CN106364122B - A kind of production method of the unleaded low dielectric type copper coated foil plates of high Tg - Google Patents
A kind of production method of the unleaded low dielectric type copper coated foil plates of high Tg Download PDFInfo
- Publication number
- CN106364122B CN106364122B CN201610735468.4A CN201610735468A CN106364122B CN 106364122 B CN106364122 B CN 106364122B CN 201610735468 A CN201610735468 A CN 201610735468A CN 106364122 B CN106364122 B CN 106364122B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- adhesive
- modified
- coated foil
- low dielectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to a kind of production methods of the high unleaded low dielectric type copper coated foil plates of Tg, using following steps：Adhesive is recycled to gluing machine, by preimpregnation, main leaching, adhesive is evenly applied on glass fabric；The glass fabric of application of adhesive is toasted through 120 DEG C~250 DEG C drying boxes, and solvent is made to volatilize, and prepreg is made in the solidification of adhesive initial reaction；Prepreg is torn open and is cut into same size size, 1~18 one group, then overlapped with copper foil, it then suppresses and cures to obtain copper coated foil plate.Compared with prior art, the present invention has very low water absorption rate and good machining property, and the fire-retardant demand for reaching 0 grade of UL94V, can fully meeting that leadless process and multi-layer board produce in the fields high-frequency high-speed PCB.
Description
Technical field
The present invention relates to copper coated foil plate preparation fields, more particularly, to a kind of system of the high unleaded low dielectric type copper coated foil plates of 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 corner in people's life, human lives are just developed towards the direction of advanced IT application steadily, information processing and information
Communication constitutes developing two big technology pillar of advanced IT application science and technology field.Institute is developed rapidly in order to meet information technology
The hard requirement of the transmission of vast capacity information and supper-fast ultrahigh density processing that bring, to printed circuit board and covers
More stringent requirements are proposed for copper coin, and it is swollen that the specific requirement of product shows as high heat resistance, excellent dielectric properties, low heat
Swollen coefficient and water absorption rate, environmental protection flame retardant performance etc..
On 2 13rd, 2003, European Union《Electrical and electronic product waste instruction case (WEEE)》With《About electric
Certain Hazardous Substances Directive cases (RoHS) are forbidden to use in equipment》It is formal to announce, started formal implementation in 1 day July in 2006,
The formal implementation of the 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 are generally higher than tin-lead solder 30
DEG C or more, the raising of welding temperature necessarily puts forward higher requirements copper-clad plate heat resistance.
Traditional common curing agent of FR-4 substrates has polyamines, phenolic resin etc., contains in this kind of solidification agent molecule active
Hydrogen, there are a large amount of hydroxyl in cured epoxy resin, 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 can no longer meet leadless process even multi-layer board production in PCB productions
Demand.
Chinese patent CN104553229A discloses a kind of preparation method of the low dielectric type copper coated foil plate of high Tg Halogens, including
Following steps：It is prepared by one, adhesives；Two, are glued, prepreg processed；Three, typesettings, compacting.Wherein adhesive is by styrene-first
Base carbic anhydride, low dielectric-epoxy resin, benzoxazine colophony, phosphonium flame retardant, high spheroiding silica, imidazoles
Accelerating agent, organic solvent are prepared.But it is above-mentioned patent disclosed that Halogen system, Halogen and it is unleaded be two different bodies
System, Halogen system relative cost is higher, and the resist delamination time is slightly short；And processing performance is poor, and peel strength is relatively low, and the application is just
It is the improved technique scheme proposed to overcome above-mentioned technical problem, further increases the resist delamination time.
