CN1272424A - Composite base laminated board covered with copper foil and its production method - Google Patents
Composite base laminated board covered with copper foil and its production method Download PDFInfo
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- CN1272424A CN1272424A CN 99106157 CN99106157A CN1272424A CN 1272424 A CN1272424 A CN 1272424A CN 99106157 CN99106157 CN 99106157 CN 99106157 A CN99106157 A CN 99106157A CN 1272424 A CN1272424 A CN 1272424A
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Abstract
The present invention relates to a composite base laminated board covered with copper foil and its manufacture method. The composition of its impregnant A contains bisphenol A type epoxy resin, phenolic aldehyde type epoxy resin, dicyandiamide, 2-ethyl-4-methyl imidazole, melamine cyanurate, aluminium hydroxide, organic silicon dipsersing agent, epoxy silane coupling agent and solvent, and the composition of its impregnant B is formed from bisphenol A type epoxy resin, phenolic aldehyde type epoxy resin, thermoplastic phenolic resin, 2-ethyl-4-methyl imidazole, melamine cyanurate, ammonium polyphosphate, aluminium hydroxide, magnesium hydroxide, organic silicon dispersing agent, epoxy silane coupling agent and solvent. It is a "green" fire-retardant CEM-3.
Description
The present invention relates to a kind of composite base laminated board covered with copper foil and manufacture method thereof that is used for printed circuit board (PCB), particularly, make it to become " green " flame retardant grade composite base laminated board covered with copper foil of environment-friendly type at being that glass fabric/epoxy resin composite material, internal layer are that the impregnating agent of the composite base laminated board covered with copper foil that constitutes of the glass fibre non-woven/epoxy resin composite material manufacture method of filling a prescription is extremely improved by skin.
Printed circuit board (PCB) is the most basic carrying body of electronic product element, and copper clad laminate is basic material of making printed circuit board (PCB).At present the standard of civilian copper clad laminate and name all are that National electrial manrfarcturers Assication (NEMA) by the subordinate of NBS (ANSI) formulates in the world, and the safety detection by American insurance dealer federation (UL) authenticates and just can be applied to electric equipment products.Copper clad laminate is distinguished by manufacturing materials at present, mainly contains: and phenolic resins/paper substrate copper clad laminate (FR-1, FR-2), epoxy resin/glass fabric base copper-clad laminate (FR-4), composite base laminated board covered with copper foil (CEM-1, CEM-3).CEM-3 has been applied to fields such as mobile communication phone, mobile communication base station, telephone exchanger, GSM equipment and the commercial satellite communication apparatus at present.Composite base laminated board covered with copper foil is the copper clad laminate that contains the different reinforcing material of two or more type.CEM-3 is that skin is the composite base laminated board covered with copper foil that glass fibre non-woven/epoxy resin composite material constitutes for glass fabric/epoxy resin composite material, internal layer.
