CN101735456A - High weather-proof thermosetting resin composite and prepreg and copper-clad laminate prepared thereby - Google Patents
High weather-proof thermosetting resin composite and prepreg and copper-clad laminate prepared thereby Download PDFInfo
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Abstract
The invention relates to a high weather-proof thermosetting resin composite and prepreg and copper-clad laminate prepared thereby. The high weather-proof thermosetting resin composite comprises the following components in parts by weight: 10-40 parts of allyl compound, 8-80 parts of bismaleimide compound, 0-30 parts of epoxy resin and 0.05-5 parts of catalyst, wherein the molar ratio of allyl compound to bismaleimide compound is 1:2-4. The high weather-proof thermosetting resin composite provided by the invention has higher heat resistance, and the coefficient of thermal expansion (CTE) can be lowered to be below 2.0% to satisfy the requirements of manufacturing high multi-layer PCB. The prepreg prepared by the high weather-proof thermosetting resin composite has simple manufacture, better heat-resistant effect and high heat conductivity. The copper-clad laminate of the invention can be applied to heat-resisting and high multi-layer circuits and has simple manufacturing technology and low cost.
Description
Technical field
The present invention relates to a kind of compositions of thermosetting resin, relate in particular to a kind of compositions of thermosetting resin of the high heat resistance that is used for the copper-clad laminate field and utilize the prepreg and the copper-clad laminate of its making.
Background technology
Along with the develop rapidly of electronic information technology, the appearance of surface mounting technique, PCB (tellite) develops to the direction of high-density, high-speed, low-loss, high frequency, highly reliable, multiple stratification, low cost and automatic continuous production.Meanwhile, have higher requirement with the thermotolerance and the reliability of substrate for PCB.Be used widely as the PCB substrate based on the epoxy resin fiberglass cloth copper-clad plate (FR4-CCL) of Resins, epoxy all the time.But, can't be used for high frequency, high temperature resistant and high reliability circuit because FR-4 has the shortcoming that high thermal resistance is poor, specific inductivity is big.When PCB in when boring, the heating of drill bit high speed rotating makes resin softening.When the High Density Packaging high power device,, thereby make easily that copper conductor comes off, the PCB distortion because the second-order transition temperature (Tg) of FR4-CCL is low.When multi-ply wood welding and high low temperature round-robin thermal shocking, the z direction of principal axis coefficient of expansion of FR4-CCL is bigger than the coefficient of expansion of copper layer in the plated through-hole, thereby produces heavily stressedly, causes the plated through-hole reliability decrease.
Polyimide (PI) since its excellent performance be widely used always, but it is after extensive, the stable production of bismaleimides (BMI) as the PCB base material really.Dielectric properties, the dimensional stability of PI are preferable, and PI uses in giant-powered computer at most as the PCB base material, and the multi-ply wood of 10-20 layer adopts PI or BT resin (bismaleimide-triazine resin) more, and the plate more than 20 layers then adopts PI entirely.What be used for the copper-clad plate field at present mainly is BMI type PI resin.
The BMI resin can satisfy makes high-speed figure and high frequency printed circuit boards substrate requirements, is usually used in making the high-performance multilayer plate.Bimaleimide resin monomer reactivity height does not have molecule and discharges during polymerization, end properties is stable, can keep higher physical and mechanical properties in wide temperature range.The Tg that the bimaleimide resin tool is higher, its dipolar loss is little in wide temperature range, so electrical property is very good, has advantages such as specific inductivity is lower, dielectric loss is little, volume resistance is big.These performances still can remain on higher level in the temperature of broad and range of frequency.
Present bi-maleimide modified aspect is used morely aromatic diamine modification, epoxy resin modification, allylic cpd modification, modified rubber, cyanate modified, polyphenyl ether modified, thermoplastic resin modified etc.In the copper-clad plate field, allyl group modified bismaleimide application of compound receives publicity always and studies.
Chinese patent 1493610 has adopted diallyl bisphenol compound and Resins, epoxy that bismaleimides is carried out modification.The mol ratio of allylic cpd and bismaleimides is 1 in its proportioning: (mass ratio is 100 to 0.83-1.96: 50-90), do not relate to the application outside this ratio range.The second-order transition temperature of the sheet material that makes under this condition has only about 200 ℃, and is well-known, and more than second-order transition temperature, the thermal expansivity of sheet material can increase, can make like this sheet material 50 ℃ until 260 ℃ thermal expansion coefficient more than 3%.And product solidifies required time and reaches more than the 10h, and energy consumption is unfavorable for the industrialization continuous production greatly.
