the Resins, epoxy of structural formula (I), and cyanate ester resin;
Wherein R is:
N and m are natural number, m/n=0.8～19.
The present invention also provides the prepreg of the described compositions of thermosetting resin preparation of a kind of usefulness, comprises that base-material reaches by the impregnation drying afterwards attached to the compositions of thermosetting resin on the base-material.
The present invention also comprises the laminate for printed circuits that the described compositions of thermosetting resin of a kind of usefulness is made, comprise the prepreg that several are superimposed, and be located at the tinsel of the single or double of the prepreg after superimposed, each prepreg comprise base-material and by the impregnation drying afterwards attached to the compositions of thermosetting resin on the base-material.
The invention has the beneficial effects as follows: composition epoxy resin of the present invention is because contain the low vinylbenzene structure of polarity in the molecular structure, therefore the dielectric properties of this resin have obtained optimization, specific inductivity is compared with general Resins, epoxy with dielectric loss angle tangent, the reduction that has obtained, along with the increase of styrene units content in the structure, specific inductivity and dielectric loss angle tangent are littler.In addition, this resin combination is compared with the maleic anhydride styrol copolymer that tradition adopts, and has better thermostability and humidity resistance.The Resins, epoxy of composition epoxy resin kind of the present invention can use separately, perhaps mix and use with other Resins, epoxy, it has low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder, wet fastness, humidity resistance and and the cohesiveness of Copper Foil characteristics preferably; This resin combination is coated in preimpregnation sheet material that obtains on the base material and the veneer sheet of making by this preimpregnation sheet material of lamination, it has low-k, the low-dielectric loss factor simultaneously, thermotolerance, anti-immersed solder, wet fastness, humidity resistance and and the cohesiveness of Copper Foil characteristics preferably, can be used as the electronic machine printed circuit board.
Embodiment
The invention provides a kind of compositions of thermosetting resin, it comprises, and to have a kind of component at least be the Resins, epoxy of structural formula (I), and cyanate ester resin,
Wherein R is:
N and m are natural number.
The multi-group epoxy compound who contains low polarity vinylbenzene structure among the present invention is to use a kind of polyphenolic substance and epihalohydrin, and reaction obtains under inert atmosphere.
The polyphenolic substance that is used for making the Resins, epoxy that contains low polarity vinylbenzene structure among the present invention contains low polar vinylbenzene structure in structure, polyphenolic substance among the present invention is a kind of unsaturated phenol and cinnamic multipolymer, and this unsaturated phenol is para hydroxybenzene ethene.Para hydroxybenzene ethylene/styrene multipolymer can be synthetic by known method, as JP61-275307, DongJin Woo, and Polymer47 (2006): 3287-3291, JungKi Kim, Polymer47 (2006): the method described in the 5799-5809.The para hydroxybenzene ethylene/styrene multipolymer that uses among the present invention has following structure, wherein m/n=0.8～19.
Preferred Epicholorohydrin of the epihalohydrin that uses among the present invention and table bromhydrin are preferably Epicholorohydrin again, and the inert atmosphere that uses is nitrogen.
The method that a kind of the present invention of preparation contains the Resins, epoxy of low polarity vinylbenzene structure is to adopt single stage method, promptly the mixture thing of para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin directly under the effect of alkali condensation obtain Resins, epoxy.Its concrete steps are: organic solvent, para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin are mixed; para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin feed intake by 1: 1～20 mol ratio; under protection of inert gas 50-150 ℃ of reacting by heating 1～5 hour; the while dripping alkali liquid; the mol ratio of alkali lye and para hydroxybenzene ethylene/styrene multipolymer is 1～2: 1; after reaction finishes through filtering; washing removes freshen; excess epichlorohydrin is removed in underpressure distillation, obtains containing the polyfunctional epoxy resin of low polarity vinylbenzene structure at last.
Use therein alkali lye can adopt sodium hydroxide, potassium hydroxide etc., and used alkali lye is preferably selected denseer solution for use, and preferred concentration is between 20-50wt%.
The mol ratio of para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin is preferably 1: 2-15.
Representative examples of organic comprises ketone such as methyl ethyl ketone and methyl iso-butyl ketone (MIBK), hydro carbons such as toluene and dimethylbenzene, alcohols such as methyl alcohol, ethanol, primary alconol, cellosolve such as methylcyclohexane and ethyl cellosolve, ethers such as diox and diethoxyethane, dimethyl sulfoxide (DMSO) and dimethyl formamide.
The method that contains the polyfunctional epoxy resin of low polarity vinylbenzene structure among another kind of preparation the present invention is to adopt two step method, i.e. first etherificate under the effect of catalyzer with para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin, closed loop obtains Resins, epoxy under the effect of alkali lye then, specifically comprises following steps:
1, under the inert nitrogen gas protection; in para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin, add catalyzer; carried out etherification reaction 1～5 hour 50-120 ℃ of heating, wherein para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin mol ratio are: 1: 1～20.
