CN107298831A - Improve proof tracking index and Drilling operation performance prepreg and its application - Google Patents
Improve proof tracking index and Drilling operation performance prepreg and its application Download PDFInfo
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- CN107298831A CN107298831A CN201710595839.8A CN201710595839A CN107298831A CN 107298831 A CN107298831 A CN 107298831A CN 201710595839 A CN201710595839 A CN 201710595839A CN 107298831 A CN107298831 A CN 107298831A
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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
- B32B15/00—Layered products comprising a layer of metal
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- B32—LAYERED PRODUCTS
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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- 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
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B2457/08—PCBs, i.e. printed circuit boards
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Abstract
The present invention relates to prepreg and its application for improving proof tracking index and Drilling operation performance, the prepreg is made using following methods and obtained：It is 6 15m/min to control gluing linear velocity, and adhesive is recycled into gluing machine, and by preimpregnation, main leaching, adhesive is evenly applied on glass fabric；The glass fabric of application of adhesive is toasted through 100 DEG C of 250 DEG C of drying bakers, solvent is volatilized, the solidification of adhesive initial reaction, and prepreg is made.Compared with prior art, the proof tracking index of the unleaded copper coated foil plates of Tg during the present invention can not only be improved, and the multiple-plate Drilling operation performance prepared with this prepreg can be significantly improved.
Description
Technical field
The present invention relates to covering copper sheet to make field, proof tracking index and Drilling operation are improved more particularly, to one kind
Performance prepreg and its application.
Background technology
As electronic and electrical equipment to light, thin, small and multifunction and high-performance direction develops the number of plies, it is necessary to PCB
More thinner, structures are more diversified, and such as pitch of holes is less and less, empty dense degree more and more higher, traditional prepreg system
The problem of standby multi-layer sheet gradually exposes all multi-processing aspects, is mainly manifested in：Some structure multi-layer sheet dense holes be in through
Cross after thermal shock and the bad phenomenons such as layering plate bursting, substrate generation micro-crack, resin shrinkage easily occur, therefore traditional need to be matched somebody with somebody
Side optimizes improvement, to lift the toughness and drill processability of material, so that the need for meeting the making of PCB special constructions.
At present, due to PCB routing density more and more higher, it is new one that ultra-large, ultrahigh speed, superelevation, which become more meticulous,
For the development trend of integrated circuit, this is just used as support it is necessary to have the copper-clad laminate of high reliability.Therefore, copper-clad plate
It is particularly important that electrical security and reliability just become, particularly high phase ratio creepage tracking index (Comparative
Tracking Index) it is an important reference index, CTI values are bigger, and proof tracking index is higher, and insulating properties is better.
In order to improve the electrical security of sheet material, high CTI turns into inevitable choice, and CTI reaches that 400V, even 600V requirement is more next
It is more universal, but traditional FR-4 copper-clad plates often can only achieve 175V or so.
Chinese patent CN102173131A discloses a kind of high creepage trace index copper coated foil plate and preparation method thereof, and this covers
Copper foil plate is mainly by polyfunctional epoxy resin and auxiliary material with the adhesive after special proportioning modulation, and coating glue is in glass fibre
On cloth, then be covered with copper foil and prepared through hot pressing, thickness of slab is 0.05~3.2mm, copper thickness used be 1/3oz~
5oz.But the printed circuit board toughness for utilizing the material to prepare is not enough, especially easily occurs in process at dense holes micro-
Crackle, this exactly the application technical issues that need to address.
The content of the invention
It can not only be improved it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of
The proof tracking index of the middle unleaded copper coated foil plates of Tg, and the multiple-plate brill prepared with this prepreg can be significantly improved
The prepreg of hole machined performance and its application.
The purpose of the present invention can be achieved through the following technical solutions：
Improve proof tracking index and the prepreg of Drilling operation performance, it is 6-15m/ to control gluing linear velocity
Min, gluing machine is recycled to by adhesive, and by preimpregnation, main leaching, adhesive is evenly applied on glass fabric；Coating is viscous
The glass fabric of mixture is toasted through 100 DEG C of -250 DEG C of drying bakers, solvent is volatilized, the solidification of adhesive initial reaction, is made half
Cured sheets.
Make obtained prepreg physical parameter control：Gelation time：250-350 seconds；Resin content:40%-
70% (referring to mass percent of the resin component in prepreg)；Resin flow：20%-35%；Fugitive constituent:0.29-
0.39%.