Invention content
Having very low suction it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of
The production method of water rate and the good unleaded low dielectric type copper coated foil plates of high Tg of good machining property, flame retardant property.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of production method of the unleaded low dielectric type copper coated foil plates of high Tg, using following steps：
(1) prepreg is made；
Adhesive is recycled to gluing machine by (1-1), and the wire velocity control of gluing machine is 6~27m/min, by presoaking, leading
Leaching, adhesive is evenly applied on glass fabric；
The glass fabric of (1-2) application of adhesive is toasted through 120 DEG C~250 DEG C drying boxes, so that solvent is volatilized, adhesive
Initial reaction cures, and prepreg is made；
(2) typesetting, compacting；
Prepreg is torn open and is cut into same size size, 1~18 one group, then overlapped with copper foil, it then suppresses and cures
Obtaining copper coated foil plate, when carrying out press curing, control pressure is 80~550psi, and temperature is 60~230 DEG C, vacuum degree is-
0.03~0.1Mpa, 90~240min of pressing time, hardening time：60~180min.
The adhesive includes following components and parts by weight content：Epoxy resin 10-80, the isocyanates of bromination modification
Modified epoxy resin 5-80, -4 methylimidazole 0.005-0.03 of modified poly acid anhydrides 20-70,2- ethyl, 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 epoxy resin of bromination modification uses GPC (gel infiltration colors
Spectrum) method test.One kind in brominated bisphenol a type epoxy resin, bromination phenol aldehyde type or dibromo season pentanediol type epoxy resin
Or it is a variety of.Such as may be used Dow Chemical production the trade mark be 8005R2 resins, weight average molecular weight be 500~
3000。
Bromination modified epoxy ingredient 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 easy to process, and can improve the resistance of material after solidification
Performance is fired, and good with glass fibre impregnation, resin kinetic viscosity changes the advantages that slow in hot pressing.
As preferred embodiment, isocyanate-modified epoxy resin is aromatic series methyl diphenylene diisocyanate
One or both of the epoxy resin that modified epoxy resin or toluene di-isocyanate(TDI) are modified.
As preferred embodiment, modified poly acid anhydrides weight average molecular weight is tested using GPC (gel permeation chromatography) method.
The resin for the 8005H that EF-30, EF-40 or Dow Chemical that modified poly acid anhydrides is produced by Sartomer Company are produced
One or more of.
As more preferred embodiment, modified poly acid anhydrides is 8005H by the trade mark that Dow Chemical produces
Resin.
Modified poly sour component is as follows：
| Project | Specifications parameter |
| Solid | 55% |
| Viscosity | 3000~10000mPa*s |
| Density | 1.0g/cm3 |
| Anhydride equivalent | 700~750 |
Modified poly acid anhydrides can be obviously improved dielectric properties and heat resistance after material solidification after adding by a certain percentage
Energy.
As preferred embodiment, the average grain diameter of preparing spherical SiO 2 is 0.5 μm, and maximum particle diameter is no more than 24 μm,
Purity is in 99.0wt% or more.
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- the third oxygen of epoxy) propyl
It is one or more in trimethoxy silane, vinyltrimethoxysilane or vinyltriethoxysilane.
As preferred embodiment, FORTEGRA 351 resin or day of the toughener using Dow Chemical production
One or more of 158 core shell rubbers of MX of this KANEKA companies production.
As preferred embodiment, organic solvent is dimethylformamide, acetone, methyl ethyl ketone, methyl-isobutyl
One or more of ketone or propylene glycol monomethyl ether.
The adhesive is prepared using following methods：
(1) it stocks up according to formula composition；
(2) impregnation
(2-1) sequentially adds organic solvent, silane by formula ratio in stirring grain, opens high speed agitator, rotating speed 1000-
It 1500 revs/min, keeps lasting stirring and control flume temperature is at 20-50 DEG C, preparing spherical SiO 2 is being added, is being held after addition
Continuous stirring 20-60 minutes；
(2-2) sequentially adds the epoxy resin of bromination modification, isocyanate-modified epoxy in stirred tank by formula ratio
Resin, modified poly acid anhydrides and toughener are stirred 20-40 minutes with 1000-1500 revs/min of rotating speed, and open cooling simultaneously
Water recycles and with stirring 1-4 hours of 1800 revs/min of rotating speed, control flume temperature is at 20-50 DEG C；
(2-3) weighs -4 methylimidazole of 2- ethyls by formula ratio and is added in stirred tank, is completely dissolved with organic solvent, confirms
- 4 methylimidazole of 2- ethyls being completely dissolved is added in stirred tank after nodeless mesh, 1-3 is stirred with 1000-1500 revs/min of rotating speed
Hour, adhesive is prepared.