2, etherification reaction finishes back dropping alkaline solution and carries out ring-closure reaction, reacted 1～5 hour down at 80-120 ℃, the add-on of alkali lye is that para hydroxybenzene ethylene/styrene multipolymer is 1～2: 1 in molar ratio, after reaction finishes through filtering, washing removes freshen, excessive Epicholorohydrin is removed in underpressure distillation, obtains containing the polyfunctional epoxy resin of low polarity vinylbenzene structure at last.
Wherein in the step 1 mol ratio of para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin between 1: 1～20, preferred 1: 2-15.
Catalyzer can use choline and salt, triphenyl phosphorus hydrochlorate, ammonium salt etc.Ammonium salt can be selected from 4 bromide, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, cetyl trimethylammonium bromide, tetraethylammonium bromide etc.
Use therein alkali lye can adopt sodium hydroxide, and used alkali lye such as potassium hydroxide is preferably selected denseer solution for use, and preferred concentration is between 20-50wt%.
More than the reaction chemical equation be expressed as follows:
Wherein
R：
X:Br or Cl or I or F
The structural formula (I) of the Resins, epoxy that contains low polarity vinylbenzene structure in the final synthetic compositions of thermosetting resin of the present invention.
The number-average molecular weight (Wn) of the Resins, epoxy of structural formula among the present invention (I) is between 1000-50000.Number-average molecular weight is by using tetrahydrofuran (THF) as moving phase, is the gel permeation chromatography of stationary phase with polystyrene standard.
Resins, epoxy shown in the structural formula of the present invention (I) is because contain the low vinylbenzene structure of polarity in the molecular structure, therefore the dielectric properties of this resin have obtained optimization, specific inductivity is compared with general Resins, epoxy with dielectric loss angle tangent, the reduction that has obtained, along with the increase of styrene units content in the structure, specific inductivity and dielectric loss angle tangent are littler.In addition, this resin is compared with the maleic anhydride styrol copolymer that contrast is adopted in the patent, has better thermostability and humidity resistance.
Also comprise cyanate ester resin in the compositions of thermosetting resin of the present invention.When the Resins, epoxy shown in the structural formula (I) and cyanate ester resin are used, can obtain excellent more dielectric properties and favorable manufacturability energy, thermotolerance, humidity resistance.
Among the present invention, object lesson as the cyanate esters that uses in the cyanate ester resin, for example 2, (4-cyanate ester based-3 for 2-two (cyanate ester based phenyl) propane, two (cyanate ester based phenyl) ethane, two (cyanate ester based phenyl) methane, two, the 5-3,5-dimethylphenyl) methane, 2, the cyanate of 2-two (the cyanate ester based phenyl of 4-) HFC-236fa, two (the cyanate ester based phenyl of 4-) thioether, phenol phenol aldehyde type cyanate, phenol and dicyclopentadiene multipolymer etc., can use one or more monomers and (or) their prepolymer mix to use.Consider the cohesiveness of second-order transition temperature, anti-immersed solder and Copper Foil and the balance of dielectric characteristics, the Resins, epoxy shown in the structural formula (I): cyanate=1: 0.1～10, note by weight..
In addition, as the example of ethylene rhodanate resin curing catalyzer, organic catalysts such as zinc naphthenate, manganese naphthenate, cobalt naphthenate, nickel naphthenate, etheric acid cobalt, ethanoyl venus crystals for example.In addition, as the example that solidifies cocatalyst, for example phenol, nonyl phenol and to polyphenol compounds such as single phenolic compound such as cumyl phenol, dihydroxyphenyl propane, phenol resol.As curing catalysts, from the angle of dielectric characteristics and thermotolerance and curing reaction speed and glue stability, preferred zinc naphthenate, manganese naphthenate, preferred again zinc naphthenate.The consumption of curing catalysts is 0.01～2.00 weight % with respect to cyanate ester resin.In addition, as solidifying cocatalyst, from the angle of thermotolerance and dielectric characteristics, preferred single phenolic compound is more preferably to cumyl phenol.The consumption of cocatalyst is expressed as 0.01～1.00 with respect to the cyanate equivalent of cyanate ester resin with the phenol hydroxyl equivalent.
When the Resins, epoxy shown in the structural formula (I) when and the Resins, epoxy of other type when being used, can obtain favorable manufacturability energy and thermotolerance.In addition, because the Resins, epoxy shown in the structural formula (I) has low polar vinylbenzene structure, the dielectric properties of hybrid resin system have been optimized.
