CN103963379A - Metal-based CCL (copper clad laminate) and preparation method thereof - Google Patents
Metal-based CCL (copper clad laminate) and preparation method thereof Download PDFInfo
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- CN103963379A CN103963379A CN201410079080.4A CN201410079080A CN103963379A CN 103963379 A CN103963379 A CN 103963379A CN 201410079080 A CN201410079080 A CN 201410079080A CN 103963379 A CN103963379 A CN 103963379A
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- epoxy resin
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 4
- 239000010949 copper Substances 0.000 title claims abstract description 4
- 239000003292 glue Substances 0.000 claims abstract description 74
- 238000005507 spraying Methods 0.000 claims abstract description 21
- 239000011889 copper foil Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 239000003365 glass fiber Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 239000011256 inorganic filler Substances 0.000 claims description 26
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 23
- 239000003822 epoxy resin Substances 0.000 claims description 22
- 229920000647 polyepoxide Polymers 0.000 claims description 22
- 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 19
- 239000011347 resin Substances 0.000 claims description 19
- 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 16
- 239000002994 raw material Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000004888 barrier function Effects 0.000 claims description 12
- 239000002904 solvent Substances 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
- 239000002245 particle Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 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
- 229940015043 glyoxal Drugs 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 239000011521 glass Substances 0.000 claims description 6
- 239000004843 novolac epoxy resin Substances 0.000 claims description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims description 5
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 claims description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-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
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical group CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 150000002460 imidazoles Chemical class 0.000 claims description 5
- 229920005749 polyurethane resin Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- 150000003512 tertiary amines Chemical class 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- 229910000976 Electrical steel Inorganic materials 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000004744 fabric Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000007921 spray Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract 4
- 239000004020 conductor Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 39
- 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
- 238000002156 mixing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000007639 printing Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
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- 238000007655 standard test method Methods 0.000 description 1
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Abstract
The invention discloses a metal-based CCL (copper clad laminate) and a preparation method thereof. The metal-based CCL comprises a copper foil layer, an insulation layer and a metal base layer which are sequentially stacked, wherein the insulation layer contains no glass fiber and is a coating formed by directly spraying a glue solution on the metal base layer, and the thickness of the insulation layer is 50-200 mu m. According to the metal-based CCL, glass fiber cloth which is a bad heat conductor in the insulation layer is removed, the heat conductivity coefficient of the metal-based CCL is increased, heat resistance is reduced, and the heat conductivity of a product is improved. According to a spraying technology in the provided preparation method of the metal-based CCL, compared with the conventional spraying technology with a spray gun, fixture protection is not needed, and few glue solution is scattered; and compared with a smearing technology with a brush, the advantages of fastness and accurate thickness are provided, the coating thickness can be accurate to 0.02 mm, and production requirements can be met completely.
Description
Technical field
The present invention relates to printed circuit board field, relate in particular to a kind of metal-based copper-clad plate and preparation method thereof.
Background technology
Resource further shortage today, LED, as a kind of new type light source of energy-conserving and environment-protective, is more and more subject to people's attention.But the active region area of LED chip is little, operating current is large, causes the operating temperature of LED chip high.Especially great power LED, the heat flow that chip bears is larger, if do not take effective cooling measure, can make chip temperature too high, the optical efficiency that causes LED is reduced, chip emission spectrum generation red shift, colour temperature Quality Down, and accelerate LED chip degeneration, the life-span of device is shortened.And the heat overwhelming majority that chip produces is to pass on the substrate of chip bottom by heat conducting mode, then dissipate in the mode of thermal convection current.Therefore, LED baseplate material requires to possess higher heat conductivility, and conventional LED baseplate material is all aluminium base conventionally at present, thus, improves as much as possible the heat transfer efficiency of aluminium base, has become the research topic of those skilled in the art's a outbalance.
Summary of the invention
Technical problem to be solved by this invention has been to overcome the low defect of thermal conductivity of insulating barrier in aluminium base of the prior art, and a kind of metal-based copper-clad plate and preparation method thereof is provided.