The main manufacture craft flow process of CEM-3 is: impregnating agent preparation → dipping gluing → dry semi-solid preparation → prepreg section → Copper Foil and face prepreg and the matching board → vacuum hotpressing of core prepreg are solidified → are cut out → finished product.Most important four performances of composite base laminated board covered with copper foil are respectively electrical property, anti-flammability, heat resistance and mechanical property.The anti-flammability of common flame retardant grade composite base laminated board covered with copper foil is to realize by the prescription of the impregnating agent of adjusting the copper clad laminate prepreg.The flame-retardant standard that the phenolic resin type copper clad laminate will reach UL94 V-0 is to realize than being easier to, main cause is that the phenolic resin type copper clad laminate is not too high to stable on heating requirement, the standard of NEMA does not claim to its glass transition temperature (Tg), therefore can make the anti-flammability of copper clad laminate reach the standard of UL by adding various organic fire-retardants.According to the regulation of NEMA, CEM-3 is for satisfying stable on heating requirement, and its Tg must be greater than 130 ℃; Anti-flammability must reach the standard-required of UL94 V-0, has only the curing system that adopts tetrabromobisphenol A type epoxy resin could satisfy thermal endurance and the anti-flammability of CEM-3 simultaneously, and the curing agent major part also is to use the bromine compounds.For example: with tetrabromobisphenol A (TBBPA).At " PCB base material one copper coated foil plate technical foundation " (" printed circuit information " 1997 the 9th phase P32～P37) introduced current composite base laminated board covered with copper foil technology in the literary composition, article is pointed out in the used resin formula composition of CEM-3, employing has the brominated epoxy resin of flame retardant type, for performances such as the thermal endurance that improves plate and moisture resistances, add a spot of other epoxy resin, played modifying function.These resins have: polyfunctional epoxy resin, contain ester based epoxy resin, ethers epoxy resin and epoxy curing agent (being generally dicyandiamide, novolac resin etc.), catalyst (being generally benzyl dimethylamine or imidazoles).In the resin formula component, also have fire retardant (as: tetrabromobisphenol A), fire retarding synergist (as: antimonous oxide).In order to guarantee the dimensional stability of copper clad laminate, in resin formula, to add the inorganic filler about 30%.The general filler that adds has: aluminium hydroxide, calcium carbonate, silicon dioxide etc.The adding of filler also helps anti-metal ion transport, thermal endurance, anti-tracking, anti-flammability, the punching processing that improves plate.Flameretardant B-staged epoxy resin prepregs and laminates made therefrom (United States Patent (USP) 4,501,787) is disclosed to be to adopt the epoxy resin of no bromine and brominated fire retardant.Flame-retarded copper clad laminates (United States Patent (USP) 4,486,505) is disclosed to be to adopt brominated unsaturated-resin.Contain halogen element or antimonous oxides such as bromine among the common CEM-3.
Copper clad laminate is as the stock of electric equipment products, in its processing with make the environmental issue that relates in the process still trouble manufacturer.Its main cause has: (1) copper clad laminate must satisfy the UL flame-retardant standard, and the fire proofing that uses all has noxious substances such as halogen element such as chlorine, bromine and antimonous oxide, and goods can discharge a large amount of toxic gases when breaking out of fire, and the amount of being fuming is very big.(2) in the course of processing of making printed circuit board (PCB), it is that copper clad laminate is immersed in 250 ℃ of solder baths that one procedure is arranged, and makes printed circuit board (PCB) hang up scolding tin, and the components and parts of burn-oning; This process can discharge the bromine of trace because of copper clad laminate is subjected to the influence of high temperature usually, thereby operator's health is brought harm.(3) after electric equipment products were scrapped, the printed circuit board (PCB) that wherein goes out of use can be to reclaiming and utilization make troubles, and environment is polluted and endangers." green " CEM-3 of research and development environment-friendly type has crucial environment protection significance.UL is defined as " Holegen Antimony Free " to " green " flame retardant grade CEM-3 (GREEN CEM-3) of environment-friendly type, promptly can not contain halogen element and antimonous oxides such as any chlorine, bromine among " green " flame retardant grade CEM-3.Do not meet the regulation of " green " flame retardant grade CEM-3 in the component of present common CEM-3.Each manufacturer researches and develops new resin solidification system in succession, to reach the requirement of " green " flame retardant grade CEM-3 regulation.
" green " flame retardant grade of Japan's exploitation at present CEM-3 makes fast progress, as: new Kobe motor " green " CEM-3 product is claimed not brominated antimony based flame retardant in its resin.The compositing formula of relevant " green " CEM-3 yet there are no open report.
