CN101550264A - Resin matching fluid used for metal foil laminated board - Google Patents
Resin matching fluid used for metal foil laminated board Download PDFInfo
- Publication number
- CN101550264A CN101550264A CNA2009100313679A CN200910031367A CN101550264A CN 101550264 A CN101550264 A CN 101550264A CN A2009100313679 A CNA2009100313679 A CN A2009100313679A CN 200910031367 A CN200910031367 A CN 200910031367A CN 101550264 A CN101550264 A CN 101550264A
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- China
- Prior art keywords
- resin
- crystal whisker
- matching fluid
- inorganic crystal
- coupling agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920005989 resin Polymers 0.000 title claims abstract description 105
- 239000011347 resin Substances 0.000 title claims abstract description 105
- 239000012530 fluid Substances 0.000 title claims abstract description 47
- 239000011888 foil Substances 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 58
- -1 borate ester Chemical class 0.000 claims abstract description 41
- 239000007822 coupling agent Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000004593 Epoxy Substances 0.000 claims description 31
- 238000005303 weighing Methods 0.000 claims description 18
- 239000004327 boric acid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 abstract description 13
- 229920000647 polyepoxide Polymers 0.000 abstract description 13
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- PGJJHMBDWLEWCO-UHFFFAOYSA-N (2-methylpropan-2-yl)oxyboronic acid Chemical compound CC(C)(C)OB(O)O PGJJHMBDWLEWCO-UHFFFAOYSA-N 0.000 abstract 1
- HJVAFZMYQQSPHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boric acid Chemical compound OB(O)O.OCCN(CCO)CCO HJVAFZMYQQSPHF-UHFFFAOYSA-N 0.000 abstract 1
- DWEWYNUOSFBXMY-UHFFFAOYSA-N B(O)(O)OCCCC.N(CCO)CCO Chemical compound B(O)(O)OCCCC.N(CCO)CCO DWEWYNUOSFBXMY-UHFFFAOYSA-N 0.000 abstract 1
- WHBHPSSRJUJPKW-UHFFFAOYSA-N butan-2-yloxyboronic acid 2-(2-hydroxyethylamino)ethanol Chemical compound B(O)(O)OC(C)CC.N(CCO)CCO WHBHPSSRJUJPKW-UHFFFAOYSA-N 0.000 abstract 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 13
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000004381 surface treatment Methods 0.000 description 9
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 229920003987 resole Polymers 0.000 description 7
- 239000011120 plywood Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 125000000213 sulfino group Chemical group [H]OS(*)=O 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
The invention discloses a resin matching fluid, comprising the following components: epoxy resin, a curing agent, a curing accelerator, a solvent, an inorganic crystal whisker and a surface coupling agent; the surface coupling agent is one or mixture of two or more than two selected form triethanolamine borate, diethanolamine n-butanol-borate, diethanolamine sec-butanol-borate or diethanolamine t-butanol-borate; due to the use of borate ester surface coupling agent, the resin matching fluid improves the compatibility of inorganic crystal whisker and thermosetting resin, thus obtaining the metal foil laminated board with high rigidity, low coefficient of thermal expansion and high cohesiveness; and a printed circuit board of the metal foil laminated board has high circuit processability in manufacture, thus being capable of meeting the requirements of thin multi-layer printed circuit boards and being applicable to HDI boards and IC package substrates.
Description
Technical field
The present invention relates to prepare the required resin matching fluid of metal foil laminate, specific design is applied to prepare the resin matching fluid in high density interconnect multi-ply wood or the IC encapsulation field.
Background technology
In recent years, electronic product makes printed circuit board develop towards meticulous, slim, multiple stratification direction to miniaturization, multifunction development, and increasing high-end product all uses high density interconnect (HDI) multi-ply wood; Owing to produce and use technology increasingly sophisticated,, require sheet material to possess higher hot physical strength and low-thermal-expansion rate, second-order transition temperature to the demands for higher performance of PCB baseplate material; Simultaneously because the base plate for packaging material is thinner, add for the IC base plate for packaging and pursue thin spaceization, many pinizations more, make and guarantee that the layer insulation problem of thin base material is more outstanding, particularly to solve the rigidity that the thin base material is prone to, the problem that causes insulating reliability to descend.