Described adhesive is prepared using following methods：
(1) got the raw materials ready according to the raw material of following components and parts by weight content：
It is phenol aldehyde type epoxy resin 5~50, isocyanate-modified epoxy resin 5~50, High Bromine epoxy Resin 2~30, double
Phenol A types brominated epoxy resin 5~50, phenolic resin curative 10~50, imidazoles accelerator 0.001~0.100, amine are solid
Agent 0.010~2.000, silane 0.005~1.000, toughener 0.1~10.0, barium sulfate 10~80, inorganic filler 5~80；
(2) organic solvent, silane are sequentially added in stirring grain by formula ratio, silane concentration is controlled in 0.5~5wt ‰,
High speed agitator is opened, 1000-1500 revs/min of rotating speed keeps lasting stirring and control flume temperature is at 20-50 DEG C, adds
Barium sulfate and inorganic filler, addition are persistently stirred 20-60 minutes after finishing；
(3) sequentially add phenol aldehyde type epoxy resin by formula ratio in tank diameter, isocyanate-modified epoxy resin, height
Brominated eopxy resin, bisphenol A type bromide epoxy resin, phenolic resin curative, toughener, are stirred with 1000-1500 revs/min of rotating speed
Mix 20-40 minutes, and open cooling water circulation simultaneously and stirred 1-4 hours with 1800 revs/min of rotating speed, control flume temperature exists
20-50℃；
(4) imidazoles accelerator and amine curing agent are weighed by formula ratio and is completely dissolved with organic solvent, confirmed without knot
It will be stirred 1-3 hours with 1000-1500 revs/min of rotating speed in the mixed accelerators being completely dissolved addition tank diameter after crystalline substance, impregnation
Complete, that is, adhesive is made.
Described isocyanate-modified epoxy resin is that aromatic series methyl diphenylene diisocyanate (MDI) is modified
One or both of epoxy resin or the modified epoxy resin of toluene di-isocyanate(TDI) (TDI) mixture；
Described phenol aldehyde type epoxy resin is bisphenol A-type novolac epoxy resin, bisphenol-f type novolac epoxy resin or orthoresol
Mixing more than one or both of formaldehyde epoxy resin, preferably the BNE200 resins of TaiWan, China Changchun Chemical Manufacture or Korea Spro
State can grand Chemical Manufacture KEB-3165.
Described bisphenol A type bromide epoxy resin is the GEBR456A80 epoxies that Guangzhou Hong Chang Electronic Materials Corps produce
The 540A80 of resin or TaiWan, China Changchun Chemical Manufacture,
Described High Bromine epoxy Resin is from BET400 resins or Yixing ancient cooking vessel wound of TaiWan, China Changchun Chemical Manufacture
DCE-K60。
Described phenolic resin curative be phenol novolacs or bisphenol A phenolic resin or the mixture of the two,
Described toughener is that KANEKA companies of Japan produce core shell rubbers, and the trade mark is MX227*, its kernel is butylbenzene rubber
Glue, shell is polymethyl methacrylate；Kernel content 70-80%, shell content 20-30%, the stable distribution of core-shell particles
In phenolic resin curative.
Described inorganic filler is aluminium nitride, aluminium hydroxide, aluminium borate, magnesia, magnesium carbonate, cubic boron nitride, crystallization
Silica, synthetic silica, hollow silica, preparing spherical SiO 2, fused silica, talcum powder, aluminum oxide, hydrogen
One or more in aluminum oxide, barium titanate, strontium titanates, calcium carbonate or titanium dioxide, the particle diameter of inorganic filler is 0.01-24 μ
M, purity is more than 99.0%.
Described barium sulfate average grain diameter is 0.1~10 μm, and preferably average grain diameter is 0.5~0.7 μm, and purity exists
More than 98.0%,
Described silane is selected from gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, anilinomethyl three
Methoxy silane, γ-(β-aminoethyl) aminopropyl trimethoxysilane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane,
One or more in vinyltrimethoxy silane or VTES.
Described imidazoles accelerator is 2-methylimidazole, the methylimidazole of 2- ethyls -4, DMIZ 1,2 dimethylimidazole, 2- benzene
Base imidazoles, the methylimidazole of 2- phenyl -4,2-methylimidazole quinoline, 2- benzylimidazolines, 1- cyano ethyl -2- undecyl imidazoles
Or the one or more in 1- cyano ethyl -2- phenylimidazoles,
Described amine curing agent is in dicyandiamide, diaminodiphenylsulfone, diaminodiphenyl ether or MDA
One kind.