The purpose of a kind of composite base laminated board covered with copper foil of the present invention and manufacture method thereof is " green " flame retardant grade CEM-3 composite base laminated board covered with copper foil that proposes a kind of environment-friendly type and preparation method thereof.Be to be that glass fabric/epoxy resin composite material, internal layer are that the prescription of the impregnating agent of the CEM-3 that constitutes of glass fibre non-woven/epoxy resin composite material has proposed improvement to skin, make the impregnating agent that is adopted to satisfy the performance requirement of copper clad laminate, and reach the flame-retardant standard of U.S. UL94 V-0, can meet the requirement of halogen elements such as not containing chlorine, bromine among " green " flame retardant grade CEM-3 and antimonous oxide again, can reduce that in producing and using human and environment is produced harmful substance, also help the recycling of waste and old CEM-3.
The present invention improves the face prepreg of CEM-3 composite base laminated board covered with copper foil and the impregnating agent prescription of sandwich layer prepreg.The resin of impregnating agent (A) is bisphenol A type epoxy resin and phenol aldehyde type epoxy resin; Catalyst is a 2-ethyl-4-methylimidazole; Be added with fire retardant and dispersant in the impregnating agent (A), fire retardant is the aluminium hydroxide of cyanuric acid melamine and two kinds of particle size ranges, and dispersant is the organosilicon dispersant; The composition and the parts by weight of impregnating agent (A):
Resin: bisphenol A type epoxy resin 100
Phenol aldehyde type epoxy resin 0～10;
Curing agent: dicyandiamide 2.2～2.4;
Fire retardant is arranged: cyanuric acid melamine 3～5
Aluminium hydroxide
Granularity 0.8～1.2 μ m 70～90
Granularity 10～20 μ m 10～30;
Catalyst: 2-ethyl-4-methylimidazole 0.15～0.2;
Coupling agent: epoxy silane 0.5～1;
Dispersant: organosilicon dispersant 0.2～0.3;
Solvent: methyl cellosolve 50～60;
Dimethyl formamide 40～50;
The resin of impregnating agent (B) is bisphenol A epoxide resin and phenol aldehyde type epoxy resin; Curing agent is a novolac resin; Catalyst is a 2-ethyl-4-methylimidazole; Be added with fire retardant and dispersant in the impregnating agent (B), fire retardant is the aluminium hydroxide and the magnesium hydroxide of cyanuric acid melamine, APP, two kinds of particle size ranges, and dispersant is the organosilicon dispersant; The composition and the parts by weight of impregnating agent (B):
Resin: bisphenol A type epoxy resin 100
Phenol aldehyde type epoxy resin 40～55;
Curing agent: novolac resin 60～85;
Fire retardant: cyanuric acid melamine 10～15
APP 20～25
Aluminium hydroxide
Granularity 0.8～1.2 μ m 100～125
Granularity 10～20 μ m 75～90;
Magnesium hydroxide 0～30;
Catalyst: 2-ethyl-4 methylimidazole 0.5～1;
Coupling agent: epoxy silane 1.5～2.5;
Dispersant: organosilicon dispersant 1～2;
Solvent: methyl cellosolve 60～80
Acetone 20～40.
The epoxide equivalent of the bisphenol A type epoxy resin of impregnating agent (A) is 450～500g/eq, and the phenol aldehyde type epoxy resin epoxide equivalent is 190～220g/eq.
The epoxide equivalent of the bisphenol A type epoxy resin of impregnating agent (B) is 190～203g/eq, and the phenol aldehyde type epoxy resin epoxide equivalent is 190～220g/eq.
The technological parameter that impregnating agent (A) is made the face prepreg is: gel time 180～220 seconds, 170 ± 2 ℃ of baking temperatures, 210～250 seconds drying times.
The technological parameter that impregnating agent (B) is made the core prepreg is: gel time 90～120 seconds, 170 ± 2 ℃ of baking temperatures, 240～300 seconds drying times.
