CN101643571B - 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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- CN101643571B CN101643571B CN200910189730XA CN200910189730A CN101643571B CN 101643571 B CN101643571 B CN 101643571B CN 200910189730X A CN200910189730X A CN 200910189730XA CN 200910189730 A CN200910189730 A CN 200910189730A CN 101643571 B CN101643571 B CN 101643571B
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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 with a component being the structural formula (I) and a curing agent. The molecular structure of the epoxy resin composition of the invention contains the low-polarity styrene structure, therefore, the dielectric property of the resin is optimized. The dielectric constant and the dielectric loss angle tangent are reduced compared with those of the common epoxy resins. The prepreg obtained by coating the resin composition on the substrates and the laminate manufactured by laminating the prepreg simultaneously have the characteristics of low dielectric constant, low dielectric dissipation factors, good heat resistance, good dip soldering resistance, good moisture resistance, good humidity resistance and good cohesiveness with copper foils. The resin composition of the invention can be also used for manufacturing the resin sheets, resin composition copper foils, the laminate and the printed circuit boards. R is (a), and 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 processing and laminate for printed circuits.
Background technology
The existing material that is used for tellite, the epoxy resin that the adhesion properties that is widely used is excellent.Epoxy resin is to contain two or more epoxide groups in the general reference molecule; With organic cpds such as aliphatics, alicyclic or aromatic series is skeleton, and can in the presence of suitable chemical reagent (solidifying agent), react the general name of the compound of the three-dimensional netted cured article of generation through epoxide group.It is one of kind important in the thermoset macromolecule material.Epoxy resin is owing to have good chemicalstability, 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 computingmachine 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 requirement needs epoxy resin in high humidity environment, to guarantee lower water-intake rate, lower polarity.
Yet, general specific inductivity of common epoxy resin 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.
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.
USP uses for No. 6509414 styrene-maleic anhydride copolymer, epoxy resin and tetrabromo-bisphenol to make copper-clad plate.Though this patent cooperates with styrene-maleic anhydride copolymer through employing 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 styrene-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.
On the other hand, in electronic material, the polymer through epoxy resin quantizes to reduce cross-linking density and improves dielectric characteristics, and Japanese Patent discloses the technology that the aggressiveness phenol resins carries out glycidyl ether that adds of using phenol and NSC 7352 for 2001-240654 number.Though yet this epoxy resin has obtained good wet fastness and specific inductivity, has especially obtained low specific inductivity.But the dielectric loss factor under high frequency is bigger than normal, and high frequency characteristics is insufficient.
In addition; In above technical scheme; Adopt vinylbenzene one maleic anhydride and verivate thereof to come composition epoxy resin is improved as solidifying agent; Make to diminish, also make to have received limitation in the modification that promotes aspect dielectric properties and the humidity resistance as the epoxy resin 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 compositions of thermosetting resin, it contains low polarity vinylbenzene structure, thereby compares with maleic anhydride one 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 of processing with compositions of thermosetting resin, it has low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder property, wet fastness, and good characteristics of humidity resistance.
Another purpose of the present invention is to provide a kind of laminate for printed circuits of processing with compositions of thermosetting resin, and it has low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder property, wet fastness, and good characteristics of humidity resistance.To achieve these goals, the present invention provides a kind of compositions of thermosetting resin, and it comprises at least a epoxy resin with following structural formula (I), and solidifying agent;
Wherein R is:
N and m are natural number.
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 through 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 processed; 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 through 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 epoxy resin 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 epoxy resin of composition epoxy resin of the present invention can use separately; Perhaps mix and use with other epoxy resin; It has low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder property, wet fastness, humidity resistance and and the cohesiveness of Copper Foil characteristics preferably; This resin combination is coated in semicure sheet material that obtains on the base material and the veneer sheet of making through this semicure sheet material of lamination; It has low-k, the low-dielectric loss factor simultaneously; Thermotolerance, anti-immersed solder property, wet fastness, humidity resistance and and the cohesiveness of Copper Foil characteristics preferably, can be used as electronic machine and use printed circuit board.
Embodiment
The present invention provides a kind of compositions of thermosetting resin, and it includes the epoxy resin that has a kind of structural formula (I) at least, and solidifying agent;
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 epoxy resin 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, like 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.M/n=0.8～19 wherein.
Preferred Epicholorohydrin of the epihalohydrin that uses among the present invention and table bromhydrin are preferably Epicholorohydrin again.The inert atmosphere that uses is nitrogen.