Described organic solvent is selected from acetone, butanone, methylisobutylketone, DMF, N, N- dimethyl second
Mixture more than one or both of acid amides, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.
The prepreg is used to process copper coated foil plate, and 2-10 prepregs are pressed, then is overlapped with copper foil, then
Compacting；Pressing parameter is controlled：Vacuum：- 0.05~0.10Mpa；Pressure：261-564psi；Temperature of heat plate：150-220℃；
High temperature section hardening time：90-110min, making obtains copper coated foil plate.
Compared with prior art, the present invention has advantages below：
(1) barium sulfate of the present invention has core shell structure, and average grain diameter is at 0.1-10 μm, and preferably average grain diameter is
0.5-0.7 μm, its purity is more than 98%.Barium sulfate filler has relatively low electrical conductivity, good processability and easy dispersion flows
The advantages of good.The unleaded resin combination of the present invention provides excellent anti-creep track property by using barium sulfate filler,
The copper coated foil plate with high phase ratio creepage tracking index is made thereby using the unleaded resin combination, the advantage of the invention is that
Except that can provide high phase ratio creepage tracking index (CTI >=400V), and heat resistance has significant improvement.
(2) there is following reason as the plasticized modifier of material from core shell rubber：A, the core shell rubber added
For nanoscale, with high specific surface area, nano-particle can prevent epoxy by scattered and absorption external shock stress
The extension of crackle in resin；When b, core-shell structure copolymer are by external impacts, stress release can be gone out, while this nucleocapsid structure holds very much
Easily it is induced deformation, absorbs energy so that fracture-arrest or steering, significantly improve boring surface, so as to reach toughness reinforcing
Effect；C, add core shell rubber and can improve resin and copper foil, and resin and resin interlayer peel strength.
(3) present invention makes obtained epoxide glass cloth base copper coated foil plate Tg >=155 DEG C (DSC)；Z axis CTE≤3.2%；
In terms of heat resistance：TD >=358 DEG C, T288 >=40min；CTI≥400V；Peel strength of copper foil (1OZ) >=1.3N/mm；Especially have
Standby good Drilling operation performance, and it is fire-retardant reach UL94V-0 grade, the dense holes height for being suitable for high CTI performance requirements is more
Layer PCB leadless process processed and applieds.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1~3
A kind of adhesive primary raw material of the Tg lead-free printed circuit substrate Drilling operation performances suitable for improving is phenolic aldehyde
Type epoxy resin, isocyanate-modified epoxy resin, High Bromine epoxy Resin, bisphenol A type bromide epoxy resin, phenolic resin are solid
Agent, imidazoles accelerator, amine curing agent, silane, inorganic filler, barium sulfate, organic solvent and toughener etc. are constituted, such as table
Shown in 1.
Table 1
| Title material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Phenol aldehyde type epoxy resin | 12 | 10 | 11 | 12 | 10 | 13 |
| Isocyanate-modified epoxy resin | 10 | 10 | 9 | 10 | 10 | 8 |
| High Bromine epoxy Resin | 5 | 4 | 4 | 5 | 4 | 6 |
| Bisphenol A type bromide epoxy resin | 26 | 29 | 30 | 26 | 29 | 25 |
| Phenolic resin curative | 18 | 17 | 17 | 18 | 17 | 18 |
| Imidazoles accelerator | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 | 0.02 |
| Amine curing agent | 0.18 | 0.17 | 0.17 | 0.18 | 0.17 | 0.18 |
| Silane | 0.10 | 0.09 | 0.08 | 0.10 | 0.09 | 0.09 |
| Toughener | 0.7 | 8 | 5 | ---- | 2 | ---- |
| Barium sulfate | 20 | 21 | 20 | ---- | ---- | 21 |
| Aluminium hydroxide | 6 | 6 | 6 | 6 | 6 | 6 |
| Silicon powder | ---- | ---- | ---- | 20 | 16 | ---- |
1. specific preparation process is as follows：
A. organic solvent, silane are sequentially added in stirring grain by formula ratio, opens high speed agitator, rotating speed 1000-
1500 revs/min, keep lasting stirring and control flume temperature is at 20-50 DEG C, add barium sulfate, inorganic filler and hydroxide
Aluminium, addition is persistently stirred 20-60 minutes after finishing；
B. sequentially add phenol aldehyde type epoxy resin by formula ratio in tank diameter, isocyanate-modified epoxy resin, height
Brominated eopxy resin, bisphenol A type bromide epoxy resin, phenolic resin curative, toughener, with 1000-1500 revs/min of rotating speed
Stirring 20-40 minute, and cooling water circulation is opened simultaneously and with stirring 1-4 hours of 1800 revs/min of rotating speed, control flume temperature
At 20-50 DEG C；
C. imidazoles accelerator and amine curing agent are weighed by formula ratio and is completely dissolved with appropriate organic solvent, confirmed
It will be stirred 1-3 hours with 1000-1500 revs/min of rotating speed in the mixed accelerators being completely dissolved addition tank diameter after nodeless mesh,
Impregnation is completed, that is, adhesive is made.