The PCB base material is the structural sheet (being copper-clad laminate) that copper conductor and insulating material bond together, provide printed board required electric and mechanical property, most insulating material is that fortifying fibre and organic resin are formed, aspect fortifying fibre, using always has glass fibre, belong to high temperature material, form so the thermotolerance of sheet material depends on resin.
In the PCB baseplate material that with the woven fiber glass is strongthener, the FR-4 plate of epoxy systems is owing to have such as high Copper Foil stripping strength, good insulation performance performance and workability, and become the present universal product, but, common FR-4 plate Z-direction thermal expansivity is big, thermotolerance is low, and second-order transition temperature is between 130～140 ℃, and it is greasy dirty easily to produce resin during boring, add and shrink man-hour greatly, shortcomings such as unfavorable contraposition have certain limitation in the use, especially for making multi-ply wood, common FR-4 material can only just seem somewhat unable to do what one wishes during greater than 10 layers with the multi-ply wood below 10 layers.
The basic method that improves the thermosetting resin resistance toheat is to change resinous molecular structure and crosslinking structure, in addition, influence such as the interpolation of the rigidity intensity of main polymer chain, solidification value, softening agent and the steric effect of macromolecular chain side group is also very big, in the thermosetting resin molecule, introducing can participate in polymeric polar group (imide, cyanic acid base, sulfino) and the bigger group (as aromatic base) of steric hindrance, improve the cured article cross-linking density, all can effectively improve the polymkeric substance thermotolerance.But the cross-linking density height, cured article is more crisp, toughness and impact resistance are poor, influences printed circuit board boring processibility.
In traditional resin matching fluid, the general aluminium hydroxide that adds, mineral fillers such as silicon-dioxide improve the rigidity of sheet material, hot expansibility, be applied in high density interconnect (HDI) and the IC encapsulation field, but the cohesiveness between tinsel and the traditional resin, thermotolerance is wanting in, and influences the quality of product.
Publication number is that the Japanese Patent of flat 11-207868, flat 09-254313,2001-316563 and 2001-316564 discloses a kind of copper-clad laminate (abbreviation copper-clad plate), and this copper-clad plate is slim, stable, production cost is low; Insulation layer in the described copper-clad plate is made up of thermosetting resin and insulating inorganic crystal whisker; Wherein, inorganic crystal whisker is handled through surface treatment agent, and described surface treatment agent is selected from: silane series coupling agent, titanium are that coupling agent, aluminium are that coupling agent, phosphorus are that coupling agent, amino acid are that coupling agent or boron are a kind of in the coupling agent; But whisker and the consistency between the resin in the above-mentioned patent are poor, do not bring into play the effect of whisker in resin fully, therefore influence the over-all properties of resin cured matter.
Therefore need overcome the problem that traditional F R-4 metal foil laminate exists, research and develop the manufacture method of resin matching fluid and the bonding sheet and the metal foil laminate of the low thermal coefficient of expansion of a kind of suitable HDI and the requirement of IC base plate for packaging, high rigidity, high-adhesion.
Summary of the invention
The object of the invention provides a kind of resin matching fluid that is applied to high density interconnect (HDI) multi-ply wood and IC base plate for packaging, to overcome the defective of prior art, improve the consistency of inorganic crystal whisker and thermosetting resin, thereby reduce the thermal expansivity of thermosetting resin, the cohesiveness between raising resin and the Copper Foil and the rigidity of thermosetting resin;
Another object of the present invention provides a kind of bonding sheet and metal foil laminate.
