CN103963379B - Metal-based copper-clad plate and preparation method thereof - Google Patents
Metal-based copper-clad plate and preparation method thereof Download PDFInfo
- Publication number
- CN103963379B CN103963379B CN201410079080.4A CN201410079080A CN103963379B CN 103963379 B CN103963379 B CN 103963379B CN 201410079080 A CN201410079080 A CN 201410079080A CN 103963379 B CN103963379 B CN 103963379B
- Authority
- CN
- China
- Prior art keywords
- metal
- glue
- clad plate
- preparation
- based copper
- 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.)
- Expired - Fee Related
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 46
- 239000002184 metal Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003292 glue Substances 0.000 claims abstract description 74
- 238000005507 spraying Methods 0.000 claims abstract description 19
- 230000004888 barrier function Effects 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011889 copper foil Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 239000003365 glass fiber Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 239000011256 inorganic filler Substances 0.000 claims description 25
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 239000003822 epoxy resin Substances 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 17
- 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 claims description 15
- 239000002994 raw material Substances 0.000 claims description 13
- 230000005070 ripening Effects 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- 229910017083 AlN Inorganic materials 0.000 claims description 7
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052582 BN Inorganic materials 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 239000004843 novolac epoxy resin Substances 0.000 claims description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229910000976 Electrical steel Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 41
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000011521 glass Substances 0.000 abstract description 6
- 239000004744 fabric Substances 0.000 abstract description 5
- 239000007921 spray Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000615 nonconductor Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 description 38
- 238000004026 adhesive bonding Methods 0.000 description 23
- 238000007731 hot pressing Methods 0.000 description 14
- 238000003475 lamination Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 4
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-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
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of metal-based copper-clad plate and preparation method thereof. Described metal-based copper-clad plate is made up of the copper foil layer being sequentially stacked, insulating barrier and metal-based layer; Described insulating barrier does not contain glass fibre; Described insulating barrier is that in the way of spraying, glue is directly spread upon the coating formed on metal-based layer; The thickness of described insulating barrier is 50～200 μm. The metal-based copper-clad plate of the present invention eliminates the non-conductor of this heat of glass fabric in insulating barrier, improves the heat conductivity of metal-based copper-clad plate, reduces thermal resistance, improves product heat conductivity. Spraying coating process in the preparation method of metal-based copper-clad plate provided by the invention, mutually more conventional spray gun spraying technique, it is not necessary to fixture protection, glue are floated in the air few; Comparing the technique smeared with hairbrush, have quick, the accurate advantage of thickness, coating thickness can be as accurate as 0.02mm, is entirely capable of meeting production requirement.
Description
Technical field
The present invention relates to printed circuit board field, particularly relate to a kind of metal-based copper-clad plate and preparation method thereof.
Background technology
In today of resource shortage further, LED, as the new type light source of a kind of energy-conserving and environment-protective, is increasingly subject to people's attention. But, the active region area of LED chip is little, and operating current is big, and the operating temperature causing LED chip is high. Especially great power LED, the heat flow that chip bears is bigger, if not taking effective cooling measure, chip temperature can be made too high, the light efficiency causing LED is reduced, chip emission spectrum generation red shift, colour temperature Quality Down, and accelerate LED chip degeneration, make the reduced lifetime of device. And the heat that chip produces is mostly the mode by conduction of heat and passes on the substrate of chip bottom, then dissipate in the way of thermal convection current. Therefore, LED-baseplate material requirements possesses higher heat conductivility, and LED-baseplate material conventional at present is generally all aluminium base, thus, improves the heat transfer efficiency of aluminium base as much as possible, it has also become a comparatively important research topic of those skilled in the art.
Summary of the invention
The technical problem to be solved is in that to overcome the defect that in aluminium base of the prior art, the heat conductivity of insulating barrier is low, it is provided that a kind of metal-based copper-clad plate and preparation method thereof.
The present invention solves above-mentioned technical problem by following technical proposals:
The invention provides a kind of metal-based copper-clad plate, described metal-based copper-clad plate is made up of the copper foil layer being sequentially stacked, insulating barrier and metal-based layer; Described insulating barrier does not contain glass fibre; Described insulating barrier is that in the way of spraying, glue is directly spread upon the coating formed on metal-based layer; The thickness of described insulating barrier is 50～200 μm.
In the present invention, described metal-based layer is preferably aluminium sheet, copper coin, silicon steel plate, corrosion resistant plate or aluminium alloy plate.
In the present invention, the composition of raw materials of described glue is preferably comprised the component of following mass parts: resin 450～500 parts, 8～12 parts of firming agent, curing accelerator 0.2～0.3 part, solvent 100～120 parts and account for described glue gross mass 0～75% inorganic filler.
