CN102079875A - High-heat-resistance halogen-free phosphorus-free thermosetting resin composition, and bonding sheet and copper foil-coated laminated board made of same - Google Patents
High-heat-resistance halogen-free phosphorus-free thermosetting resin composition, and bonding sheet and copper foil-coated laminated board made of same Download PDFInfo
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Abstract
The invention relates to a high-heat-resistance halogen-free phosphorus-free thermosetting resin composition, and a bonding sheet and a copper foil-coated laminated board made of the same. The high-heat-resistance halogen-free phosphorus-free thermosetting resin composition comprises aromatic amine compounds, bismaleimide compounds, diphenyl epoxy resins, amine curing agents, catalyst, filler and solvent. The copper foil-coated laminated board made of the resin composition comprises a laminated board and copper foil/copper foils coated on one or both sides of the laminated board, wherein the laminated board comprises a plurality of bonding sheets which are bonded together; and each bonding sheet comprises a base material and the high-heat-resistance halogen-free phosphorus-free thermosetting resin composition which is attached to the base material by soaking and drying. The high-heat-resistance halogen-free phosphorus-free thermosetting resin composition provided by the invention has the advantages of environmental protection and favorable fire retardancy. The bonding sheet and the copper foil-coated laminated board made of the high-heat-resistance halogen-free phosphorus-free thermosetting resin composition have the advantage of high heat resistance, the coefficient of thermal expansion (CTE) can be reduced to lower than 2.0%, and the bonding sheet and the copper foil-coated laminated board can be used for manufacturing high-temperature-resistance and multilayer circuits to satisfy the demand for manufacturing of multilayer PCBs (Printed Circuit Boards).
Description
Technical field
The present invention relates to a kind of resin combination, relate in particular to a kind of high heat-stable non-halogen non-phosphate compositions of thermosetting resin and use the bonding sheet and the copper-clad laminate of its making.
Background technology
Traditional printed electronic circuit copper-clad laminate mainly adopts brominated epoxy resin, realizes the anti-flaming function of sheet material by bromine.But in recent years, in the products of combustion of the waste electrical and electronic equipment of halogens such as brominated, chlorine, check out carcinogenic substances such as dioxin, diphenylene-oxide, and Cold Dew, product might discharge the highly toxic substance hydrogen halide in combustion processes.On July 1st, 2006, two parts of environmental protection instructions of European Union " about scrapping the electric/electronic device instruction " and " ROHS " formal enforcement.The enforcement of these two parts of instructions makes the exploitation of halogen-free flameproof copper-clad laminate become the focus of industry.The producer of each copper-clad laminate all releases the halogen-free flameproof copper-clad laminate of oneself one after another.
Development through the several years, at present, the major technique approach that realizes the copper-clad laminate halogen-free flameproof has two kinds, first kind of approach, the employing phosphorous epoxy resin is a matrix resin, adopting Dyhard RU 100 or resol then is solidifying agent, add mineral fillers such as a certain amount of aluminium hydroxide, adopt the solidifying agent of Dyhard RU 100 as phosphorous epoxy resin, the poor heat resistance of sheet material, water-absorbent is big; Adopt the solidifying agent of resol as phosphorous epoxy resin, prepreg apparent poor, the fragility of sheet material is big, poor in processability.Second kind of approach, adopting the benzoxazine resin is matrix resin, adds an amount of phosphorous epoxy resin or phosphorous, nitrogenous solidifying agent, add an amount of organic or inorganic filler again, the benzoxazine resin has good resistance toheat and low water-intake rate, but fragility is big, the poor processability of sheet material.In addition, more than the copper-clad laminate of two kinds of technological approaches manufacturings all exist second-order transition temperature low (＜190 ℃ 〉, the problem of CTE higher (＞2.5%).
In above-mentioned two kinds of technological approaches, all adopted phosphorus as main fire retardant.Yet, use phosphorus fire-retardant, the various intermediates and the production process of phosphorus flame retardant all have certain toxicity; Phosphorus flame retardant might produce toxic gas (as methylphosphine) and toxic substance (as triphenylphosphine etc.) in the incendiary process, its waste may cause potential hazard to aquatic environment simultaneously.