The method that a kind of the present invention of preparation contains the epoxy resin 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 epoxy resin.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, dripping alkali liquid simultaneously, the mol ratio of alkali lye and para hydroxybenzene ethylene/styrene multipolymer is 1～2: 1; After reaction finishes through filtering; Washing removes freshen, and 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, Pottasium Hydroxide etc., and used alkali lye is preferably selected denseer solution for use, and preferred concentrations 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 MIBK; Hydro carbons such as toluene and YLENE, alcohols such as methyl alcohol, ethanol, primary alconol, cellosolve such as methylcyclohexane and ethyl cellosolve; Ethers such as diox and diethoxyethane, DMSO 99.8MIN. and N.
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; Promptly earlier with para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin etherificate under the effect of catalyzer; Closed loop obtains epoxy resin under the effect of alkali lye then, specifically comprises following steps:
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.
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, and through filtering, washing removed freshen after reaction finished; 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 Pottasium Hydroxide is preferably selected denseer solution for use, and preferred concentrations is between 20-50wt%.
More than the reaction reaction formula represent as follows:
Wherein
X:Br or Cl or I or F
R：
The structural formula (I) of the epoxy resin 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 epoxy resin of structural formula among the present invention (I) is between 1000-50000.Number-average molecular weight is through using THF as moving phase, using the gel permeation chromatography of polystyrene standard as stationary phase.
Epoxy resin 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 epoxy resin 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.
Epoxy resin shown in the structural formula among the present invention (I) can use separately, also can mix with the epoxy resin of other type and use.
When the epoxy resin shown in the said structure formula (I) is used when the epoxy resin with other type, can obtain favorable manufacturability ability and thermotolerance.In addition, because the epoxy resin shown in the structural formula (I) has low polar vinylbenzene structure, the dielectric properties of hybrid resin system have been optimized.
Epoxy resin as other type; What can mention is in 1 molecule resin, to have the epoxy resin more than two or more epoxide groups; The epoxy resin of bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin, naphthalene based epoxy resin, alicyclic based epoxy resin, Resorcinol type epoxy resin, polyethylene glycol type epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin and phenol aldehyde type epoxy resin and other type for example; The epoxy resin of other type is not only for above-mentioned several kinds, and the epoxy resin of above-mentioned other type can mix use more than a kind or 2 kinds.
As the preferred embodiments of the present invention, that can enumerate has the epoxy resin shown in the following general formula:
Wherein R1 represents Wasserstoffatoms, 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
(II)
Wherein R2 represent Wasserstoffatoms, halogen atom, alkyl or the alicyclic alkyl of ring-type of 1-8 linear, side chain arranged, alkoxyl group, the phenyl of a 1-10 carbon atom, n represents 0 to 20 integer.
Wherein R3 represent Wasserstoffatoms, halogen atom, alkyl or the alicyclic alkyl of ring-type of 1-8 linear, side chain arranged, alkoxyl group, the phenyl of a 1-10 carbon atom, n represents 0 to 20 integer.
Wherein R4 represents Wasserstoffatoms, halogen atom or phenyl, and m comprises 0 integer
Wherein R5 represent Wasserstoffatoms, halogen atom, alkyl or the alicyclic alkyl of ring-type of 1-8 linear, side chain arranged, alkoxyl group, the phenyl of a 1-10 carbon atom, n represents 0 to 20 integer.
As the epoxy resin of other types, can improve the wet fastness, thermotolerance of resin combination, particularly improve thermotolerance after the moisture absorption.Remember the epoxy resin shown in the structural formula (I): the epoxy resin of other type=1: 0.1～10 by weight.
Solidifying agent in the compositions of thermosetting resin of the present invention; Can use epoxy resin solidifying agent commonly used; For example acid anhydrides, amine, phenols, polyhydroxy phenol and resol, benzoxazine colophony, bis-phenol, brominated bisphenol A, phenol, dihydroxy-benzene (like pyrocatechol, Resorcinol, Resorcinol), carboxylic acid, siloxanes, ZGK 5 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, MDA (DDM), diaminodiphenylsulfone(DDS) (DDS), mphenylenediamine, diaminodiphenyl oxide (DDE), m-xylene diamine, p-diaminodiphenyl, quadrol, NSC 446, 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, gather 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 etc.