Wherein, described resin can be the conventional use of various resins of this area glue used for printed circuit board, it is preferred that carrys out one or more in amide resin and polyurethane resin for epoxy resin, span. Described epoxy resin is preferably comprised one or more in novolac epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, brominated epoxy resin and phosphorous epoxy resin. The epoxide equivalent of described epoxy resin is preferably 400～550.
Wherein, described firming agent can be conventional use of various firming agent in the glue used for printed circuit board of this area, it is preferred that for one or more in amine curing agent, acid anhydride type curing agent and high score subclass firming agent. Described amine curing agent can be selected for the amine curing agent of the various routine in this area, it is preferred that for one or more in ethylenediamine, 2-ethylene-3-amine, 2-amino-2-phenylmethane, dicyandiamide, 2-amino-2-phenol and organic hydrazides. Described acid anhydride type curing agent can be selected for the acid anhydride type curing agent of the various routine in this area, it is preferred that for phthalic anhydride and/or 2-phenylate-4-anhydride. Described high score subclass firming agent can be selected for the high score subclass firming agent of the various routine in this area, it is preferred that for phenolic resin and/or benzoxazine resin.
Wherein, described curing accelerator can be selected for conventional use of various curing accelerators in the glue used for printed circuit board of this area, including tertiary amines curing accelerator and/or imidazoles curing accelerator. Described tertiary amines curing accelerator can be selected for the tertiary amines curing accelerator of the various routine in this area, it is preferred that for benzyl-2-aniline and/or triethanolamine. Described imidazoles curing accelerator can be selected for the imidazoles curing accelerator of the various routine in this area, it is preferred that for one or more in 1-Methylimidazole., 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-undecyl imidazole.
Wherein, described solvent can be selected for conventional use of various solvents in the glue used for printed circuit board of this area, it is preferred that for one or more in acetone, butanone, Ketohexamethylene, hexone, dimethylformamide, dimethyl acetylamide, ethylene glycol monomethyl ether and propylene glycol monomethyl ether.
Wherein, described inorganic filler can be selected for conventional use of various inorganic fillers in the glue used for printed circuit board of this area, it is preferred that for one or more in aluminium nitride, boron nitride, silicon nitride, aluminium oxide, beryllium oxide, silicon dioxide, magnesium oxide, carborundum, ceramics and glass dust. The particle diameter of described inorganic filler is preferably 1～100 μm.
The composition of raw materials of described glue is preferably any one in following formula: formula one: in mass parts, resin is the novolac epoxy resin of 450-460 part, firming agent is the ethylenediamine of 8-9 part, curing accelerator is the benzyl-2-aniline of 0.2-0.3 part, solvent is the acetone of 105-115 part, and inorganic filler is the boron nitride of 15%-20%; Formula two: in mass parts, resin is the bisphenol A type epoxy resin of 480-490 part, and firming agent is the 2-amino-2-phenylmethane of 10-12 part, and curing accelerator is the 2-methylimidazole of 0.2-0.3 part, solvent is the dimethylformamide of 95-105 part, and inorganic filler is the aluminium nitride of 25%-30%; Formula three: in mass parts, resin is the brominated epoxy resin of 490-500 part, and firming agent is the phthalic anhydride of 10-12 part, and curing accelerator is the triethanolamine of 0.2-0.3 part, solvent is the ethylene glycol monomethyl ether of 95-105 part, and inorganic filler is the ceramics of 35%-40%;Formula four: in mass parts, resin is double; two maleic anhydride resins of 450-460 part, firming agent is the 2-amino-2-phenylmethane of 10-12 part, curing accelerator is the 2-undecyl imidazole of 0.2-0.3 part, solvent is the hexone of 95-105 part, and inorganic filler is the carborundum of 50%-55%; Formula five: in mass parts, resin is the polyurethane resin of 450-460 part, and firming agent is the 2-amino-2-phenol of 8-10 part, and curing accelerator is the 2-phenyl-4-methylimidazole of 0.2-0.3 part, solvent is the propylene glycol monomethyl ether of 95-105 part, and inorganic filler is the silicon nitride of 70%-75%.
In the present invention, the preparation method of described glue preferably comprises the steps: that described firming agent, described curing accelerator and described solvent are mixed by (1), and stirring is to dissolving to obtain mixture A; (2) by described mixture A and described mixed with resin, stir to obtain mixture B; (3) when the composition of raw materials of described glue includes inorganic filler, being mixed with described inorganic filler by described mixture B, high speed shear, after ripening; When the composition of raw materials of described glue does not include inorganic filler, by described mixture B ripening.
