CN102924869B - Application of black modified silicon dioxide - Google Patents
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- CN102924869B CN102924869B CN201210458553.2A CN201210458553A CN102924869B CN 102924869 B CN102924869 B CN 102924869B CN 201210458553 A CN201210458553 A CN 201210458553A CN 102924869 B CN102924869 B CN 102924869B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 140
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011888 foil Substances 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 239000011889 copper foil Substances 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 68
- 239000003292 glue Substances 0.000 claims description 43
- 239000002362 mulch Substances 0.000 claims description 32
- 229910052802 copper Inorganic materials 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 2
- 239000004568 cement Substances 0.000 abstract 2
- 239000007788 liquid Substances 0.000 abstract 2
- 239000011256 inorganic filler Substances 0.000 abstract 1
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 1
- 239000012764 mineral filler Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 229960001866 silicon dioxide Drugs 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 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 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
- 208000011580 syndromic disease Diseases 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- -1 glasscloth Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000012779 reinforcing material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
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- 230000008023 solidification Effects 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to application of black modified silicon dioxide; inorganic filler black modified silicon dioxide is added in liquid cement which is used for forming copper-clad plates and cover films, in order to provide the black characteristic to the copper-clad foil substrates and the cover films; in addition, the black modified silicon dioxide has an excellent dark surface and relatively low transmissivity, and can be used for preparing the copper-clad foil substrates, the cover films, printed circuit boards and resin-coated copper foils. With the adoption of the application, cost of the liquid cement is greatly reduced, coefficient of thermal expansion of a product is reduced, and reliability in preparation of the printed circuit boards is improved; a black characteristic is provided to the product while a mechanical property and an electrical property of the product are ensured, so that the product has a dark surface and has extremely low transmissivity.
Description
Technical field
The invention belongs to copper-clad plate technical field, particularly a kind of application of black improved silica.
Background technology
In recent years, due to LED(photodiode) less energy-consumption, high efficiency outstanding feature, be widely used in the fields such as electrical equipment instruction, LED display, LED backlight, Landscape Lighting, upholstery.Due to the high speed development of LED, also promote the development of functional copper-clad plate and mulch film.Why be referred to as copper-clad plate and mulch film, that is because for the copper-clad plate of LED and mulch film except the performances such as the insulation that needs to possess common copper-clad plate and mulch film and have, also need that there is good shade function, avoid as much as possible the light of LED light source from plate back through, waste energy, reduce luminance brightness.
In order to give copper-clad plate and mulch film with dark nature, current industry more often uses the material such as carbon black, nigrosine to add in copper-clad plate and mulch film to give sheet material black function.
Patent CN102010578A discloses a kind of black halogen-free resin combination making copper-clad plate, and it contains colour carbon black, and functional imparting copper-clad plate is with dark nature.
Patent CN102190865A discloses a kind of composition epoxy resin making copper-clad plate, and it contains nigrosine, and functional imparting copper-clad plate is with dark nature.
Patent CN 101851390A discloses a kind of black covering film, and it contains carbon powder, and functional imparting mulch film is with dark nature.
Prepare black copper-clad plate and mulch film seems simple, use black pigment can give copper-clad plate and mulch film with dark nature.But, black pigment also often brings variety of problems: the black pigment carbon black meeting remarkably influenced copper-clad plate based on carbon and the insulating property of mulch film, then remarkably influenced copper-clad plate and mulch film the resistance toheat of the copper-clad plate of halogen system and mulch film can be especially had with phenyl ring and the elementary composition black pigment nigrosine of nitrogen, and nigrosine limits its application containing chromium element, also must take in during use on physiological impact.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of glue for the preparation of copper clad foil substrate, and described glue can reduce costs, and improves mechanical property and the electric property of product, and gives product with dark nature.