2. gluing is toasted：
Prepreg gluing speed：6-15m/min
3. prepreg control parameter：
Gel time：250-350 seconds
Resin content:40%-70%
Resin flow：20%-35%
Fugitive constituent:0.29-0.39%
4. sheet material composing structure：Thickness is 0.6mm after 5 2116 prepregs pressings
5. pressing plate parameter：
Vacuum：- 0.05~0.10Mpa
Pressure：261-564psi
Temperature of heat plate：150-220℃
High temperature section hardening time：90-110min
Processability：In being drilled on above-mentioned copper clad laminate, hole wall spacing is 0.30mm, and aperture is 0.25mm, and calculates 25
In individual drilling, micro-crack number between resin and glass cloth at dense holes.Crackle number is fewer, then it represents that substrate possesses preferably drilling and added
Work.
Copper-clad plate performance to preparation detects, as a result as shown in table 2.
Table 2
It was found from the physical data of table 2, comparative example 1 produces more micro-crack when drilling, CTI and T288 values are relatively low, resists
Shell intensity general；Comparative example 2 with the addition of drill hole micro-crack phenomenon after toughener and make moderate progress, but CTI values and T288 values compared with
It is low；Peel strength and CTI are worth to obvious improvement in comparative example 3, but still occur micro-crack at dense holes.Embodiment 1-
3 in addition to possessing good Drilling operation performance, is also equipped with excellent proof tracking index and peel strength, heat resistance are good
And the advantages of relatively low thermal coefficient of expansion.It therefore, it can be entirely applied in middle Tg lead-free PCBs processing procedure to dense holes drillman
The requirement of skill.
Embodiment 4
Improve proof tracking index and the prepreg of Drilling operation performance, it is 6m/min to control gluing linear velocity, will
Adhesive is recycled to gluing machine, and by preimpregnation, main leaching, adhesive is evenly applied on glass fabric；Application of adhesive
Glass fabric is toasted through 100 DEG C of drying bakers, solvent is volatilized, the solidification of adhesive initial reaction, and prepreg is made.
Make obtained prepreg physical parameter control：Gelation time：250 seconds；Resin content:40% (refers to resin
Mass percent of the composition in prepreg)；Resin flow：20%；Fugitive constituent:0.29%.
Adhesive is prepared using following methods：
(1) got the raw materials ready according to the raw material of following components and parts by weight content：
Phenol aldehyde type epoxy resin 5, isocyanate-modified epoxy resin 5, High Bromine epoxy Resin 2, bisphenol-A type brominated
Oxygen tree fat 5, phenolic resin curative 10, imidazoles accelerator 0.001, amine curing agent 0.010, silane 0.005, toughener
0.1st, barium sulfate 10, inorganic filler 5, the isocyanate-modified epoxy resin used are aromatic series diphenylmethane diisocyanate
The modified epoxy resin of ester (MDI), phenol aldehyde type epoxy resin is bisphenol A-type novolac epoxy resin, bisphenol-f type novolac epoxy resin
Or mixing more than one or both of o-cresol formaldehyde epoxy resin, the present embodiment uses the chemical industry life of TaiWan, China Changchun
The BNE200 resins of production, bisphenol A type bromide epoxy resin is the GEBR456A80 epoxies that Guangzhou Hong Chang Electronic Materials Corps produce
Resin, High Bromine epoxy Resin selects the BET400 resins of TaiWan, China Changchun Chemical Manufacture, and phenolic resin curative is phenol phenol
Urea formaldehyde, toughener is that KANEKA companies of Japan produce core shell rubbers, and the trade mark is MX227*, its kernel is butadiene-styrene rubber, shell
For polymethyl methacrylate；Kernel content 70wt%, shell content 30wt%, what core-shell particles were stablized is distributed in phenolic aldehyde tree
In fat curing agent.Inorganic filler is the aluminium nitride of 0.01 μm of particle diameter, and purity is more than 99.0%.Barium sulfate average grain diameter is 0.1 μ
M, purity is more than 98.0%, and silane is gamma-aminopropyl-triethoxy-silane.Imidazoles accelerator is 2-methylimidazole, amine
Curing agent is dicyandiamide；
(2) organic solvent-acetone, silane are sequentially added in stirring grain by formula ratio, silane concentration is controlled in 0.5wt ‰,
Open high speed agitator, 1000 revs/min of rotating speed keeps lasting stirring and control flume temperature is at 20 DEG C, add barium sulfate and
Inorganic filler, addition is persistently stirred 60 minutes after finishing；
(3) sequentially add phenol aldehyde type epoxy resin by formula ratio in tank diameter, isocyanate-modified epoxy resin, height