In step (1), the time of described stirring is so that described firming agent and described curing accelerator are completely dissolved and are as the criterion, it is preferred that be 2～5 hours. The rotating speed of described stirring is preferably 800～1500rpm.
In step (2), the time of described stirring is preferably 3～5 hours. The rotating speed of described stirring is preferably 1000～1500rpm.
In step (3), the time of described high speed shear is preferably 30～120 minutes. The rotating speed of described high speed shear is preferably 2500～5000rpm. The ripening operation that described ripening can adopt this area conventional carries out, it is preferred that stir 6～8 hours for the rotating speed with 1000～1500rpm.
The preparation method that the present invention also provides for a kind of metal-based copper-clad plate, it comprises the steps: that described glue is directly spread upon on metal-based layer by (1) by the mode sprayed, and is placed in baking oven and heats, makes glue semi-solid preparation, obtains prepreg containing metal-based layer; (2) prepreg described in step (1) is covered with copper foil layer, is assemblied in press, carry out suppressing.
In step (1), described spraying preferably adopts application system to carry out. Described application system is preferably comprised be sequentially connected with one automatic connection platform, a Selective coating machine, a monitor station and a curing oven. Described application system is preferably Fa Luowei intelligence application system SC-45A or the application system of Dongguan Anda Automatic Equipment Co., Ltd.. The pressure of described spraying is preferably 200KPa～500KPa.
In step (1), the temperature of described heating is preferably 170～210 DEG C; The gel time of described glue is preferably 70～130s. The fluidity of described prepreg is preferably 5%～20%, and the volatile matter of described prepreg is preferably≤0.75%. In described prepreg, the thickness of glue is preferably 50～200 μm.
In step (2), the temperature of described compacting is preferably 135～220 DEG C, and the pressure of described compacting is preferably 20～40Kg/m2, the time of described compacting is preferably 60～150min.
After prepared metal-based copper-clad plate, it is preferred that further comprising the steps of: dismounting, processing and inspection.
Meeting on the basis of this area general knowledge, above-mentioned each optimum condition, can combination in any, obtain the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material are all commercially.
The actively progressive effect of the present invention is in that:
The metal-based copper-clad plate of the present invention eliminates the use of the non-conductor of this heat of glass fabric in insulating barrier, improves the heat conductivity of metal-based copper-clad plate, reduces thermal resistance, improves product heat conductivity. Spraying coating process in the preparation method of metal-based copper-clad plate provided by the invention, mutually more conventional spray gun spraying technique, it is not necessary to fixture protection, glue are floated in the air few; The technique comparing hairbrush printing, has quick, the accurate advantage of thickness, and coating thickness can be as accurate as 0.02mm, is entirely capable of meeting production requirement.
Detailed description of the invention
Mode by the examples below further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments. The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue.
In following embodiment, the application system adopted is Fa Luowei intelligence application system SC-45A, or the application system that Dongguan Anda Automatic Equipment Co., Ltd. provides, it includes the automatic connection platform, a Selective coating machine, a monitor station and the curing oven that are sequentially connected with.
Embodiment 1
In the present embodiment, the raw material components of glue is shown in Table 1:
The material composition table of the glue of table 1 embodiment 1
| Novolac epoxy resin | 450Kg |
| Ethylenediamine | 8Kg |
| Benzyl-2-aniline | 0.2Kg |
| Acetone | 110Kg |
| Boron nitride (particle diameter D50 is 5 μm) | 110Kg |
Wherein, inorganic filler accounts for the 16.22% of the gross mass of glue.
The preparation method of glue: ethylenediamine, benzyl-2-aniline and acetone are mixed, stirs 4 hours with rotating speed for 1000rpm; After it is completely dissolved, add novolac epoxy resin, be sufficiently stirred for 3 hours with rotating speed for 1200rpm; After mix homogeneously, add boron nitride, disperse 45 minutes for 3500rpm high speed shear with rotating speed, then stir 6 hours for 1200rpm with rotating speed, after complete ripening.
Adopt manufacture method commonly used in the art to prepare metal-based copper-clad plate, sequentially pass through the processing procedure of gluing, lamination, compacting, dismounting, sharp processing.
Wherein, the processing procedure of gluing is: adopts the mode of spraying directly to spread upon on aluminium sheet by application system glue, is dried into gel, can be prepared by prepreg. Its technological parameter is: oven for gluing machine temperature is 220 DEG C, and heat time heating time is 2min, gel time 70s, fluidity 15%, volatile matter≤0.75%, and the THICKNESS CONTROL of prepreg is at 45～50 μm.
The processing procedure of lamination is: above-mentioned prepreg and Copper Foil is overlapped according to the order of sequence, obtains applications as laminates.
