CN106364122A - Manufacturing method of high-Tg lead-free low-dielectric copper-foil-coated board - Google Patents
Manufacturing method of high-Tg lead-free low-dielectric copper-foil-coated board Download PDFInfo
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- CN106364122A CN106364122A CN201610735468.4A CN201610735468A CN106364122A CN 106364122 A CN106364122 A CN 106364122A CN 201610735468 A CN201610735468 A CN 201610735468A CN 106364122 A CN106364122 A CN 106364122A
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- epoxy resin
- low dielectric
- manufacture method
- copper coated
- coated foil
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B2037/1269—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives multi-component adhesive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention relates to a manufacturing method of a high-Tg lead-free low-dielectric copper-foil-coated board. The method comprises the following steps: circulating an adhesive onto an adhesive applicator, and carrying out preimpregnation and primary impregnation to uniformly coat the adhesive onto glass cloth; drying the adhesive-coated glass cloth in a 120-250-DEG C drying box to volatilize the solvent and preliminarily cure the adhesive by reaction, thereby obtaining a prepreg; and dividing the prepreg into multiple groups (1-18 pieces with the same size in each group), laminating with copper foil, pressing and curing to obtain the copper-foil-coated board. Compared with the prior art, the copper-foil-coated board has low water absorptivity and favorable machinability; the flame retardancy reaches UL94V-0; and the copper-foil-coated board can completely satisfy the demands for the lead-free preparation procedure and multilayer board production in the field of high-frequency high-speed PCBs (printed circuit boards).
Description
Technical field
The present invention relates to copper coated foil plate preparation field, especially relate to a kind of system of the unleaded low dielectric type copper coated foil plate of high tg
Make method.
Background technology
21 century enters the society of advanced IT application, computer, mobile communication, network etc. gradually penetrated into society and
Each of people's life corner, human lives just develop towards the direction of advanced IT application steadily, information processing and information
Communication constitutes the developing two big technology pillars of advanced IT application science and technology field.Develop rapidly institute in order to meet information technology
The vast capacity information transfer brought, and the hard requirement that supper-fast, ultrahigh density is processed, to printed circuit board and cover
Copper coin is put forward higher requirement, and it is swollen that the specific requirement of its product shows as high thermostability, excellent dielectric properties, low heat
Swollen coefficient and water absorption rate, environmental protection flame retardant performance etc..
On 2 13rd, 2003, " electrical and electronic product garbage instruction case (weee) " of European Union with " with regard to electric
Some Hazardous Substances Directive cases (rohs) are prohibitted the use of in equipment " formal announcement, started formal enforcement in 1 day July in 2006,
The formal enforcement of this two instructions, indicates that global electronic industry enters the pb-free solder epoch.Traditional tin-lead solder
(sn63/pb37) eutectic point is 183 DEG C.The lead-free solder developed at present, eutectic point is generally higher than tin-lead solder 30
More than DEG C, the raising of welding temperature, necessarily higher requirement is proposed to copper-clad plate thermostability.
The firming agent that traditional fr-4 substrate is commonly used has polyamines, phenolic resin etc., containing active in this kind of solidification agent molecule
, there is substantial amounts of hydroxyl in the epoxy resin of its solidification in hydrogen, this can lead to the rising of the water absorption rate of solidfied material, wet-hot aging performance and
The decline of dielectric properties.These very important performances cannot meet leadless process or even multi-layer sheet during pcb produces and produce
Demand.
Chinese patent cn104553229a discloses a kind of preparation method of the low dielectric type copper coated foil plate of high tg Halogen, including
Following steps: one. prepared by binding agent；Two. gluing, prepreg processed；Three. typesetting, compacting.Wherein binding agent is by styrene-first
Base carbic anhydride, low dielectric-epoxy resin, benzoxazine resins, phosphonium flame retardant, high spheroiding silicon dioxide, imidazoles
Accelerator, organic solvent are prepared from.But above-mentioned patent disclosed that Halogen system, Halogen with unleaded be two different bodies
System, Halogen system relative cost is higher, and the resist delamination time is slightly short；And processing characteristics is poor, peel strength is relatively low, and the application is just
It is the improved technique scheme proposing to overcome above-mentioned technical problem, improve the resist delamination time further.