Brominated eopxy resin, bisphenol A type bromide epoxy resin, phenolic resin curative, toughener, 40 are stirred with 1000 revs/min of rotating speed
Minute, and open cooling water circulation simultaneously and stirred 1 hour with 1800 revs/min of rotating speed, control flume temperature is at 50 DEG C；
(4) imidazoles accelerator and amine curing agent are weighed by formula ratio and is completely dissolved with organic solvent, confirmed without knot
It will be stirred 3 hours with 1000 revs/min of rotating speed in the mixed accelerators being completely dissolved addition tank diameter after crystalline substance, impregnation is completed, i.e.,
Adhesive is made.
The prepreg is used to process copper coated foil plate, and 2 prepregs are pressed, then is overlapped with copper foil, then presses
System；Pressing parameter is controlled：Vacuum：-0.05Mpa；Pressure：261psi；Temperature of heat plate： 150℃；High temperature section hardening time：
90min, making obtains copper coated foil plate.
Embodiment 5
Improve proof tracking index and the prepreg of Drilling operation performance, it is 10m/min to control gluing linear velocity,
Adhesive is recycled to gluing machine, by preimpregnation, main leaching, adhesive is evenly applied on glass fabric；Application of adhesive
Glass fabric toasted through 200 DEG C of drying bakers, solvent is volatilized, adhesive initial reaction solidification, be made prepreg.
Make obtained prepreg physical parameter control：Gelation time：300 seconds；Resin content:60% (refers to resin
Mass percent of the composition in prepreg)；Resin flow：30%；Fugitive constituent:0.35%.
Adhesive is prepared using following methods：
(1) got the raw materials ready according to the raw material of following components and parts by weight content：
Phenol aldehyde type epoxy resin 20, isocyanate-modified epoxy resin 20, High Bromine epoxy Resin 15, bisphenol A type bromide
Epoxy resin 25, phenolic resin curative 25, imidazoles accelerator 0.05, amine curing agent 1, silane 0.5, toughener 8, sulfuric acid
Barium 60, inorganic filler 60, the isocyanate-modified epoxy resin used are aromatic series methyl diphenylene diisocyanate (MDI)
The mixture of the modified epoxy resin epoxy resin modified with toluene di-isocyanate(TDI) (TDI)；Phenol aldehyde type epoxy resin is double
Phenol A types novolac epoxy resin, the mixture of bisphenol-f type novolac epoxy resin.Bisphenol A type bromide epoxy resin is that TaiWan, China is long
The 540A80 of spring Chemical Manufacture, High Bromine epoxy Resin selects the DCE-K60 that Yixing ancient cooking vessel is created.Phenolic resin curative is bisphenol-A phenol
Urea formaldehyde or the mixture of the two, toughener are that KANEKA companies of Japan produce core shell rubbers, and the trade mark is MX227*, and its kernel is
Butadiene-styrene rubber, shell is polymethyl methacrylate；Kernel content 75%, shell 25%, what core-shell particles were stablized is distributed in phenol
In urea formaldehyde curing agent.Inorganic filler is magnesia, the mixture of magnesium carbonate, and particle diameter is 10 μm, and purity is more than 99.0%.Sulphur
Sour barium average grain diameter is 0.7 μm, and purity is more than 98.0%, and silane is anilinomethyl trimethoxy silane, γ-(β-aminoethyl)
The mixture of aminopropyl trimethoxysilane, imidazoles accelerator 2- phenylimidazoles, the mixture of the methylimidazole of 2- phenyl -4, amine
Class curing agent is diaminodiphenyl ether；
(2) organic solvent DMF, silane, silane concentration control are sequentially added in stirring grain by formula ratio
System opens high speed agitator in 1wt ‰, and 1200 revs/min of rotating speed keeps lasting stirring and control flume temperature is at 40 DEG C, then adds
Enter barium sulfate and inorganic filler, addition is persistently stirred 30 minutes after finishing；
(3) sequentially add phenol aldehyde type epoxy resin by formula ratio in tank diameter, isocyanate-modified epoxy resin, height
Brominated eopxy resin, bisphenol A type bromide epoxy resin, phenolic resin curative, toughener, 30 are stirred with 1200 revs/min of rotating speed
Minute, and open cooling water circulation simultaneously and stirred 2 hours with 1800 revs/min of rotating speed, control flume temperature is at 20-50 DEG C；
(4) imidazoles accelerator and amine curing agent are weighed by formula ratio and is completely dissolved with organic solvent, confirmed without knot
It will be stirred 2 hours with 1200 revs/min of rotating speed in the mixed accelerators being completely dissolved addition tank diameter after crystalline substance, impregnation is completed, i.e.,
Adhesive is made.