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 stacked successively copper foil layer, insulating barrier and metal-based layer; Described insulating barrier does not contain glass fibre; The coating of described insulating barrier for glue is directly spread upon on metal-based layer to be formed in the mode of spraying; The thickness of described insulating barrier is 50～200 μ m.
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 preferably comprises the component of following mass parts: 450～500 parts of resins, 8～12 parts, curing agent, 0.2～0.3 part of curing accelerator, 100～120 parts of solvents and 0～75% the inorganic filler that accounts for described glue gross mass.
Wherein, described resin can be the conventional various resins that use of this area glue used for printed circuit board, is preferably that epoxy resin, span carry out one or more in amide resin and polyurethane resin.Described epoxy resin preferably comprises 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 curing agent can be the conventional various curing agent that use in the glue used for printed circuit board of this area, is preferably one or more in amine curing agent, acid anhydride type curing agent and high score subclass curing agent.Described amine curing agent can be selected the amine curing agent of the various routines in this area, is preferably one or more in ethylenediamine, 2-ethene-3-amine, 2-amino-2-phenylmethane, dicyandiamide, 2-amino-2-phenol and organic hydrazides.Described acid anhydride type curing agent can be selected the acid anhydride type curing agent of the various routines in this area, is preferably phthalic anhydride and/or 2-phenylate-4-acid anhydrides.Described high score subclass curing agent can be selected the high score subclass curing agent of the various routines in this area, is preferably phenolic resins and/or benzoxazine resin.
Wherein, described curing accelerator can be selected the conventional various curing accelerators that use in the glue used for printed circuit board of this area, comprises tertiary amines curing accelerator and/or imidazoles curing accelerator.Described tertiary amines curing accelerator can be selected the tertiary amines curing accelerator of the various routines in this area, is preferably benzyl-2-aniline and/or triethanolamine.Described imidazoles curing accelerator can be selected the imidazoles curing accelerator of the various routines in this area, is preferably one or more in 1-methylimidazole, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-undecyl imidazole.
Wherein, described solvent can be selected the conventional various solvents that use in the glue used for printed circuit board of this area, is preferably one or more in acetone, butanone, cyclohexanone, hexone, dimethyl formamide, dimethylacetylamide, EGME and propylene glycol monomethyl ether.
Wherein, described inorganic filler can be selected the conventional various inorganic fillers that use in the glue used for printed circuit board of this area, is preferably one or more in aluminium nitride, boron nitride, silicon nitride, aluminium oxide, beryllium oxide, silica, magnesia, carborundum, ceramic powder and glass dust.The particle diameter of described inorganic filler is preferably 1～100 μ m.
The composition of raw materials of described glue is preferably any in following formula: formula one: in mass parts, resin is the novolac epoxy resin of 450-460 part, curing agent is the ethylenediamine of 8-9 part, curing accelerator is benzyl-2-aniline of 0.2-0.3 part, solvent is the acetone of 105-115 part, the boron nitride that inorganic filler is 15%-20%; Formula two: in mass parts, resin is the bisphenol A type epoxy resin of 480-490 part, and curing agent is 2-amino-2-phenylmethane of 10-12 part, and curing accelerator is the glyoxal ethyline of 0.2-0.3 part, solvent is the dimethyl formamide of 95-105 part, the aluminium nitride that inorganic filler is 25%-30%; Formula three: in mass parts, resin is the brominated epoxy resin of 490-500 part, and curing agent is the phthalic anhydride of 10-12 part, and curing accelerator is the triethanolamine of 0.2-0.3 part, solvent is the EGME of 95-105 part, the ceramic powder that inorganic filler is 35%-40%; Formula four: in mass parts, resin is two maleic anhydride resins of 450-460 part, curing agent is 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, the carborundum that inorganic filler is 50%-55%; Formula five: in mass parts, resin is the polyurethane resin of 450-460 part, and curing agent is 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, the silicon nitride that inorganic filler is 70%-75%.