For achieving the above object, the concrete technical scheme of the present invention is, a kind of resin matching fluid, and described resin matching fluid comprises following component: Resins, epoxy, solidifying agent, curing catalyst, solvent, inorganic crystal whisker and surperficial coupling agent;
In the technique scheme, selectable kind of described Resins, epoxy, solidifying agent, curing catalyst, solvent and inorganic crystal whisker and proportioning are for well known to a person skilled in the art technology, and those skilled in the art can select proportioning voluntarily according to practical situation;
Generally, Resins, epoxy is selected from: one or more in two functional group epoxy resins or the polyfunctional epoxy resin; Solidifying agent is selected from: a kind of in amine curing agent or the phenolic aldehyde promise furac type resin; Curing catalyst is selected from a kind of in the glyoxaline compound; Inorganic crystal whisker is selected from a kind of in the borate whisker compounds; The surface coupling agent is selected from one or more in the boric acid ester compound;
In the optimized technical scheme, described Resins, epoxy is selected the Resins, epoxy that contains 2 above epoxy group(ing) in 1 molecular structure for use, is selected from: one or both in bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, dihydroxyphenyl propane promise furac type Resins, epoxy, phenolic aldehyde promise furac type Resins, epoxy, the Bisphenol F promise furac type Resins, epoxy and two or more mixtures; Wherein the higher resin of thermotolerance is a dihydroxyphenyl propane promise furac type Resins, epoxy;
In the optimized technical scheme, described solidifying agent is selected from: a kind of in dicy-curing agent or the phenolic resin curative;
In the optimized technical scheme, described curing catalyst is a glyoxaline compound, is selected from: a kind of in glyoxal ethyline (2-MI), 2-ethyl-4-methylimidazole (2E4MI) or the 2-phenylimidazole (2-PI);
In the optimized technical scheme, according to mass ratio, Resins, epoxy: solidifying agent: curing catalyst=100: 5～80: 0.01～5;
In the optimized technical scheme, described solvent is selected from: one or both in acetone, butanone, toluene or the dimethyl formamide and two or more mixtures;
In the optimized technical scheme, described inorganic crystal whisker is selected from: a kind of in magnesium borate crystal whisker, aluminium borate whisker, potassium titanate crystal whisker, silicon nitride crystal whisker or the ceramic whisker, the mean diameter of described inorganic crystal whisker is 0.5～5 μ m, and the diameter of inorganic crystal whisker is 0.2～9.9 μ m; The length of inorganic crystal whisker is greater than 10 times of diameter, and less than 100 μ m, the Young's modulus of inorganic crystal whisker is greater than 200GPa; The quality of inorganic crystal whisker account for the resin matching fluid solids content weight percent 10～60%;
Inorganic crystal whisker is through surperficial coupling agent treatment, in the optimized technical scheme, described surperficial coupling agent is a boric acid ester compound, be selected from: one or both in triethanolamine borate ester (BE3), boric acid propyl carbinol-diethanolamine ester (n-BE4), boric acid sec-butyl alcohol-diethanolamine ester (sec-BE4) or the trimethyl carbinol-diethanolamine ester (tert-BE4 changes 4) and two or more mixtures; Wherein, the structural formula of triethanolamine borate ester (BE3), boric acid propyl carbinol-diethanolamine ester (n-BE4), boric acid sec-butyl alcohol-diethanolamine ester (sec-BE4) and the trimethyl carbinol-diethanolamine ester (tert-BE4) is as follows respectively:
Triethanolamine borate ester (BE3):
Boric acid propyl carbinol-diethanolamine ester (n-BE4):
Boric acid sec-butyl alcohol-diethanolamine ester (sec-BE4):
The trimethyl carbinol-diethanolamine ester (tert-BE4):
In the technique scheme, according to mass ratio, inorganic crystal whisker: the mass ratio of surperficial coupling agent=1: 1～4: 1;
In the technique scheme, the method that disposes above-mentioned resin matching fluid may further comprise the steps:
(1) in the ratio of above-mentioned setting, take by weighing Resins, epoxy, solidifying agent, curing catalyst, be dissolved in solvent, be made into resin solution; In the ratio of above-mentioned setting, take by weighing inorganic crystal whisker and coupling agent, be dissolved in solvent, mix inorganic crystal whisker solution;
(2) inorganic crystal whisker solution is added in the resin solution; Solids content 50～70% mass percents of gained resin matching fluid, under 171 ℃, gelation time is 150～250 seconds;
The present invention also comprises a kind of preparation method of bonding sheet, may further comprise the steps: (model: 7628), the above-mentioned resin solution of impregnation in 150 ℃～170 ℃ bakings 3-6 minute, is made bonding sheet with the E glasscloth; The resin content of gained bonding sheet is 40～60%.