Resins, epoxy as other type, it is included in the Resins, epoxy that has in 1 molecule resin more than two or more epoxide groups, bisphenol A type epoxy resin for example, bisphenol f type epoxy resin, biphenyl type epoxy resin, the naphthalene based epoxy resin, alicyclic based epoxy resin, Resorcinol type Resins, epoxy, polyethylene glycol type Resins, epoxy, trifunctional Resins, epoxy, the Resins, epoxy of four-functional group epoxy resin and phenol aldehyde type epoxy resin and other type, yet not only for therewith, the Resins, epoxy of above-mentioned other type can mix use more than a kind or 2 kinds again.
As the preferred embodiments of the present invention, that can enumerate has the Resins, epoxy shown in the following general formula:
Wherein R1 represents hydrogen atom, halogen atom or phenyl, and n comprises 0 integer,
Wherein X be-CH2-,-O-,-CO-,-SO2-,-S-,-CH (C6H5)-, C (C6H5) 2-, CH (CH3), C (CH3) 2 or chemical formula
Wherein R2 represent hydrogen atom, halogen atom, the alkyl of 1-8 linear, side chain or the alicyclic alkyl of ring-type arranged, alkoxyl group, the phenyl of a 1-10 carbon atom, n represents 0 to 20 integer.
Wherein R3 represent hydrogen atom, halogen atom, the alkyl of 1-8 linear, side chain or the alicyclic alkyl of ring-type arranged, alkoxyl group, the phenyl of a 1-10 carbon atom, n represents 0 to 20 integer.
Wherein R5 represent hydrogen atom, halogen atom, the alkyl of 1-8 linear, side chain or the alicyclic alkyl of ring-type arranged, alkoxyl group, the phenyl of a 1-10 carbon atom, n represents 0 to 20 integer.
Wherein R4 represents hydrogen atom, halogen atom or phenyl, and m comprises 0 integer.
As the Resins, epoxy of other types, can improve the wet fastness, thermotolerance of resin combination, particularly improve thermotolerance after the moisture absorption.Remember the Resins, epoxy shown in the structural formula (I): the Resins, epoxy of other type=1: 0.1～10 by weight.
Can use Resins, epoxy solidifying agent commonly used as curing agent for epoxy resin, for example bis-phenol, brominated bisphenol A, phenol, dihydroxy-benzene (as pyrocatechol, Resorcinol, Resorcinol), polyhydroxy phenol and resol, acid anhydrides, carboxylic acid, amine, siloxanes, polysiloxane and have-Ph-X-Ph-group (wherein X is CH2, C (CH3) 2, CH (CH3), O, S, C=O, SO2 etc.) or other contain can with the compound of epoxide group reaction, the use that can separately or cooperatively interact of these solidifying agent.
The specific examples of amine comprises: Dicyanodiamide, diaminodiphenylmethane (DDM), diaminodiphenylsulfone(DDS) (DDS), mphenylenediamine, diaminodiphenyl oxide (DDE), m-xylene diamine, p-diaminodiphenyl, quadrol, diethylenetriamine, isophorone diamine, 2,4,6-three (dimethylamino methyl) phenol (commodity are called DMP-30), 1,8-diaza-dicyclo [5.4.0] hendecene-7 (being called for short DBU) etc.
The specific examples of acid anhydrides comprises: Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl carbic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, chlorendic anhydride, MALEIC ANHYDRIDE, poly-nonane diacid acid anhydride, pyromellitic acid anhydride, trimellitic acid 1,2-anhydride etc.
Carboxylic acid comprises: phthalic acid, m-phthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydro-phthalic acid 4-hydroxy-benzoic acid, Whitfield's ointment, 1,3-dicarboxyl hexanaphthene etc.
Polyhydroxy phenol comprises: three (4-hydroxy phenyl) methane, three (4 hydroxy phenyl) ethane, three (4-hydroxy phenyl) propane, three (4-hydroxy phenyl) butane, three (3-methyl-4-hydroxy phenyl) methane, three (3,5-dimethyl-hydroxy phenyl) methane, four (4 hydroxy phenyl) ethane, four (3-methyl-4-hydroxy phenyl) ethane etc.
The specific examples of bis-phenol comprises: 2,6-dihydroxy naphthlene, 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) of 2-, 2-(3-hydroxy phenyl) 2-(4 '-hydroxy phenyl) propane, two (4-hydroxy phenyl) methane (Bisphenol F), two (4-hydroxy phenyl) sulfones (bisphenol S), two (4-hydroxy phenyl) methylcyclohexane etc.
The specific examples of resol comprises: phenol formaldehyde (PF) condenses, cresols phenolic condensation compound, benzoxazine colophony, bisphenol-A phenolic condenses, benzoxazine etc.