In the present invention, the preparation method of described glue preferably comprises the steps: that (1) is by described curing agent, described curing accelerator and described solvent, is stirred to and dissolves to obtain mixture A; (2), by described mixture A and described mixed with resin, mixture B stirs to obtain; (3) in the time that the composition of raw materials of described glue comprises inorganic filler, described mixture B to be mixed with described inorganic filler, high speed shear, after slaking; In the time that the composition of raw materials of described glue does not comprise inorganic filler, by described mixture B slaking.
In step (1), the time of described stirring, so that described curing agent and described curing accelerator completely dissolve and are as the criterion, is preferably 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.Described slaking can adopt the slaking operation of this area routine to carry out, and is preferably to stir 6～8 hours with the rotating speed of 1000～1500rpm.
The present invention also provides a kind of preparation method of metal-based copper-clad plate, and it comprises the steps: that (1) directly spreads upon described glue on metal-based layer by the mode of spraying, is placed in baking oven and heats, and makes glue semi-solid preparation, obtains the prepreg of containing metal basic unit; (2) prepreg step (1) Suo Shu is covered with to copper foil layer, is assemblied in press, suppress.
In step (1), described spraying preferably adopts application system to carry out.Described application system preferably comprises the automatic connection platform, a Selective coating machine, a monitor station and the curing oven that connect successively.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 μ m.
In step (2), the temperature of described compacting is preferably 135～220 DEG C, and the pressure of described compacting is preferably 20～40Kg/m
2, the time of described compacting is preferably 60～150min.
Making after metal-based copper-clad plate, preferably further comprising the steps of: dismounting, processing and inspection.
Meeting on the basis of this area general knowledge, above-mentioned each optimum condition, can be combined, and obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is:
Metal-based copper-clad plate of the present invention has been removed the use of this hot non-conductor of glass fabric in insulating barrier, has improved the thermal conductivity factor of metal-based copper-clad plate, reduces thermal resistance, has improved product thermal conductivity.Spraying coating process in the preparation method of metal-based copper-clad plate provided by the invention, compares conventional spray gun spraying technique, does not need fixture protection, glue to float in the air few; Compare the technique of hairbrush printing, have quick, the accurate advantage of thickness, coating thickness can be as accurate as 0.02mm, can meet production requirement completely.
Detailed description of the invention
Mode below by embodiment 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, according to conventional method and condition, or selects according to catalogue.
In following embodiment, the application system adopting is Fa Luowei intelligence application system SC-45A, or the application system that provides of Dongguan Anda Automatic Equipment Co., Ltd., it comprises the automatic connection platform, a Selective coating machine, a monitor station and the curing oven that connect successively.
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 be 5 μ m) | 110Kg |
Wherein, inorganic filler account for glue gross mass 16.22%.
The preparation method of glue: ethylenediamine, benzyl-2-aniline and acetone are mixed, stir 4 hours taking rotating speed as 1000rpm; After it dissolves completely, then add novolac epoxy resin, fully stir 3 hours taking rotating speed as 1200rpm; After mixing, then add boron nitride, disperse 45 minutes taking rotating speed as 3500rpm high speed shear, then stir 6 hours taking rotating speed as 1200rpm, completely after slaking.
Adopt conventional manufacture method in this area to prepare metal-based copper-clad plate, pass through successively the processing procedure of gluing, lamination, compacting, dismounting, sharp processing.
Wherein, the processing procedure of gluing is: adopt the mode of spraying directly to spread upon on aluminium sheet by application system glue, be dried into gel, can make prepreg.Its technological parameter is: oven for gluing machine temperature is 220 DEG C, and the heat time is 2min, gel time 70s, and fluidity 15%, volatile matter≤0.75%, the THICKNESS CONTROL of prepreg is at 45～50 μ m.
The processing procedure of lamination is: by superimposed according to the order of sequence to above-mentioned prepreg and Copper Foil, obtain applications as laminates.