The prescription of provided by the invention prepreg impregnating agent (A) does not adopt tetrabromobisphenol A type epoxy resin; And the bisphenol A type epoxy resin of employing epoxide equivalent 450～500g/eq and the phenol aldehyde type epoxy resin of epoxide equivalent 190～220g/eq, curing agent adopts dicyandiamide to add employing cyanuric acid cyanuric acid ammonium and makes fire retardant, when its purpose is to improve the curing system crosslink density, in curing system, introduce a large amount of nitrogen elements, thereby, can improve the fire resistance of " green " CEM-3 again in the stable on heating while of guaranteeing " green " CEM-3.Use has the aluminium hydroxide of two kinds of particle size ranges that the common drying means of process of fire resistance handled: coarseness (10～20 μ m) aluminium hydroxide can improve the rheological property of semi-solid preparation resin, the caking property of prepreg is improved, and the aluminium hydroxide of ultra-fine granularity (0.8～1.2 μ m) can guarantee the fire resistance of " green " CEM-3, the aluminium hydroxide drying is handled the water absorption that can lower copper clad laminate, thereby improves the electrical insulating property of " green " CEM-3.In prescription, add the epoxy resin of different degrees of functionality, by regulating itself and the ratio of main resin, thereby adjust the crosslink density of curing system, make the moisture resistance damp condition electrical breakdown performance down of " green " CEM-3---contrast vestige index (CTI) and reach anti-600V voltage.
The prescription of the impregnating agent of core prepreg provided by the invention (B) adopts many epoxy-functionals epoxy resin, for example adopt the bisphenol A type epoxy resin of epoxide equivalent 190～203g/eq and the phenol aldehyde type epoxy resin of epoxide equivalent 190～220g/eq, and be curing agent with the novolac resin; Employing has the cyanuric acid melamine of anti-flammability, APP, aluminium hydroxide and magnesium hydroxide, magnesium hydroxide can improve fire-retardant cooperative effect and caking property, employing has the aluminium hydroxide of two kinds of particle size ranges that the common drying means of process of fire resistance handled: the aluminium hydroxide of coarseness (10～20 μ m) can improve the rheological characteristic of semi-solid preparation resin, make the caking property of prepreg good, and the aluminium hydroxide of ultra-fine granularity (0.8～1.2 μ m) can guarantee the fire resistance of " green " CEM-3, the aluminium hydroxide drying is handled the water absorption that can reduce " green " CEM-3, thereby improves the electrical insulating property of " green " CEM-3.The adhesion property and the compatibility of filler and resin strengthened in above measure, also improves the crosslink density of internal layer composite bed curing system simultaneously, guaranteed that the internal layer composite bed of " green " CEM-3 has high Tg and low heat shrinkage.Because the inorganic fire-retarded dosage that adds in impregnating agent prescription of the present invention is more, can cause curing rate to descend, therefore the present invention adopted efficient coupling agent (for example: epoxy silane) and the organosilicon dispersant (for example: the W940 dispersant of commercially available German BYK company), make the curing system can be under the situation that does not have bromine and antimonous oxide, guarantee that composite material does not reduce thermal endurance and mechanical property again when having the excellent flame retardancy energy, and make the peel strength of face composite bed and Copper Foil be unlikely to excessive descent.The present invention is by the improvement of the impregnating agent prescription of opposite prepreg and core prepreg, adopt the raw material of harmful substances such as halogen element such as not chloride, bromine and antimonous oxide, and fire resistance, electric property, mechanical property and the heat resistance of the copper clad laminate of making is guaranteed on the whole " green " CEM-3 can be coordinated to improve.
The making of prepreg is very important operation in the CEM-3 production process, has directly influenced the various performances of copper clad laminate.Because the change of the impregnating agent of " green " CEM-3 prescription, its process conditions and performance parameter change thereupon.Impregnating agent of the present invention (A) at the working process parameter that is used to make the face prepreg is: gel time was transferred to 180～220 seconds baking temperature with catalyst: 170 ± 2 ℃, and drying time: 200～250 seconds.The physical parameter of the face prepreg that makes: face prepreg (with 7628 type glass fabric impregnation process) weight: 18.5 ± 0.5 gram/(4 * 16 square inches), resin flow 15～20%, EIC gel time 300～350 seconds, MV minium viscosity 20～30 centipoises.The processing technology of impregnating agent (B) when being used to make the core prepreg: gel time was transferred to 90～120 seconds baking temperature with catalyst: 170 ± 2 ℃, drying time: 240～300 seconds.The physical parameter of the core prepreg that makes: core prepreg (with 85 gram type glass fibre non-woven impregnation process) weight: 25.0 ± 0.5 gram/(4 * 16 square inches), resin flow 18～20%.