For achieving the above object, the present invention adopts following technical scheme:
The described glue for the preparation of copper clad foil substrate, the black improved silica as mineral filler containing 0.1 ~ 70 quality %, with copper clad foil substrate prepared by this glue, the many-sided performance of copper clad foil substrate can be improved, and give product with dark nature, described glue to refer in the mixed solution that resin and solvent and other additive (such as solidifying agent, filler, fire retardant etc.) form the mixture of other component in addition to the solvents.
The content of described black improved silica can be 0.11 quality %, 0.12 quality %, 0.15 quality %, 0.2 quality %, 0.5 quality %, 1 quality %, 2 quality %, 4 quality %, 6 quality %, 10 quality %, 14 quality %, 15 quality %, 16 quality %, 18 quality %, 20 quality %, 25 quality %, 45 quality %, 49 quality %, 51 quality %, 55 quality %, 65 quality %, 68 quality %, 69 quality % etc., be preferably 0.1 ~ 60 quality %, be more preferably 0.1 ~ 50 quality %, be particularly preferably 3 ~ 17 quality %; Described massfraction refers to that described black improved silica accounts for the percentage ratio of described glue total mass.
Preferably, the carbon element content of described black improved silica, at below 2 quality %, is particularly preferably below 1 quality %, and the content of described carbon refers to the mass percentage of carbon in described black improved silica.
Preferably, the particle diameter of described black improved silica is 0.1 ~ 100 micron, such as 0.11 micron, 0.12 micron, 0.2 micron, 0.4 micron, 0.6 micron, 2 microns, 5 microns, 9 microns, 11 microns, 20 microns, 30 microns, 45 microns, 49 microns, 51 microns, 70 microns, 90 microns, 95 microns, 98 microns, 99 microns etc., more preferably 0.5 ~ 50 micron, be particularly preferably 1 ~ 10 micron.
Preferably, the specific conductivity of described black improved silica is 300 below μ s/cm, is particularly preferably 200 below μ s/cm.
An object of the present invention is also to provide a kind of prepreg, it is characterized in that, described prepreg is above-mentioned for the preparation of after the glue of copper clad foil substrate by being infiltrated on by strongthener, and drying obtains.Described strongthener is affiliated field conventional reinforcing material, such as glasscloth, non-woven fabrics or wood pulp paper etc., and the expertise that one of ordinary skill in the art can grasp according to it and actual needs are selected.
An object of the present invention is also to provide a kind of copper clad foil substrate, and described copper clad foil substrate contains at least 1 above-mentioned prepreg containing black silicon-dioxide.The number that described copper clad foil substrate contains the above-mentioned prepreg containing black silicon-dioxide can be 1,2,3,5 etc.Described copper clad foil substrate thermal expansivity is lower, and it is black, has matting, and has extremely low transmissivity.The number that described copper clad foil substrate contains Copper Foil is 0,1 or 2, that is, described copper clad foil substrate can be insulcrete, single sided board or dual platen.
An object of the present invention is also to provide a kind of printed circuit board (pcb), it is characterized in that, described printed circuit board contains at least 1 above-mentioned prepreg containing black silicon-dioxide.The number that described printed circuit board contains the above-mentioned prepreg containing black silicon-dioxide can be 1,2,3,5 etc.
An object of the present invention is also to provide a kind of glue for the preparation of mulch film.The described glue for the preparation of mulch film, the black improved silica as mineral filler containing 0.1 ~ 70 quality %, with mulch film prepared by this glue, its many-sided performance can be improved, and give product with dark nature, described glue refers to the mixture for the preparation of other component in addition to the solvents in the material of mulch film and the mixed solution of solvent composition, and one of ordinary skill in the art can select as required, do not repeat them here.
The content of described black improved silica can be 0.11 quality %, 0.12 quality %, 0.15 quality %, 0.2 quality %, 0.5 quality %, 1 quality %, 2 quality %, 4 quality %, 6 quality %, 10 quality %, 14 quality %, 15 quality %, 16 quality %, 18 quality %, 20 quality %, 25 quality %, 45 quality %, 49 quality %, 51 quality %, 55 quality %, 65 quality %, 68 quality %, 69 quality % etc., be preferably 0.1 ~ 60 quality %, be more preferably 0.1 ~ 50 quality %, be particularly preferably 3 ~ 17 quality %; Described massfraction refers to that described black improved silica accounts for the percentage ratio of described glue total mass.