The glass fabric selects E grades, and specification selects 101,104,106,1078,1080,2113,2116,1506
Or 7628 classification；The copper foil selects 1/3oz, Hoz, 1oz, 2oz, 3oz, 4oz or RTF copper foil or VLP copper foils.
Compared with prior art, the present invention has the following advantages：
(1) present invention uses High Bromine epoxy Resin, reaches good flame retardant effect, fire-retardant rank reaches UL94V-0 grades.Together
When brominated epoxy resin solidification after TG >=160 DEG C, good toughness is easy to process, can improve solidification after material flame retardant property, and
Good with glass fibre impregnation, the variation of resin kinetic viscosity is slow in hot pressing.
(2) the cured epoxy resin cured product function admirable of polymeric anhydride is especially stablized with heat resistance and chemically-resistant
Property height is characterized.Acid anhydride curable epoxy resin, although needing high temperature, curing reaction is slower, and exothermic heat of reaction amount is small, and shrinking percentage is small.
It is small with volatility compared with amine curing agent, toxicity is low, with epoxy resin use level big, viscosity small to skin irritation
It is small, it can be added filler modified, advantageously reduce cost, validity period is long, convenient for construction.
(3) in the cured epoxy-resin systems of polymeric anhydride, because the amine type accelerators such as imidazoles there are epoxies to tend to
Ester bond is generated with anhydride reaction, and inhibits part etherification reaction, reduces the hydroxy radical content in system, can significantly be improved solid
The dielectric properties and wet-hot aging performance of change system, thus the necks such as high-frequency high-speed speed and high density interconnection can be advantageously applied to
Domain.
(4) the epoxide glass cloth base copper coated foil plate Tg prepared using adhesive of the present invention>170℃；Z axis CTE ＜
3.0%；In terms of heat resistance：TD >=360 DEG C, T288 ＞ 60min；In terms of electrical property：Dielectric constant (5GHZ)≤4.1；Dielectric is damaged
Consume (5GHZ) ＜ 0.007；；It is provided additionally with very low water absorption rate and good machining property, and fire-retardant reaches UL94V-0
Grade can fully meet leadless process and the demand of multi-layer board production in the fields high-frequency high-speed PCB.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.
Examples 1 to 3
The primary raw material for preparing the unleaded low dielectric type copper coated foil plates of high Tg is that epoxy resin, the isocyanates that bromination is modified change
Epoxy resin, polymeric anhydride curing agent, -4 methylimidazole of 2- ethyls, preparing spherical SiO 2, organic solvent and the toughener group of property
At.
Table 3
| Title material | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| The epoxy resin (%) that bromination is modified | 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 |
| - 4 methylimidazole of 2- ethyls (%) | 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. organic solvent, silane are sequentially added in stirring grain, open high speed agitator by formula ratio, 1500 turns of rotating speed/
Point, it keeps lasting stirring and control flume temperature is at 45 DEG C, preparing spherical SiO 2 is added, 60 points are persistently stirred after addition
Clock；
B. the epoxy resin of bromination modification, isocyanate-modified asphalt mixtures modified by epoxy resin are sequentially added by formula ratio in stirred tank
Fat, anhydride curing agent and toughener are stirred 40 minutes with 1500 revs/min of rotating speed, and open cooling water circulation simultaneously and to turn
1800 revs/min of speed stirs 3 hours, and control flume temperature is at 45 DEG C；
C. -4 methylimidazole of 2- ethyls is weighed by formula ratio to be added in stirred tank, it is small with 1500 revs/min of rotating speed stirring 3
When, impregnation is completed.