In the compositions of thermosetting resin of the present invention, depending on the circumstances or the needs of the situation add catalyzer in addition, catalyzer comprises tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt or imidazolium compoundss.The example of tertiary amine is: triethylamine, tributylamine, dimethyl amine ethanol, N, N-dimethyl-aminomethyl phenol, benzyl dimethyl amine etc.; The example of three grades of phosphines comprises: triphenylphosphine etc.; The example of quaternary ammonium salt comprises: 4 bromide, tetramethyl ammonium chloride, Tetramethylammonium iodide, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, cetyl trimethylammonium bromide etc.; The specific examples of quaternary alkylphosphonium salt comprises: 4-butyl phosphonium chloride, four butyl phosphonium bromides, four butyl phosphonium iodides, tetraphenyl phosphonium chloride, 4-phenyl phosphonium bromide, tetraphenyl phosphonium iodide, ethyl triphenyl phosphonium chloride, propyl group triphenyl phosphonium chloride, propyl group three phenyl phosphonium bromides, propyl group triphenyl phosphonium iodide, butyl triphenyl phosphonium chloride, butyl triphenyl phosphonium bromide, butyl triphenyl phosphonium iodide etc.; The glyoxaline compound example comprises: glyoxal ethyline, 2-ethyl-4 Methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, 1 benzyl 2 methyl imidazole, 2-heptadecyl imidazoles, 2 isopropyl imidazole, 2-phenyl-4-methylimidazole, 2-dodecyl imidazoles, 1-1-cyanoethyl-2-methylimidazole etc., above-mentioned catalyzer can be that single form or its mixture use.
According to the present invention as the example of fire retardant, two tetrabromo phthalimides, 1 of bromination phenolic resin, ethylene for example, 2-two (2,3,4,5,6-penta-bromophenyl) halogen fire retardant such as ethane, hexabromobenzene, brominated polycarbonate, the two phosphoric acid ester fire retardants such as (diphenyl phosphoesters) of triphenylphosphate and dihydroxyphenyl propane, inorganic combustion inhibitors such as red phosphorus, aluminium hydroxide, magnesium hydroxide and ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.
According to the present invention, the Resins, epoxy shown in the structural formula (I) can and polyphenylene oxide (PPO) resin be used, when being used, can obtain more excellent dielectric properties and favorable manufacturability energy, thermotolerance, humidity resistance with polyphenylene oxide resin.
Can also include filler in the compositions of thermosetting resin of the present invention, selected filler, what can mention is for example aluminium hydroxide of filler, magnesium hydroxide, kaolin, hydrotalcite, titanium oxide, Calucium Silicate powder, beryllium oxide, boron nitride, glass powder or silicon powder, zinc borate, the aluminium nitrogen compound, silicon nitride, silicon carbide, magnesium oxide, zirconium white, mullite, titanium dioxide, barium titanate, strontium titanate, strontium-barium titanate, potassium titanate, hollow glass microbead, polytetrafluorethylepowder powder, the polystyrene powder, powder and silicon carbide such as polyphenylene oxide, silicon nitride, single crystal fibres such as aluminum oxide, staple glass fibre etc.Thermoplastics can comprise brominated Polystyrene, brominated polyphenylether, polyphenylene oxide, polystyrene, PES, polyethylene, polypropylene, polycarbonate, vibrin etc.Silicon powder can be spherical silica, fused silica, crystallinity silicon-dioxide.The interpolation of filler can be that one or more above mixing are used, and its usage quantity accounts for 0～60wt% in thermosetting resin combination composition.
According to the present invention, compositions of thermosetting resin also comprises solvent.The example of spendable solvent comprises ketone such as acetone, methyl ethyl ketone and methyl iso-butyl ketone (MIBK); Hydro carbons such as toluene and dimethylbenzene; Alcohols such as methyl alcohol, ethanol, primary alconol; Ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether; Ester class such as 1-Methoxy-2-propyl acetate, ethyl acetate; Aprotic solvent such as N, dinethylformamide, N, the N-diethylformamide, one or more in the above-mentioned solvent can mix use arbitrarily with another kind.
According to the present invention, the Resins, epoxy shown in the structural formula (I) uses separately, when perhaps using with other mixed with resin, also can comprise dyestuff, pigment, tensio-active agent, flow agent, UV light absorber.
The present invention also provides the prepreg of the described compositions of thermosetting resin preparation of a kind of usefulness, comprises that base-material reaches by the impregnation drying afterwards attached to the compositions of thermosetting resin on the base-material.
The present invention also comprises the laminate for printed circuits that the described compositions of thermosetting resin of a kind of usefulness is made, comprise the prepreg that several are superimposed, and be located at the tinsel of the single or double of the prepreg after superimposed, each prepreg comprise base-material and by the impregnation drying afterwards attached to the compositions of thermosetting resin on the base-material.In addition, resin combination of the present invention can also be used as and make resin sheet, resin complexes metal copper foil, veneer sheet, printed circuit board.