The processing procedure of compacting is: applications as laminates is placed in to press 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/m
2.
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 |
| Glyoxal ethyline | 0.25Kg |
| Dimethyl formamide | 100Kg |
| Aluminium nitride (particle diameter D50 be 20 μ m) | 200Kg |
Wherein, inorganic filler account for glue gross mass 25.24%.
The preparation method of glue: 2-amino-2-phenylmethane, glyoxal ethyline and dimethyl formamide are mixed, stir 2 hours taking rotating speed as 1500rpm; After it dissolves completely, then add bisphenol A type epoxy resin, fully stir 5 hours taking rotating speed as 1000rpm; After mixing, then add aluminium nitride, disperse 30 minutes taking rotating speed as 5000rpm high speed shear, then stir 6 hours taking rotating speed as 1500rpm, completely after slaking.
Adopt conventional manufacture method in this area to prepare metal-based copper-clad plate, pass through successively the processing procedure of gluing, lamination, compacting, dismounting, sharp processing.
Wherein, the processing procedure of gluing is: adopt the mode of spraying directly to spread upon on aluminium sheet by application system glue, be placed in baking oven and heat, make glue semi-solid preparation.Its technological parameter is: oven for gluing machine temperature is 210 DEG C, and the heat time is 2.5min, gel time 130s, and fluidity 20%, volatile matter≤0.75%, the THICKNESS CONTROL of prepreg is at 70～75 μ m.
The processing procedure of lamination is: above-mentioned prepreg and Copper Foil are pressed superimposed according to the order of sequence.
The processing procedure of compacting is: the applications as laminates of above-mentioned prepreg is placed in to press 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/m
2.
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 |
| EGME | 100Kg |
| Ceramic powder (particle diameter D50 be 35 μ m) | 400Kg |
Wherein, inorganic filler account for glue gross mass 39.51%.
The preparation method of glue: phthalic anhydride, triethanolamine and EGME are mixed, stir 3 hours taking rotating speed as 800rpm; After it dissolves completely, then add brominated epoxy resin, fully stir 4 hours taking rotating speed as 1300rpm; After mixing, then add ceramic powder, disperse 120 minutes taking rotating speed as 2500rpm high speed shear, then stir 8 hours taking rotating speed as 1000rpm, completely after slaking.
Adopt conventional manufacture method in this area to prepare metal-based copper-clad plate, pass through successively the processing procedure of gluing, lamination, compacting, dismounting, sharp processing.
Wherein, the processing procedure of gluing is: adopt the mode of spraying directly to spread upon on aluminium sheet by application system glue, be placed in baking oven and heat, make glue semi-solid preparation.Its technological parameter is: oven for gluing machine temperature is 200 DEG C, and the heat time is 3.5min, gel time 90s, and fluidity 5%, volatile matter≤0.75%, the THICKNESS CONTROL of prepreg is at 90～95 μ m.
The processing procedure of lamination is: by superimposed according to the order of sequence to above-mentioned prepreg and Copper Foil, obtain applications as laminates.
The processing procedure of compacting is: the applications as laminates of above-mentioned prepreg is placed in to press 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/m
2.
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
| Two maleic anhydride resins | 460Kg |
| 2-amino-2-phenylmethane | 12Kg |
| 2-undecyl imidazole | 0.3Kg |
| Hexone | 100Kg |
| Carborundum (particle diameter D50 be 60 μ m) | 600Kg |
Wherein, inorganic filler account for glue gross mass 51.18%.
The preparation method of glue: 2-amino-2-phenylmethane, 2-undecyl imidazole and hexone are mixed, stir 2 hours taking rotating speed as 1400rpm; After it dissolves completely, then add two maleic anhydride resins, fully stir 5 hours taking rotating speed as 1000rpm; After mixing, then add carborundum, disperse 90 minutes taking rotating speed as 4500rpm high speed shear, then stir 7 hours taking rotating speed as 1400rpm, completely after slaking.