And along with the develop rapidly of electronic information technology, the appearance of surface mounting technique, PCB (tellite) more and more develops to the direction of high-density, highly reliable, multiple stratification, low cost and automatic continuous production, and PCB is had higher requirement with the thermotolerance and the reliability of substrate.All the time based on the FR-4 of Resins, epoxy because the shortcoming of high thermal resistance difference, unable to do what one wishes in the application that requires high temperature resistant and high reliability circuit: when the High Density Packaging high power device, the heating of PCB boring bit high speed rotating makes resin softening, and the second-order transition temperature of FR4 (Tg) is low, thus make easily that copper conductor comes off, the PCB distortion.When multi-ply wood welding and high low temperature round-robin thermal shocking, the Z-direction coefficient of expansion of FR4 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.In addition, because electronic mounting is more and more intensive now, and circuit card to be able to take acid or alkali environment in the course of processing and 288 degree down repeatedly cold cycling impact, and factors 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 the 17ppm/ degree, and the thermal expansivity of general thermosetting resin is more than the 200ppm/ degree, bigger thermal expansion coefficient difference can cause in the course of processing fracture of plated through-hole in the thermal shock of (PCB does not have the processing temperature of lead welding at 240 degree-270 degree at present), cause the short circuit of opening circuit, make product rejection.Especially concerning high multiwalled PCB (more than 20 layers), Z-CTE is the smaller the better.
Therefore, the printed electronic circuit copper-clad laminate of a kind of high heat-stable non-halogen non-phosphate of the market requirement (high second-order transition temperature,＞200 ℃, the low Z-direction coefficient of expansion,＜2.0%).
Polyimide (PI) since its excellent performance be widely used always, but it is after extensive, the stable production of bismaleimides (BMI) as the PCB baseplate material really.Dielectric properties, the dimensional stability of PI are preferable, with thermosetting resin and with having high glass transition, PI uses in giant-powered computer at most as the PCB base material, the multi-ply wood of 10-20 layer adopts PI or BT resin (bismaleimide-triazine resin), 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.Yet simple bimaleimide resin fragility is very big, does not have cohesive force again, must carry out toughness reinforcing and adhesiveness increasing and modifying could both keep its thermotolerance and electrical property, improves its toughness and cohesiveness again.At present bimaleimide resin modification main path has aromatic diamine modification, allylic cpd modification, cyanate ester modification, polyphenyl ether modified, thermoplastic resin modified, modified rubber, epoxy resin modification or the like.In the copper-clad plate field, aromatic diamine modified bismaleimide application of compound receives publicity always and studies.
U.S. Pat, 3920768 (1975) disclose a kind of diamine modified bismaleimide, though use diamine modified bismaleimide system to have good thermotolerance, mechanical property, the prepreg of making does not almost have viscosity, and manufacturability is not good.
Improve the toughness and the cohesiveness of bismaleimide modified epoxy though China's publication number is the patent of 101037528A, yet had the problem of PCT poor-performing, be unfavorable for suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of high heat-stable non-halogen non-phosphate compositions of thermosetting resin, the tool environmental protection characteristic has high second-order transition temperature, heat decomposition temperature, thermally stratified layer time, good good characteristics such as boring processibility.
Another object of the present invention is to provide a kind of bonding sheet that uses the heat-stable non-halogen non-phosphate compositions of thermosetting resin of above-mentioned height to make, have better heat-resisting, and its making is simple, cost is lower.
Another purpose of the present invention is to provide a kind of copper-clad laminate that uses the heat-stable non-halogen non-phosphate compositions of thermosetting resin of above-mentioned height to make, have high glass transition, pyrolytic decomposition temperature, long thermally stratified layer time, low-expansion coefficient and excellent dielectric properties, can be applied to satisfy the demand that high multi-layer PCB is made in the high temperature resistant and high multilayer circuit making.