The consumption of solidifying agent is looked the epoxy equivalent (weight) of reactive behavior hydrogen equivalent and epoxy resin in the solidifying agent and is decided.The epoxy equivalent (weight) of reactive behavior hydrogen equivalent and epoxy resin is than between 0.5～1.5 in the solidifying agent.The reactive behavior hydrogen equivalent is preferably 0.7-1.4 with the epoxy equivalent (weight) ratio of epoxy resin.This ratio control is preferably 0.4-0.7 between 0.3-0.8 for Dicyanodiamide.
Can also include filler in the compositions of thermosetting resin of the present invention; The filler of being selected for use, what can mention is for example single crystal fibre, staple glass fibre etc. such as powder such as white lake, Marinco H, kaolin, hydrotalcite, titanium oxide, Calucium Silicate powder, beryllium oxide, SP 1, glass powder or silicon powder, zinc borate, aluminium nitrogen compound, silicon nitride, silit, Natural manganese dioxide, zirconium white, mullite, titanium oxide, potassium titanate, hollow glass microbead, polytetrafluorethylepowder powder, PS powder and potassium titanate, silit, silicon nitride, aluminum oxide of mineral filler.Silicon powder can make 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 compsn.
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 instance of tertiary amine is: triethylamine, TBuA, dimethyl amine ethanol, N, N-dimethyl--aminomethyl phenol, benzyl dimethyl amine etc.; The instance of three grades of phosphines comprises: triphenylphosphine etc.; The instance 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 instance 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.
The usage quantity of catalyzer is looked kind and the catalyst type of epoxy resin kind, solidifying agent and is decided.Catalyst consumption is 0.001～5.0wt% with respect to the total amount of compositions of thermosetting resin among the present invention, is preferably 0.05～4.0wt%, more preferably 0.005～3.0wt%.Catalyst consumption too much (surpasses 5.0wt%) will cause the reactive too fast of composition epoxy resin, to the homogeneity generation detrimentally affect of the transformation efficiency of the generation of by product and curing reaction; If catalyst consumption is lower than 0.005wt% in the compsn, reactivity is slow excessively, is unfavorable for the making of prepreg.Using a principle of catalyzer is that the gelation time of glue should not be lower than 120s.
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, white lake, Marinco H and ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.
Can add solvent in the composition epoxy resin of the present invention and be modulated into glue.The example of spendable solvent comprises ketone such as acetone, methyl ethyl ketone and MIBK; Hydro carbons such as toluene and YLENE; 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, ETHYLE ACETATE; Aprotic solvent such as N, dinethylformamide, N, the N-DEF, one or more in the above-mentioned solvent can mix use arbitrarily with another kind.
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 through 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 processed; 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 through 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 preparing resin sheet, resin complexes metal copper foil, veneer sheet, printed circuit board.
The method of composition epoxy resin preparing resin sheet of the present invention 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 of composition epoxy resin preparing resin composition metal Copper Foil of the present invention (RCC) is listed below, yet the method for preparing resin composition metal Copper Foil is not limited only to this.As tinsel, can use the alloy or the composite metallic material of copper, brass, aluminium, nickel and these metals, the thickness of tinsel is at 5-150 μ m.Through manual or mechanical roll-on device described composition epoxy resin glue is coated on the above-mentioned tinsel; Then this tinsel that is coated with composition epoxy resin is carried out heat drying; Make composition epoxy resin be in semi-cured state (B-Stage); The Heating temperature here is at 100-250 ℃; Be 10 seconds-30 minutes heat-up time, and the resin layer thickness of the resin laminated metal that forms at last is at 1-150 μ m, 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 here) is immersed on the base-material; And the prepreg that is impregnated with composition epoxy resin carried out heat drying; Make the composition epoxy resin in the prepreg be in the semicure stage (B-Stage), can obtain prepreg.The base-material that wherein uses can be inorganic or organic materials.Specifiable woven fabric or non-woven fabrics or the paper that spun glass, thomel, 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, ROHM, polyimide, aramid fiber, tetrafluoroethylene, syndiotactic polystyrene.Yet strongthener is not limited thereto.Specifiable Heating temperature to prepreg 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 is explained 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 to be carried out sending into behind the lamination and carries 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 through hot-forming.Can use the alloy or the composite metallic material of copper, brass, aluminium, nickel and these metals as tinsel,, should select suitable lamination condition of cure according to the practical situation of composition epoxy resin as the pressing conditions of veneer sheet.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 come pressed sheet to reach required requirement through the suitable pressure that satisfies moulding.Common governing principle for the neutralizing layer pressing plate of routine does, 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 through addition or subtract layer legal system and make printed circuit board or complicated multilayer circuit board.