Adopt conventional manufacture method in this area to prepare metal-based copper-clad plate, pass through successively the processing procedure of gluing, lamination, compacting, dismounting, sharp processing.
Wherein, the processing procedure of gluing is: adopt the mode of spraying directly to spread upon on aluminium sheet by application system glue, be placed in baking oven and heat, make glue semi-solid preparation.Its technological parameter is: oven for gluing machine temperature is 170 DEG C, and the heat time is 5min, gel time 90s, and fluidity 15%, volatile matter≤0.75%, the THICKNESS CONTROL of prepreg is at 135～145 μ m.
The processing procedure of lamination is: by superimposed according to the order of sequence to above-mentioned prepreg and Copper Foil, obtain applications as laminates.
The processing procedure of compacting is: the applications as laminates of above-mentioned prepreg is placed in to press 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/m
2.
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 be 85 μ m) | 1300Kg |
Wherein, inorganic filler account for glue gross mass 70.0%.
The preparation method of glue: 2-amino-2-phenol, 2-phenyl-4-methylimidazole and propylene glycol monomethyl ether are mixed, stir 4 hours taking rotating speed as 1300rpm; After it dissolves completely, then add polyurethane resin, fully stir 5 hours taking rotating speed as 1500rpm; After mixing, then add silicon nitride, disperse 60 minutes taking rotating speed as 4500rpm high speed shear, then stir 7 hours taking rotating speed as 1500rpm, completely after slaking.
Adopt conventional manufacture method in this area to prepare metal-based copper-clad plate, pass through successively the processing procedure of gluing, lamination, compacting, dismounting, sharp processing.
Wherein, the processing procedure of gluing is: adopt the mode of spraying directly to spread upon on aluminium sheet by application system glue, be placed in baking oven and heat, make glue semi-solid preparation.Its technological parameter is: oven for gluing machine temperature is 210 DEG C, and the heat time is 2.5min, gel time 130s, and fluidity 15%, volatile matter≤0.75%, the THICKNESS CONTROL of prepreg is at 180～190 μ m.
The processing procedure of lamination is: by superimposed according to the order of sequence to above-mentioned prepreg and Copper Foil, obtain applications as laminates.The processing procedure of compacting is: the applications as laminates of above-mentioned prepreg is placed in to press 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/m
2.
Embodiment 6
In the present embodiment, in glue, the content of inorganic filler is to account for 75% of glue gross mass, and all the other processing steps and condition are all with embodiment 1.
Embodiment 7
In the present embodiment, for the preparation of not containing inorganic filler in the glue of insulating barrier, 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, stir 4 hours taking rotating speed as 1000rpm; After it dissolves completely, then add novolac epoxy resin, fully stir 3 hours taking rotating speed as 1200rpm; After mixing, then add boron nitride, disperse 45 minutes taking rotating speed as 3500rpm high speed shear, then stir 6 hours taking rotating speed as 1200rpm, completely after slaking.
Adopt conventional manufacture method in this area to prepare metal-based copper-clad plate, pass through successively the processing procedure of gluing, lamination, compacting, dismounting, sharp processing.
Wherein, the processing procedure of gluing is: glue is spread upon on the glass cloth of 1080 these specifications by the mode of conventional gluing, be dried into gel, can make prepreg.Its technological parameter is: oven for gluing machine temperature is 180 DEG C, and the heat time is 2.5min, gel time 70s, and fluidity 15%, volatile matter≤0.75%, the weight indicator of prepreg is controlled at 1.0g/dm
2.
The processing procedure of lamination is: above-mentioned prepreg and Copper Foil is superimposed by copper foil layer, prepreg, metal-based layer order.
The processing procedure of compacting is: applications as laminates is placed in to press 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/m
2.
Comparative example 2
In the present embodiment, the raw material components of glue is shown in Table 6:
The material composition table of table 6 comparative example 2 glue
| Bisphenol A type epoxy resin | 480Kg |
| 2-amino-2-phenylmethane | 12Kg |
| Glyoxal ethyline | 0.25Kg |
| Dimethyl formamide | 100Kg |
| Aluminium nitride (particle diameter D50 be 20 μ m) | 100Kg |
Wherein, inorganic filler account for glue gross mass 14.4%.