For achieving the above object, the invention provides a kind of high heat-stable non-halogen non-phosphate compositions of thermosetting resin, press total weight of solids part and calculate, it comprises that component and weight part thereof are: aromatic amine compound 5-40 part, bismaleimide compound 50-350 part, biphenyl type epoxy resin 50-250 part, amine curing agent 0.1-5 part, catalyzer 0.01-5 part, filler 50-200 part, and solvent an amount of.
Further, a kind of bonding sheet that uses the heat-stable non-halogen non-phosphate compositions of thermosetting resin of above-mentioned height to make is provided, it comprises base-material and by the high heat-stable non-halogen non-phosphate compositions of thermosetting resin of the dry postadhesion of impregnation on base-material, the content of high heat-stable non-halogen non-phosphate compositions of thermosetting resin is 25-80% in this bonding sheet.
Described base-material is inorganic or organic materials, inorganic materials comprises woven fabric or the non-woven fabrics or the paper of glass fibre, carbon fiber, boron fibre, metal, and 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 uses the heat-stable non-halogen non-phosphate compositions of thermosetting resin of above-mentioned height to make, comprise veneer sheet and be overlaid on the Copper Foil of veneer sheet one or both sides, this veneer sheet comprises the bonding sheet that several pieces are bonding, each bonding sheet comprises base-material and by the high heat-stable non-halogen non-phosphate compositions of thermosetting resin of the dry postadhesion of impregnation on base-material, the content of high heat-stable non-halogen non-phosphate compositions of thermosetting resin is 25-80% in the bonding sheet.
Beneficial effect of the present invention: the heat-stable non-halogen non-phosphate compositions of thermosetting resin of height of the present invention, it possesses the halogen-free phosphor-free environmental protection characteristic, have high second-order transition temperature, heat decomposition temperature, thermally stratified layer time, good good characteristics such as boring processibility, have high thermotolerance, flame retardant properties has reached the UL94V-0 level.With its bonding sheet of making and copper-clad laminate, have higher thermotolerance, high second-order transition temperature, pyrolytic decomposition temperature, long thermally stratified layer time, low thermal coefficient of expansion and excellent dielectric properties, its thermal expansivity (CTE) can be reduced to below 2.0%, can be applied in the high temperature resistant and high multilayer circuit making, satisfy the demand that high multilayer (more than 20 layers) PCB makes, also can be used as the IC encapsulating carrier plate; And manufacture craft is simple, and cost is lower, is suitable for suitability for industrialized production.
Embodiment
The heat-stable non-halogen non-phosphate compositions of thermosetting resin of height provided by the invention, press total weight of solids part and calculate, it comprises that component and weight part thereof are: aromatic amine compound 5-40 part, bismaleimide compound 50-350 part, biphenyl type epoxy resin 50-250 part, amine curing agent 0.1-5 part, catalyzer 0.01-5 part, filler 50-200 part, and solvent an amount of.
Aromatic amine compound described in the present invention is the diamino compounds, and it comprises diaminodiphenylsulfone(DDS), diaminodiphenylmethane or diaminodiphenyl oxide etc.
Described bismaleimide compound is to contain the compound of two maleimide base groups in the molecular structure, as can be in diphenyl methane dimaleimide, phenyl ether bismaleimides or the sulfobenzide bismaleimides etc. one or more.
The biphenyl type epoxy resin that the present invention uses is the Resins, epoxy that contains biphenyl structural, and its chemical structural formula is:
Wherein R represents hydrogen atom, and halogen atom has the alkyl or the ring-type alicyclic ring group alkyl of 1-8 linear, side chain, and the alkoxyl group of 1-10 carbon atom, or phenyl, n are represented 0 to 20 integer.
The amine curing agent that the present invention uses is Dyhard RU 100.Described catalyzer comprises tertiary amine, three grades of phosphorus, quaternary amine, quaternary alkylphosphonium salt or imidazolium compoundss.
Described filler is one or more in aluminium hydroxide, silicon-dioxide, magnesium hydroxide, kaolin, the hydrotalcite etc.Described solvent is the combination that comprises 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.