Embodiment:
The prescription of the face prepreg impregnating agent (A) of the composite base laminated board covered with copper foil that the present invention proposes and the embodiment of process conditions and performance parameter are shown in embodiment 1～embodiment 6 in the table 1.
The prescription of the core prepreg impregnating agent (B) of the composite base laminated board covered with copper foil that the present invention proposes and the embodiment of process conditions and performance parameter are shown in embodiment 1～embodiment 6 in the table 2.
The face prepreg that adopts 7628 type glass fabrics to be processed into prescription and the process conditions of table 1 illustrated embodiment 1～embodiment 6, with the core prepreg that adopts 85 gram type glass fibre non-woven to be processed into prescription and the process conditions of table 2 illustrated embodiment 1～embodiment 6, the surface is Copper Foil matching board and two aspect prepregs and middle three layers of core prepreg matching board of 1 ounce with specification, solidify through vacuum hotpressing, making specification is " green " CEM-3 composite base laminated board covered with copper foil of 1.6 millimeters thick, and its performance: anti-flammability reaches UL94 V-0 level; 260 ℃ of anti-immersed solder 〉=140 second; Insulation resistance 〉=1 * 10
13Ω; Thermo-mechanical analysis (TMA) Tg 〉=130 ℃; Thermo-mechanical analysis (TMA) expansion rate≤3.5%; Contrast vestige index CTI reaches 600V.The performance of the present invention " green " CEM-3 and common CEM-3 relatively, " green " of the present invention CEM-3 is not only in fire resistance, electric property, important performance such as mechanical property and heat resistance all meets or exceeds the performance index of CEM-3, and because the composition of its impregnating agent does not contain chlorine, halogen element and antimonous oxides such as bromine, can reduce in the manufacture process of composite base laminated board covered with copper foil and the print circuit plates making process in pernicious gas operator ' s health is damaged, also can reduce simultaneously the generation of fire incident, avoid the injury of toxic gas, also help discarded printed circuit board (PCB) is recycled the electrical equipment user of service.The present invention is a kind of environment-friendly type " green " flame retardant grade composite base laminated board covered with copper foil that belongs to.
Of the present invention prepreg impregnating agent prescription of table 1 and process conditions
Annotate:
*Granularity is 0.8～1.0 μ m,
*Granularity is 10～20 μ m.
| Title | Weight (umber) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Raw material | Bisphenol A type epoxy resin | ????100 | ??100 | ????100 | ????100 | ????100 | ????100 | ????100 |
| Phenol aldehyde type epoxy resin | ????0～10 | ??0 | ????10 | ????7 | ????10 | ????5 | ????8 | |
| Two cyanogen ammoniums | ????2.2～2.4 | ??2.2 | ????2.4 | ????2.2 | ????2.3 | ????2.3 | ????2.2 | |
| The cyanuric acid melamine | ????3～5 | ??3 | ????5 | ????3 | ????4 | ????5 | ????5 | |
| Ultrafine aluminium hydroxide | ????70～90 | ??80 | ????85 | ????90 | ????75 | ????85 | ????70 | |
| Coarse grain footpath aluminium hydroxide | ????10～30 | ??20 | ????25 | ????15 | ????30 | ????10 | ????25 | |