2. gluing baking：
Prepreg glues speed：10.0m/min.
3. prepreg control parameter：
Gel time：265s
Resin content:53.8%
Resin flow：23.5%
Fugitive constituent:0.31%
4. plank composing structure：Thickness is 0.785mm after 6 2116 prepregs pressings
5. pressing plate parameter：
Vacuum degree -0.106Mpa
Pressure 261-564psi
150-220 DEG C of temperature of heat plate
Hardening time 200min
Its performance is detected, the results are shown in Table 4.
Table 4
The heat-resisting of the adhesive of the unleaded low dielectric type copper coated foil plates of high Tg is prepared in the application it can be seen from upper table
Property can obtain the promotion of bigger, the resist delamination time can be more than 120min, be doubled more than 60min than Halogen system
Time.
Embodiment 4
A kind of production method of the unleaded low dielectric type copper coated foil plates of high Tg, using following steps：
(1) it glues, prepreg is made；
Adhesive is recycled to gluing machine by (1-1), and the wire velocity control for controlling gluing machine is 6m/min, by presoaking, leading
Adhesive is evenly applied on the E grade fiberglass cloths that specification is 101 by leaching；
The glass fabric of (1-2) application of adhesive is toasted through 120 DEG C of drying boxes, so that solvent is volatilized, adhesive is tentatively anti-
It should cure, prepreg is made；
(2) typesetting, compacting；
Prepreg is torn open and is cut into same size size, 18 one group, then overlapped with 1/3oz copper foils, control pressure is
80psi, temperature of heat plate are 60 DEG C, and vacuum degree is -0.03Mpa, pressing time 90min, hardening time：60min is suppressed and is cured
Obtain copper coated foil plate.
Adhesive used in step (1-1) uses following components and parts by weight content：The epoxy resin that bromination is modified
10, isocyanate-modified epoxy resin 5, modified poly acid anhydrides 20, -4 methylimidazole 0.005 of 2- ethyls, preparing spherical SiO 2
10.0, silane 0.10, toughener 1.00, organic solvent 10.0.
Wherein, the epoxy resin that the bromination used is modified is brominated bisphenol a type epoxy resin, isocyanate-modified ring
Oxygen resin is the epoxy resin that aromatic series methyl diphenylene diisocyanate is modified, and modified poly acid anhydrides is given birth to for Sartomer Company
The trade mark of production is the resin of EF-30, and the average grain diameter of preparing spherical SiO 2 is 0.5 μm, and maximum particle diameter is no more than 24 μm, and purity exists
99.0wt% or more.Silane uses gamma-aminopropyl-triethoxy-silane, toughener to be produced using Dow Chemical
351 resins of FORTEGRA.
Above-mentioned adhesive is prepared using following steps：
(1) it stocks up according to formula composition；
(2) impregnation
(2-1) sequentially adds organic solvent, silane by formula ratio in stirring grain, opens high speed agitator, rotating speed 1000
Rev/min, it keeps lasting stirring and control flume temperature is at 20 DEG C, preparing spherical SiO 2 is being added, is persistently being stirred after addition
20 minutes；
(2-2) sequentially adds the epoxy resin of bromination modification, isocyanate-modified epoxy in stirred tank by formula ratio
Resin, modified poly acid anhydrides and toughener are stirred 20 minutes with 1000 revs/min of rotating speed, and open cooling water circulation simultaneously simultaneously
It is stirred 1 hour for 1800 revs/min with rotating speed, control flume temperature is at 20 DEG C；
(2-3) weighs -4 methylimidazole of 2- ethyls by formula ratio and is added in stirred tank, is completely dissolved with organic solvent, confirms
- 4 methylimidazole of 2- ethyls being completely dissolved is added in stirred tank after nodeless mesh and is stirred 1 hour with 1000 revs/min of rotating speed, system
It is standby to obtain adhesive.