As selectivity embodiment of the present invention, also can comprise dyestuff, pigment, tensio-active agent, flow agent, UV light absorber in the compositions of thermosetting resin of the non-halogen non-phosphate of this high heat resistance.
The compositions of thermosetting resin of the non-halogen non-phosphate of high heat resistance of the present invention in the preparation, only diamino compounds, bismaleimide compound, promotor need be reacted 10-300 minute in the 100-160 degree in solvent, after being cooled to room temperature, can obtain in aprotic solvent dissolving good homogeneous transparent resin solution, in this resin solution, add then and obtain the glue of solid content after Resins, epoxy, solidifying agent, promotor, filler and stirring solvent mix at the described resin combination of 50-80%.
The bonding sheet that the compositions of thermosetting resin of the non-halogen non-phosphate of the above-mentioned high heat resistance of use of the present invention is made comprises that base-material reaches by the high heat-stable non-halogen non-phosphate compositions of thermosetting resin of the dry postadhesion of impregnation on base-material.The content of high heat-stable non-halogen non-phosphate compositions of thermosetting resin is 25-80% in this bonding sheet.Described base-material is inorganic or organic materials, and inorganic materials comprises woven fabric or the non-woven fabrics or the paper of glass fibre, carbon fiber, boron fibre, metal; 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.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.
The method of using the compositions of thermosetting resin of the non-halogen non-phosphate of high heat resistance of the present invention to make bonding sheet is listed below, yet the method for making bonding sheet is not limited only to this: the glue (having used solvent adjustment viscosity herein) of the compositions of thermosetting resin of the non-halogen non-phosphate of high heat resistance of the present invention is immersed on the base-material, and the preliminary-dip piece of the compositions of thermosetting resin of the non-halogen non-phosphate that is impregnated with high heat resistance carried out heat drying, make the compositions of thermosetting resin of non-halogen non-phosphate of the high heat resistance in the preliminary-dip piece be in the semicure stage (B-stage), can obtain bonding sheet.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.
The copper-clad laminate that the compositions of thermosetting resin of the non-halogen non-phosphate of the above-mentioned high heat resistance of use of the present invention is made, comprise veneer sheet and be overlaid on the Copper Foil of one or both sides on the veneer sheet, veneer sheet comprises the bonding sheet that several pieces are bonding, and each bonding sheet comprises that base-material reaches by the high heat-stable non-halogen non-phosphate compositions of thermosetting resin of the dry postadhesion of impregnation on base-material.Wherein the content of high heat-stable non-halogen non-phosphate compositions of thermosetting resin is 25-80% in the bonding sheet.Described Copper Foil is an electrolytic copper foil, and replacements such as all right nickel foil of Copper Foil, aluminium foil and SUS paper tinsel are covered nickel foil veneer sheet, cladded aluminum foil veneer sheet and covered SUS foil laminate etc. thereby make, and its material is not limit.
In industrial production, veneer sheet, copper-clad laminate, printed circuit board all can adopt above-mentioned bonding sheet to make.In the present embodiment, we are that example illustrates this production method with the copper-clad laminate: when using bonding sheet to make copper-clad laminate, one or more bonding sheets are cut into certain size to be carried out sending into after superimposed and carries out lamination in the laminating apparatus, simultaneously Copper Foil is placed on the one or both sides of the bonding sheet that is superimposed, forms copper-clad laminate by hot-forming compacting.Can use copper or brass foil as Copper Foil, can also use the alloy of copper, brass, aluminium, nickel and these metals or composite metallic material to replace Copper Foil.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 by the suitable pressure that satisfies molding, make it the requirement that reaches required.The common governing principle that gets the neutralizing layer pressing plate for 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.
Survey performances such as its Tg, incendivity, second-order transition temperature, stripping strength, thermally stratified layer time, heat decomposition temperature at the above-mentioned copper-clad laminate of making, further give to illustrate in detail and describe as following embodiment.