The present invention also comprises a kind of preparation method of metal foil laminate, may further comprise the steps: get 8 above-mentioned bonding sheets, and superimposed neat, the two-sided electrolytic copper foil of mixing, be placed between the stainless steel plate of two minute surfaces, place vacuum press then, at 180 ℃～200 ℃, 20～40Kkg/cm
2Suppressed 90～120 minutes, and made the metal foil laminate that thickness is 1.6mm.
Principle of the present invention is: inorganic crystal whisker has excellent mechanical property, chemical property stabilizer pole, electrical insulation capability, and can improve the shrinking percentage of resin matrix, the interface that reduces shrinking percentage between matrix and the fiber is poor, in addition, whisker with certain length-to-diameter ratio can be pricked interlayer at resin material as the nail riveting, this pinning effect makes the connection between fiber and the resin matrix become the three-dimensional connection with steric effect from original simple interface connection (two dimension), thereby improves the interlayer performance of Resins, epoxy.Simultaneously, high-strength, the high-modulus characteristic of whisker can further improve the intensity and the modulus of resin.But the difference of used surface treatment coupling agent, the mechanical property of resin system and consistency have certain difference.The contriver makes the mechanical property of Resins, epoxy and consistency obtain in various degree improvement with the surface-treated inorganic crystal whisker of Borate Ester as Coupling, wherein the borate ester whisker is to resin compatible aspect best results, but the length-to-diameter ratio of whisker is had very high requirement.The mean diameter scope is controlled at 0.5～5 μ m, and length range is greater than 10 times of diameter, and less than 100 μ m, Young's modulus is greater than 200GPa.If the mean diameter of whisker is less than 0.5 μ m or length 10 times words less than diameter, cohesion easily, influence the dispersiveness in the resin,, influence the surfaceness and the anti-metal ion transport (CAF) of sheet material if the mean diameter of whisker surpasses 100 μ m greater than 5 μ m or length.The content 10～60% (the total amount per-cent of resin solid content) of inorganic crystal whisker in resin Composition.If the content of inorganic crystal whisker is less than 10%, panel stiffness does not reach requirement, if the content of inorganic crystal whisker influence the thermotolerance of sheet material greater than 60%, and influences resin fillibility between internal layer circuit in the multi-ply wood manufacturing.
The surface treatment coupling agent can be used boric acid ester compound, boric acid ester compound has the boron atom of close inorganic crystal whisker and the butoxy of close resin, can effectively improve the interaction of two-phase interface, the consistency of raising and resin is therefore good than silane coupling agent commonly used to borate whisker surface-treated effect.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
Owing to use borate ester surface coupling agent among the present invention, improved the consistency of inorganic crystal whisker and thermosetting resin, thereby obtained to have the metal foil laminate of high rigidity, low thermal coefficient of expansion, high-adhesion; And therefore circuit processibility height during gained metal foil laminate printed circuit board is made can satisfy the requirement of slim multilayer printed wiring board, is suitable on HDI plate, the IC base plate for packaging.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one
(1) preparation of epoxy resin solution: take by weighing 100 weight part dihydroxyphenyl propane promise furac type Resins, epoxy, 67 weight part resol, 0.5 weight part 2-ethyl-4-methylimidazole joins in the butanone solvent of 100 weight parts and stirs, mixes the system resin matching fluid.
(2) inorganic crystal whisker surface treatment: (mean diameter is 0.8 μ m to take by weighing the magnesium borate crystal whisker of 72 weight parts, mean length is 20 μ m, Young's modulus is greater than 200GPa) and 29 weight part boric acid ester couplers (boric acid propyl carbinol-diethanolamine ester, n-BE4), the butanone solution that adds 30 weight parts then mixes fully.
Then magnesium borate crystal whisker solution is joined in the resin matching fluid, continue to stir, mix.Solids content is the Resins, epoxy fluid,matching of 60% boronic acid containing magnesium whisker.
(3) immerse in the resin matching fluid of above-mentioned boronic acid containing magnesium whisker with 8 7628E glasscloths, carry out gluing, baking is 3 minutes in 155 ℃ of baking ovens, makes the bonding sheet of semi-cured state.