The prepreg is used to process copper coated foil plate, and 5 prepregs are pressed, then is overlapped with copper foil, then presses
System；Pressing parameter is controlled：Vacuum：0.10Mpa；Pressure：500psi；Temperature of heat plate： 200℃；High temperature section hardening time：
100min, making obtains copper coated foil plate.
Embodiment 6
Improve proof tracking index and the prepreg of Drilling operation performance, it is 15m/min to control gluing linear velocity,
Adhesive is recycled to gluing machine, by preimpregnation, main leaching, adhesive is evenly applied on glass fabric；Application of adhesive
Glass fabric toasted through 250 DEG C of drying bakers, solvent is volatilized, adhesive initial reaction solidification, be made prepreg.
Make obtained prepreg physical parameter control：Gelation time：350 seconds；Resin content:70% (refers to resin
Mass percent of the composition in prepreg)；Resin flow：35%；Fugitive constituent:0.39%.
Described adhesive is prepared using following methods：
(1) got the raw materials ready according to the raw material of following components and parts by weight content：
Phenol aldehyde type epoxy resin 50, isocyanate-modified epoxy resin 50, High Bromine epoxy Resin 30, bisphenol A type bromide
Epoxy resin 50, phenolic resin curative 50, imidazoles accelerator 0.100, amine curing agent 2.000, silane 1.000, toughness reinforcing
Agent 10.0, barium sulfate 80, inorganic filler 80, the isocyanate-modified epoxy resin used is or toluene di-isocyanate(TDI)
(TDI) modified epoxy resin, phenol aldehyde type epoxy resin is bisphenol-f type novolac epoxy resin, and bisphenol A type bromide epoxy resin is
The GEBR456A80 epoxy resin of Guangzhou Hong Chang Electronic Materials Corps production, High Bromine epoxy Resin selects the DCE- that Yixing ancient cooking vessel is created
K60.Phenolic resin curative is bisphenol A phenolic resin, and toughener is that KANEKA companies of Japan produce core shell rubbers, and the trade mark is
MX227*, its kernel is butadiene-styrene rubber, and shell is polymethyl methacrylate；Kernel content 80%, shell 20%, core-shell particles
Stable is distributed in phenolic resin curative.Inorganic filler is aluminum oxide, and particle diameter is 24 μm, and purity is more than 99.0%.Sulphur
Sour barium average grain diameter is 10 μm, and purity is more than 98.0%, and silane is VTES.Imidazoles accelerator is 1-
Cyano ethyl -2- phenylimidazoles, amine curing agent is one kind in MDA；
(2) organic solvent propylene glycol monomethyl ether, silane are sequentially added in stirring grain by formula ratio, silane concentration control exists
5wt ‰, opens high speed agitator, and 1500 revs/min of rotating speed keeps lasting stirring and control flume temperature is at 50 DEG C, adds sulphur
Sour barium and inorganic filler, addition are persistently stirred 20 minutes after finishing；
(3) sequentially add phenol aldehyde type epoxy resin by formula ratio in tank diameter, isocyanate-modified epoxy resin, height
Brominated eopxy resin, bisphenol A type bromide epoxy resin, phenolic resin curative, toughener, 40 are stirred with 1500 revs/min of rotating speed
Minute, and open cooling water circulation simultaneously and stirred 4 hours with 1800 revs/min of rotating speed, control flume temperature is at 20 DEG C；
(4) imidazoles accelerator and amine curing agent are weighed by formula ratio and is completely dissolved with organic solvent, confirmed without knot
It will be stirred 1 hour with 1500 revs/min of rotating speed in the mixed accelerators being completely dissolved addition tank diameter after crystalline substance, impregnation is completed, i.e.,
Adhesive is made.