Embodiment 5
A kind of production method of the unleaded low dielectric type copper coated foil plates of high Tg, using following steps：
(1) it glues, prepreg is made；
Adhesive is recycled to gluing machine by (1-1), and the wire velocity control for controlling gluing machine is 10m/min, by presoaking, leading
Adhesive is evenly applied on the E grade fiberglass cloths that specification is 104 by leaching；
The glass fabric of (1-2) application of adhesive is toasted through 200 DEG C of drying boxes, so that solvent is volatilized, adhesive is tentatively anti-
It should cure, prepreg is made；
(2) typesetting, compacting；
Prepreg is torn open and is cut into same size size, 10 one group, then overlapped with RTF copper foils, it then suppresses and cures,
Control pressure is 300psi, and temperature of heat plate is 100 DEG C, vacuum degree 0.05Mpa, pressing time 120min, hardening time：
120min obtains copper coated foil plate.
The adhesive used in step (1) includes following components and parts by weight content：The epoxy resin 50, different that bromination is modified
Cyanate modified epoxy resin 40, modified poly acid anhydrides 40, -4 methylimidazole 0.01 of 2- ethyls, preparing spherical SiO 2 50.0,
Silane 0.15, toughener 5.0, organic solvent 40.0.
Wherein, the epoxy resin that bromination is modified is bromination phenol aldehyde type epoxy resin, and isocyanate-modified epoxy resin is
The epoxy resin that toluene di-isocyanate(TDI) is modified, the resin for the 8005H that modified poly acid anhydrides is produced by Dow Chemical,
The average grain diameter of preparing spherical SiO 2 is 0.5 μm, and maximum particle diameter is no more than 24 μm, and purity is in 99.0wt% or more.Silane uses
The mixture of γ-aminopropyltrimethoxysilane and anilinomethyl trimethoxy silane, toughener are given birth to using Dow Chemical
The mixture for the MX158 core shell rubbers that 351 resins of FORTEGRA of production are produced with KANEKA companies of Japan.
Above-mentioned adhesive is prepared using following steps：
(1) it stocks up according to formula composition；
(2) impregnation
(2-1) sequentially adds organic solvent, silane by formula ratio in stirring grain, opens high speed agitator, rotating speed 1200
Rev/min, it keeps lasting stirring and control flume temperature is at 30 DEG C, preparing spherical SiO 2 is being added, is persistently being stirred after addition
30 minutes；
(2-2) sequentially adds the epoxy resin of bromination modification, isocyanate-modified epoxy in stirred tank by formula ratio
Resin, modified poly acid anhydrides and toughener are stirred 30 minutes with 1200 revs/min of rotating speed, and open cooling water circulation simultaneously simultaneously
It is stirred 2 hours for 1800 revs/min with rotating speed, control flume temperature is at 30 DEG C；
(2-3) weighs -4 methylimidazole of 2- ethyls by formula ratio and is added in stirred tank, is completely dissolved with organic solvent, confirms
- 4 methylimidazole of 2- ethyls being completely dissolved is added in stirred tank after nodeless mesh and is stirred 2 hours with 1200 revs/min of rotating speed, system
It is standby to obtain adhesive.
Embodiment 6
A kind of production method of the unleaded low dielectric type copper coated foil plates of high Tg, using following steps：
(1) it glues, prepreg is made；
Adhesive is recycled to gluing machine by (1-1), and the wire velocity control for controlling gluing machine is 27m/min, by presoaking, leading
Adhesive is evenly applied on the E grade fiberglass cloths that specification is 7628 by leaching；
The glass fabric of (1-2) application of adhesive is toasted through 250 DEG C of drying boxes, so that solvent is volatilized, adhesive is tentatively anti-
It should cure, prepreg is made；
(2) typesetting, compacting；
Prepreg is torn open and is cut into same size size, 1 one group, then overlapped with VLP copper foils, it then suppresses and cures,
When press curing, control pressure 550psi, temperature of heat plate is 230 DEG C, vacuum degree 0.1Mpa, pressing time 240min, Gu
Change time 180min.Obtain copper coated foil plate.