| 2 ethyls-4 methylimidazole | ????0.15～0.2 | ??0.15 | ????0.2 | ????0.15 | ????0.17 | ????0.15 | ????0.15 | |
| Epoxy silane coupling agent | ????0.5～1.0 | ??0.6 | ????0.6 | ????0.5 | ????0.7 | ????0.7 | ????1.0 | |
| The BYK-W940 dispersant | ????0.2～0.3 | ??0.2 | ????0.3 | ????0.2 | ????0.25 | ????0.2 | ????0.2 | |
| Methyl cellosolve | ????50～60 | ??50 | ????60 | ????50 | ????50 | ????55 | ????50 | |
| Dimethyl formamide | ????40～50 | ??50 | ????40 | ????50 | ????50 | ????45 | ????50 | |
| Process conditions and parameter | Gel time: | ????180～220(sec.) | ??180 | ????216 | ????205 | ????191 | ????196 | ????219 |
| Baking temperature: | ????170±2(℃) | ??170 | ????170 | ????170 | ????170 | ????170 | ????170 | |
| Drying time: | ????200～250(sec.) | ??230 | ????220 | ????200 | ????240 | ????250 | ????210 | |
| Prepreg weight: | ????18.5±0.5(g) | ??18.5 | ????18.5 | ????18.8 | ????18.7 | ????18.6 | ????18.1 | |
| Resin flow: | ????15～20(％) | ??16.8 | ????19.5 | ????17.7 | ????18.3 | ????15.6 | ????15.3 | |
| The EIC gel time: | ????300～350(sec.) | ??312 | ????340 | ????300 | ????325 | ????350 | ????319 | |
| MV minium viscosity: | ????20～30(cp) | ??25 | ????29 | ????20 | ????23 | ????23 | ????30 |
Table 2 core prepreg of the present invention impregnating agent prescription and process conditions
| Effect | Raw material | Weight (umber) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Raw material | Bisphenol A type epoxy resin | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 |
| Phenol aldehyde type epoxy resin | ????40～55 | ????40 | ????40 | ????55 | ????40 | ????50 | ????55 | |
| Novolac resin | ????60～85 | ????60 | ????80 | ????85 | ????70 | ????70 | ????65 | |
| The cyanuric acid melamine | ????10～15 | ????10 | ????10 | ????15 | ????10 | ????13 | ????15 | |
| APP | ????20～25 | ????22 | ????23 | ????25 | ????20 | ????23 | ????25 | |
| Ultrafine aluminium hydroxide * | ????100～125 | ????100 | ????110 | ????125 | ????105 | ????120 | ????125 | |
| Coarse grain footpath aluminium hydroxide * * | ????75～90 | ????75 | ????80 | ????90 | ????80 | ????85 | ????90 | |
| Magnesium hydroxide | ????0～30 | ????15 | ????30 | ????0 | ????20 | ????25 | ????5 | |
| 2 ethyls-4 methylimidazole | ????0.5～1.0 | ????0.5 | ????0.5 | ????0.7 | ????0.5 | ????1.0 | ????1.0 | |
| Epoxy silane coupling agent | ????1.5～2.5 | ????1.5 | ????2.0 | ????2.5 | ????2.0 | ????2.0 | ????2.5 | |
| The BYK-W940 dispersant | ????1.0～2.0 | ????1.0 | ????1.5 | ????2.0 | ????1.5 | ????2.0 | ????2.0 | |
| Methyl cellosolve | ????60～80 | ????70 | ????80 | ????60 | ????65 | ????75 | ????60 | |
| Acetone | ????20～40 | ????30 | ????20 | ????35 | ????25 | ????30 | ????40 | |
| Technological parameter | Gel time: | ????90～120(sec.) | ????98 | ????90 | ????114 | ????109 | ????110 | ????118 |
| Baking temperature: | ????170±2?(℃) | ????170 | ????170 | ????170 | ????170 | ????170 | ????170 | |
| Drying time: | ????240～300(sec.) | ????250 | ????270 | ????260 | ????240 | ????300 | ????290 | |
| Prepreg weight: | ????25.0±0.5(g) | ????25.2 | ????25.5 | ????25.1 | ????24.9 | ????25.4 | ????25.5 | |
| Resin flow: | ????18～20(％) | ????18.2 | ????19.4 | ????19.6 | ????18.7 | ????19.7 | ????18.4 |
Annotate:
*Granularity is 0.8～1.0 μ m,
*Granularity is 10～20 μ m.