Content of the invention
The purpose of the present invention is exactly to provide to overcome the defect that above-mentioned prior art exists a kind of to possess very low suction
Water rate and the manufacture method of the good unleaded low dielectric type copper coated foil plate of high tg of good machining property, fire resistance.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of manufacture method of the unleaded low dielectric type copper coated foil plate of high tg, using following steps:
(1) make prepreg；
(1-1) binding agent is recycled to gluing machine, the wire velocity control of gluing machine is 6～27m/min, through preimpregnation, master
Leaching, binding agent is evenly applied on glass fabric；
(1-2) glass fabric of application of adhesive toasts through 120 DEG C～250 DEG C drying bakers, so that solvent is volatilized, binding agent
Initial reaction solidifies, prepared prepreg；
(2) typesetting, compacting；
Prepreg is torn open and is cut into same size size, 1～18 one group, then overlap with Copper Foil, then suppress and solidify
Obtain copper coated foil plate, when carrying out press curing, control pressure be 80～550psi, temperature be 60～230 DEG C, vacuum be-
0.03～0.1mpa, press time 90～240min, hardening time: 60～180min.
Described binding agent includes following components and weight portion content: the modified epoxy resin 10-80 of bromination, isocyanates
The epoxy resin 5-80 of modification, modified poly anhydride 20-70,2- ethyl -4 Methylimidazole. 0.005-0.03, preparing spherical SiO 2
10.0-60.0, silane 0.10-0.20, toughener 1.00-10.0, organic solvent 10.0-60.0.
As preferred embodiment, the weight average molecular weight of the modified epoxy resin of bromination adopts gpc (gel infiltration color
Spectrum) method test.Selected from one of brominated bisphenol a type epoxy resin, bromination phenol aldehyde type or dibromo season pentanediol type epoxy resin
Or it is multiple.For example can using Dow Chemical produce the trade mark be 8005r2 resin, its weight average molecular weight be 500～
3000.
Bromination modified epoxy composition is as follows:
| Project | Specifications parameter |
| Solid | 75.1% |
| Viscosity | 1555mpa*s |
| Epoxide equivalent | 410 |
| Density | 1.47g/cm3 |
| Br% | 42% |
Tg >=160 DEG C after brominated epoxy resin solidification, good toughness is it is easy to process, and can improve the resistance of material after solidification
Combustion performance is and good with glass fibre impregnation, the advantages of in hot pressing, the change of resin kinetic viscosity is slow.
As preferred embodiment, isocyanate-modified epoxy resin is aromatic series methyl diphenylene diisocyanate
One of modified epoxy resin or the modified epoxy resin of toluene di-isocyanate(TDI) or two kinds.
As preferred embodiment, modified poly anhydride weight average molecular weight adopts gpc (gel permeation chromatography) method to test.
Ef-30, ef-40 that modified poly anhydride produces by sartomer company or the resin of the 8005h that Dow Chemical is produced
One or more of.
As more preferred embodiment, the trade mark that modified poly anhydride is produced by Dow Chemical is 8005h
Resin.
Modified poly acid composition is as follows:
| Project | Specifications parameter |
| Solid | 55% |
| Viscosity | 3000～10000mpa*s |
| Density | 1.0g/cm3 |
| Anhydride equivalent | 700～750 |
Modified poly anhydride can be obviously improved material solidification after adding by a certain percentage after dielectric properties and thermostability
Energy.
As preferred embodiment, the mean diameter of preparing spherical SiO 2 is 0.5 μm, and maximum particle diameter is less than 24 μm,
Purity is in more than 99.0wt%.
As preferred embodiment, silane is selected from gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy silicon
Alkane, anilinomethyl trimethoxy silane, γ-(β-aminoethyl) aminopropyl trimethoxysilane, γ-(2,3- epoxy the third oxygen) propyl group
One or more of trimethoxy silane, vinyltrimethoxy silane or VTES.
As preferred embodiment, toughener uses fortegra 351 resin or the day of Dow Chemical production
One or more of mx 158 core shell rubbers that this kaneka company produces.