The adhesive used in step (1) includes following components and parts by weight content：The epoxy resin 80, different that bromination is modified
Cyanate modified epoxy resin 80, modified poly acid anhydrides 70, -4 methylimidazole 0.03 of 2- ethyls, preparing spherical SiO 2 60.0,
Silane 0.20, toughener 10.0, organic solvent 60.0.
Wherein, the epoxy resin that bromination is modified is dibromo season pentanediol type epoxy resin, isocyanate-modified asphalt mixtures modified by epoxy resin
Fat is the epoxy resin that the epoxy resin that aromatic series methyl diphenylene diisocyanate is modified is modified with toluene di-isocyanate(TDI)
Mixture, modified poly acid anhydrides are EF-30, EF-40 resin of Sartomer Company production.The average grain diameter of preparing spherical SiO 2
It it is 0.5 μm, maximum particle diameter is no more than 24 μm, and purity is in 99.0wt% or more.Silane is vinyltrimethoxysilane, toughener
The MX158 core shell rubbers produced using Japanese KANEKA companies.
Above-mentioned adhesive is prepared using following steps：
(1) it stocks up according to formula composition；
(2) impregnation
(2-1) sequentially adds organic solvent, silane by formula ratio in stirring grain, opens high speed agitator, rotating speed 1500
Rev/min, it keeps lasting stirring and control flume temperature is at 50 DEG C, preparing spherical SiO 2 is being added, is persistently being stirred after addition
60 minutes；
(2-2) sequentially adds the epoxy resin of bromination modification, isocyanate-modified epoxy in stirred tank by formula ratio
Resin, modified poly acid anhydrides and toughener are stirred 40 minutes with 1500 revs/min of rotating speed, and open cooling water circulation simultaneously simultaneously
It is stirred 4 hours for 1800 revs/min with rotating speed, control flume temperature is at 50 DEG C；
(2-3) weighs -4 methylimidazole of 2- ethyls by formula ratio and is added in stirred tank, is completely dissolved with organic solvent, confirms
- 4 methylimidazole of 2- ethyls being completely dissolved is added in stirred tank after nodeless mesh and is stirred 3 hours with 1500 revs/min of rotating speed, system
It is standby to obtain adhesive.
Claims (8)
1. a kind of production method of the unleaded low dielectric type copper coated foil plates of high Tg, which is characterized in that this method uses following steps：
(1) prepreg is made；
Adhesive is recycled to gluing machine by (1-1), and by preimpregnation, main leaching, adhesive is evenly applied on glass fabric；
The glass fabric of (1-2) application of adhesive is toasted through 120 DEG C~250 DEG C drying boxes, so that solvent is volatilized, adhesive is preliminary
Reaction solidification, is made prepreg；
(2) typesetting, compacting；
Prepreg is torn open and is cut into same size size, 1~18 one group, then overlapped with copper foil, it then suppresses and cures to obtain
Copper coated foil plate；
The adhesive includes following components and parts by weight content：The epoxy resin 10-80, isocyanate-modified that bromination is modified
Epoxy resin 5-80, -4 methylimidazole 0.005-0.03 of modified poly acid anhydrides 20-70,2- ethyl, preparing spherical SiO 2 10.0-
60.0, silane 0.10-0.20, toughener 1.00-10.0, organic solvent 10.0-60.0, are prepared using following methods：
(1) it stocks up according to formula composition；
(2) impregnation
(2-1) sequentially adds organic solvent, silane by formula ratio in stirring grain, opens high speed agitator, rotating speed 1000-1500
Rev/min, it keeps lasting stirring and control flume temperature is at 20-50 DEG C, add preparing spherical SiO 2, continue after addition
Stirring 20-60 minutes；
(2-2) in stirred tank by formula ratio sequentially add bromination modification epoxy resin, isocyanate-modified epoxy resin,
Modified poly acid anhydrides and toughener are stirred 20-40 minutes with 1000-1500 revs/min of rotating speed, and open cooling water circulation simultaneously
And with stirring 1-4 hours of 1800 revs/min of rotating speed, control flume temperature is at 20-50 DEG C；
(2-3) weighs -4 methylimidazole of 2- ethyls by formula ratio and is added in stirred tank, is completely dissolved with organic solvent, confirms without knot
It will be small with 1000-1500 revs/min of rotating speed stirring 1-3 in -4 methylimidazole of 2- ethyls being completely dissolved addition stirred tank after crystalline substance
When, adhesive is prepared.