Claims (5)
1, a kind of composite base laminated board covered with copper foil that is used for printed circuit board (PCB) is made of Copper Foil, glass fabric/epoxy resin composite bed, glass fibre non-woven/epoxy resin composite bed, and its manufacture method is that glass cloth is made the face prepreg through dipping gluing, dry semi-solid preparation; Through dipping gluing, dry semi-solid preparation, be made for the core prepreg with the glass nonwoven fabrics; Copper Foil and face prepreg, core prepreg are made composite base laminated board covered with copper foil through vacuum hotpressing, the impregnating agent (A) that is used for the machined surface prepreg is by resin, curing agent, fire retardant, catalyst, coupling agent and solvent composition, the impregnating agent (B) that is used for the core prepreg be is characterized in that by resin, curing agent, fire retardant, filler, catalyst, coupling agent and solvent composition:
(1) resin of impregnating agent (A) is bisphenol A type epoxy resin and phenol aldehyde type epoxy resin; Catalyst is a 2-ethyl-4-methylimidazole; Be added with fire retardant and dispersant in the impregnating agent (A), fire retardant is the aluminium hydroxide of cyanuric acid melamine and two kinds of particle size ranges, and dispersant is the organosilicon dispersant; The composition and the parts by weight of impregnating agent (A):
Resin: bisphenol A type epoxy resin 100
Phenol aldehyde type epoxy resin 0～10;
Curing agent: dicyandiamide 2.2～2.4;
Fire retardant is arranged: cyanuric acid melamine 3～5
Aluminium hydroxide
Granularity 0.8～1.2 μ m 70～90
Granularity 10～20 μ m 10～30;
Catalyst: 2-ethyl-4-methylimidazole 0.15～0.2;
Coupling agent: epoxy silane 0.5～1;
Dispersant: organosilicon dispersant 0.2～0.3;
Solvent: methyl cellosolve 50～60;
Dimethyl formamide 40～50;
(2) resin of impregnating agent (B) is bisphenol A epoxide resin and phenol aldehyde type epoxy resin; Curing agent is a novolac resin; Catalyst is a 2-ethyl-4-methylimidazole; Be added with fire retardant and dispersant in the impregnating agent (B), fire retardant is the aluminium hydroxide and the magnesium hydroxide of cyanuric acid melamine, APP, two kinds of particle size ranges, and dispersant is the organosilicon dispersant; The composition and the parts by weight of impregnating agent (B):
Resin: bisphenol A type epoxy resin 100
Phenol aldehyde type epoxy resin 40～55;
Curing agent: novolac resin 60～85;
Fire retardant: cyanuric acid melamine 10～15
APP 20～25
Aluminium hydroxide
Granularity 0.8～1.2 μ m 100～125
Granularity 10～20 μ m 75～90;
Magnesium hydroxide 0～30;
Catalyst: 2-ethyl-4 methylimidazole 0.5～1;
Coupling agent: epoxy silane 1.5～2.5;
Dispersant: organosilicon dispersant 1～2;
Solvent: methyl cellosolve 60～80
Acetone 20～40.
2, composite base laminated board covered with copper foil according to claim 1 and manufacture method thereof is characterized in that: the epoxide equivalent of the bisphenol A type epoxy resin of impregnating agent (A) is 450～500g/eq, and the phenol aldehyde type epoxy resin epoxide equivalent is 190～220g/eq.
3, composite base laminated board covered with copper foil according to claim 1 and manufacture method thereof is characterized in that: the epoxide equivalent of the bisphenol A type epoxy resin of impregnating agent (B) is 190～203g/eq, and the phenol aldehyde type epoxy resin epoxide equivalent is 190～220g/eq.