As preferred embodiment, organic solvent is dimethylformamide, acetone, methyl ethyl ketone, methyl-isobutyl
One or more of ketone or propylene glycol monomethyl ether.
Described binding agent is prepared using following methods:
(1) get the raw materials ready according to formula composition；
(2) impregnation
(2-1) sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, rotating speed 1000-
1500 revs/min, keep continuously stirred and control flume temperature at 20-50 DEG C, adding preparing spherical SiO 2, adding and hold after finishing
Continuous stirring 20-60 minute；
(2-2) the modified epoxy resin of bromination, isocyanate-modified epoxy are sequentially added by formula ratio in agitator tank
Resin, modified poly anhydride and toughener, stir 20-40 minute with 1000-1500 rev/min of rotating speed, and open cooling simultaneously
Water circulation with 1800 revs/min of rotating speed stirring 1-4 hours, control flume temperature is at 20-50 DEG C；
(2-3) weigh 2- ethyl -4 Methylimidazole. by formula ratio to add in agitator tank, be completely dissolved with organic solvent, confirm
After nodeless mesh, the 2- being completely dissolved ethyl -4 Methylimidazole. is added in agitator tank and 1-3 is stirred with 1000-1500 rev/min of rotating speed
Hour, prepare binding agent.
E level selected by described glass fabric, and specification selects 101,104,106,1078,1080,2113,2116,1506
Or 7628 classifications；Described Copper Foil selects 1/3oz, hoz, 1oz, 2oz, 3oz, 4oz or rtf Copper Foil or vlp Copper Foil.
Compared with prior art, the invention has the advantages that
(1) present invention adopts High Bromine epoxy Resin, reaches good flame retardant effect, and fire-retardant rank reaches ul94v-0 level.With
When brominated epoxy resin solidification after tg >=160 DEG C, good toughness it is easy to processing, the fire resistance of material after solidification can be improved, and
Good with glass fibre impregnation, in hot pressing, the change of resin kinetic viscosity is slow.
(2) the epoxy resin cured product function admirable of polymeric anhydride solidification is especially stable with heat resistance and chemically-resistant
Property height is characterized.Acid anhydride curable epoxy resin is although need high temperature, but curing reaction is slower, and exothermic heat of reaction amount is little, and shrinkage factor is little.
It is had compared with amine curing agent, and volatility is little, toxicity is low, little to skin irritation, big with epoxy resin use level, viscosity
Little, can add filler modified, advantageously reduce cost, validity period is long, be easy to construct.
(3) in the epoxy-resin systems of polymeric anhydride solidification, the presence epoxy because of amine type accelerators such as imidazoles tends to
Generate ester bond with anhydride reaction, and suppress part etherification reaction, reduce the hydroxy radical content in system, can significantly improve solid
The dielectric properties of change system and wet-hot aging performance, thus the neck such as high-frequency high-speed speed and high density interconnection can be advantageously applied to
Domain.
(4) adopt epoxide glass cloth base copper coated foil plate tg > 170 DEG C of binding agent preparation of the present invention；Z-axis cte ＜
3.0%；Thermostability aspect: td >=360 DEG C, t288 ＞ 60min；Electrical property aspect: dielectric constant (5ghz)≤4.1；Dielectric is damaged
Consumption (5ghz) ＜ 0.007；；It is provided additionally with very low water absorption rate and good machining property, and fire-retardant reach ul94v-0
Level, can fully meet the demand of leadless process and multi-layer sheet production in high-frequency high-speed pcb field.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1～3
The primary raw material preparing the unleaded low dielectric type copper coated foil plate of high tg is the modified epoxy resin of bromination, isocyanates change
The epoxy resin of property, polymeric anhydride firming agent, 2- ethyl -4 Methylimidazole., preparing spherical SiO 2, organic solvent and toughener group
Become.