The method that composition epoxy resin of the present invention is made resin sheet is listed below, but the method for preparing resin sheet is not limited thereto.Above-mentioned composition epoxy resin is coated on the carrier film, and this carrier film can be polyester film or polyimide film, and thickness is at 5-150 μ m.Heated 10 seconds-30 minutes down at 100-250 ℃ then, form sheet material, formed resin sheet thickness is at 5-100 μ m.
The method that composition epoxy resin of the present invention is made resin laminated metal Copper Foil (RCC) is listed below, yet the method for making the resin laminated metal Copper Foil is not limited only to this, as tinsel, can use copper, brass, aluminium, nickel, and the alloy of these metals or composite metallic material, the thickness of tinsel is at 5-150 μ m, by manual or mechanical roll-on device described composition epoxy resin glue is coated on the above-mentioned tinsel, the tinsel that then this is coated with composition epoxy resin is carried out heat drying, make composition epoxy resin be in semi-cured state (B-Stage), Heating temperature herein is at 100-250 ℃, be 10 seconds-30 minutes heat-up time, the resin layer thickness of the resin laminated metal of Xing Chenging is at 1-150 μ m at last, and this resin complexes metal copper foil can be used as the internal layer of printed circuit board or outer and printed circuit board is increased layer.
The method of using composition epoxy resin of the present invention to make prepreg (prepreg) is listed below, yet the method for making prepreg is not limited only to this.Composition epoxy resin glue (having used the solvent adjustment viscosity herein) is immersed on the strongthener, and the preliminary-dip piece that is impregnated with composition epoxy resin carried out heat drying, make the composition epoxy resin in the preliminary-dip piece be in the semicure stage (B-Stage), can obtain prepreg.The strongthener that wherein uses can be inorganic or organic materials.Specifiable woven fabric or non-woven fabrics or the paper that glass fibre, carbon fiber, boron fibre, metal etc. are arranged of inorganic materials.Glasscloth wherein or non-woven fabrics can make E-glass, Q type cloth, NE cloth, D type cloth, S type cloth, high silica cloth etc.Weaving cotton cloth or non-woven fabrics or paper of manufacturings such as organic fibre such as polyester, polyamine, polyacrylic acid, polyimide, aramid fiber, tetrafluoroethylene, syndiotactic polystyrene.Yet strongthener is not limited thereto.Specifiable Heating temperature to preliminary-dip piece is 80-250 ℃, and the time is 1-30 minute.Resin content in the prepreg is between 25-70%.
Veneer sheet, copper-clad laminate, printed circuit board can use above-mentioned resin sheet, resin laminated metal paper tinsel and prepreg to make.With the copper-clad laminate is that example illustrates this production method, but is not limited only to this.When using prepreg to make copper-clad laminate, one or more prepregs are cut into certain size carry out sending into behind the lamination and carry out lamination in the laminating apparatus.Simultaneously tinsel is placed on the one or both sides of prepreg, the semicure compacting is formed metal-clad laminate by hot-forming.Can use the alloy or the composite metallic material of copper, brass, aluminium, nickel and these metals as tinsel.As the pressing conditions of veneer sheet, should select suitable lamination condition of cure according to the practical situation of composition epoxy resin.If pressing pressure is low excessively, can make to have the space in the veneer sheet, its electrical property can descend; Lamination pressure is crossed conference and is made and have too much internal stress in the veneer sheet, makes the dimensional stability of veneer sheet descend, and these all need to come pressed sheet to reach required requirement by the suitable pressure that satisfies molding.Common governing principle for the neutralizing layer pressing plate of routine is, laminating temperature is at 130～250 ℃, pressure: 3-50kgf/cm2, hot pressing time: 60-240 minute.Can use resin sheet, resin laminated metal paper tinsel, prepreg, metal-coated laminated board by addition or subtract layer legal system and make printed circuit board or complicated multilayer circuit board.
Composition epoxy resin of the present invention is made resin sheet, resin complexes metal copper foil, prepreg, veneer sheet, copper-clad laminate, the printed circuit board except being used as, also can be used for being used for making sizing agent, coating, also can be used for building, aviation, boats and ships, automotive industry.
Following examples explanation each embodiment of the present invention.Yet these embodiment also do not limit the present invention in any way.Embodiment is as follows.
Synthesis example 1:
Para hydroxybenzene ethylene/styrene multipolymer, Epicholorohydrin He diox are mixed, and para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin feed intake by 1: 5 mol ratio.Diox is a para hydroxybenzene ethylene/styrene multipolymer weight ratio 1.89.It is synthetic that para hydroxybenzene ethylene/styrene multipolymer is pressed currently known methods, and Wn is 4300.Said mixture heats under nitrogen protection; Heating temperature is at 80 degree; and constantly stir; while dropping sodium solution; the concentration of used sodium hydroxide solution is 25wt%, and the mol ratio of sodium hydroxide and para hydroxybenzene ethylene/styrene multipolymer is 2/1, and alkali lye dropwised in 3 hours; moisture in reaction process in the system and Epicholorohydrin azeotropic are constantly told from system, and the Epicholorohydrin after the layering returns system.Excessive Epicholorohydrin and diox are removed in underpressure distillation, add mibk in residuum, by washing and removing by filter salinity, then make to be washed with water to neutrality, obtain Resins, epoxy (1).The Wn of Resins, epoxy (1) is 4900.