Along with electronic product develops to light, thin, short, little direction, make the wiring of circuit card thinner, closeer, the number of plies is more and more, electronic mounting is crypto set more, and the cold cycling that circuit card will be able to take under acid or alkali environment in the course of processing and 288 ℃ is repeatedly impacted, and factor such as the external impacts in the use, environmental aging, the reliability of circuit board material seems more and more important.In general in multilayer circuit board, circuit turn-on between layer and the layer is realized by hole metallization (copper), the thermal expansivity of metallic copper is 17ppm/ ℃, and the thermal expansivity of general thermosetting resin is more than 200ppm/ ℃, bigger thermal expansion coefficient difference can cause the fracture of plated through-hole in the thermal shock of the course of processing (PCB does not have the processing temperature of lead welding at 240 ℃～270 ℃ at present), cause and open circuit, make product rejection.Especially concerning high multiwalled PCB (more than 20 layers), Z-CTE is the smaller the better.
Summary of the invention
The object of the present invention is to provide a kind of high heat-stable compositions of thermosetting resin, it has good characteristics such as high second-order transition temperature, heat decomposition temperature, thermally stratified layer time.
Another object of the present invention is to, the prepreg that provides a kind of resin combination that adopts above-mentioned high heat resistance to make, this prepreg is made simple, has the better heat-resisting effect.
Another purpose of the present invention is, the copper-clad laminate that provides a kind of resin combination that adopts above-mentioned high heat resistance to make, this copper-clad laminate can be applied in the high temperature resistant and high multilayer circuit making, not only manufacture craft is simple, and cost lower, have high second-order transition temperature, pyrolytic decomposition temperature, long thermally stratified layer time, low thermal coefficient of expansion, a superior dielectric properties.
To achieve these goals, the invention provides a kind of high heat-stable compositions of thermosetting resin, its contained component and mass fraction thereof are as follows: allylic cpd 10-40 part, bismaleimide compound 8-80 part, Resins, epoxy 0-30 part, catalyzer 0.05-5 part, wherein, the mol ratio of allylic cpd and bismaleimide compound is 1: 2-4.
Described allylic cpd is a diallyl biphenol compounds, and it comprises diallyl bisphenol, diallyl Bisphenol F or diallyl bisphenol S.
Described bismaleimide compound is the compound that contains two maleimide base groups in the molecular structure, and it comprises diphenyl methane dimaleimide, phenyl ether bismaleimides or sulfobenzide bismaleimides.
Described Resins, epoxy is the Resins, epoxy that contains two or more epoxide groups in 1 molecule resin, and it comprises 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, brominated epoxy resin, four-functional group epoxy resin and the phenol aldehyde type epoxy resin one or more.
Described catalyzer comprises tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt or imidazolium compoundss, and this tertiary amine comprises triethylamine, tributylamine, dimethyl amine ethanol, N, N-dimethyl-aminomethyl phenol or benzyl dimethyl amine; Three grades of phosphines comprise triphenylphosphine; Quaternary ammonium salt comprises 4 bromide, tetramethyl ammonium chloride, Tetramethylammonium iodide, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride or cetyl trimethylammonium bromide; 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 or butyl triphenyl phosphonium iodide; Imidazolium compounds 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 or 1-1-cyanoethyl-2-methylimidazole.
Further, the prepreg that the present invention also provides a kind of resin combination that adopts described high thermal conductivity to make, it comprise base-material, and by the impregnation drying afterwards attached to the high heat-stable compositions of thermosetting resin on the base-material.
The content of high heat-stable compositions of thermosetting resin is 25%-75% in this prepreg.
Described base-material is inorganic or organic materials, this inorganic materials comprises woven fabric or the non-woven fabrics or the paper of glass fibre, carbon fiber, boron fibre, metal, and this organic materials comprises weaving cotton cloth of polyester, polyamine, polyacrylic acid, polyimide, aramid fiber, tetrafluoroethylene or syndiotactic polystyrene manufacturing or non-woven fabrics or paper.