Table 3
| Title material | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| The modified epoxy resin (%) of bromination | 16.7 | 15.36 | 14.71 |
| Isocyanate-modified epoxy resin (%) | 12.6 | 13.4 | 14.3 |
| Modified poly anhydride curing agent (%) | 24.6 | 22.5 | 20.4 |
| 2- ethyl -4 Methylimidazole. (%) | 0.01 | 0.01 | 0.01 |
| Preparing spherical SiO 2 (%) | 21.8 | 24.5 | 27.4 |
| Silane (%) | 0.11 | 0.12 | 0.14 |
| Organic solvent (%) | 20.6 | 21.6 | 20.28 |
| Toughener (%) | 3.58 | 3.51 | 3.38 |
1. specific preparation process is as follows:
A. sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, 1500 turns of rotating speed/
Point, keep continuously stirred and control flume temperature at 45 DEG C, add preparing spherical SiO 2, add continuously stirred 60 points after finishing
Clock；
B. the modified epoxy resin of bromination, isocyanate-modified asphalt mixtures modified by epoxy resin are sequentially added by formula ratio in agitator tank
Fat, anhydride curing agent and toughener, are stirred 40 minutes with 1500 revs/min of rotating speed, and open cooling water circulation and to turn simultaneously
1800 revs/min of speed stirs 3 hours, and control flume temperature is at 45 DEG C；
C. weigh 2- ethyl -4 Methylimidazole. by formula ratio to add in agitator tank, little with 1500 revs/min of rotating speed stirring 3
When, impregnation completes.
2. gluing baking:
Prepreg gluing speed: 10.0m/min.
3. prepreg control parameter:
Gel time: 265s
Resin content: 53.8%
Resin flow: 23.5%
Fugitive constituent: 0.31%
4. sheet material composing structure: after 6 2116 prepreg pressings, thickness is 0.785mm
5. pressing plate parameter:
Vacuum -0.106mpa
Pressure 261-564psi
150-220 DEG C of temperature of heat plate
Hardening time 200min
, being detected, result is as shown in table 4 to its performance.
Table 4
By in upper table as can be seen that the application prepare the unleaded low dielectric type copper coated foil plate of high tg binding agent heat-resisting
Property can obtain bigger lifting, and its resist delamination time can be more than 120min, is doubled more than 60min than Halogen system
Time.
Embodiment 4
A kind of manufacture method of the unleaded low dielectric type copper coated foil plate of high tg, using following steps:
(1) gluing, prepared prepreg；
(1-1) binding agent is recycled to gluing machine, the wire velocity control controlling gluing machine is 6m/min, through preimpregnation, master
Leaching, binding agent is evenly applied on the e grade fiberglass cloth that specification is 101；
(1-2) glass fabric of application of adhesive toasts through 120 DEG C of drying bakers, so that solvent is volatilized, binding agent is tentatively anti-
Should solidify, prepared prepreg；
(2) typesetting, compacting；
Prepreg is torn open and is cut into same size size, 18 one group, then overlap with 1/3oz Copper Foil, control pressure is
80psi, temperature of heat plate is 60 DEG C, and vacuum is -0.03mpa, press time 90min, hardening time: 60min, suppresses and solidifies
Obtain copper coated foil plate.
Binding agent used in step (1-1) adopts following components and weight portion content: the modified epoxy resin of bromination
10th, isocyanate-modified epoxy resin 5, modified poly anhydride 20,2- ethyl -4 Methylimidazole. 0.005, preparing spherical SiO 2
10.0th, silane 0.10, toughener 1.00, organic solvent 10.0.
Wherein, employing the modified epoxy resin of bromination be brominated bisphenol a type epoxy resin, isocyanate-modified ring
Oxygen tree fat is the modified epoxy resin of aromatic series methyl diphenylene diisocyanate, and modified poly anhydride is given birth to for sartomer company
The trade mark producing is the resin of ef-30, and the mean diameter of preparing spherical SiO 2 is 0.5 μm, and maximum particle diameter is less than 24 μm, and purity exists
More than 99.0wt%.Silane adopts gamma-aminopropyl-triethoxy-silane, and toughener uses Dow Chemical to produce
Fortegra 351 resin.