Composition epoxy resin of the present invention is except being used as preparing resin sheet, resin complexes metal copper foil, prepreg, veneer sheet, copper-clad laminate, the printed circuit board; Also can be used for being used for making sizing agent, coating, matrix material, 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 following.
Synthetic 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, and Heating temperature is at 80 degree, and constantly stirring; 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, in residuum, add mibk, through washing and removing by filter salinity, then make to be washed with water to neutrality, obtain epoxy resin (1).The Wn of epoxy resin (1) is 4900.
Synthetic 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, and Heating temperature is at 100 degree, and constantly stirring; 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, in residuum, add mibk, through washing and removing by filter salinity, then make to be washed with water to neutrality, obtain epoxy resin (2).The Wn of epoxy resin (2) is 34000.
Synthetic example 3:
Add para hydroxybenzene ethylene/styrene multipolymer, Epicholorohydrin and tetraethylammonium bromide 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, and it is synthetic that para hydroxybenzene ethylene/styrene multipolymer is pressed currently known methods, and 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 epoxy resin (3) at last.The Wn of epoxy resin (3) is 22000.
Synthetic 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 epoxy resin (3) at last.The Wn of epoxy resin (3) is 10000.
Embodiment (1～4):
The epoxy resin of gained among the synthetic routine 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 through thermocompressor and obtain doublesided copperclad laminate.Lamination is following: 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 is seen table one.
Comparative Examples 1:
Use 40 parts, 60 parts N695 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 through thermocompressor and obtain doublesided copperclad laminate.Lamination is following: 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 is seen table one.
Comparative Examples 2
Use 80 parts, 20 parts PSM4357 of DER530 resin 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 through thermocompressor and obtain doublesided copperclad laminate.Lamination is identical with Comparative Examples 1, and respective performances is seen table one.
Comparative Examples 3
Use 80 parts, 20 parts PSM4357 of HP7200 resin and be aided with catalyzer 2-MI, 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 through thermocompressor and obtain doublesided copperclad laminate.Lamination is seen table one with Comparative Examples 1 identical respective performances.
Table one
Annotate 1:
Each component is all remembered with the solids content weight part in the table one
DER530 is the bisphenol A-type bromination bifunctional epoxy resin of DOW
N690 is the adjacent sylvan formaldehyde epoxy resin of DIC
HP7200 is the NSC 7352 epoxy resin of DIC
PSM4357 is the resol of Japan crowd Rong Huaxue
SMA3000 is the Zelan 338 of Sartomer
DDM is 4 of Huifeng Synthetic Material Co., Ltd., Jiangyin, 4 '-MDA
Annotate 2:
Second-order transition temperature (Tg): use the DSC test, measure according to the DSC testing method of IPC-TM-6502.4.25 defined.
Stripping strength is tested according to " after the thermal stresses " experiment condition in the IPC-TM-6502.4.8 method
Specific inductivity and dielectric loss factor: according to the method test of IPC-TM-6502.5.5.9 defined
The evaluation of anti-immersed solder property: 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, through observing the anti-immersed solder property of ocular estimate,
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 1 hour, measured the water-intake rate of substrate.
Anti-immersed solder property 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.
Can find out from table one, embodiments of the invention, low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder property, 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 property, wet fastness, humidity resistance and and the cohesiveness of Copper Foil all bad.
Epoxy resin shown in the structural formula of the present invention (I) uses separately; Perhaps mix the resin combination that forms when using with other epoxy resin, low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder property, wet fastness, humidity resistance and and the cohesiveness of Copper Foil all good.This resin combination is coated in semicure sheet material that obtains on the base material and the veneer sheet of making through this semicure sheet material of lamination; Low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder property, wet fastness, humidity resistance and and the cohesiveness of Copper Foil all good, can be used as electronic machine and use 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 epoxy resin 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 epoxy resin of composition epoxy resin kind of the present invention can use separately; Perhaps mix and use with other epoxy resin; It has low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder property, wet fastness, humidity resistance and and the cohesiveness of Copper Foil characteristics preferably; This resin combination is coated in semicure sheet material that obtains on the base material and the veneer sheet of making through this semicure sheet material of lamination; It has low-k, the low-dielectric loss factor simultaneously; Thermotolerance, anti-immersed solder property, wet fastness, humidity resistance and and the cohesiveness of Copper Foil characteristics preferably, can be used as electronic machine and use printed circuit board.
The above; Be merely 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 the technical scheme and the technical conceive of this aspect.