Preferably, the carbon element content of described black improved silica, at below 2 quality %, is particularly preferably below 1 quality %, and the content of described carbon refers to the mass percentage of carbon in described black improved silica.
Preferably, the particle diameter of described black improved silica is 0.1 ~ 100 micron, such as 0.11 micron, 0.12 micron, 0.2 micron, 0.4 micron, 0.6 micron, 2 microns, 5 microns, 9 microns, 11 microns, 20 microns, 30 microns, 45 microns, 49 microns, 51 microns, 70 microns, 90 microns, 95 microns, 98 microns, 99 microns etc., more preferably 0.5 ~ 50 micron, be particularly preferably 1 ~ 10 micron.
Preferably, the specific conductivity of described black improved silica is 300 below μ s/cm, is particularly preferably 200 below μ s/cm.
An object of the present invention is also to provide a kind of mulch film, and described mulch film is prepared by the above-mentioned glue for the preparation of mulch film.Described mulch film has mechanical protection and electric insulating quality, and is black due to it, can also play the effect of covering circuit and delustring.
An object of the present invention is also to provide a kind of resin coated copper foil, it is characterized in that, described resin coated copper foil is coated with the above-mentioned glue for the preparation of mulch film.
Described black improved silica is a kind of matrix material of uniqueness, it obtains in silica by making organism high temperature cabonization and adsorb in the process preparing black improved silica, it contains trace carbon element, this kind of black improved silica color is very lasting, insulating property are good, be applicable to various field, carbon dust can be replaced to be used in epoxy mold packaged material (EMC), and the product performance being wherein SSB0020 with Bengbu Xinyuan Quartz Material Co., Ltd.'s trade mark are good.
Resin of the present invention can be the known resin in affiliated field, also can be new resin, such as, in the resin systems such as cyanate ester resin, polyphenylene oxide resin, bimaleimide resin, polyimide resin, benzoxazine colophony, polybutadiene a kind or the combination of at least 2 kinds, those skilled in the art can select as required.
Compared with prior art, beneficial effect of the present invention is:
(1) the adding of mineral filler black improved silica, the production cost of copper clad foil substrate and mulch film can greatly be reduced;
(2) the adding of mineral filler black improved silica, greatly can reduce the thermal expansivity of copper clad foil substrate and mulch film, and improve its reliability in printed circuit board (PCB) preparation;
(3) due to the dark nature of mineral filler black improved silica, it is added and makes copper clad foil substrate and mulch film have matting and there is extremely low transmissivity.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
In embodiment and comparative example each code name used and composition as follows:
Epoxy resin A: represent the novolac epoxy that Hexion Specialty Chemicals company (Bowden chemical company of the former U.S. and German Berlet company) produces, commodity are called EPR627-MEK80, and its epoxy equivalent (weight) is between 160 ~ 250g/eq.
Epoxy resin B: represent the epoxy resin that Dow Chemical company produces, commodity are called DER-592A80, and its epoxy equivalent (weight) is between 300 ~ 460g/eq.
Epoxy resin C: represent the high brominated eopxy that Japanese ink chemical company produces, commodity are called EPICLON153, and its epoxy equivalent (weight) is between 350 ~ 450g/eq
Stiffening agent represents the phenolic resin hardener that Hexion Specialty Chemicals company produces, and commodity are called PHL6635M65.
Promotor represents the 2MI that Japanese four countries change into company's production.
Mineral filler A represents black improved silica and represents the improved silica that Bengbu Xinyuan Quartz Material Co., Ltd.'s trade mark is SSB0020.
Mineral filler B represents the commodity that German Degussa produces and is called the carbon powder of FW200.
Pigment dyestuff C represents the commodity that German Degussa produces and is called the nigrosine of BS890.