2. a kind of production method of high unleaded low dielectric type copper coated foil plates of Tg according to claim 1, which is characterized in that institute
The epoxy resin that the bromination stated is modified is brominated bisphenol a type epoxy resin, bromination phenol aldehyde type or dibromo season pentanediol type asphalt mixtures modified by epoxy resin
It is one or more in fat.
3. a kind of production method of high unleaded low dielectric type copper coated foil plates of Tg according to claim 1, which is characterized in that institute
The isocyanate-modified epoxy resin stated is the epoxy resin or toluene two that aromatic series methyl diphenylene diisocyanate is modified
One or both of isocyanate-modified epoxy resin.
4. a kind of production method of high unleaded low dielectric type copper coated foil plates of Tg according to claim 1, which is characterized in that institute
The 8005H's that EF-30, EF-40 or Dow Chemical that the modified poly acid anhydrides stated is produced by Sartomer Company are produced
One or more of resin.
5. a kind of production method of high unleaded low dielectric type copper coated foil plates of Tg according to claim 1, which is characterized in that institute
The average grain diameter for the preparing spherical SiO 2 stated is 0.5 μm, and maximum particle diameter is no more than 24 μm, and purity is in 99.0wt% or more.
6. a kind of production method of high unleaded low dielectric type copper coated foil plates of Tg according to claim 1, which is characterized 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- the third oxygen of epoxy) propyl trimethoxy silicane, vinyl front three
It is one or more in oxysilane or vinyltriethoxysilane, what the toughener was produced using Dow Chemical
351 resins of FORTEGRA or one or more of the MX158 core shell rubbers of KANEKA companies of Japan production.
7. a kind of production method of high unleaded low dielectric type copper coated foil plates of Tg according to claim 1, which is characterized in that step
Suddenly in (1-1) gluing machine wire velocity control be 6~27m/min, step (2) carry out press curing when, control pressure be 80~
550psi, temperature of heat plate are 60~230 DEG C, and vacuum degree is -0.03~0.1Mpa, 90~240min of pressing time, hardening time：
60~180min.
8. a kind of production method of high unleaded low dielectric type copper coated foil plates of Tg according to claim 1, which is characterized in that institute
The glass fabric stated selects E grades, and specification selects 101,104,106,1078,1080,2113,2116,1506 or 7628 classifications；
The copper foil selects 1/3oz, Hoz, 1oz, 2oz, 3oz, 4oz or RTF copper foil or VLP copper foils.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610735468.4A CN106364122B (en) | 2016-08-26 | 2016-08-26 | A kind of production method of the unleaded low dielectric type copper coated foil plates of high Tg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610735468.4A CN106364122B (en) | 2016-08-26 | 2016-08-26 | A kind of production method of the unleaded low dielectric type copper coated foil plates of high Tg |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106364122A CN106364122A (en) | 2017-02-01 |
| CN106364122B true CN106364122B (en) | 2018-09-25 |
Family
ID=57902665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610735468.4A Active CN106364122B (en) | 2016-08-26 | 2016-08-26 | A kind of production method of the unleaded low dielectric type copper coated foil plates of high Tg |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106364122B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298831A (en) * | 2017-07-20 | 2017-10-27 | 南亚新材料科技股份有限公司 | Improve proof tracking index and Drilling operation performance prepreg and its application |