Above-mentioned binding agent is prepared using following steps:
(1) get the raw materials ready according to formula composition；
(2) impregnation
(2-1) sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, rotating speed 1000
Rev/min, keep continuously stirred and control flume temperature at 20 DEG C, adding preparing spherical SiO 2, adding continuously stirred after finishing
20 minutes；
(2-2) the modified epoxy resin of bromination, isocyanate-modified epoxy are sequentially added by formula ratio in agitator tank
Resin, modified poly anhydride and toughener, are stirred 20 minutes with 1000 revs/min of rotating speed, and open simultaneously cooling water circulation simultaneously
With rotating speed, 1800 revs/min are stirred 1 hour, and control flume temperature is at 20 DEG C；
(2-3) weigh 2- ethyl -4 Methylimidazole. by formula ratio to add in agitator tank, be completely dissolved with organic solvent, confirm
After nodeless mesh, the 2- being completely dissolved ethyl -4 Methylimidazole. is added in agitator tank and stirred 1 hour with 1000 revs/min of rotating speed, system
Standby obtain binding agent.
Embodiment 5
A kind of manufacture method of the unleaded low dielectric type copper coated foil plate of high tg, using following steps:
(1) gluing, prepared prepreg；
(1-1) binding agent is recycled to gluing machine, the wire velocity control controlling gluing machine is 10m/min, through preimpregnation, master
Leaching, binding agent is evenly applied on the e grade fiberglass cloth that specification is 104；
(1-2) glass fabric of application of adhesive toasts through 200 DEG C of drying bakers, so that solvent is volatilized, binding agent is tentatively anti-
Should solidify, prepared prepreg；
(2) typesetting, compacting；
Prepreg is torn open and is cut into same size size, 10 one group, then overlap with rtf Copper Foil, then suppress and solidify,
Control pressure is 300psi, and temperature of heat plate is 100 DEG C, and vacuum is 0.05mpa, press time 120min, hardening time:
120min obtains copper coated foil plate.
Used in step (1), binding agent includes following components and weight portion content: the modified epoxy resin 50 of bromination, different
Cyanate modified epoxy resin 40, modified poly anhydride 40,2- ethyl -4 Methylimidazole. 0.01, preparing spherical SiO 2 50.0,
Silane 0.15, toughener 5.0, organic solvent 40.0.
Wherein, the modified epoxy resin of bromination is bromination phenol aldehyde type epoxy resin, and isocyanate-modified epoxy resin is
The modified epoxy resin of toluene di-isocyanate(TDI), the resin of the 8005h that modified poly anhydride is produced by Dow Chemical,
The mean diameter of preparing spherical SiO 2 is 0.5 μm, and maximum particle diameter is less than 24 μm, and purity is in more than 99.0wt%.Silane adopts
γ-aminopropyltrimethoxysilane and the mixture of anilinomethyl trimethoxy silane, toughener is given birth to using Dow Chemical
The mixture of the mx158 core shell rubbers that fortegra 351 resin producing is produced with Japanese kaneka company.
Above-mentioned binding agent is prepared using following steps:
(1) get the raw materials ready according to formula composition；
(2) impregnation
(2-1) sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, rotating speed 1200
Rev/min, keep continuously stirred and control flume temperature at 30 DEG C, adding preparing spherical SiO 2, adding continuously stirred after finishing
30 minutes；
(2-2) the modified epoxy resin of bromination, isocyanate-modified epoxy are sequentially added by formula ratio in agitator tank
Resin, modified poly anhydride and toughener, are stirred 30 minutes with 1200 revs/min of rotating speed, and open simultaneously cooling water circulation simultaneously
With rotating speed, 1800 revs/min are stirred 2 hours, and control flume temperature is at 30 DEG C；
(2-3) weigh 2- ethyl -4 Methylimidazole. by formula ratio to add in agitator tank, be completely dissolved with organic solvent, confirm
After nodeless mesh, the 2- being completely dissolved ethyl -4 Methylimidazole. is added in agitator tank and stirred 2 hours with 1200 revs/min of rotating speed, system
Standby obtain binding agent.