Synthesis example 2:
Para hydroxybenzene ethylene/styrene multipolymer, Epicholorohydrin and toluene are mixed, and para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin feed intake by 1: 10 mol ratio.Diox is that para hydroxybenzene ethylene/styrene multipolymer weight ratio is 1.89.It is synthetic that para hydroxybenzene ethylene/styrene multipolymer is pressed currently known methods, and Wn is 30000.Said mixture heats under nitrogen protection; Heating temperature is at 100 degree; and constantly stir; while dropping sodium solution; the concentration of used sodium hydroxide solution is 25wt%, and the mol ratio of sodium hydroxide and para hydroxybenzene ethylene/styrene multipolymer is 2/1, and alkali lye dropwised in 2 hours; moisture in reaction process in the system and Epicholorohydrin azeotropic are constantly told from system, and the Epicholorohydrin after the layering returns system.Excessive Epicholorohydrin and toluene are removed in underpressure distillation, add mibk in residuum, by washing and removing by filter salinity, then make to be washed with water to neutrality, obtain Resins, epoxy (2).The Wn of Resins, epoxy (2) is 34000.
Synthesis example 3:
With para hydroxybenzene ethylene/styrene multipolymer; Epicholorohydrin and tetraethylammonium bromide are added in the four-hole boiling flask together; para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin feed intake by 1: 8 mol ratio; the tetraethylammonium bromide consumption is 0.5% (mol ratio) of para hydroxybenzene ethylene/styrene multipolymer; it is synthetic that para hydroxybenzene ethylene/styrene multipolymer is pressed currently known methods; Wn is that 20000 said mixtures heat under nitrogen protection; Heating temperature is 90 degree; reacted 3 hours; the sodium hydroxide solution that etherification reaction finishes back dropping 40wt% carries out the ring-closure reaction temperature of reaction in 110 degree, 3 hours reaction times.Reacted after-filtration, washing removes freshen, and excessive Epicholorohydrin is removed in underpressure distillation, obtains Resins, epoxy (3) at last.The Wn of Resins, epoxy (3) is 22000.
Synthesis example 4:
Add para hydroxybenzene ethylene/styrene multipolymer, Epicholorohydrin and benzyltriethylammoinium chloride in the four-hole boiling flask together, para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin feed intake by 1: 12 mol ratio, the benzyltriethylammoinium chloride consumption is 1% (mol ratio) of para hydroxybenzene ethylene/styrene multipolymer, it is synthetic that para hydroxybenzene ethylene/styrene multipolymer is pressed currently known methods, and Wn is 8500.Said mixture heats under nitrogen protection, and Heating temperature is 100 degree, reacts 2 hours, and the sodium hydroxide solution that etherification reaction finishes back dropping 40wt% carries out the ring-closure reaction temperature of reaction in 110 degree, 3 hours reaction times.Reacted after-filtration, washing removes freshen, and excessive Epicholorohydrin is removed in underpressure distillation, obtains Resins, epoxy (3) at last.The Wn of Resins, epoxy (3) is 10000.
Embodiment (1～4):
The Resins, epoxy of gained among the synthesis example 1-4 is prepared the glue shown in the table one, use 2116 type electronic-grade glass fully to soak in this glue, and in 155 degree baking ovens, remove and desolvate, obtain the prepreg sample of B-stage.
The electrolytic copper foil of eight prepregs and two one ounce is superimposed together, carries out lamination by thermocompressor and obtain doublesided copperclad laminate.Lamination is as follows: 1, material temperature when 80-120 spends, heat-up rate be controlled at the 1.0-3.0 degree/minute; 2, pressure is set to 20kg/cm2; 3, solidification value is spent 190, and keeps this temperature 90 minutes.Respective performances sees Table one.
Comparative Examples 1:
Use 40 parts, 60 parts N690 of SMA3000 Zelan 338 and be aided with catalyzer 2-MI, use MEK120 part that above-claimed cpd is dissolved, and be modulated into the glue of appropriate viscosity.Use 2116 type electronic-grade woven fiber glass to soak into this glue, and in 155 degree baking ovens, remove and desolvate, obtain the prepreg sample of B-stage.
The electrolytic copper foil of eight prepregs and two one ounce is superimposed together, carries out lamination by thermocompressor and obtain doublesided copperclad laminate.Lamination is as follows: 1, material temperature when 80-120 spends, heat-up rate be controlled at the 1.0-3.0 degree/minute; 2, pressure is set to 20kg/cm2; 3, solidification value is spent 190, and keeps this temperature 90 minutes.Respective performances sees Table one.