In addition, the present invention also provides a kind of copper-clad laminate that adopts the heat-stable compositions of thermosetting resin of described height to make, it comprises 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 by the impregnation drying afterwards attached to the high heat-stable compositions of thermosetting resin on the base-material.
The content of high heat-stable compositions of thermosetting resin is 25%-75% in the described prepreg, base-material is inorganic or organic materials, this inorganic materials comprises woven fabric or the non-woven fabrics or the paper of glass fibre, carbon fiber, boron fibre, metal, and this organic materials comprises weaving cotton cloth of polyester, polyamine, polyacrylic acid, polyimide, aramid fiber, tetrafluoroethylene or syndiotactic polystyrene manufacturing or non-woven fabrics or paper.
Beneficial effect of the present invention: the heat-stable compositions of thermosetting resin of height provided by the invention, it has higher thermotolerance, and its thermal expansivity (CTE) can be reduced to below 2.0%, satisfies the demand that high multilayer (more than 20 layers) PCB makes; The prepreg of making by the heat-stable compositions of thermosetting resin of this height, has better heat-resisting equally, it can also be used to making the copper-clad laminate that printed electronic circuit is used, this copper-clad laminate can be applied in the high temperature resistant and high multilayer circuit, also can be used as the IC encapsulating carrier plate, not only resistance toheat is good, and manufacture craft is simple, have high second-order transition temperature, pyrolytic decomposition temperature, long thermally stratified layer time, low thermal coefficient of expansion, superior dielectric properties, and cost is lower, is suitable for suitability for industrialized production.
Embodiment
The invention provides a kind of high heat-stable compositions of thermosetting resin, its contained component and mass fraction thereof are as follows: allylic cpd 10-40 part, bismaleimide compound 8-80 part, Resins, epoxy 0-30 part, catalyzer 0.05-5 part, wherein, the mol ratio of allylic cpd and bismaleimide compound is 1: 2-4.
Allylic cpd among the present invention is a diallyl biphenol compounds, as diallyl bisphenol, diallyl Bisphenol F, diallyl bisphenol S etc.
Bismaleimide compound is the compound that contains two maleimide base groups in the molecular structure, as in diphenyl methane dimaleimide, phenyl ether bismaleimides or the sulfobenzide bismaleimides etc. one or more.Because the amount of bismaleimide compound is obvious to the thermal characteristics influence of product, bigger ratio helps obtaining the good product of thermotolerance, therefore among the present invention the mol ratio of allylic cpd and bismaleimides we be selected in 1: (2-4), the mol ratio of allylic cpd and bismaleimides is 1 in its more traditional proportioning: the resin combination (0.83-1.96) has better resistance toheat.
The Resins, epoxy that the present invention uses is the Resins, epoxy that contains two or more epoxide groups in 1 molecule resin, for example one or more in the Resins, epoxy 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 Resins, epoxy, polyethylene glycol type Resins, epoxy, trifunctional Resins, epoxy, brominated epoxy resin, four-functional group epoxy resin and phenol aldehyde type epoxy resin and other type.As selectivity embodiment of the present invention, we can select the described Resins, epoxy of following general formula for use:
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 R4 represents hydrogen atom, halogen atom or phenyl, and m comprises 0 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.
The heat-stable compositions of thermosetting resin of height of the present invention also comprises catalyzer, this catalyzer comprises tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt or imidazolium compoundss, the example of this 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 multiple mixing are used.
Further, the present invention can also comprise filler and solvent.The filler here can be selected silicon-dioxide for use, aluminium hydroxide, 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, potassium titanate, hollow glass microbead, polytetrafluorethylepowder powder, polystyrene, powder and potassium titanates such as polyphenylene oxide powder, silicon carbide, silicon nitride, single crystal fibres such as aluminum oxide, glass, staple fibre etc.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.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, N-diethylformamide.Solvent can be one or more above-mentioned mixing uses arbitrarily.
As selectivity embodiment of the present invention, also can comprise dyestuff, pigment, tensio-active agent, flow agent, UV light absorber in the heat-stable compositions of thermosetting resin of this height.