Embodiment 6
A kind of manufacture method of the unleaded low dielectric type copper coated foil plate of high tg, using following steps:
(1) gluing, prepared prepreg；
(1-1) binding agent is recycled to gluing machine, the wire velocity control controlling gluing machine is 27m/min, through preimpregnation, master
Leaching, binding agent is evenly applied on the e grade fiberglass cloth that specification is 7628；
(1-2) glass fabric of application of adhesive toasts through 250 DEG C of drying bakers, so that solvent is volatilized, binding agent is tentatively anti-
Should solidify, prepared prepreg；
(2) typesetting, compacting；
Prepreg is torn open and is cut into same size size, 1 one group, then overlap with vlp Copper Foil, then suppress and solidify,
During press curing, control pressure is 550psi, and temperature of heat plate is 230 DEG C, and vacuum is 0.1mpa, press time 240min, Gu
Change time 180min.Obtain copper coated foil plate.
The binding agent adopting in step (1) includes following components and weight portion content: the modified epoxy resin 80 of bromination, different
Cyanate modified epoxy resin 80, modified poly anhydride 70,2- ethyl -4 Methylimidazole. 0.03, preparing spherical SiO 2 60.0,
Silane 0.20, toughener 10.0, organic solvent 60.0.
Wherein, the modified epoxy resin of bromination is dibromo season pentanediol type epoxy resin, isocyanate-modified asphalt mixtures modified by epoxy resin
Fat is the modified epoxy resin of the aromatic series methyl diphenylene diisocyanate epoxy resin modified with toluene di-isocyanate(TDI)
Mixture, ef-30, ef-40 resin that modified poly anhydride produces for sartomer company.The mean diameter of preparing spherical SiO 2
For 0.5 μm, maximum particle diameter is less than 24 μm, and purity is in more than 99.0wt%.Silane is vinyltrimethoxy silane, toughener
The mx158 core shell rubbers being produced using Japanese kaneka company.
Above-mentioned binding agent is prepared using following steps:
(1) get the raw materials ready according to formula composition；
(2) impregnation
(2-1) sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, rotating speed 1500
Rev/min, keep continuously stirred and control flume temperature at 50 DEG C, adding preparing spherical SiO 2, adding continuously stirred after finishing
60 minutes；
(2-2) the modified epoxy resin of bromination, isocyanate-modified epoxy are sequentially added by formula ratio in agitator tank
Resin, modified poly anhydride and toughener, are stirred 40 minutes with 1500 revs/min of rotating speed, and open simultaneously cooling water circulation simultaneously
With rotating speed, 1800 revs/min are stirred 4 hours, and control flume temperature is at 50 DEG C；
(2-3) weigh 2- ethyl -4 Methylimidazole. by formula ratio to add in agitator tank, be completely dissolved with organic solvent, confirm
After nodeless mesh, the 2- being completely dissolved ethyl -4 Methylimidazole. is added in agitator tank and stirred 3 hours with 1500 revs/min of rotating speed, system
Standby obtain binding agent.
Claims (10)
1. a kind of manufacture method of the unleaded low dielectric type copper coated foil plate of high tg is it is characterised in that the method adopts following steps:
(1) make prepreg；
(1-1) binding agent is recycled to gluing machine, through preimpregnation, main leaching, binding agent is evenly applied on glass fabric；
(1-2) glass fabric of application of adhesive toasts through 120 DEG C～250 DEG C drying bakers, so that solvent is volatilized, binding agent is preliminary
Reaction solidification, prepared prepreg；
(2) typesetting, compacting；
Prepreg is torn open and is cut into same size size, 1～18 one group, then with Copper Foil overlapping, then suppress and solidify and obtain
Copper coated foil plate.
2. a kind of manufacture method of the unleaded low dielectric type copper coated foil plate of high tg according to claim 1 is it is characterised in that institute
The binding agent stated includes following components and weight portion content:
The modified epoxy resin 10-80 of bromination, isocyanate-modified epoxy resin 5-80, modified poly anhydride 20-70,2- second
Base -4 Methylimidazole. 0.005-0.03, preparing spherical SiO 2 10.0-60.0, silane 0.10-0.20, toughener 1.00-10.0, have
Machine solvent 10.0-60.0.