The processing procedure of compacting is: is placed in press by applications as laminates and carries out vacuum pressing-combining. Technological parameter is: hot pressing temperature is 135 DEG C, and hot pressing time is 60min, and pressure is 20Kg/m2。
Embodiment 2
In the present embodiment, the raw material components of glue is shown in Table 2:
The material composition table of the glue of table 2 embodiment 2
| Bisphenol A type epoxy resin | 480Kg |
| 2-amino-2-phenylmethane | 12Kg |
| 2-methylimidazole | 0.25Kg |
| Dimethylformamide | 100Kg |
| Aluminium nitride (particle diameter D50 is 20 μm) | 200Kg |
Wherein, inorganic filler accounts for the 25.24% of the gross mass of glue.
The preparation method of glue: 2-amino-2-phenylmethane, 2-methylimidazole and dimethylformamide are mixed, stirs 2 hours with rotating speed for 1500rpm; After it is completely dissolved, add bisphenol A type epoxy resin, be sufficiently stirred for 5 hours with rotating speed for 1000rpm; After mix homogeneously, add aluminium nitride, disperse 30 minutes for 5000rpm high speed shear with rotating speed, then stir 6 hours for 1500rpm with rotating speed, after complete ripening.
Adopt manufacture method commonly used in the art to prepare metal-based copper-clad plate, sequentially pass through the processing procedure of gluing, lamination, compacting, dismounting, sharp processing.
Wherein, the processing procedure of gluing is: adopts the mode of spraying directly to spread upon on aluminium sheet by application system glue, is placed in baking oven and heats, make glue semi-solid preparation. Its technological parameter is: oven for gluing machine temperature is 210 DEG C, and heat time heating time is 2.5min, gel time 130s, fluidity 20%, volatile matter≤0.75%, and the THICKNESS CONTROL of prepreg is at 70～75 μm.
The processing procedure of lamination is: by above-mentioned prepreg and Copper Foil by overlapping according to the order of sequence.
The processing procedure of compacting is: is placed in press by the applications as laminates of above-mentioned prepreg and carries out vacuum pressing-combining. Technological parameter is: hot pressing temperature is 220 DEG C, and hot pressing time is 150min, and pressure is 40Kg/m2。
Embodiment 3
In the present embodiment, the raw material components of glue is shown in Table 3:
The material composition table of the glue of table 3 embodiment 3
| Brominated epoxy resin | 500Kg |
| Phthalic anhydride | 12Kg |
| Triethanolamine | 0.3Kg |
| Ethylene glycol monomethyl ether | 100Kg |
| Ceramics (particle diameter D50 is 35 μm) | 400Kg |
Wherein, inorganic filler accounts for the 39.51% of the gross mass of glue.
The preparation method of glue: phthalic anhydride, triethanolamine and ethylene glycol monomethyl ether are mixed, stirs 3 hours with rotating speed for 800rpm; After it is completely dissolved, add brominated epoxy resin, be sufficiently stirred for 4 hours with rotating speed for 1300rpm; After mix homogeneously, add ceramics, disperse 120 minutes for 2500rpm high speed shear with rotating speed, then stir 8 hours for 1000rpm with rotating speed, after complete ripening.
Adopt manufacture method commonly used in the art to prepare metal-based copper-clad plate, sequentially pass through the processing procedure of gluing, lamination, compacting, dismounting, sharp processing.
Wherein, the processing procedure of gluing is: adopts the mode of spraying directly to spread upon on aluminium sheet by application system glue, is placed in baking oven and heats, make glue semi-solid preparation. Its technological parameter is: oven for gluing machine temperature is 200 DEG C, and heat time heating time is 3.5min, gel time 90s, fluidity 5%, volatile matter≤0.75%, and the THICKNESS CONTROL of prepreg is at 90～95 μm.
The processing procedure of lamination is: above-mentioned prepreg and Copper Foil is overlapped according to the order of sequence, obtains applications as laminates.
The processing procedure of compacting is: is placed in press by the applications as laminates of above-mentioned prepreg and carries out vacuum pressing-combining. Technological parameter is: hot pressing temperature is 200 DEG C, and hot pressing time is 110min, and pressure is 25Kg/m2。
Embodiment 4
In the present embodiment, the raw material components of glue is shown in Table 4:
The material composition table of the glue of table 4 embodiment 4
| Double; two maleic anhydride resins | 460Kg |
| 2-amino-2-phenylmethane | 12Kg |
| 2-undecyl imidazole | 0.3Kg |
| Hexone | 100Kg |
| Carborundum (particle diameter D50 is 60 μm) | 600Kg |
Wherein, inorganic filler accounts for the 51.18% of the gross mass of glue.