Now the embodiment of the invention is described in detail as follows, but the present invention is confined to scope of embodiments.
Embodiment 1:
25g diamino two methyl-phenoxides (DDE), 200g diphenyl methane dimaleimide (BDM) are joined in the there-necked flask, open to stir, in 150 ℃ of isothermal reactions 50 minutes, obtain the thick liquid resin after being cooled to room temperature under the condensing reflux.The biphenyl type epoxy resin that in this resin solution, adds 150g, 1.0g dicy-curing agent, 0.4g 2-methyl-4-ethyl imidazol(e) catalyzer, add 60g aluminium hydroxide again, 80g fusion silicon-dioxide and an amount of solvent N, behind the dinethylformamide, mix after regulating solid content and be 65%, form the compositions of thermosetting resin glue of the non-halogen non-phosphate of high heat resistance.
Adopt woven fiber glass in above-mentioned glue, behind the impregnation, in baking oven,, to obtain the bonding sheet of semi-cured state in 155 ℃ of bakings 6 minutes.8 bonding sheets are stacked, two-sided be covered with Copper Foil after, in vacuum press 220 ℃, hot pressing obtains thickness after 90 minutes be 1.6 copper-clad laminate.Plate property sees Table 1.
Embodiment 2:
25g diamino two methyl-phenoxides (DDE), 260g diphenyl methane dimaleimide (BDM) are joined in the there-necked flask, open to stir, in 150 ℃ of isothermal reactions 60 minutes, obtain the thick liquid resin after being cooled to room temperature under the condensing reflux.The biphenyl epoxy that in this resin solution, adds 120g, 1.0g dicy-curing agent, 0.35g 2-methyl-4-ethyl imidazol(e) catalyzer, add 80g aluminium hydroxide again, 60g fusion silicon-dioxide and an amount of solvent N, behind the dinethylformamide, mix after regulating solid content and be 65%, form the compositions of thermosetting resin glue of the non-halogen non-phosphate of high heat resistance.Make copper-clad laminate according to the method among the embodiment 1 then, its performance sees Table 1.
Embodiment 3:
25g diamino two methyl-phenoxides (DDE), 300g diphenyl methane dimaleimide (BDM) are joined in the there-necked flask, open to stir, in 150 ℃ of isothermal reactions 70 minutes, obtain the thick liquid resin after being cooled to room temperature under the condensing reflux.The biphenyl epoxy that in this resin solution, adds 100g, 1.0g dicy-curing agent, 0.3g 2-methyl-4-ethyl imidazol(e) catalyzer, add 100g aluminium hydroxide again, 40g fusion silicon-dioxide and an amount of solvent N, behind the dinethylformamide, mix after regulating solid content and be 65%, form the compositions of thermosetting resin glue of the non-halogen non-phosphate of high heat resistance.Make copper-clad laminate according to the method among the embodiment 1 then, its performance sees Table 1.
Comparative example 1:
25g diamino two methyl-phenoxides (DDE), 200g diphenyl methane dimaleimide (BDM) are joined in the there-necked flask, open to stir, in 150 ℃ of isothermal reactions 50 minutes, obtain the thick liquid resin after being cooled to room temperature under the condensing reflux.The bisphenol A-type multi-functional epoxy who in this resin solution, adds 140g, 1.0g dicy-curing agent, 0.3g 2-methyl-4-ethyl imidazol(e) catalyzer, add 60g aluminium hydroxide again, 80g fusion silicon-dioxide and an amount of solvent N, behind the dinethylformamide, mix after regulating solid content and be 65%, form the compositions of thermosetting resin glue of the non-halogen non-phosphate of high heat resistance.Make copper-clad laminate according to the method in the example 1 then, its performance sees Table 1.