The prepreg is used to process copper coated foil plate, and 10 prepregs are pressed, then is overlapped with copper foil, then presses
System；Pressing parameter is controlled：Vacuum：0.10Mpa；Pressure：564psi；Temperature of heat plate：220℃；High temperature section hardening time：
110min, making obtains copper coated foil plate.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (10)
1. improve the prepreg of proof tracking index and Drilling operation performance, it is characterised in that the prepreg use with
Lower section method makes and obtained：It is 6-15m/min to control gluing linear velocity, and adhesive is recycled into gluing machine, by preimpregnation, main leaching,
Adhesive is evenly applied on glass fabric；The glass fabric of application of adhesive is toasted through 100 DEG C of -250 DEG C of drying bakers,
Solvent is set to volatilize, prepreg is made in the solidification of adhesive initial reaction.
2. according to claim 1 improve proof tracking index and the prepreg of Drilling operation performance, its feature exists
In described adhesive is prepared using following methods：
(1) got the raw materials ready according to the raw material of following components and parts by weight content：
Phenol aldehyde type epoxy resin 5~50, isocyanate-modified epoxy resin 5~50, High Bromine epoxy Resin 2~30, bisphenol A-type
Brominated epoxy resin 5~50, phenolic resin curative 10~50, imidazoles accelerator 0.001~0.100, amine curing agent
0.010~2.000, silane 0.005~1.000, toughener 0.1~10.0, barium sulfate 10~80, inorganic filler 5~80；
(2) organic solvent, silane are sequentially added in stirring grain by formula ratio, silane concentration control is opened in 0.5~5wt ‰
High speed agitator, 1000-1500 revs/min of rotating speed keeps lasting stirring and control flume temperature is at 20-50 DEG C, adds sulfuric acid
Barium and inorganic filler, addition are persistently stirred 20-60 minutes after finishing；
(3) sequentially add phenol aldehyde type epoxy resin by formula ratio in tank diameter, isocyanate-modified epoxy resin, high bromine ring
Oxygen tree fat, bisphenol A type bromide epoxy resin, phenolic resin curative, toughener, are stirred with 1000-1500 revs/min of rotating speed
20-40 minutes, and open cooling water circulation simultaneously and stirred 1-4 hours with 1800 revs/min of rotating speed, control flume temperature is in 20-
50℃；
(4) imidazoles accelerator and amine curing agent are weighed by formula ratio and is completely dissolved with organic solvent, confirmed after nodeless mesh
It will be stirred 1-3 hours with 1000-1500 revs/min of rotating speed in the mixed accelerators being completely dissolved addition tank diameter, impregnation is completed,
Adhesive is made.
3. according to claim 2 improve proof tracking index and the prepreg of Drilling operation performance, its feature exists
In,
Described isocyanate-modified epoxy resin is the modified asphalt mixtures modified by epoxy resin of aromatic series methyl diphenylene diisocyanate (MDI)
One or both of fat or the modified epoxy resin of toluene di-isocyanate(TDI) (TDI) mixture；
Described phenol aldehyde type epoxy resin is bisphenol A-type novolac epoxy resin, bisphenol-f type novolac epoxy resin or o-cresol formaldehyde ring
Mixing more than one or both of oxygen tree fat, preferably the BNE200 resins of TaiWan, China Changchun Chemical Manufacture or South Korea can be grand
The KEB-3165 of Chemical Manufacture.
4. according to claim 2 improve proof tracking index and the prepreg of Drilling operation performance, its feature exists
In,
Described bisphenol A type bromide epoxy resin be Guangzhou Hong Chang Electronic Materials Corps produce GEBR456A80 epoxy resin or
The 540A80 of TaiWan, China Changchun Chemical Manufacture,
DCE- of the described High Bromine epoxy Resin from BET400 resins or Yixing ancient cooking vessel wound of TaiWan, China Changchun Chemical Manufacture
K60。
5. according to claim 2 improve proof tracking index and the prepreg of Drilling operation performance, its feature exists
In,
Described phenolic resin curative is phenol novolacs or bisphenol A phenolic resin or the mixture of the two；
Described toughener is core shell rubbers, and kernel is butadiene-styrene rubber, and shell is polymethyl methacrylate；Kernel content 70-
80wt%, shell content 20-30wt%, core-shell particles are stable to be distributed in phenolic resin curative, preferably Japan KANEKA
The trade mark of company's production is MX227*Core shell rubbers.