The preparation method of glue: 2-amino-2-phenylmethane, 2-undecyl imidazole and hexone are mixed, stirs 2 hours with rotating speed for 1400rpm; After it is completely dissolved, adds double; two maleic anhydride resin, be sufficiently stirred for 5 hours with rotating speed for 1000rpm; After mix homogeneously, add carborundum, disperse 90 minutes for 4500rpm high speed shear with rotating speed, then stir 7 hours for 1400rpm with rotating speed, after complete ripening.
Adopt manufacture method commonly used in the art to prepare metal-based copper-clad plate, sequentially pass through the processing procedure of gluing, lamination, compacting, dismounting, sharp processing.
Wherein, the processing procedure of gluing is: adopts the mode of spraying directly to spread upon on aluminium sheet by application system glue, is placed in baking oven and heats, make glue semi-solid preparation. Its technological parameter is: oven for gluing machine temperature is 170 DEG C, and heat time heating time is 5min, gel time 90s, fluidity 15%, volatile matter≤0.75%, and the THICKNESS CONTROL of prepreg is at 135～145 μm.
The processing procedure of lamination is: above-mentioned prepreg and Copper Foil is overlapped according to the order of sequence, obtains applications as laminates.
The processing procedure of compacting is: is placed in press by the applications as laminates of above-mentioned prepreg and carries out vacuum pressing-combining. Technological parameter is: hot pressing temperature is 155 DEG C, and hot pressing time is 100min, and pressure is 40Kg/m2。
Embodiment 5
In the present embodiment, the raw material components of glue is shown in Table 5:
The material composition table of the glue of table 5 embodiment 5
| Polyurethane resin | 450Kg |
| 2-amino-2-phenol | 8Kg |
| 2-phenyl-4-methylimidazole | 0.2Kg |
| Propylene glycol monomethyl ether | 100Kg |
| Silicon nitride (particle diameter D50 is 85 μm) | 1300Kg |
Wherein, inorganic filler accounts for the 70.0% of the gross mass of glue.
The preparation method of glue: 2-amino-2-phenol, 2-phenyl-4-methylimidazole and propylene glycol monomethyl ether are mixed, stirs 4 hours with rotating speed for 1300rpm; After it is completely dissolved, add polyurethane resin, be sufficiently stirred for 5 hours with rotating speed for 1500rpm; After mix homogeneously, add silicon nitride, disperse 60 minutes for 4500rpm high speed shear with rotating speed, then stir 7 hours for 1500rpm with rotating speed, after complete ripening.
Adopt manufacture method commonly used in the art to prepare metal-based copper-clad plate, sequentially pass through the processing procedure of gluing, lamination, compacting, dismounting, sharp processing.
Wherein, the processing procedure of gluing is: adopts the mode of spraying directly to spread upon on aluminium sheet by application system glue, is placed in baking oven and heats, make glue semi-solid preparation. Its technological parameter is: oven for gluing machine temperature is 210 DEG C, and heat time heating time is 2.5min, gel time 130s, fluidity 15%, volatile matter≤0.75%, and the THICKNESS CONTROL of prepreg is at 180～190 μm.
The processing procedure of lamination is: above-mentioned prepreg and Copper Foil is overlapped according to the order of sequence, obtains applications as laminates. The processing procedure of compacting is: is placed in press by the applications as laminates of above-mentioned prepreg and carries out vacuum pressing-combining. Technological parameter is: hot pressing temperature is 220 DEG C, and hot pressing time is 60min, and pressure is 30Kg/m2。
Embodiment 6
In the present embodiment, in glue, the content of inorganic filler is account for glue gross mass 75%, and all the other processing steps and condition are all with embodiment 1.
Embodiment 7
In the present embodiment, for preparing in the glue of insulating barrier without there being inorganic filler, all the other processing steps and condition are all with embodiment 1.
Comparative example 1
In this comparative example, the raw material components of glue is with embodiment 1.
The preparation method of glue: ethylenediamine, benzyl-2-aniline and acetone are mixed, stirs 4 hours with rotating speed for 1000rpm; After it is completely dissolved, add novolac epoxy resin, be sufficiently stirred for 3 hours with rotating speed for 1200rpm; After mix homogeneously, add boron nitride, disperse 45 minutes for 3500rpm high speed shear with rotating speed, then stir 6 hours for 1200rpm with rotating speed, after complete ripening.
Adopt manufacture method commonly used in the art to prepare metal-based copper-clad plate, sequentially pass through the processing procedure of gluing, lamination, compacting, dismounting, sharp processing.