Comparative example 2:
25g diamino two methyl-phenoxides (DDE), 200g diphenyl methane dimaleimide (BDM) are joined in the there-necked flask, open to stir, in 150 ℃ of isothermal reactions 50 minutes, obtain the thick liquid resin after being cooled to room temperature under the condensing reflux.The biphenyl epoxy that in this resin solution, adds 150g, the 1.0g dicy-curing agent, 0.4g 2-methyl-4-ethyl imidazol(e) catalyzer mixes after regulating solid content and be 65%, forms the compositions of thermosetting resin glue of the non-halogen non-phosphate of high heat resistance.Make copper-clad laminate according to the method among the embodiment 1 then, its performance sees Table 1.
Comparative example 3:
In the biphenyl epoxy of 300g, add line style phenol phenolic curing agent 100g, catalyzer 2-methyl-4-ethyl imidazol(e) 0.55g, add aluminium hydroxide 60g again, fusion silicon-dioxide 80g and an amount of solvent N behind the dinethylformamide, mix after regulating solid content and be 65%.Make copper-clad laminate according to the method among the embodiment 1 then, its performance sees Table 1.
The copper-clad laminate performance table that each embodiment of table 1. and comparative example make
The testing method of above characteristic is as follows:
1), thermal expansivity Z axle CTE: measure according to thermomechanical analysis.
2), second-order transition temperature (Tg): test according to dynamic thermomechanical analysis.
3), incendivity: measure according to UL94 vertical combustion method.
4), stripping strength:, test the stripping strength of metal cladding according to " after the thermal stresses " experiment condition in the IPC-TM-650 method.
5), the thermally stratified layer time: measure according to methods involving among the IPC-TM-650.
6), heat decomposition temperature Td: measure according to methods involving among the IPC-TM-650.
7), PCT: in IPC-TM-650 on the basis of methods involving, make sample stand more strictness reach 1 hour boiling (105KPa/60min) be placed on a kind of testing method that 288 ℃ of tin stoves are tested the anti-immersed solder time.
8), content of halogen test: measure according to their-650 methods involvings of TPC-.
In sum, the heat-stable non-halogen non-phosphate compositions of thermosetting resin of height of the present invention, it possesses the halogen-free phosphor-free environmental protection characteristic, have high second-order transition temperature, heat decomposition temperature, thermally stratified layer time, good good characteristics such as boring processibility, have high thermotolerance, flame retardant properties has reached the UL94V-0 level.With its bonding sheet of making and copper-clad laminate, have higher thermotolerance, high second-order transition temperature (being higher than 200 ℃), pyrolytic decomposition temperature, long thermally stratified layer time, low thermal coefficient of expansion and excellent dielectric properties, its thermal expansivity (CTE) can be reduced to below 2.0%, can be applied in the high temperature resistant and high multilayer circuit making, satisfy the demand that high multilayer (more than 20 layers) PCB makes, also can be used as the IC encapsulating carrier plate; And manufacture craft is simple, and cost is lower, is suitable for suitability for industrialized production.
Above embodiment, be not that content to composition of the present invention imposes any restrictions, every foundation technical spirit of the present invention or composition composition or content all still belong in the scope of technical solution of the present invention any trickle modification, equivalent variations and modification that above embodiment did.
Claims (10)
1. one kind high heat-stable non-halogen non-phosphate compositions of thermosetting resin, it is characterized in that it comprises that component and weight part thereof are: aromatic amine compound 5-40 part, bismaleimide compound 50-350 part, biphenyl type epoxy resin 50-250 part, amine curing agent 0.1-5 part, catalyzer 0.01-5 part, filler 50-200 part, and solvent an amount of.
2. the heat-stable non-halogen non-phosphate compositions of thermosetting resin of height as claimed in claim 1 is characterized in that described aromatic amine compound is the diamino compounds, and it comprises diaminodiphenylsulfone(DDS), diaminodiphenylmethane or diaminodiphenyl oxide.
3. the heat-stable non-halogen non-phosphate 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 non-halogen non-phosphate compositions of thermosetting resin of height as claimed in claim 1 is characterized in that described biphenyl type epoxy resin is the Resins, epoxy that contains biphenyl structural, and its chemical structural formula is:
Wherein R represents hydrogen atom, and halogen atom has the alkyl or the ring-type alicyclic ring group alkyl of 1-8 linear, side chain, and the alkoxyl group of 1-10 carbon atom, or phenyl, n are represented 0 to 20 integer.