4, composite base laminated board covered with copper foil according to claim 1 and manufacture method thereof is characterized in that: the technological parameter that impregnating agent (A) is made the face prepreg is: gel time 180～220 seconds, 170 ± 2 ℃ of baking temperatures, 210～250 seconds drying times.
5, composite base laminated board covered with copper foil according to claim 1 and manufacture method thereof is characterized in that: the technological parameter that impregnating agent (B) is made the core prepreg is: gel time 90～120 seconds, 170 ± 2 ℃ of baking temperatures, 240～300 seconds drying times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99106157 CN1121942C (en) | 1999-04-29 | 1999-04-29 | Composite base laminated board covered with copper foil and its production method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99106157 CN1121942C (en) | 1999-04-29 | 1999-04-29 | Composite base laminated board covered with copper foil and its production method |
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| Publication Number | Publication Date |
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| CN1272424A true CN1272424A (en) | 2000-11-08 |
| CN1121942C CN1121942C (en) | 2003-09-24 |
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Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| US7109262B2 (en) | 2001-11-02 | 2006-09-19 | Basf Coatings Ag | Effect-producing, aqueous coating material, method for the production and use thereof |
| WO2003038004A1 (en) * | 2001-11-02 | 2003-05-08 | Basf Coatings Ag | Effect-producing, aqueous coating material, method for the production and use thereof |
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| CN102407630A (en) * | 2011-08-12 | 2012-04-11 | 东华大学 | Halogen-free flame-retardant phenolic epoxy glass cloth laminate and preparation method thereof |
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| CN103287016A (en) * | 2012-03-01 | 2013-09-11 | 深圳光启创新技术有限公司 | Copper foil layer-clad laminate and preparation method thereof |
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| CN102627904A (en) * | 2012-04-10 | 2012-08-08 | 上海大学 | Preparation method for high-heat-conductivity insulating coating between aluminum-based copper-clad laminates |
| CN103935095A (en) * | 2013-01-17 | 2014-07-23 | 信越化学工业株式会社 | Silicone-organic resin composite laminate and manufacturing method thereof, and light-emitting semiconductor apparatus using the same |
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| CN104972727A (en) * | 2014-04-09 | 2015-10-14 | 广东生益科技股份有限公司 | Halogen-free composite-base CEM-3 copper-coated board and preparation method thereof |
| CN104972727B (en) * | 2014-04-09 | 2018-01-05 | 广东生益科技股份有限公司 | A kind of copper-clad plates of Halogen composite base CEM 3 and preparation method thereof |
| CN106810819A (en) * | 2015-11-30 | 2017-06-09 | 比亚迪股份有限公司 | Composition epoxy resin and prepreg and preparation method thereof and fibre reinforced epoxy resin composite and preparation method thereof |
| CN106739295A (en) * | 2016-12-28 | 2017-05-31 | 江阴市明康绝缘玻纤有限公司 | Heat-proof combustion-resistant self-extinguishment expoxy glass felt single-side coated copper plate |
| CN109548279A (en) * | 2018-12-29 | 2019-03-29 | 广州兴森快捷电路科技有限公司 | Prepreg lamination design method |
| CN110435254A (en) * | 2019-08-29 | 2019-11-12 | 山东金宝电子股份有限公司 | A kind of high heat resistance, high CTI CEM-3 copper-clad plate preparation method |
| CN110435254B (en) * | 2019-08-29 | 2021-12-03 | 山东金宝电子股份有限公司 | Preparation method of CEM-3 copper-clad plate with high heat resistance and high CTI (comparative tracking index) |
| CN114516208A (en) * | 2021-12-17 | 2022-05-20 | 久耀电子科技（江苏）有限公司 | Preparation method of flame-retardant epoxy/organic silicon hybrid laminated copper-clad plate |
| CN114516208B (en) * | 2021-12-17 | 2024-04-19 | 久耀电子科技（江苏）有限公司 | Preparation method of flame-retardant epoxy/organic silicon hybrid laminated copper-clad plate |
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