Wherein, the processing procedure of gluing is: is spread upon on the glass cloth of 1080 these specifications by the mode of conventional gluing by glue, is dried into gel, can be prepared by prepreg. Its technological parameter is: oven for gluing machine temperature is 180 DEG C, and heat time heating time is 2.5min, gel time 70s, fluidity 15%, volatile matter≤0.75%, and the weight indicator of prepreg controls at 1.0g/dm2。
The processing procedure of lamination is: above-mentioned prepreg and Copper Foil are overlapped by copper foil layer, prepreg, metal-based layer order.
The processing procedure of compacting is: is placed in press by applications as laminates and carries out vacuum pressing-combining.Technological parameter is: hot pressing temperature is 135 DEG C, and hot pressing time is 60min, and pressure is 20Kg/m2。
Comparative example 2
In the present embodiment, the raw material components of glue is shown in Table 6:
The material composition table of the glue of table 6 comparative example 2
| Bisphenol A type epoxy resin | 480Kg |
| 2-amino-2-phenylmethane | 12Kg |
| 2-methylimidazole | 0.25Kg |
| Dimethylformamide | 100Kg |
| Aluminium nitride (particle diameter D50 is 20 μm) | 100Kg |
Wherein, inorganic filler accounts for the 14.4% of the gross mass of glue.
The preparation method of glue: 2-amino-2-phenylmethane, 2-methylimidazole and dimethylformamide are mixed, stirs 2 hours with rotating speed for 1500rpm; After it is completely dissolved, add bisphenol A type epoxy resin, be sufficiently stirred for 5 hours with rotating speed for 1000rpm; After mix homogeneously, add aluminium nitride, disperse 30 minutes for 5000rpm high speed shear with rotating speed, then stir 6 hours for 1500rpm with rotating speed, after complete ripening.
Adopt manufacture method commonly used in the art to prepare metal-based copper-clad plate, sequentially pass through the processing procedure of gluing, lamination, compacting, dismounting, sharp processing.
Wherein, the processing procedure of gluing is: is spread upon on the glass cloth of 1080 these specifications by the mode of conventional gluing by glue, is dried into gel, can be prepared by prepreg. Its technological parameter is: oven for gluing machine temperature is 210 DEG C, and heat time heating time is 2.5min, gel time 130s, fluidity 20%, volatile matter≤0.75%, and the weight indicator of prepreg controls at 1.5g/dm2. Prepreg becomes insulating barrier, 1.5g/dm after plate compression moulding2Weight indicator correspondence thickness of insulating layer be about 75 μm.
The processing procedure of lamination is: by above-mentioned prepreg and Copper Foil by overlapping according to the order of sequence.
The processing procedure of compacting is: is placed in press by the applications as laminates of above-mentioned prepreg and carries out vacuum pressing-combining. Technological parameter is: hot pressing temperature is 220 DEG C, and hot pressing time is 150min, and pressure is 40Kg/m2。
Effect example 1
Shown in basic mechanical design feature the testing result such as table 7 and table 8 of the metal-based copper-clad plate that embodiment 1～7 and comparative example 1～2 produce. The method of testing of the heat conductivity in the present invention is stable state hot plate method, is specially ASTMD5470(thin heat-conductive solid insulant heat conductivity standard test method). The method of testing of the thermal resistance in the present invention is TO-220, and reference standard is: the testing standard of thermal conductance solid electrical insulation material heat transfer performance thin for ASTMD5470-2006().
The test result of the basic mechanical design feature of table 7 embodiment 1～3 and comparative example 1～2
The test result of the basic mechanical design feature of table 8 embodiment 4～7
From table 7 and table 8 it can be seen that by spraying the metal-based copper-clad plate that the mode of glue is made, owing to eliminating the use of glass fabric, thus improve the heat conductivity of sheet material, reduce thermal resistance. Meanwhile, the traditional performance of metal-based copper-clad plate have also been obtained bigger lifting.
Simultaneously, the viscosity of the glue of the present invention can change along with the change of formula and temperature, but it is generally kept in 0.15MPa s～0.5MPa s, spraying coating process in the preparation method of metal-based copper-clad plate provided by the invention can guarantee that glue obtains good turnover rate, and the technique of mutually more conventional spray gun spraying and hairbrush printing, can ensure that the thickness of glue layer evenly, without causing glue to float in the air, there is superiority very much.