The preparation method of glue: 2-amino-2-phenylmethane, glyoxal ethyline and dimethyl formamide are mixed, stir 2 hours taking rotating speed as 1500rpm; After it dissolves completely, then add bisphenol A type epoxy resin, fully stir 5 hours taking rotating speed as 1000rpm; After mixing, then add aluminium nitride, disperse 30 minutes taking rotating speed as 5000rpm high speed shear, then stir 6 hours taking rotating speed as 1500rpm, completely after slaking.
Adopt conventional manufacture method in this area to prepare metal-based copper-clad plate, pass through successively the processing procedure of gluing, lamination, compacting, dismounting, sharp processing.
Wherein, the processing procedure of gluing is: glue is spread upon on the glass cloth of 1080 these specifications by the mode of conventional gluing, be dried into gel, can make prepreg.Its technological parameter is: oven for gluing machine temperature is 210 DEG C, and the heat time is 2.5min, gel time 130s, and fluidity 20%, volatile matter≤0.75%, the weight indicator of prepreg is controlled at 1.5g/dm
2.Prepreg becomes insulating barrier, 1.5g/dm after plate compression moulding
2the corresponding thickness of insulating layer of weight indicator be 75 μ m left and right.
The processing procedure of lamination is: above-mentioned prepreg and Copper Foil are pressed superimposed according to the order of sequence.
The processing procedure of compacting is: the applications as laminates of above-mentioned prepreg is placed in to press 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/m
2.
Effect embodiment 1
The basic mechanical design feature testing result of the metal-based copper-clad plate that embodiment 1～7 and comparative example 1～2 produce is as shown in table 7 and table 8.The method of testing of the thermal conductivity factor in the present invention is stable state hot plate method, is specially the standard test method of the thin heat conduction solid insulating material of ASTM D5470(heat conductivity).The method of testing of the thermal resistance in the present invention is TO-220, and normative reference is: the testing standard of the thermal conductance solid electrically insulating material heat transfer property that ASTM D5470-2006(is thin).
The test result of table 7 embodiment 1～3 and comparative example's 1～2 basic mechanical design feature
The test result of the basic mechanical design feature of table 8 embodiment 4～7
Can find out from table 7 and table 8, the metal-based copper-clad plate of making by the mode of spraying glue, owing to having removed the use of glass fabric, thereby has improved the thermal conductivity factor of sheet material, has reduced thermal resistance.Meanwhile, the traditional performance of metal-based copper-clad plate has also obtained larger lifting.
Simultaneously, the viscosity of glue of the present invention can change along with the variation of formula and temperature, but generally remain in 0.15MPas～0.5MPas, spraying coating process in the preparation method of metal-based copper-clad plate provided by the invention can ensure that glue obtains good turnover rate, and compare the technique of conventional spray gun spraying and hairbrush printing, the thickness that can ensure glue layer is more even, also can not cause glue free-and-easy, has very much superiority.
Claims (10)
1. a metal-based copper-clad plate, is characterized in that, described metal-based copper-clad plate is made up of stacked successively copper foil layer, insulating barrier and metal-based layer; Described insulating barrier does not contain glass fibre; The coating of described insulating barrier for glue is directly spread upon on metal-based layer to be formed in the mode of spraying; The thickness of described insulating barrier is 50～200 μ m.
2. metal-based copper-clad plate as claimed in claim 1, is characterized in that, 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 comprises the component of following mass parts: 450～500 parts of resins, 8～12 parts, curing agent, 0.2～0.3 part of curing accelerator, 100～120 parts of solvents and 0～75% the inorganic filler that accounts for described glue gross mass.