Mineral filler D represents the commodity that western BIC Corp produces and is called the compound silica powder of G2-C.
It is 0.1 ~ 20 micron that mineral filler E represents self-control particle diameter, and carbon content is the improved silica of 2 quality %.
It is 30 ~ 100 microns that mineral filler F represents self-control particle diameter, and carbon content is the improved silica of 1.5 quality %.
It is 50 ~ 70 microns that mineral filler G represents self-control particle diameter, and carbon content is the improved silica of 1.0 quality %.
Embodiment 1-7
Embodiment 1-7 solids component formula composition refers to table 1, and utilizes butanone to be modulated into the thermosetting resin varnish of fabrication layer pressing plate use, and wherein solids component accounts for 67%.
The copper clad foil substrate of embodiment 1-7 is prepared according to following preparation technology:
(1) glue: added by solvent in proportion container, adds the solution of resin, curing agent solution and curing catalyst respectively under stirring; Stir after 2 hours, add mineral filler, continue to stir after 4-8 hour, the gel time (170 DEG C of constant temperature hot plates) of sampling and testing glue is 200 ~ 300 seconds.
(2) impregnation: by the layers of reinforcement of dipped glue by vertical or horizontal type impregnation machine, by controlling the conditions such as extruding wheel speed, linear speed, wind-warm syndrome and furnace temperature, with vertical impregnation machine demonstration example is specifically: extruding wheel speed :-1.3 ~-2.5 ± 0.1M/min; Main line speed: 4 ~ 18m/min; Wind-warm syndrome: 120 ~ 170 DEG C; Furnace temperature: 130 ~ 220 DEG C, obtains prepreg by above condition.
(3) suppress: after the prepreg reduced and Copper Foil being combined, put into vacuum hotpressing machine, by certain temperature, time and pressure is final obtained copper coated foil plate also, and concrete demonstration example is:
Temperature formula: 130 DEG C/30min+155 DEG C/30min+190 DEG C/90min+220 DEG C/60min;
Pressure formula:
25Kgf.cm-2/30min+50Kgf.cm-2/30min+90Kgf.cm-2/120min+30Kgf.cm-2/90min；
Vacuum formula: 30mmHg/130min+800mmHg/130min.
By said procedure, adopt 8 thickness to be that the prepreg of 0.2mm is stacked layer by layer between 35 μm of thick Copper Foils, the thick veneer sheet of 1.6mm can be obtained after hot pressing.After obtaining copper coated foil plate, test plate property, table 2 is depicted as plate property contrast.
Comparative example 1-3
Comparative example 1-3 solids component formula composition refers to table 1, and utilizes butanone to be modulated into the thermosetting resin varnish of fabrication layer pressing plate use, and wherein solids component accounts for 67%.The preparation method of comparative example 1-3 is as embodiment 1-7.
Table 1
Adopt following methods to measure the coefficient of expansion, heat decomposition temperature, surface resistivity and volume specific resistance, transmissivity to copper clad foil substrate prepared by embodiment 1-7 and comparative example 1-3, test result is as shown in table 2.
1, the coefficient of expansion
According to IPC-TM-650 2.4.24(12/94 version) test.
2, heat decomposition temperature
According to IPC-TM-650 2.4.24.6(4/06 version) test.
3, surface resistivity and volume specific resistance
According to IPC-TM-650 2.5.17.1(12/94A version) test.
4, transmissivity
The Transflective rate tester using Lan Fei company of the U.S. to produce uses the test of integration ball.
Table 2
As shown in Table 2, copper clad foil substrate of the present invention adopts black improved silica, adds in glue and makes copper coated foil plate, compares and adopts carbon black, nigrosine and common modifications composite silicon dioxide, have following technique effect:
(1) add the thermal expansivity that black improved silica effectively can reduce copper coated foil plate, along with the continuous increase of add-on, thermal expansivity is also in continuous reduction;
(2) add the insulating property impact of black improved silica on copper coated foil plate little, adopt carbon black then to affect larger;
(3) add the heat decomposition temperature impact of black improved silica on copper coated foil plate little, adopt nigrosine then to affect comparatively large, and sheet material thermal expansivity is larger;
(4) add black improved silica, copper coated foil plate can be given with dark nature, adopt common modifications composite silicon dioxide then cannot give copper coated foil plate with dark nature;
(5) add black improved silica, can give copper coated foil plate with lower transmissivity, then copper coated foil plate transmissivity is comparatively large to adopt common modifications composite silicon dioxide, is unfavorable for save energy.
Embodiment 8
Epoxy resin (marque NC-3000-H, epoxy equivalent (weight) 290g/eq, Japanese chemical drug manufacture) 35 weight parts; Nbr carboxyl terminal (marque Nipol 1072CG, acrylonitrile content 27 quality %, ZeonCorporation manufacture) 21 weight parts; Acrylated epoxy (commodity-type BPF307, elastomer content 20 quality %, Nippon Shokubai Co., Ltd manufactures) 9.1 weight parts; Diaminodiphenylsulfone(DDS) (DDS) 6.63 weight part; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.163 weight part; Mineral filler A18.73 weight part; Titanium dioxide (marque R-706, Du Pont manufactures) 6.5 weight parts; Phosphonium flame retardant (marque OP-935, German Clariant manufacture) 13 weight parts; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. manufactures) 0.05 weight part.The solids content regulating glue with butanone solvent is 38%, mixes and makes black halogen-free epoxy resin composition.Said composition is coated in by spreadometer on the polyimide insulative film of thickness 12.5 μm, rubberization thickness is 15 μm, put into again in the baking oven of 160 DEG C and heat 3 minutes, with the composition layer of the solidification of forming section on polyimide insulative film, then itself and separate-type paper are passed through roll-in laminating, rolling obtains the mulch film of black.
Embodiment 9-12
The composition of embodiment 9-12 and the difference of embodiment 8 are only kind and the parts by weight of resin and mineral filler, refer to table 3.Its preparation method is as embodiment 8.
Comparative example 4-6
The composition of comparative example 4-6 and the difference of embodiment 8 are only kind and the parts by weight of mineral filler, refer to table 3.Its preparation method is as embodiment 8.
Table 3
The black covering film made for embodiment 9-12 and comparative example 4-6 observes its color and luster and light transmission, and test its thermotolerance, flame retardant resistance and stripping strength, result is as shown in table 4.
The testing method of above characteristic is as follows:
(1) testing method of printing opacity: by sample facing to high light, visual whether printing opacity.
(2) surface resistivity after damp and hot and volume specific resistance are tested according to IPC-TM-650 2.5.17 method.
(3) stripping strength (PS) is according to IPC-TM-650 2.4.9 method, the stripping strength of test crown cap.
(4) resistance toly dip solderabilityly to test according to IPC-TM-650 2.4.13.
(5) incendivity (flame retardant resistance): measure according to UL 94 vertical combustion.
Table 4
As shown in Table 4, mulch film of the present invention adopts black improved silica, adds in glue and makes mulch film, compares and adopts carbon black, nigrosine and common modifications composite silicon dioxide, have following technique effect:
Prepared black covering film, has shaded effect, surface resistivity and volume specific resistance up to standard, flame retardant resistance reaches UL94 V-0 level, has high-peeling strength, excellent dimensional stability, flexibility and processing characteristics.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (23)
1. for the preparation of a glue for copper clad foil substrate, it is characterized in that, described glue contains the black improved silica of 0.1 ~ 70 quality %; Described black improved silica obtains in silica by making organism high temperature cabonization and adsorb in the process preparing black improved silica, and it contains trace carbon element, and carbon element content is at below 2 quality %, and particle diameter is 0.1 ~ 100 micron.
2. glue as claimed in claim 1, it is characterized in that, the content of described black improved silica is 0.1 ~ 60 quality %.
3. glue as claimed in claim 2, it is characterized in that, the content of described black improved silica is 0.1 ~ 50 quality %.
4. glue as claimed in claim 3, it is characterized in that, the content of described black improved silica is 3 ~ 17 quality %.
5. glue as claimed in claim 1, it is characterized in that, the carbon element content of described black improved silica is below 1 quality %.
6. the glue as described in claim 1 or 5, is characterized in that, the particle diameter of described black improved silica is 0.5 ~ 50 micron.
7. glue as claimed in claim 6, it is characterized in that, the particle diameter of described black improved silica is 1 ~ 10 micron.
8. glue as claimed in claim 1, it is characterized in that, the specific conductivity of described black improved silica is 300 below μ s/cm.
9. glue as claimed in claim 1, it is characterized in that, the specific conductivity of described black improved silica is 200 below μ s/cm.
10. a prepreg, is characterized in that, described prepreg is by after being infiltrated on the glue described in any one of claim 1-9 by strongthener, drying obtains.
11. 1 kinds of copper clad foil substrates, is characterized in that, described copper clad foil substrate contains at least 1 prepreg according to claim 10.
12. 1 kinds of printed circuit boards, is characterized in that, described printed circuit board contains at least 1 prepreg according to claim 10.
13. 1 kinds, for the preparation of the glue of mulch film, is characterized in that, described glue contains the black improved silica of 0.1 ~ 70 quality %; Described black improved silica obtains in silica by making organism high temperature cabonization and adsorb in the process preparing black improved silica, and it contains trace carbon element, and carbon element content is at below 2 quality %, and particle diameter is 0.1 ~ 100 micron.
14. glues as claimed in claim 13, is characterized in that, the content of described black improved silica is 0.1 ~ 60 quality %.
15. glues as claimed in claim 14, is characterized in that, the content of described black improved silica is 0.1 ~ 50 quality %.
16. glues as claimed in claim 15, is characterized in that, the content of described black improved silica is 3 ~ 17 quality %.
17. glues as claimed in claim 13, is characterized in that, the carbon element content of described black improved silica is below 1 quality %.
18. glues as claimed in claim 13, is characterized in that, the particle diameter of described black improved silica is 0.5 ~ 50 micron.
19. glues as claimed in claim 18, is characterized in that, the particle diameter of described black improved silica is 1 ~ 10 micron.
20. glues as claimed in claim 13, is characterized in that, the specific conductivity of described black improved silica is 300 below μ s/cm.
21. glues as claimed in claim 20, is characterized in that, the specific conductivity of described black improved silica is 200 below μ s/cm.
22. 1 kinds of mulch films, is characterized in that, described mulch film is prepared by the glue for the preparation of mulch film one of claim 13-21 Suo Shu.
23. 1 kinds of resin coated copper foils, is characterized in that, described resin coated copper foil are coated with the glue for the preparation of mulch film that one of claim 13-21 is described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210458553.2A CN102924869B (en) | 2012-11-14 | 2012-11-14 | Application of black modified silicon dioxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210458553.2A CN102924869B (en) | 2012-11-14 | 2012-11-14 | Application of black modified silicon dioxide |
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| CN102924869B true CN102924869B (en) | 2015-04-15 |
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| CN103571156B (en) * | 2013-09-17 | 2016-04-06 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and uses thereof |
| CN105196678A (en) * | 2015-09-02 | 2015-12-30 | 铜陵翔宇商贸有限公司 | Method for manufacturing gray copper-clad plate |
| CN113603103A (en) * | 2021-08-13 | 2021-11-05 | 浙江三时纪新材科技有限公司 | Semiconductor packaging material, preparation method of substrate material, semiconductor packaging material obtained by preparation method, substrate material and application of substrate material |
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| CN102190865B (en) * | 2010-03-16 | 2012-12-26 | 上海国纪电子有限公司 | Epoxy resin glue solution, prepreg and copper clad panel containing epoxy resin glue solution, and preparation method thereof |
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