Claims (9)
1. a metal-based copper-clad plate, it is characterised in that described metal-based copper-clad plate is made up of the copper foil layer being sequentially stacked, insulating barrier and metal-based layer; Described insulating barrier does not contain glass fibre; Described insulating barrier is that in the way of spraying, glue is directly spread upon the coating formed on metal-based layer; The thickness of described insulating barrier is 50～200 μm;Described metal-based layer is aluminium sheet, copper coin, silicon steel plate, corrosion resistant plate or aluminium alloy plate;
The composition of raw materials of described glue is any one in following formula: formula one: in mass parts, resin is the novolac epoxy resin of 450-460 part, firming agent is the ethylenediamine of 8-9 part, curing accelerator is the benzyl-2-aniline of 0.2-0.3 part, solvent is the acetone of 105-115 part, and inorganic filler is the boron nitride of the 15%-20% accounting for described glue gross mass; Formula two: in mass parts, resin is the bisphenol A type epoxy resin of 480-490 part, firming agent is the 2-amino-2-phenylmethane of 10-12 part, curing accelerator is the 2-methylimidazole of 0.2-0.3 part, solvent is the dimethylformamide of 95-105 part, and inorganic filler is the aluminium nitride of the 25%-30% accounting for described glue gross mass; Formula three: in mass parts, resin is the brominated epoxy resin of 490-500 part, firming agent is the phthalic anhydride of 10-12 part, curing accelerator is the triethanolamine of 0.2-0.3 part, solvent is the ethylene glycol monomethyl ether of 95-105 part, and inorganic filler is the ceramics of the 35%-40% accounting for described glue gross mass.
2. metal-based copper-clad plate as claimed in claim 1, it is characterised in that the particle diameter of described inorganic filler is 1～100 μm.
3. metal-based copper-clad plate as claimed in claim 1 or 2, it is characterised in that the preparation method of described glue comprises the steps: that described firming agent, described curing accelerator and described solvent are mixed by (1), and stirring is to dissolving to obtain mixture A; (2) by described mixture A and described mixed with resin, stir to obtain mixture B; (3) being mixed with described inorganic filler by described mixture B, high speed shear, after ripening.
4. metal-based copper-clad plate as claimed in claim 3, it is characterised in that in step (1), the time of described stirring is 2～5 hours; The rotating speed of described stirring is 800～1500rpm;
And/or, in step (2), the time of described stirring is 3～5 hours; The rotating speed of described stirring is 1000～1500rpm;
And/or, in step (3), the time of described high speed shear is 30～120 minutes; The rotating speed of described high speed shear is 2500～5000rpm; Described ripening is stir 6～8 hours with the rotating speed of 1000～1500rpm.
5. the preparation method of the metal-based copper-clad plate as described in any one of Claims 1 to 4, it is characterized in that, it comprises the steps: that described glue is directly spread upon on metal-based layer by (1) by the mode sprayed, it is placed in baking oven and heats, make glue semi-solid preparation, obtain prepreg containing metal-based layer; (2) prepreg described in step (1) is covered with copper foil layer, is assemblied in press, carry out suppressing.
6. preparation method as claimed in claim 5, it is characterised in that in step (1), described spraying adopts application system to carry out; The pressure of described spraying is 200KPa～500KPa.
7. preparation method as claimed in claim 6, it is characterised in that described application system includes the automatic connection platform, a Selective coating machine, a monitor station and the curing oven that are sequentially connected with.
8. preparation method as claimed in claim 5, it is characterised in that in step (1), the temperature of described heating is 170～210 DEG C; The gel time of described glue is 70～130s; The fluidity of described prepreg is 5%～20%, and the volatilization of described prepreg is divided into≤0.75%;In described prepreg, the thickness of glue is 50～200 μm.
9. preparation method as claimed in claim 5, it is characterised in that in step (2), the temperature of described compacting is 135～220 DEG C, and the pressure of described compacting is 20～40Kg/m2, the time of described compacting is 60～150min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410079080.4A CN103963379B (en) | 2014-03-05 | 2014-03-05 | Metal-based copper-clad plate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410079080.4A CN103963379B (en) | 2014-03-05 | 2014-03-05 | Metal-based copper-clad plate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103963379A CN103963379A (en) | 2014-08-06 |
| CN103963379B true CN103963379B (en) | 2016-06-15 |
Family
ID=51233598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410079080.4A Expired - Fee Related CN103963379B (en) | 2014-03-05 | 2014-03-05 | Metal-based copper-clad plate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103963379B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106467668B (en) * | 2015-08-19 | 2021-07-30 | 广东生益科技股份有限公司 | Organic silicon resin aluminum-based copper-clad plate and preparation method thereof |
| CN106585044A (en) * | 2016-11-01 | 2017-04-26 | 广东全宝科技股份有限公司 | Manufacturing method for metal-based copper clad laminate |
| CN107502253A (en) * | 2017-07-26 | 2017-12-22 | 江苏诺德新材料股份有限公司 | A kind of glue for high heat conduction type copper-clad plate aluminium base and preparation method thereof |
| CN108995346A (en) * | 2018-08-17 | 2018-12-14 | 咸阳华电电子材料科技有限公司 | A kind of resin adhesive liquid and preparation method thereof and its application |
| CN113386416B (en) * | 2021-07-08 | 2022-12-16 | 江西柔顺科技有限公司 | Heat-conducting double-sided copper-clad plate and preparation method thereof |
| CN113524870A (en) * | 2021-07-22 | 2021-10-22 | 安徽鸿海新材料股份有限公司 | Preparation method of high-heat-resistance copper-clad plate |
| CN117066081B (en) * | 2023-10-18 | 2023-12-29 | 山西赛科德科技有限公司 | Coating method of non-oriented silicon steel thin strip self-adhesive coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101068452A (en) * | 2007-05-15 | 2007-11-07 | 杭州裕兴层压板材有限公司 | Aluminium-based copper foil clad laminated board and producing technology |
| CN103057213A (en) * | 2012-12-31 | 2013-04-24 | 金安国纪科技股份有限公司 | Environment-friendly copper clad laminate for LED monochrome display, glue solution and preparation method |
-
2014
- 2014-03-05 CN CN201410079080.4A patent/CN103963379B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101068452A (en) * | 2007-05-15 | 2007-11-07 | 杭州裕兴层压板材有限公司 | Aluminium-based copper foil clad laminated board and producing technology |
| CN103057213A (en) * | 2012-12-31 | 2013-04-24 | 金安国纪科技股份有限公司 | Environment-friendly copper clad laminate for LED monochrome display, glue solution and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103963379A (en) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103963379B (en) | Metal-based copper-clad plate and preparation method thereof | |
| CN102558765B (en) | Halogen-free fire-retardant high heat conducting insulating resin composition and heat dissipation metal-base copper clad plate | |
| CN106147132B (en) | Resin combination and the glue containing it, prepreg and copper-clad plate and preparation method | |
| CN103057214B (en) | Environment-friendly glue solution for LED full-color display, copper clad laminate and preparation method thereof | |
| CN106633675B (en) | A kind of highly thermal-conductive resin composition and its application | |
| EP3112422A1 (en) | Halogen-free flame retardant type resin composition | |
| JP2009263549A (en) | Epoxy resin composition of vegetable origin, and various instruments using the same | |
| CN109575523B (en) | High-thermal-conductivity resin composition for copper-clad plate | |
| CN1311042C (en) | Thermosetting adhesive composition and adhesive band used said composition for electronic member | |
| CN103963378A (en) | High thermal conductivity type metal-based copper clad laminate and preparation method thereof | |
| CN103160229B (en) | Glue liquor for environment-friendly light laminated board, laminated board and preparation method of glue liquor | |
| CN104610707A (en) | Metal-base copper clad laminate manufactured through high-performance RCC (resin coated copper foil) and applied to high-power LED | |
| CN104559888A (en) | Copper-clad plate applicable to production of high multi-layer PCB (printed circuit board) and preparation method of copper-clad plate | |
| CN105150662A (en) | Manufacturing method of epoxy glass-cloth-matrix copper clad laminate | |
| CN103963386B (en) | Metal-based copper-clad plate and preparation method thereof | |
| CN1847351A (en) | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same | |
| CN105199619B (en) | Aluminum-based copper-clad plate high-heat-conductivity glue membrane preparation method | |
| CN114932727A (en) | Heat-resistant hydrocarbon resin-based copper-clad plate and preparation method thereof | |
| CN103649185B (en) | The manufacture method of prepreg, laminate, semiconductor package part and laminate | |
| CN103963381B (en) | Metal-based copper-clad plate and preparation method thereof | |
| JP4793277B2 (en) | Manufacturing method of epoxy resin varnish, manufacturing method of prepreg, manufacturing method of laminated board and wiring board | |
| CN104210181B (en) | LED highly heat-conductive copper-clad plate and preparation method thereof | |
| CN112848559A (en) | Lead-free compatible copper-clad plate and preparation method thereof | |
| CN116528487B (en) | High-strength aluminum-based PCB and preparation method thereof | |
| CN115505259B (en) | Resin composition, resin glue solution, prepreg and copper-clad plate thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160815 Address after: 201613 Shanghai city Songjiang District Baosheng Road No. 33 Patentee after: SHANGHAI GUOJI ELECTRONIC MATERIAL Co.,Ltd. Address before: 201613 Shanghai city Songjiang District Baosheng Industrial Zone Songjiang Road No. 33 Patentee before: GOLDENMAX INTERNATIONAL TECHNOLOGY Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160615 |