The heat-stable compositions of thermosetting resin of height of the present invention in the preparation, only allylic cpd, bismaleimide compound, Resins, epoxy need be reacted 1～5h in 130-160 ℃ in solvent, after being cooled to room temperature, can obtain in ketones solvent dissolving good homogeneous transparent resin solution, in this resin solution, add then and obtain the solution of solid content after solidifying agent, catalyzer, filler and stirring solvent mix at 50-80%.Among the preparation method embodiment of the heat-stable compositions of thermosetting resin of height of the present invention, used each material component and proportioning thereof are shown in Table 1.
Table 1 raw material and content
| Component | Mass parts |
| Resins, epoxy | ??0-30 |
| Allylic cpd | ??10-40 |
| Bismaleimides | ??20-80 |
| Catalyzer | ??0.05-5 |
| The constituent total amount | ??100 |
The prepreg that the present invention also provides a kind of resin combination that adopts described high thermal conductivity to make, it comprise base-material, and by the impregnation drying afterwards attached to the high heat-stable compositions of thermosetting resin on the base-material.The content of high heat-stable compositions of thermosetting resin is 25%-75% in this prepreg.
The method of using the heat-stable compositions of thermosetting resin of height of the present invention to make prepreg (prepreg) is listed below, yet the method for making prepreg is not limited only to this.The heat-stable compositions of thermosetting resin glue of height of the present invention (having used the solvent adjustment viscosity herein) is immersed on the strongthener as base-material, and the preliminary-dip piece that is impregnated with high heat-stable compositions of thermosetting resin carried out heat drying, make the high heat-stable compositions of thermosetting 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.Inorganic materials can include woven fabric or the non-woven fabrics or the paper of glasscloth, carbon fiber, boron fibre, metal etc.Glasscloth wherein or non-woven fabrics can be E-glass, Q type cloth, NE cloth, D type cloth, S type cloth, high silica cloth etc.; This organic materials can comprise weaving cotton cloth or non-woven fabrics or paper of manufacturings such as polyester, polyamine, polyacrylic acid, polyimide, aramid fiber, tetrafluoroethylene or syndiotactic polystyrene.Yet strongthener is not limited thereto.As a kind of selectivity embodiment of the present invention, the Heating temperature of preliminary-dip piece be can be 80-250 ℃, the time is 1-30 minute.
In addition, the present invention also provides a kind of copper-clad laminate that adopts the heat-stable compositions of thermosetting resin of described height to make, it comprises 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 by the impregnation drying afterwards attached to the high heat-stable compositions of thermosetting resin on the base-material.The content of high heat-stable compositions of thermosetting resin is 25%-75% in the described prepreg, and base-material is inorganic or organic materials, and this inorganic materials comprises woven fabric or the non-woven fabrics or the paper of glass fibre, carbon fiber, boron fibre, metal; This organic materials can comprise weaving cotton cloth or non-woven fabrics or paper of manufacturings such as polyester, polyamine, polyacrylic acid, polyimide, aramid fiber, tetrafluoroethylene or syndiotactic polystyrene.
In industrial production, veneer sheet, copper-clad laminate, printed circuit board all can use above-mentioned prepreg to make.In the present embodiment, we are that example illustrates this production method with the copper-clad laminate: 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 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 compositions of thermosetting 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/cm
2, hot pressing time: 60-240 minute.In above-mentioned making processes, 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.
Example 1
Diallyl bisphenol (DABPA) 100g, Resins, epoxy (EP) 70g, diphenyl methane dimaleimide (BDM) 250g are joined in the there-necked flask, open and stir, condensing reflux down with 155 ℃ of isothermal reaction 2.5h, obtain the thick liquid resin after being cooled to room temperature.
After in above-mentioned resin solution, adding 0.5% 2-methyl 4-ethyl imidazol(e), 3% diaminodiphenylmethane and solvent DMF (dimethyl formamide), mix after regulating solid content and be 65%.After adopting the woven fiber glass impregnation, in baking oven,, obtain the bonding sheet of semi-cured state in 155 ℃ of bakings 6 minutes.8 bonding sheets are stacked, and the two sides is covered with Copper Foil, and in vacuum press 220 ℃, hot pressing obtained the copper-clad plate that thickness is 1.6mm in 90 minutes.Plate property sees Table 2.
Example 2
Diallyl bisphenol (DABPA) 100g, Resins, epoxy (EP) 110g, diphenyl methane dimaleimide (BDM) 340g are joined in the there-necked flask, open and stir, condensing reflux down with 155 ℃ of isothermal reaction 3h, obtain the thick liquid resin after being cooled to room temperature.Make copper-clad plate according to the method in the example 1 then, its performance sees Table 2.