5. the heat-stable non-halogen non-phosphate compositions of thermosetting resin of height as claimed in claim 1 is characterized in that, described catalyzer comprises tertiary amine, three grades of phosphorus, quaternary amine, quaternary alkylphosphonium salt or imidazolium compoundss, and amine curing agent is a Dyhard RU 100.
6. the heat-stable non-halogen non-phosphate compositions of thermosetting resin of height as claimed in claim 1 is characterized in that described filler is one or more in aluminium hydroxide, silicon-dioxide, magnesium hydroxide, kaolin, the hydrotalcite.
7. the heat-stable non-halogen non-phosphate compositions of thermosetting resin of height as claimed in claim 1 is characterized in that, described solvent is the combination that comprises 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.
8. bonding sheet that adopts the heat-stable non-halogen non-phosphate compositions of thermosetting resin of height as claimed in claim 1 to make, it is characterized in that, comprise that base-material reaches by the high heat-stable non-halogen non-phosphate compositions of thermosetting resin of the dry postadhesion of impregnation on base-material, the content of high heat-stable non-halogen non-phosphate compositions of thermosetting resin is 25-80% in this bonding sheet.
9. bonding sheet as claimed in claim 8, it is characterized in that, described base-material is inorganic or organic materials, inorganic materials comprises woven fabric or the non-woven fabrics or the paper of glass fibre, carbon fiber, boron fibre, metal, and 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.
10. copper-clad laminate that adopts the heat-stable non-halogen non-phosphate compositions of thermosetting resin of height as claimed in claim 1 to make, it is characterized in that, comprise veneer sheet and be overlaid on the Copper Foil of veneer sheet one or both sides, this veneer sheet comprises the bonding sheet that several pieces are bonding, and each bonding sheet comprises that base-material reaches by the high heat-stable non-halogen non-phosphate compositions of thermosetting resin of the dry postadhesion of impregnation on base-material.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504489A (en) * | 2011-11-08 | 2012-06-20 | 桂林电器科学研究院 | Thermosetting resin composition, preparation method thereof and laminate |
| CN102533191A (en) * | 2011-12-23 | 2012-07-04 | 云南云天化股份有限公司 | High temperature-resistant halogen-free ion migration-resistant epoxy resin adhesive |
| CN102558861A (en) * | 2011-12-27 | 2012-07-11 | 广东生益科技股份有限公司 | Halogen-free phosphate-free high-heat-resistance thermosetting resin composition as well as bonding sheet and copper clad laminate prepared from same |
| CN102796281A (en) * | 2012-08-16 | 2012-11-28 | 广东生益科技股份有限公司 | Heat resistant filling material used for brominated modified epoxy copper clad laminate and brominated epoxy resin composition used for copper clad laminate |
| CN102977337A (en) * | 2012-12-06 | 2013-03-20 | 衡阳恒缘电工材料有限公司 | C-grade modified bismaleimide glass fiber reinforced mould plastic |
| CN103740313A (en) * | 2013-12-13 | 2014-04-23 | 青岛海洋新材料科技有限公司 | Preparation method of high temperature-resistant epoxy resin adhesive |
| CN108314984A (en) * | 2018-02-05 | 2018-07-24 | 深圳市鑫东邦科技有限公司 | A kind of one-component high-temp glue and preparation method thereof |
| CN108623786A (en) * | 2017-03-24 | 2018-10-09 | 新日铁住金化学株式会社 | Composition epoxy resin, its manufacturing method, curable resin composition and the hardening thing of Han oxazolidine ketone rings |
| CN109294496A (en) * | 2018-09-10 | 2019-02-01 | 南亚电子材料(昆山)有限公司 | It is a kind of for the heat resistance filler of copper-clad plate and for the resin combination of copper-clad plate |
| CN109666297A (en) * | 2018-11-30 | 2019-04-23 | 中国航空工业集团公司基础技术研究院 | A kind of sacrificial layer Ultraluminescence bimaleimide resin carbon fiber prepreg |
| CN109810504A (en) * | 2019-01-24 | 2019-05-28 | 江苏澳盛复合材料科技有限公司 | A kind of bismaleimide resin composition and its solidfied material and composite material |
| KR20190131095A (en) * | 2017-03-28 | 2019-11-25 | 히타치가세이가부시끼가이샤 | Prepregs, coreless substrates and semiconductor packages for coreless substrates |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102504489A (en) * | 2011-11-08 | 2012-06-20 | 桂林电器科学研究院 | Thermosetting resin composition, preparation method thereof and laminate |
| CN102533191A (en) * | 2011-12-23 | 2012-07-04 | 云南云天化股份有限公司 | High temperature-resistant halogen-free ion migration-resistant epoxy resin adhesive |
| CN102558861A (en) * | 2011-12-27 | 2012-07-11 | 广东生益科技股份有限公司 | Halogen-free phosphate-free high-heat-resistance thermosetting resin composition as well as bonding sheet and copper clad laminate prepared from same |
| CN102796281A (en) * | 2012-08-16 | 2012-11-28 | 广东生益科技股份有限公司 | Heat resistant filling material used for brominated modified epoxy copper clad laminate and brominated epoxy resin composition used for copper clad laminate |
| CN102977337A (en) * | 2012-12-06 | 2013-03-20 | 衡阳恒缘电工材料有限公司 | C-grade modified bismaleimide glass fiber reinforced mould plastic |
| CN102977337B (en) * | 2012-12-06 | 2015-03-25 | 衡阳恒缘电工材料有限公司 | C-grade modified bismaleimide glass fiber reinforced mould plastic |
| CN103740313A (en) * | 2013-12-13 | 2014-04-23 | 青岛海洋新材料科技有限公司 | Preparation method of high temperature-resistant epoxy resin adhesive |
| CN108623786A (en) * | 2017-03-24 | 2018-10-09 | 新日铁住金化学株式会社 | Composition epoxy resin, its manufacturing method, curable resin composition and the hardening thing of Han oxazolidine ketone rings |
| CN108623786B (en) * | 2017-03-24 | 2022-04-05 | 日铁化学材料株式会社 | Oxazolidone ring-containing epoxy resin composition, method for producing same, curable resin composition, and cured product |
| KR20190131095A (en) * | 2017-03-28 | 2019-11-25 | 히타치가세이가부시끼가이샤 | Prepregs, coreless substrates and semiconductor packages for coreless substrates |
| US11581212B2 (en) * | 2017-03-28 | 2023-02-14 | Showa Denko Materials Co., Ltd. | Prepreg for coreless substrate, coreless substrate and semiconductor package |
| KR102603152B1 (en) | 2017-03-28 | 2023-11-16 | 가부시끼가이샤 레조낙 | Prepreg for coreless substrates, coreless substrates and semiconductor packages |
| CN108314984A (en) * | 2018-02-05 | 2018-07-24 | 深圳市鑫东邦科技有限公司 | A kind of one-component high-temp glue and preparation method thereof |
| CN109294496A (en) * | 2018-09-10 | 2019-02-01 | 南亚电子材料(昆山)有限公司 | It is a kind of for the heat resistance filler of copper-clad plate and for the resin combination of copper-clad plate |
| CN109666297A (en) * | 2018-11-30 | 2019-04-23 | 中国航空工业集团公司基础技术研究院 | A kind of sacrificial layer Ultraluminescence bimaleimide resin carbon fiber prepreg |
| CN109666297B (en) * | 2018-11-30 | 2021-08-03 | 中国航空工业集团公司基础技术研究院 | Ultraviolet fluorescent bismaleimide resin carbon fiber prepreg for sacrificial layer |
| CN109810504A (en) * | 2019-01-24 | 2019-05-28 | 江苏澳盛复合材料科技有限公司 | A kind of bismaleimide resin composition and its solidfied material and composite material |
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