Claims (8)
1. compositions of thermosetting resin, it is characterized in that: it comprises:
Having a kind of component at least is the epoxy resin of structural formula (I);
Solidifying agent;
Wherein R is:
N and m are natural number;
Structural unit m/n=0.8～19 in the epoxy resin of structural formula (I);
The number-average molecular weight of the epoxy resin of structural formula (I) is between 1000-50000.
2. compositions of thermosetting resin as claimed in claim 1 is characterized in that, the epoxy resin of structural formula (I) is accomplished by the following formula reaction through 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 is characterized in that, the epoxy resin of structural formula (I) uses separately or mixes use with the epoxy resin of other type.
4. compositions of thermosetting resin as claimed in claim 3; It is characterized in that; The epoxy resin of said other type is the epoxy resin that has two above epoxide groups in 1 the molecule epoxy resin, 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 epoxy resin, polyethylene glycol type epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin or the phenol aldehyde type epoxy resin.
5. compositions of thermosetting resin as claimed in claim 4 is characterized in that, the epoxy resin of structural formula (I): the epoxy resin of other type=1: 0.1～10, remember with weight.
6. compositions of thermosetting resin as claimed in claim 1; It is characterized in that; Said solidifying agent is acid anhydrides, amine, phenols and resol, benzoxazine colophony, carboxylic acid, siloxanes, ZGK 5 and have-the Ph-X-Ph-group contain can with the compound of epoxide group reaction, wherein X is CH
2, C (CH
3)
2, CH (CH
3), O, S, C=O, SO
2
7. a prepreg of processing with the described compositions of thermosetting resin of claim 1 is characterized in that, comprises that base-material reaches through the impregnation drying afterwards attached to the compositions of thermosetting resin on the base-material.
8. laminate for printed circuits of processing with 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 sheet prepreg comprise base-material and through the impregnation drying afterwards attached to the compositions of thermosetting resin on the base-material.
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| JP5674610B2 (en) * | 2011-09-21 | 2015-02-25 | 日東電工株式会社 | Silicone resin sheet, manufacturing method thereof, sealing sheet, and light emitting diode device |
| CN103296447B (en) * | 2012-02-29 | 2017-09-29 | 深圳光启创新技术有限公司 | Manufacture method, metamaterial antenna cover and its manufacture method of metamaterial plate |
| CN103296437B (en) * | 2012-02-29 | 2017-04-26 | 深圳光启创新技术有限公司 | Manufacturing method for metamaterial board, metamaterial antenna housing and manufacturing method for metamaterial antenna housing |
| CN102731966A (en) * | 2012-07-09 | 2012-10-17 | 广东生益科技股份有限公司 | Thermosetting epoxy resin composition as well as prepreg and copper-foil-plated laminated board manufactured by using same |
| EP2915848B1 (en) | 2012-10-31 | 2018-05-30 | Shengyi Technology Co., Ltd. | Thermosetting resin composition and use thereof |
| CN104582248B (en) * | 2014-12-23 | 2017-11-03 | 广东生益科技股份有限公司 | A kind of production method of FR4 stiffening plates and FPC reinforcement |
| CN106832226B (en) * | 2015-12-04 | 2019-06-14 | 广东生益科技股份有限公司 | A kind of halogen-free epoxy resin composition and prepreg, laminate and printed circuit board containing it |
| CN106905459A (en) * | 2015-12-22 | 2017-06-30 | 广东生益科技股份有限公司 | A kind of epoxy resin modification polystyrene resin, preparation method and its usage |
| CN108255018B (en) * | 2018-01-05 | 2020-12-11 | 湖北固润科技股份有限公司 | Photoresist composition comprising poly (p-hydroxystyrene) epoxy resin as film-forming resin |
| CN109796728B (en) | 2019-01-30 | 2020-04-17 | 常州中英科技股份有限公司 | Polyphenol-modified hydrocarbon composition-based prepreg and copper-clad plate prepared from same |
| CN113025037A (en) * | 2021-02-09 | 2021-06-25 | 林州致远电子科技有限公司 | Thermosetting resin composition and preparation method and application thereof |
| CN113278251A (en) * | 2021-04-26 | 2021-08-20 | 厦门理工学院 | Epoxy resin for flexible circuit board, preparation method and device thereof, and computer equipment |
| CN114478623B (en) * | 2021-12-29 | 2024-04-09 | 浙江华正新材料股份有限公司 | Antioxidant and preparation method and application thereof |
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