Example 3
Diallyl bisphenol (DABPA) 50g, Resins, epoxy (EP) 70g, diphenyl methane dimaleimide (BDM) 230g are joined in the there-necked flask, open to stir, condensing reflux down with 155 ℃ of isothermal reaction 4h, obtain the thick liquid resin after being cooled to room temperature.Make copper-clad plate according to the method in the example 1 then, its performance sees Table 2.
Example 4
Diallyl Bisphenol F (DABPF) 50g, Resins, epoxy (EP) 60g, diphenyl methane dimaleimide (BDM) 200g are joined in the there-necked flask, open to stir, condensing reflux down with 155 ℃ of isothermal reaction 2h, obtain the thick liquid resin after being cooled to room temperature.Make copper-clad plate according to the method in the example 1 then, its performance sees Table 2.
Example 5
With diallyl bisphenol S (DABPS) 50g, Resins, epoxy (EP) (? g), diphenyl methane dimaleimide (BDM) 180g joins in the there-necked flask, open and stir, condensing reflux down with 155 ℃ of isothermal reaction 1.5h, obtain the thick liquid resin after being cooled to room temperature.Make copper-clad plate according to the method in the example 1 then, its performance sees Table 2.
Comparative example
Diallyl bisphenol (DABPA) 60g, Resins, epoxy (EP) 150g, diphenyl methane dimaleimide (BDM) 100g are joined in the there-necked flask, open and stir, be warming up to 155 ℃ of reaction 0.5h under the condensing reflux.Add 0.2% 2-methyl 4-ethyl imidazol(e), solvent DMF in this prepolymer after, stirring and making solid content is 60% solution.Make copper-clad plate according to the method in the example 1 then, its performance sees Table 2.
Table 2 plate property table
Above embodiment and comparative example all detect copper-clad plate with reference to the IPC4101 standard, detection method
As follows:
1 second-order transition temperature (Tg)
Detection method: dynamic thermomechanical analysis (DMA)
2 heat decomposition temperatures (Td)
Detection method: thermogravimetry.Condition is: 10 ℃/minute of temperature rise rates, thermal weight loss 5%.
3 thermally stratified layer times (T-300)
The T-300 thermally stratified layer time is meant sheet material under 300 design temperature, because time that is continued before this demixing phenomenon appears, in the effect of heat.
Detection method: thermomechanical analysis (TMA)
4 anti-immersed solder
Anti-immersed solder is meant that sheet material enters in 288 ℃ the fusion scolding tin, no layering and the time of bubbling and being continued.
5 thermal expansivity (CTE)
Detection method: thermomechanical analysis (TMA)
In sum, the heat-stable compositions of thermosetting resin of height provided by the invention, it has higher thermotolerance, and its thermal expansivity (CTE) can be reduced to below 2.0%, satisfies the demand that high multi-layer PCB is made; The prepreg of making by the heat-stable compositions of thermosetting resin of this height, has better heat-resisting equally, it can also be used to making the copper-clad laminate that printed electronic circuit is used, this copper-clad laminate can be applied in the high temperature resistant and high multilayer circuit, also can be used as the IC encapsulating carrier plate, not only resistance toheat is good, and manufacture craft is simple, have high second-order transition temperature, pyrolytic decomposition temperature, long thermally stratified layer time, low thermal coefficient of expansion, superior dielectric properties, and cost is lower, is suitable for suitability for industrialized production.
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 the technical scheme and the technical conceive of this aspect.
Claims (10)
1. one kind high heat-stable compositions of thermosetting resin, it is characterized in that, contained component and mass fraction thereof are as follows: allylic cpd 10-40 part, bismaleimide compound 8-80 part, Resins, epoxy 0-30 part, catalyzer 0.05-5 part, wherein, the mol ratio of allylic cpd and bismaleimide compound is 1: 2-4.
2. the heat-stable compositions of thermosetting resin of height as claimed in claim 1 is characterized in that, described allylic cpd is a diallyl biphenol compounds, and it comprises diallyl bisphenol, diallyl Bisphenol F or diallyl bisphenol S.