3. metal-based copper-clad plate as claimed in claim 2, is characterized in that, described resin is that epoxy resin, span carry out one or more in amide resin and polyurethane resin; Described curing agent is one or more in amine curing agent, acid anhydride type curing agent and high score subclass curing agent; Described curing accelerator comprises tertiary amines curing accelerator and/or imidazoles curing accelerator; Described solvent is one or more in acetone, butanone, cyclohexanone, hexone, dimethyl formamide, dimethylacetylamide, EGME and propylene glycol monomethyl ether; Described inorganic filler is one or more in aluminium nitride, boron nitride, silicon nitride, aluminium oxide, beryllium oxide, silica, magnesia, carborundum, ceramic powder and glass dust; The particle diameter of described inorganic filler is 1～100 μ m.
4. metal-based copper-clad plate as claimed in claim 3, is characterized in that, described epoxy resin comprises 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 400～550; Described amine curing agent is one or more in ethylenediamine, 2-ethene-3-amine, 2-amino-2-phenylmethane, dicyandiamide, 2-amino-2-phenol and organic hydrazides; Described acid anhydride type curing agent is phthalic anhydride and/or 2-phenylate-4-acid anhydrides; Described high score subclass curing agent is phenolic resins and/or benzoxazine resin; Described tertiary amines curing accelerator is benzyl-2-aniline and/or triethanolamine; Described imidazoles curing accelerator is one or more in 1-methylimidazole, glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-undecyl imidazole.
5. the metal-based copper-clad plate as described in claim 2～4 any one, is characterized in that, the preparation method of described glue comprises the steps: that (1) is by described curing agent, described curing accelerator and described solvent, is stirred to and dissolves to obtain mixture A; (2), by described mixture A and described mixed with resin, mixture B stirs to obtain; (3) in the time that the composition of raw materials of described glue comprises inorganic filler, described mixture B to be mixed with described inorganic filler, high speed shear, after slaking; In the time that the composition of raw materials of described glue does not comprise inorganic filler, by described mixture B slaking.
6. metal-based copper-clad plate as claimed in claim 5, is characterized 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 slaking is to stir 6～8 hours with the rotating speed of 1000～1500rpm.
7. the preparation method of the metal-based copper-clad plate as described in any one in claim 1～6, it is characterized in that, it comprises the steps: that (1) directly spreads upon described glue on metal-based layer by the mode of spraying, being placed in baking oven heats, make glue semi-solid preparation, obtain the prepreg of containing metal basic unit; (2) prepreg step (1) Suo Shu is covered with to copper foil layer, is assemblied in press, suppress.
8. preparation method as claimed in claim 7, is characterized in that, in step (1), described spraying adopts application system to carry out; Described application system preferably comprises the automatic connection platform, a Selective coating machine, a monitor station and the curing oven that connect successively; The pressure of described spraying is 200KPa～500KPa.
9. preparation method as claimed in claim 7, is characterized 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%, the volatilization of described prepreg is divided into≤and 0.75%; In described prepreg, the thickness of glue is 50～200 μ m.
10. preparation method as claimed in claim 7, is characterized in that, in step (2), the temperature of described compacting is 135～220 DEG C, and the pressure of described compacting is 20～40Kg/m
2, the time of described compacting is 60～150min.
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| CN106467668A (en) * | 2015-08-19 | 2017-03-01 | 广东生益科技股份有限公司 | A kind of organic siliconresin 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 |
| CN113386416A (en) * | 2021-07-08 | 2021-09-14 | 江西柔顺科技有限公司 | Heat-conducting double-sided copper-clad plate and preparation method thereof |
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| CN106467668A (en) * | 2015-08-19 | 2017-03-01 | 广东生益科技股份有限公司 | A kind of organic siliconresin aluminum-based copper-clad plate and preparation method thereof |
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| CN113386416A (en) * | 2021-07-08 | 2021-09-14 | 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 |
| CN117066081A (en) * | 2023-10-18 | 2023-11-17 | 山西赛科德科技有限公司 | Coating method of non-oriented silicon steel thin strip self-adhesive coating |
| 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 |
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