Comparative Examples 2
Use 40 parts, 60 parts DER530 of SMA4000 Zelan 338 and be aided with catalyzer 2-MI, use MEK100 part that above-claimed cpd is dissolved, and be modulated into the glue of appropriate viscosity.Use 2116 type electronic-grade woven fiber glass to soak into this glue, and in 155 degree baking ovens, remove and desolvate, obtain the prepreg sample of B-stage.
The electrolytic copper foil of eight prepregs and two one ounce is superimposed together, carries out lamination by thermocompressor and obtain doublesided copperclad laminate.Lamination is identical with Comparative Examples 1, and respective performances sees Table one.
Comparative Examples 3
Use SMA3000 50 parts, 50 parts HF-1 of Zelan 338 (cyanate) and be aided with the catalyzer zinc naphthenate, use MEK90 part that above-claimed cpd is dissolved, and be modulated into the glue of appropriate viscosity.Use 2116 type electronic-grade woven fiber glass to soak into this glue, and in 155 degree baking ovens, remove and desolvate, obtain the prepreg sample of B-stage.
The electrolytic copper foil of eight prepregs and two one ounce is superimposed together, carries out lamination by thermocompressor and obtain doublesided copperclad laminate.Lamination sees Table one with Comparative Examples 1 identical respective performances.
Table one
Annotate 1:
1, each component is all remembered with the solids content weight part in the table one
2, DER530 is the bisphenol A-type bromination bifunctional Resins, epoxy of DOW
3, N695 is the adjacent sylvan formaldehyde epoxy resin of DIC
4, HP7200 is the dicyclopentadiene Resins, epoxy of DIC
5, PSM4357 is the resol of Japan group Rong Huaxue
6, SMA3000 is the Zelan 338 of Sartomer
7, HF-1: be the bisphenol A-type bifunctional cyanate of intelligent peak scientific ﹠ trading Co., Ltd.
Annotate 2:
1, second-order transition temperature (Tg): use the DSC test, measure according to the DSC testing method of IPC-TM-650 2.4.25 defined.
2, stripping strength is tested according to " after the thermal stresses " experiment condition in the IPC-TM-6502.4.8 method
3, specific inductivity and dielectric loss factor: according to the method test of IPC-TM-6502.5.5.9 defined
4, the evaluation of anti-immersed solder: it is to take out after 20 seconds in 288 ℃ the tin stove to be cooled to room temperature that copper-clad laminate is immersed in temperature, and then is impregnated in the tin stove 5 times repeatedly, by observing the anti-immersed solder of ocular estimate,
5, measuring water absorption: copper-clad laminate is immersed in the copper etchant solution, removes surperficial Copper Foil and estimate substrate.Substrate is placed in the pressure cooker, and at 121 ℃, 2atm handled down after 2 hours, measured the water-intake rate of substrate.
6, anti-immersed solder evaluation behind the PCT: copper-clad laminate is immersed in the copper etchant solution, removes surperficial Copper Foil and estimate substrate.Substrate is placed in the pressure cooker, and at 121 ℃, 2atm handles after 2 hours down, is immersed in temperature and is in 288 ℃ the tin stove, when base material occurs bubbling or writes down the corresponding time during division.Appearance foaming or layering can finish to estimate when base material surpasses 5 minutes also in the tin stove.
As can be seen from Table I, embodiments of the invention, low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder, wet fastness, humidity resistance and and the cohesiveness of Copper Foil all good.On the other hand, the low-k of comparative example, the low-dielectric loss factor, thermotolerance, anti-immersed solder, wet fastness, humidity resistance and and the cohesiveness of Copper Foil all bad.
Resins, epoxy shown in the structural formula of the present invention (I) uses separately, the resin combination that forms when perhaps using with other mixed with resin, low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder, wet fastness, humidity resistance and and the cohesiveness of Copper Foil all good.This resin combination is coated in preimpregnation sheet material that obtains on the base material and the veneer sheet of making by this preimpregnation sheet material of lamination, low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder, wet fastness, humidity resistance and and the cohesiveness of Copper Foil all good, can be used as the electronic machine printed circuit board.