6. according to claim 2 improve proof tracking index and the prepreg of Drilling operation performance, its feature exists
In described inorganic filler is aluminium nitride, aluminium hydroxide, aluminium borate, magnesia, magnesium carbonate, cubic boron nitride, crystalline silica
Silicon, synthetic silica, hollow silica, preparing spherical SiO 2, fused silica, talcum powder, aluminum oxide, hydroxide
One or more in aluminium, barium titanate, strontium titanates, calcium carbonate or titanium dioxide, the particle diameter of inorganic filler is 0.01-24 μm, pure
Degree is more than 99.0%.
7. according to claim 2 improve proof tracking index and the prepreg of Drilling operation performance, its feature exists
In described barium sulfate average grain diameter is 0.1~10 μm, and preferably average grain diameter is 0.5~0.7 μm, and purity is more than 98.0%.
8. according to claim 2 improve proof tracking index and the prepreg of Drilling operation performance, its feature exists
In described silane is 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
One or more in trimethoxy silane or VTES；
Described organic solvent be selected from acetone, butanone, methylisobutylketone, DMF, DMA,
One or more in ethylene glycol monomethyl ether or propylene glycol monomethyl ether.
9. according to claim 2 improve proof tracking index and the prepreg of Drilling operation performance, its feature exists
In,
Described imidazoles accelerator is 2-methylimidazole, the methylimidazole of 2- ethyls -4, DMIZ 1,2 dimethylimidazole, 2- phenyl miaows
Azoles, the methylimidazole of 2- phenyl -4,2-methylimidazole quinoline, 2- benzylimidazolines, 1- cyano ethyl -2- undecyl imidazoles or 1- cyanogen
One or more in base ethyl -2- phenylimidazoles,
Described amine curing agent is one in dicyandiamide, diaminodiphenylsulfone, diaminodiphenyl ether or MDA
Kind.
10. improving the application of proof tracking index and the prepreg of Drilling operation performance as claimed in claim 1, it is special
Levy and be, the prepreg is used to process copper coated foil plate, 2-10 prepregs are pressed, then overlapped with copper foil, control
Vacuum：- 0.05~0.10Mpa；Pressure：261-564psi；Temperature of heat plate：150-220℃；High temperature section hardening time：90-
110min, compacting obtains copper coated foil plate.
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| CN109535651A (en) * | 2018-11-01 | 2019-03-29 | 吉安市宏瑞兴科技有限公司 | A kind of resin combination and preparation method thereof |
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| CN109719967B (en) * | 2018-12-29 | 2021-05-04 | 江苏联鑫电子工业有限公司 | High-toughness high-Tg lead-free copper-clad plate and preparation method thereof |
| CN110421931A (en) * | 2019-08-30 | 2019-11-08 | 重庆德凯实业股份有限公司 | Cover copper foil glass fabric laminates and preparation method thereof |
| CN114311881A (en) * | 2021-12-15 | 2022-04-12 | 江西省宏瑞兴科技股份有限公司 | Epoxy resin copper-clad plate suitable for PCB (printed circuit board) manufacturing process and having high comparative tracking index and preparation method thereof |
| CN114311881B (en) * | 2021-12-15 | 2024-01-12 | 江西省宏瑞兴科技股份有限公司 | Epoxy resin copper-clad plate with high comparative tracking index suitable for PCB (printed circuit board) manufacturing process and preparation method thereof |
| CN114589906A (en) * | 2022-03-12 | 2022-06-07 | 泉州爱丽卡新材料科技有限公司 | Novel concave-convex plastic suction product and plastic suction process |
| CN114589906B (en) * | 2022-03-12 | 2024-05-07 | 泉州爱丽卡新材料科技有限公司 | Novel concave-convex plastic uptake product and plastic uptake process |
| CN116406090A (en) * | 2023-05-15 | 2023-07-07 | 台山市科伟电子科技有限公司 | Production process of aluminum-based copper-clad aluminum foil plate |
| CN116406090B (en) * | 2023-05-15 | 2024-02-02 | 台山市科伟电子科技有限公司 | Production process of aluminum-based copper-clad aluminum foil plate |
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