(4) again with above-mentioned 8 bonding sheets stack alignment, respectively join 1 18 μ m electrolytic copper foil up and down, in vacuum press, by temperature 190, pressure 35Kgf/cm
2Condition, hot pressing 90 minutes, making thickness is the double-sided metal foil layer pressing plate of 1.6mm.
Experimental example two
(1) preparation of epoxy resin solution: take by weighing 100 weight part dihydroxyphenyl propane promise furac type Resins, epoxy, 67 weight part resol, 0.5 weight part 2-ethyl-4-methylimidazole joins in the butanone solvent of 100 weight parts and stirs, mixes the system resin matching fluid.
(2) inorganic crystal whisker surface treatment: (mean diameter is 0.8 μ m to take by weighing the magnesium borate crystal whisker of 19 weight parts, mean length is 20 μ m, Young's modulus is greater than 200GPa) and 7.6 weight part boric acid ester couplers (boric acid propyl carbinol-diethanolamine ester, n-BE4), dissolution with solvents with 16.4 weight parts mixes fully.
Then magnesium borate crystal whisker solution is joined in the resin matching fluid, continue to stir, mix.Solids content is the Resins, epoxy fluid,matching of 60% boronic acid containing magnesium whisker.
Prepare bonding sheet and metal foil laminate respectively according to the step among the embodiment one (3), (4) then.
Experimental example three
(1) preparation of epoxy resin solution: take by weighing 100 weight part dihydroxyphenyl propane promise furac type Resins, epoxy, 67 weight part resol, 0.5 weight part 2-ethyl-4-methylimidazole joins in the butanone solvent of 100 weight parts and stirs, mixes the system resin matching fluid.
(2) inorganic crystal whisker surface treatment: (mean diameter is 0.8 μ m to take by weighing the magnesium borate crystal whisker of 251 weight parts, mean length is 20 μ m, Young's modulus is greater than 200GPa) and 100 weight part boric acid ester couplers (boric acid propyl carbinol-diethanolamine ester, n-BE4), dissolution with solvents with 79 weight parts mixes fully.
Then magnesium borate crystal whisker solution is joined in the resin matching fluid, continue to stir, mix.Solids content is the Resins, epoxy fluid,matching of 60% boronic acid containing magnesium whisker.
Prepare bonding sheet and metal foil laminate respectively according to the step among the embodiment one (3), (4) then.
Experimental example four
(1) preparation of epoxy resin solution: take by weighing 70 weight part dihydroxyphenyl propane promise furac type Resins, epoxy, 30 weight part tetrabromo bisphenol-a epoxy resins, 67 weight part resol, 0.5 weight part 2-ethyl-4-methylimidazole joins in the butanone solvent of 100 weight parts and stirs, mixes the system resin matching fluid.
(2) inorganic crystal whisker surface treatment: (mean diameter is 1.5 μ m to take by weighing the magnesium borate crystal whisker of 72 weight parts, mean length is 30 μ m, Young's modulus is greater than 200GPa) and 29 weight part boric acid ester couplers (boric acid propyl carbinol-diethanolamine ester, n-BE4), dissolution with solvents with 30 weight parts mixes fully.
Then magnesium borate crystal whisker solution is joined in the resin matching fluid, continue to stir, mix.Solids content is the Resins, epoxy fluid,matching of 60% boronic acid containing magnesium whisker.
Prepare bonding sheet and metal foil laminate respectively according to the step among the embodiment one (3), (4) then.
Experimental example five
(1) preparation of epoxy resin solution: take by weighing 70 weight part dihydroxyphenyl propane promise furac type Resins, epoxy, 30 weight part tetrabromo bisphenol-a epoxy resins, 67 weight part resol, 0.5 weight part 2-ethyl-4-methylimidazole joins in the butanone solvent of 100 weight parts and stirs, mixes the system resin matching fluid.
(2) inorganic crystal whisker surface treatment: (mean diameter is 0.5 μ m to take by weighing the magnesium borate crystal whisker of 72 weight parts, mean length is 10 μ m, Young's modulus is greater than more than the 200GPa) and 29 weight part boric acid ester couplers (boric acid propyl carbinol-diethanolamine ester, n-BE4), dissolution with solvents with 30 weight parts mixes fully.
Then magnesium borate crystal whisker solution is joined in the resin matching fluid, continue to stir, mix.Solids content is the Resins, epoxy fluid,matching of 60% boronic acid containing magnesium whisker.
Prepare bonding sheet and metal foil laminate respectively according to the step among the embodiment one (3), (4) then.
Following comparative example is a prior art embodiments
Embodiment six
The preparation of epoxy resin solution: take by weighing 100 weight part dihydroxyphenyl propane promises and pay clarke type Resins, epoxy, 67 weight part resol, 0.5 weight part 2-ethyl-4-methylimidazole joins in the butanone solvent of 100 weight parts and stirs, mixes the system resin matching fluid.Take by weighing the surface-treated filling aluminium hydrate of 72 weight parts again and be dispersed in the solvent of 60 weight parts, then the aluminium hydroxide dispersion liquid is joined in the resin matching fluid, continue to stir, mix.Solids content is the Resins, epoxy fluid,matching of 60% aluminium hydroxide filler.
Prepare bonding sheet and metal foil laminate respectively according to the step among the embodiment one (3), (4) then.
Embodiment seven
The preparation of epoxy resin solution: take by weighing 100 weight part dihydroxyphenyl propane promise furac type Resins, epoxy, 67 weight part resol, 0.5 weight part 2-ethyl-4-methylimidazole joins in the butanone solvent of 100 weight parts and stirs, mixes the system resin matching fluid.
The inorganic crystal whisker surface treatment: (mean diameter is 0.8 μ m to take by weighing the magnesium borate crystal whisker of 72 weight parts, mean length is 20 μ m, Young's modulus is greater than 200GPa) carry out surface treatment with silane coupling agent, add the solvent of 60 weight parts then, mix fully.
Then magnesium borate crystal whisker solution is joined in the resin matching fluid, continue to stir, mix.Solids content is the Resins, epoxy fluid,matching of 60% boronic acid containing magnesium whisker.
Prepare bonding sheet and metal foil laminate respectively according to the step among the embodiment one (3), (4) then.
Embodiment eight, and the foregoing description gained metal foil laminate is carried out performance test
Testing method is:
Thermally stratified layer time T-288, testing method adopt hot mechanical decomposition method (TMA).
The Copper Foil stripping strength adopts 90 ℃ of peeling strength test machines to measure.
Thermal expansivity (CTE), testing method adopt hot mechanical decomposition method (TMA).
Incendivity is measured by U.S. UL94 vertical combustion method.
The rigidity of sheet material adopts Apparatus for Impacting at low-temp to test.
Detected result sees the following form:
| Embodiment one | Embodiment two | Embodiment three | Embodiment four | Embodiment five | Embodiment six | Embodiment seven | |
| Thermally stratified layer time T-288min | ≥60 | ≥60 | ≥60 | ≥60 | ≥60 | ≥60 | ≥60 |
| Copper Foil stripping strength kN/m | 1.2 | 1.1 | 1.4 | 1.4 | 1.1 | 0.9 | 1.0 |
| Thermal expansivity ppm/ ℃ | 30 | 35 | 31 | 30 | 32 | 46 | 40 |
| The rigidity of sheet material | Well 1* | Well 1* | Well 1* | Well 1* | Well 1* | Relatively poor 2* | Well 1* |
| Flame retardant resistance | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
Claims (8)
1. resin matching fluid, described resin matching fluid comprises following component: Resins, epoxy, solidifying agent, curing catalyst, solvent, inorganic crystal whisker and surperficial coupling agent; It is characterized in that: described surperficial coupling agent is a borate ester surface coupling agent, and described surperficial coupling agent is selected from: one or both in triethanolamine borate ester, boric acid propyl carbinol-diethanolamine ester, boric acid sec-butyl alcohol-diethanolamine ester or the trimethyl carbinol-diethanolamine ester and two or more mixtures.
2. resin matching fluid according to claim 1 is characterized in that: the mean diameter of inorganic crystal whisker is 0.5～5 μ m, and the diameter of inorganic crystal whisker is 0.2～9.9 μ m.
3. resin matching fluid according to claim 1 is characterized in that: the length of inorganic crystal whisker is greater than 10 times of diameter, and less than 100 μ m.
4. resin matching fluid according to claim 1 is characterized in that: the Young's modulus of inorganic crystal whisker is greater than 200GPa.
5. resin matching fluid according to claim 1 is characterized in that: the quality of inorganic crystal whisker account for the resin matching fluid solids content weight percent 10～60%.
6. resin matching fluid according to claim 1 is characterized in that: according to mass ratio, and inorganic crystal whisker: surperficial coupling agent=1: 1～4: 1.
7. an application rights requires 1～6 described resin matching fluid to prepare the method for used for metal foil laminated board bonding sheet, it is characterized in that: may further comprise the steps:
(1) according to mass ratio, Resins, epoxy: solidifying agent: curing catalyst=100: 5～80: 0.01～5, take by weighing Resins, epoxy, solidifying agent, curing catalyst, be dissolved in solvent, be made into resin solution; According to mass ratio, inorganic crystal whisker: the mass ratio of surperficial coupling agent=1: 1～4: 1, take by weighing inorganic crystal whisker and surperficial coupling agent, be dissolved in solvent, mix inorganic crystal whisker solution;
(2) inorganic crystal whisker solution is added in the resin solution, obtain resin matching fluid;
(3) the E glasscloth is contained be immersed in step (2) gained resin matching fluid, bonding sheet is made in oven dry.
8. method for preparing metal foil laminate is characterized in that: an electrolytic copper foil is respectively joined in the top and bottom at the bonding sheet of claim 7 gained, through heating, press molding and make.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2009100313679A CN101550264A (en) | 2009-04-30 | 2009-04-30 | Resin matching fluid used for metal foil laminated board |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100313679A CN101550264A (en) | 2009-04-30 | 2009-04-30 | Resin matching fluid used for metal foil laminated board |
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| CN101955678A (en) * | 2010-10-21 | 2011-01-26 | 苏州生益科技有限公司 | Flame retardant thermosetting resin composition and copper-clad plate |
| CN102321395A (en) * | 2011-08-30 | 2012-01-18 | 成都理工大学 | Method for surface modification of magnesium borate crystal whisker by using borate coupling agent |
| CN102881813A (en) * | 2012-09-27 | 2013-01-16 | 广东宏泰照明科技有限公司 | A method of manufacturing a radiator plate |
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| CN101955678A (en) * | 2010-10-21 | 2011-01-26 | 苏州生益科技有限公司 | Flame retardant thermosetting resin composition and copper-clad plate |
| CN102321395A (en) * | 2011-08-30 | 2012-01-18 | 成都理工大学 | Method for surface modification of magnesium borate crystal whisker by using borate coupling agent |
| CN102321395B (en) * | 2011-08-30 | 2013-07-24 | 成都理工大学 | Method for surface modification of magnesium borate crystal whisker by using borate coupling agent |
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| CN103254574B (en) * | 2013-05-28 | 2015-09-09 | 北京新福润达绝缘材料有限责任公司 | Glass felt layers pressing plate its preparation method |
| CN105820506A (en) * | 2016-04-11 | 2016-08-03 | 南京信息职业技术学院 | Preparation method of epoxy resin/silicon nitride composite material |
| CN105820506B (en) * | 2016-04-11 | 2018-05-01 | 南京信息职业技术学院 | Preparation method of epoxy resin/silicon nitride composite material |
| CN107722559A (en) * | 2017-09-20 | 2018-02-23 | 苏州巨峰新材料科技有限公司 | Flame-retardant resin-based copper-clad plate and preparation method thereof |
| CN107722560A (en) * | 2017-09-20 | 2018-02-23 | 苏州巨峰新材料科技有限公司 | Prepreg for flame-retardant resin-based copper-clad plate and preparation method thereof |
| CN107756985A (en) * | 2017-12-04 | 2018-03-06 | 台州学院 | A kind of layered product for printed resistor and preparation method thereof |
| CN109320911A (en) * | 2018-09-17 | 2019-02-12 | 张万里 | A kind of high tenacity insulating circuit board substrate and preparation method thereof |
| CN114990473A (en) * | 2022-04-22 | 2022-09-02 | 江西省航宇电子材料有限公司 | Stainless steel base surface treatment method, copper-clad plate and preparation method |
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Open date: 20091007 |