In sum, composition epoxy resin of the present invention is because contain the low vinylbenzene structure of polarity in the molecular structure, therefore the dielectric properties of this resin have obtained optimization, specific inductivity is compared with general Resins, epoxy with dielectric loss angle tangent, the reduction that has obtained, along with the increase of styrene units content in the structure, specific inductivity and dielectric loss angle tangent are littler.In addition, this resin combination is compared with the maleic anhydride styrol copolymer that tradition adopts, and has better thermostability and humidity resistance.The Resins, epoxy of composition epoxy resin kind of the present invention can use separately, perhaps mix and use with other Resins, epoxy, it has low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder, wet fastness, humidity resistance and and the cohesiveness of Copper Foil characteristics preferably; This resin combination is coated in preimpregnation sheet material that obtains on the base material and the veneer sheet of making by this preimpregnation sheet material of lamination, it has low-k, the low-dielectric loss factor simultaneously, thermotolerance, anti-immersed solder, wet fastness, humidity resistance and and the cohesiveness of Copper Foil characteristics preferably, can be used as the electronic machine printed circuit board.
The above; it only is preferred embodiment of the present invention; for the person of ordinary skill of the art, can make other various corresponding changes and distortion, and all these changes and distortion all should belong to the protection domain of claim of the present invention according to technical scheme of the present invention and technical conceive.
Claims (7)
1. compositions of thermosetting resin is characterized in that: comprise:
Having a kind of component at least is the Resins, epoxy of structural formula (I); And
Cyanate ester resin;
Wherein
R：
N and m are natural number;
Structural unit m/n=0.8～19 in the Resins, epoxy of structural formula (I), the number-average molecular weight of the Resins, epoxy of this structural formula (I) is between 1000-50000; The Resins, epoxy of structural formula (I): cyanate ester resin=1: 0.1～10, remember with weight.
2. compositions of thermosetting resin as claimed in claim 1 is characterized in that, the Resins, epoxy of structural formula (I) is finished by the following formula reaction by 1mol para hydroxybenzene ethylene/styrene multipolymer and 2～15mol epihalohydrin:
Wherein
R is:
X is: Br or Cl or I or F.
3. compositions of thermosetting resin as claimed in claim 1, it is characterized in that, the Resins, epoxy of structural formula (I) uses separately or uses the Resins, epoxy of structural formula (I) with the Resins, epoxy mixing of other types: the Resins, epoxy of other type=1: 0.1～10, remember with weight.
4. compositions of thermosetting resin as claimed in claim 3, it is characterized in that, the Resins, epoxy of described other type is the Resins, epoxy that has two above epoxide groups in 1 the molecule Resins, epoxy, and it comprises at least a in bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin, naphthalene based epoxy resin, alicyclic based epoxy resin, Resorcinol type Resins, epoxy, polyethylene glycol type Resins, epoxy, trifunctional Resins, epoxy, isocyanate-based Resins, epoxy, four-functional group epoxy resin or the phenol aldehyde type epoxy resin.
5. compositions of thermosetting resin as claimed in claim 1 is characterized in that, described cyanate ester resin comprises having 2 cyanate ester based cyanate ester resins in 1 molecule at least, contains triazine ring structure in this cyanate ester resin.
6. the prepreg with the described compositions of thermosetting resin preparation of claim 1 is characterized in that, comprises that base-material reaches by the impregnation drying afterwards attached to the compositions of thermosetting resin on the base-material.
7. laminate for printed circuits made from the described compositions of thermosetting resin of claim 1, it is characterized in that, comprise the prepreg that several are superimposed, and be located at the tinsel of the single or double of the prepreg after superimposed, each prepreg comprise base-material and by the impregnation drying afterwards attached to the compositions of thermosetting resin on the base-material.
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| CN101967264A (en) * | 2010-08-31 | 2011-02-09 | 广东生益科技股份有限公司 | Epoxy resin composition and high frequency circuit board made of same |
| KR101730283B1 (en) | 2012-10-31 | 2017-04-25 | 셍기 테크놀로지 코. 엘티디. | Thermosetting resin composition and use thereof |
| CN103265810B (en) * | 2013-05-29 | 2015-09-23 | 苏州生益科技有限公司 | A kind of resin combination for high-frequency high-speed substrate and use its prepreg made and veneer sheet |
| KR101738291B1 (en) * | 2013-05-30 | 2017-05-19 | 셍기 테크놀로지 코. 엘티디. | Cyanate resin composition and application thereof |
| WO2014190529A1 (en) * | 2013-05-30 | 2014-12-04 | 广东生益科技股份有限公司 | Cyanate resin composition and application thereof |
| CN105219255B (en) * | 2015-11-11 | 2018-03-09 | 江苏和成新材料有限公司 | A kind of low-dielectric loss black matt coating and preparation method and application |
| CN105238314B (en) * | 2015-11-13 | 2017-11-07 | 深圳先进技术研究院 | A kind of wet-heat resisting high reliability epoxy conductive silver glue and preparation method and application |
| CN105968722A (en) * | 2016-06-23 | 2016-09-28 | 安徽酷米智能科技有限公司 | Modified epoxy resin for thermal-resistant anti-impact circuit wiring board |
| WO2019065455A1 (en) * | 2017-09-29 | 2019-04-04 | 三井化学株式会社 | Image display device sealing material and image display device sealing sheet |
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