3. the heat-stable compositions of thermosetting resin of height as claimed in claim 1, it is characterized in that, described bismaleimide compound is the compound that contains two maleimide base groups in the molecular structure, and it comprises diphenyl methane dimaleimide, phenyl ether bismaleimides or sulfobenzide bismaleimides.
4. the heat-stable compositions of thermosetting resin of height as claimed in claim 1, it is characterized in that, described Resins, epoxy is the Resins, epoxy that contains two or more epoxide groups in 1 molecule resin, and it comprises 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, brominated epoxy resin, four-functional group epoxy resin and the phenol aldehyde type epoxy resin one or more.
5. the heat-stable compositions of thermosetting resin of height as claimed in claim 1, it is characterized in that, described catalyzer comprises tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt or imidazolium compoundss, this tertiary amine comprises triethylamine, tributylamine, dimethyl amine ethanol, N, N-dimethyl-aminomethyl phenol or benzyl dimethyl amine; Three grades of phosphines comprise triphenylphosphine; Quaternary ammonium salt comprises 4 bromide, tetramethyl ammonium chloride, Tetramethylammonium iodide, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride or cetyl trimethylammonium bromide; 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 or butyl triphenyl phosphonium iodide; Imidazolium compounds 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 or 1-1-cyanoethyl-2-methylimidazole.
6. the heat-stable compositions of thermosetting resin of height as claimed in claim 1, it is characterized in that, also comprise filler and solvent, described filler is selected silicon-dioxide for use, aluminium hydroxide, 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, potassium titanate, hollow glass microbead, polytetrafluorethylepowder powder, polystyrene, powder and potassium titanates such as polyphenylene oxide powder, silicon carbide, silicon nitride, single crystal fibres such as aluminum oxide, glass, one or more combination in the staple fibre; Described solvent comprises the combination of following one or more types: ketone is acetone, methyl ethyl ketone or methyl iso-butyl ketone (MIBK); Hydro carbons is toluene or dimethylbenzene; Alcohols is methyl alcohol, ethanol or primary alconol; Ethers is ethylene glycol monomethyl ether or propylene glycol monomethyl ether; The ester class is 1-Methoxy-2-propyl acetate or ethyl acetate; Aprotic solvent is N, dinethylformamide or N, N-diethylformamide.
7. the prepreg that the resin combination that adopts high thermal conductivity as claimed in claim 1 is made is characterized in that, comprise base-material, and by the impregnation drying afterwards attached to the high heat-stable compositions of thermosetting resin on the base-material.
8. prepreg as claimed in claim 7, it is characterized in that, the content of high heat-stable compositions of thermosetting resin is 25%-75% in this prepreg, described base-material is inorganic or organic materials, this inorganic materials comprises woven fabric or the non-woven fabrics or the paper of glass fibre, carbon fiber, boron fibre, metal, and this organic materials comprises weaving cotton cloth of polyester, polyamine, polyacrylic acid, polyimide, aramid fiber, tetrafluoroethylene or syndiotactic polystyrene manufacturing or non-woven fabrics or paper.
9. copper-clad laminate that adopts the heat-stable compositions of thermosetting resin of height as claimed in claim 1 to make, 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 by the impregnation drying afterwards attached to the high heat-stable compositions of thermosetting resin on the base-material.
10. copper-clad laminate as claimed in claim 9, it is characterized in that, the content of high heat-stable compositions of thermosetting resin is 25%-75% in the described prepreg, base-material is inorganic or organic materials, this inorganic materials comprises woven fabric or the non-woven fabrics or the paper of glass fibre, carbon fiber, boron fibre, metal, and this organic materials comprises weaving cotton cloth of polyester, polyamine, polyacrylic acid, polyimide, aramid fiber, tetrafluoroethylene or syndiotactic polystyrene manufacturing or non-woven fabrics or paper.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910189545A CN101735456A (en) | 2009-11-24 | 2009-11-24 | High weather-proof thermosetting resin composite and prepreg and copper-clad laminate prepared thereby |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910189545A CN101735456A (en) | 2009-11-24 | 2009-11-24 | High weather-proof thermosetting resin composite and prepreg and copper-clad laminate prepared thereby |
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| CN200910189545A Pending CN101735456A (en) | 2009-11-24 | 2009-11-24 | High weather-proof thermosetting resin composite and prepreg and copper-clad laminate prepared thereby |
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