3. a kind of manufacture method of the unleaded low dielectric type copper coated foil plate of high tg according to claim 2 is it is characterised in that institute
The epoxy resin of the bromination modification stated is brominated bisphenol a type epoxy resin, bromination phenol aldehyde type or dibromo season pentanediol type asphalt mixtures modified by epoxy resin
One or more of fat.
4. a kind of manufacture method of the unleaded low dielectric type copper coated foil plate of high tg according to claim 2 is it is characterised in that institute
The isocyanate-modified epoxy resin stated is the modified epoxy resin of aromatic series methyl diphenylene diisocyanate or toluene two
One of isocyanate-modified epoxy resin or two kinds.
5. a kind of manufacture method of the unleaded low dielectric type copper coated foil plate of high tg according to claim 2 is it is characterised in that institute
Ef-30, ef-40 that the modified poly anhydride stated produces by sartomer company or the 8005h's that Dow Chemical is produced
One or more of resin.
6. a kind of manufacture method of the unleaded low dielectric type copper coated foil plate of high tg according to claim 2 is it is characterised in that institute
The mean diameter of the preparing spherical SiO 2 stated is 0.5 μm, and maximum particle diameter is less than 24 μm, and purity is in more than 99.0wt%.
7. a kind of manufacture method of the unleaded low dielectric type copper coated foil plate of high tg according to claim 2 is it is characterised in that institute
The silane stated be selected from gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, anilinomethyl trimethoxy silane,
γ-(β-aminoethyl) aminopropyl trimethoxysilane, γ-(2,3- epoxy the third oxygen) propyl trimethoxy silicane, vinyl front three
One or more of TMOS or VTES, described toughener uses Dow Chemical to produce
One or more of mx158 core shell rubbers of fortegra 351 resin or the production of Japanese kaneka company.
8. a kind of manufacture method of the unleaded low dielectric type copper coated foil plate of high tg according to claim 2 is it is characterised in that institute
The binding agent stated is prepared using following methods:
(1) get the raw materials ready according to formula composition；
(2) impregnation
(2-1) sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, rotating speed 1000-1500
Rev/min, keep continuously stirred and control flume temperature at 20-50 DEG C, adding preparing spherical SiO 2, adding and persistently stir after finishing
Mix 20-60 minute；
(2-2) in agitator tank by formula ratio sequentially add the modified epoxy resin of bromination, isocyanate-modified epoxy resin,
Modified poly anhydride and toughener, stir 20-40 minute with 1000-1500 rev/min of rotating speed, and open cooling water circulation simultaneously
And with 1800 revs/min of stirring 1-4 hours of rotating speed, control flume temperature is at 20-50 DEG C；
(2-3) weigh 2- ethyl -4 Methylimidazole. by formula ratio to add in agitator tank, be completely dissolved with organic solvent, confirm no to tie
After crystalline substance, the 2- being completely dissolved ethyl -4 Methylimidazole. is added the rotating speed stirring 1-3 with 1000-1500 rev/min in agitator tank little
When, prepare binding agent.
9. a kind of manufacture method of the unleaded low dielectric type copper coated foil plate of high tg according to claim 1 is it is characterised in that step
Suddenly in (1-1) gluing machine wire velocity control be 6～27m/min, when step (2) carries out press curing, control pressure be 80～
550psi, temperature of heat plate is 60～230 DEG C, and vacuum is -0.03～0.1mpa, press time 90～240min, hardening time:
60～180min.
10. a kind of unleaded low dielectric type copper coated foil plate of high tg according to claim 1 manufacture method it is characterised in that
E level selected by described glass fabric, and specification selects 101,104,106,1078,1080,2113,2116,1506 or 7628 classes
Not；Described Copper Foil selects 1/3oz, hoz, 1oz, 2oz, 3oz, 4oz or rtf Copper Foil or vlp Copper Foil.
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| CN106364122B (en) | 2018-09-25 |
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Address after: Shanghai city Chang Cheung Road 201802 Jiading District Nanxiang Town, No. 158 Applicant after: South Asia new materials Polytron Technologies Inc Address before: Shanghai city Chang Cheung Road 201802 Jiading District Nanxiang Town, No. 158 Applicant before: Shanghai Nanya Copper Clad Laminate Co., Ltd. |
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