| CN107603149B (en) * | 2017-08-28 | 2020-08-11 | 南亚新材料科技股份有限公司 | Method for detecting electronic grade filler fish eyes |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002294034A (en) * | 2001-04-02 | 2002-10-09 | Hitachi Chem Co Ltd | Resin composition, prepreg for printed circuit board using the same and metal-clad laminated plate |
| CN103554834B (en) * | 2013-09-04 | 2016-04-20 | 东莞联茂电子科技有限公司 | A kind of halogen-less high frequency resin composition |
| CN103802394A (en) * | 2013-12-02 | 2014-05-21 | 上海南亚覆铜箔板有限公司 | Copper-clad plate suitable for lead-free process and preparation method of copper-clad laminate |
| CN103642446A (en) * | 2013-12-10 | 2014-03-19 | 上海南亚覆铜箔板有限公司 | Lead-free high heat-resisting copper-clad board and preparation method thereof |
| CN104553229B (en) * | 2014-12-23 | 2017-01-04 | 上海南亚覆铜箔板有限公司 | A kind of preparation method of high Tg Halogen low dielectric type copper coated foil plate |
-
2016
- 2016-08-26 CN CN201610735468.4A patent/CN106364122B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106364122A (en) | 2017-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103642446A (en) | Lead-free high heat-resisting copper-clad board and preparation method thereof | |
| CN101240109A (en) | Resin composition and prepreg for printed circuit board prepared by applying same | |
| CN103788576B (en) | Epoxy resin composition and preparation method thereof | |
| CN109233244B (en) | Thermosetting resin compositions, prepregs, laminates and printed circuit boards | |
| CN107298831A (en) | Improve proof tracking index and Drilling operation performance prepreg and its application | |
| CN109795188A (en) | A kind of copper clad laminate with good heat resistance and preparation method thereof | |
| CN106166874A (en) | Halogen-free copper-clad plate and preparation method thereof | |
| CN102311612A (en) | Resin composition and resin coated copper foil made of same | |
| CN104559888A (en) | Copper-clad plate applicable to production of high multi-layer PCB (printed circuit board) and preparation method of copper-clad plate | |
| CN1296433C (en) | Glue liquid no-halide fire-retardant copper-clad plate with the glue liquid and its making process | |
| CN107953629A (en) | A kind of high speed high reliability halogen-free copper-clad plate and preparation method thereof | |
| CN103044858A (en) | Thermosetting resin composition, preparation method and use thereof | |
| JP2010254819A (en) | Epoxy resin composition, prepreg, laminate and multilayer board | |
| CN104559068A (en) | Thermosetting resin composition as well as preparation method and application thereof | |
| CN106751507B (en) | A kind of high heat epoxy and combinations thereof and application | |
| CN106364122B (en) | A kind of production method of the unleaded low dielectric type copper coated foil plates of high Tg | |
| CN102093664B (en) | Thermosetting glue solution for copper-clad substrate, preparation method thereof and forming process of halogen-free flame-retardant copper-clad substrate | |
| CN108263068A (en) | A kind of method that copper coated foil plate is prepared using polyphenyl ether resin composition | |
| CN107286325A (en) | Resin combination and its application | |
| CN109439257A (en) | A kind of preparation method of the low dielectric type copper coated foil plate of the high Tg of Halogen | |
| KR101289369B1 (en) | Epoxy resin composition, prepreg, laminate board and multilayer board | |
| CN112175354A (en) | Heat-resistant epoxy resin composition, lead-free high-Tg copper-clad plate and preparation method thereof | |
| JPH04288318A (en) | Epoxy resin composition for electrical laminate board | |
| CN106381110A (en) | Adhesive for high-Tg, lead-free and low-dielectric type copper-clad plate and preparation method thereof | |
| KR100833528B1 (en) | Epoxy resin composition for hard-flex circuit boards and uses thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
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. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |