CN100539803C - Lead-free compatible high frequency copper clad laminate and preparation method thereof - Google Patents
Lead-free compatible high frequency copper clad laminate and preparation method thereof Download PDFInfo
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- CN100539803C CN100539803C CNB2007100272025A CN200710027202A CN100539803C CN 100539803 C CN100539803 C CN 100539803C CN B2007100272025 A CNB2007100272025 A CN B2007100272025A CN 200710027202 A CN200710027202 A CN 200710027202A CN 100539803 C CN100539803 C CN 100539803C
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Abstract
The present invention relates to lead-free compatible high frequency copper clad laminate that is applied to printed circuit and preparation method thereof, key technology is resin combination and the NE glass cloth that is used to make copper-clad plate, and bonding sheet of making thus and copper-clad plate, resin combination has following component and content: 30～45 parts of polyfunctional epoxy resins, 20～30 parts of phosphorus containing phenolic resins, 20～30 parts of polytetrafluoroethylene, 0.5～1.5 part of curing accelerator, 20～30 parts of inorganic fillers, solvent are an amount of.The copper-clad plate of making thus, not brominated, meet the RoHS command request, and have high thermal reliability, outstanding dielectric property, low thermal coefficient of expansion and outstanding anti-flammability.
Description
Technical field:
The present invention relates to be applied to the copper-clad plate field of printed circuit.Say so more specifically and make the resin combination and the NE glass cloth of copper-clad plate, and bonding sheet of making thus and copper-clad plate.
Background technology:
On July 1st, 2006, the formal enforcement of two instructions of European Union (using some harmful substance to instruct and instruct about scrapping electrical and electronic product about restriction in electrical and electronic product) indicates that the global electronic industry has entered the pb-free solder epoch.Because the raising of welding temperature, the requirement to the copper-clad plate thermal reliability increases substantially comprehensively.
The thermal reliability of copper-clad plate comprises vitrification point (Tg), heat decomposition temperature (Td), thermally stratified layer time (T-288), soldering resistance and the thermal coefficient of expansion (CTE) etc. of sheet material.It is an overall target.
Brominated epoxy resin is mainly adopted in traditional FR-4 copper-clad plate, by the effect of bromine (Br), makes product have anti-flaming function.In recent years, a kind of viewpoint is arranged, think that halogen (mainly referring to Br and Cl) fire retardant can produce pernicious gas in combustion process, unfriendly to human body and environment.For this reason, non-halogen requirement is proposed in copper-clad plate.2000, NEC circuit employer's organization (JPCA) took the lead in putting into effect the series standard of a cover halogen-free type copper-clad plate, to content of halogen in the copper-clad plate, has done strict regulations, and the content of Br and Cl mustn't surpass 0.09wt% respectively.
In recent years, along with developing rapidly of information industry, the demand of high-frequency copper-clad plate is progressively being increased.Require sheet material to possess lower dielectric constant and littler dielectric loss.
Summary of the invention:
At the problems referred to above, the invention provides a kind of high-performance and copper-clad plate environment amenable, that meet the european union directive requirement, this copper-clad plate need reach following index:
(1) high thermal reliability
(2) outstanding dielectric property
(3) low thermal coefficient of expansion
(4) outstanding anti-flammability
(5) not brominated, meet the RoHS command request
In order to realize above-mentioned every requirement, the present invention by the following technical solutions:
(1) adopt high performance resin combination, press the calculating of solid weight part, wherein comprise:
30～45 parts of polyfunctional epoxy resins
20～30 parts of phosphorus containing phenolic resins
20～30 parts of polytetrafluoroethylene
0.5～1.5 part of curing accelerator
20～30 parts of inorganic fillers
Solvent is an amount of
(2) NE-glass cloth
(3) making of bonding sheet
Proportioning by above-mentioned setting takes by weighing various materials, uses proper amount of solvent, is mixed with resin solution.Its solids content is 50～70%, and gelation time is 150 seconds～250 seconds (171 ℃).
NE glass cloth with 2116, the above-mentioned resin solution of impregnation through 150～170 ℃ of baking oven bakings 3～6 minutes, is made bonding sheet.
The resin content of bonding sheet is 40～60%, and gelation time is 100～150 seconds (171 ℃), and resin flow is 15～25%.
(4) making of copper-clad plate
Get the bonding sheet of setting number, superimposed neat, single or double is mixed 12～35 μ m electrolytic copper foils, is placed between two blocks of mirror face stainless steel plates, places vacuum press then, at 180～200 ℃, 20～30kg/cm
2Under the condition, the single or double copper-clad plate is made in hot pressing 90 minutes.
Technology path: copper-clad plate is by synthetic resin, glass cloth and Copper Foil, three kinds of main raw material(s) formations.Except that Copper Foil, synthetic resin and glass cloth are crucial, and it is to the properties of product decisive role.
(1) polyfunctional epoxy resin
Polyfunctional epoxy resin commonly used has the novolac epoxy resin of phenol type novolac epoxy resin, bisphenol A-type novolac epoxy resin and biphenyl contenting structure etc.
Phenol type novolac epoxy resin
N is a natural number
The bisphenol A-type novolac epoxy resin
N is a natural number.
The biphenyl type polyfunctional epoxy resin
N is a natural number.
Polyfunctional epoxy resin is compared with general epoxy resin, owing to contain a plurality of epoxy radicals in the molecular structure, solidfied material crosslink density height, thermal endurance, solvent resistance, chemical proofing and dimensional stability all improve relatively.
The biphenyl type polyfunctional epoxy resin, because aromatic rings occupies very big ratio in structure, solidfied material thermal endurance height not only, and when burning, can form more charring layer, help the improvement of anti-flammability.
In resin, owing to contain biphenyl structural, the molecular weight between the crosslinking functionality (epoxy radicals) is increased, make that solidfied material reduces at hot modulus of elasticity down, toughness increases, help the stress that product produces and reduce in the high-temperature soldering process, thermal reliability improves.
This based epoxy resin also has high hydrophobicity, helps the improvement of soldering resistance after the solidfied material moisture absorption.
(2) phosphorus containing phenolic resin
For many years, the FR-4 copper-clad plate is to adopt dicyandiamide (Dicy) to make curing agent always, but there are some blemisies in an otherwise perfect thing in dicyandiamide, and moisture absorption is bigger than normal, and thermal endurance is not good enough, in the pb-free solder process, can not meet the demands.
For the requirement of adapted to leadless welding, high thermal reliability, industry generally adopts linear phenol-aldehyde resin to make curing agent in recent years, and aspects such as the thermal endurance of product, dimensional stability and anti-ion transport all have clear improvement and improve.
The anti-flammability of phenolic resins is good than epoxy resin.If in the phenolic resins structure, introduce phosphorus-containing groups, make phosphorus containing phenolic resin, make curing agent with it, both can improve the crosslink density of solidfied material, the thermal endurance of improving product and dimensional stability, can improve the anti-flammability of product simultaneously, make the best of both worlds.
M.n is a natural number.
(3) polytetrafluoroethylene
Polytetrafluoroethylene (PTFE), molecular structural formula is:
N is 3800～8900 integer.
Because molecular structure is symmetrical, outstanding physics, chemistry and electric property are arranged so polytetrafluoroethylene gathers.The many strong corrosive medias of polytetrafluoroethylene ability, therefore still do not have so far a kind ofly can have the laudatory title of " plastics king " at its solvent of dissolving below 300 ℃.
Aspect electric property, polytetrafluoroethylene has electrical insulating property best in the plastics, and its volume resistance is up to 10
18Ω cm.Dielectric constant (1MHz) is low to reach 2.1, and 10
10Irrelevant in the Hz with frequency and temperature.Dielectric loss is 10
-4On the level.In all resins, the dielectric constant of polytetrafluoroethylene and dielectric loss minimum.
Because polytetrafluoroethylene has outstanding dielectric property (low-k and low dielectric loss), good chemical stability and thermal stability, so the polytetrafluoroethylene copper-clad plate is mainly used in fields such as satellite communication, mobile radio communication, satellite broadcasting television, radar.
(4) inorganic filler
Add an amount of inorganic filler, help the improvement of product thermal coefficient of expansion (CTE).Particularly concerning the lead-free compatible copper-clad plate, the CTE of Z-direction is even more important, be the appointment of IPC standard must survey project.Require the CTE of sheet material the smaller the better.
Inorganic filler commonly used has silicon powder, boron nitride, magnesium oxide and aluminium oxide etc.
Solvent is a butanone; Curing accelerator is an imidazoles promoter
(5) NE glass cloth
In the FR-4 copper-clad plate is produced, continue to use traditional E glass cloth always.E glass cloth, though good combination property, the ratio of performance to price is also comparatively reasonable, and dielectric property are not good enough, and dielectric constant higher (Dk6.6) has influenced product applying in the high frequency field.In recent years, the glass industry has successfully been developed a kind of new E glass cloth (NE glass cloth).NE glass cloth has outstanding dielectric property, dielectric constant 4.4, and also other performances are similar to E glass cloth.The application of NE glass cloth helps the improvement of product dielectric property.
The present invention compared with prior art has the following advantages and good effect:
High thermal reliability, outstanding dielectric property, low thermal coefficient of expansion, outstanding anti-flammability, not brominated, meet the RoHS command request.
Embodiment
In conjunction with the embodiments invention is further described
Embodiment 1:
Get 35 parts of polyfunctional epoxy resins, 23 parts of phosphorus containing phenolic resins, 21 parts of PTFE, 20 parts of silicon powders and 1 part of imidazoles promoter, add an amount of butanone and make solvent, under fully stirring, be mixed with solids content and be 65% resin solution.
With 2116NE glass cloth, the above-mentioned resin solution of impregnation,, make bonding sheet through 170 ℃ of bakings 5 minutes.The resin content of bonding sheet is 53%, and resin flow is 20%.
Get 8 bonding sheets, superimposed neat, the two-sided 35 μ m electrolytic copper foils of mixing are sandwiched between two blocks of mirror face stainless steel plates then, place vacuum press, at 195 ± 3 ℃, 30Kg/cm
2Condition under, double face copper is made in hot pressing 90 minutes.The copper-clad plate test result sees Table 1.
Embodiment 2:
Get 37 parts of polyfunctional epoxy resins, 25 parts of phosphorus containing phenolic resins, 20 parts of PTFE, 17 parts of silicon powders and 1 part of imidazoles promoter, add an amount of butanone and make solvent, under fully stirring, be mixed with solids content and be 65% resin solution.
With 2116NE glass cloth, the above-mentioned resin solution of impregnation,, make bonding sheet through 170 ℃ of bakings 5 minutes.The resin content of bonding sheet is 53%, and resin flow is 21%.
Get 8 bonding sheets, superimposed neat, the two-sided 35 μ m electrolytic copper foils of mixing are sandwiched between two blocks of mirror face stainless steel plates then, place vacuum press, at 195 ± 3 ℃, 30Kg/cm
2Condition under, double face copper is made in hot pressing 90 minutes.The copper-clad plate test result sees Table 1.
Comparative example 1:
Get 43 parts of polyfunctional epoxy resins, 28 parts of phosphorus containing phenolic resins, 28 parts of silicon powders and 1 part of imidazoles promoter.Other conditions are with reference to embodiment 1.The copper-clad plate test result sees Table 1.
Comparative example 2:
Get 43 parts of polyfunctional epoxy resins, 28 parts of phosphorus containing phenolic resins, 28 parts of PTFE and 1 part of imidazoles promoter.Other conditions are with reference to embodiment 1.The copper-clad plate test result sees Table 1.
Table 1:
Method of testing:
(1) vitrification point (Tg), method of testing adopts dynamic mechanical analysis method (DMA).
(2) heat decomposition temperature (Td), method of testing adopts thermogravimetry (TGA).
(3) the thermally stratified layer time (T-288), method of testing adopts thermomechanical analysis (TMA).
(4) thermal coefficient of expansion (CTE), method of testing adopts thermomechanical analysis (TMA).
(5) flammability is by U.S. UL94 vertical combustion method.
Claims (7)
1, lead-free compatible high frequency copper clad laminate, preparation process is as follows: a) preparation resin combination; B) make bonding sheet with NE glass cloth; C) make copper-clad plate; It is characterized in that: wherein the resin combination in a step is made up of the raw material of following weight portion:
30～45 parts of polyfunctional epoxy resins
20～30 parts of phosphorus containing phenolic resins
20～30 parts of polytetrafluoroethylene
0.5～1.5 part of curing accelerator
20～30 parts of inorganic fillers
Solvent is an amount of.
2, lead-free compatible high frequency copper clad laminate according to claim 1 is characterized in that: described polyfunctional epoxy resin has: the novolac epoxy resin of phenol type novolac epoxy resin, bisphenol A-type novolac epoxy resin and biphenyl contenting structure.
3, lead-free compatible high frequency copper clad laminate according to claim 1 is characterized in that: described phosphorus containing phenolic resin is to introduce phosphorus-containing groups in the phenolic resins structure, makes phosphorus containing phenolic resin.
4, lead-free compatible high frequency copper clad laminate according to claim 1 is characterized in that: described curing accelerator is an imidazoles promoter.
5, lead-free compatible high frequency copper clad laminate according to claim 1 is characterized in that: described inorganic filler has silicon powder, boron nitride, magnesium oxide and aluminium oxide.
6, lead-free compatible high frequency copper clad laminate according to claim 1 is characterized in that: described solvent is a butanone.
7, according to the described lead-free compatible high frequency copper clad laminate of claim 1-6, it is characterized in that: get the raw material of above-mentioned weight portion, join in an amount of solvent, be mixed with resin combination solution, its solid content is 50%～70%, and gelation time is 150 seconds～250 seconds, and gelling temperature is 171 ℃.
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| CNB2007100272025A CN100539803C (en) | 2007-03-16 | 2007-03-16 | Lead-free compatible high frequency copper clad laminate and preparation method thereof |
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| CNB2007100272025A CN100539803C (en) | 2007-03-16 | 2007-03-16 | Lead-free compatible high frequency copper clad laminate and preparation method thereof |
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| CN101733993B (en) * | 2008-11-07 | 2013-07-03 | 福建新世纪电子材料有限公司 | Manufacturing method of lead-free copper-clad plate |
| CN102223762B (en) * | 2010-04-13 | 2012-09-12 | 北京联合大学 | High-precision jacquard glass fiber fabric |
| CN102234363B (en) * | 2010-05-06 | 2014-02-19 | 宏泰电工股份有限公司 | Halogen-free flame-retardant resin composition |
| CN101942180B (en) * | 2010-09-08 | 2012-05-30 | 广东生益科技股份有限公司 | Epoxy resin composition and copper clad laminate manufactured by using same |
| CN102069615A (en) * | 2010-11-11 | 2011-05-25 | 广东生益科技股份有限公司 | Fabrication method of copper-clad plate |
| CN102173175A (en) * | 2011-02-24 | 2011-09-07 | 禹胜林 | Preparation method of modified polytetrafluoroethylene copper clad plate |
| CN102173172B (en) * | 2011-02-24 | 2013-09-18 | 禹胜林 | Method for preparing polytetrafluoroethylene copper-clad plate |
| CN102260378B (en) * | 2011-05-06 | 2013-03-20 | 广东生益科技股份有限公司 | Composite material, high-frequency circuit board manufactured therefrom and manufacturing method of high-frequency circuit board |
| CN103129042B (en) * | 2013-01-30 | 2015-09-16 | 广东生益科技股份有限公司 | A kind of carbon fiber base fabric composite material and Synthesis and applications thereof |
| CN103923589A (en) * | 2014-05-07 | 2014-07-16 | 新高电子材料（中山）有限公司 | Low-dielectric constant adhesive for flexible printed circuit board and application method thereof |
| CN104149420A (en) * | 2014-05-12 | 2014-11-19 | 华东理工大学 | Preparation for non-sintered forming of high-performance polytetrafluoroethylene copper-clad laminate for high-frequency communication |
| CN105175995B (en) * | 2015-08-03 | 2018-05-04 | 广东生益科技股份有限公司 | A kind of copper-clad plate composition epoxy resin and its application |
| CN106113802B (en) * | 2016-08-16 | 2018-04-13 | 中国电子科技集团公司第三十八研究所 | A kind of preparation method for the microwave copper-clad plate for reducing Z axis thermal coefficient of expansion |
| CN107141724A (en) * | 2017-07-05 | 2017-09-08 | 无锡宏仁电子材料科技有限公司 | It is a kind of for the Halogen of automobile copper-clad plate, resistance to CAF, high Tg, high heat resistant resin composition |
| CN107793515A (en) * | 2017-10-12 | 2018-03-13 | 江门建滔电子发展有限公司 | Tetrafluoroethene ethenol copolymer and the prepreg using its preparation and copper-clad plate |
| CN113799419A (en) * | 2021-09-13 | 2021-12-17 | 贵溪奥泰铜业有限公司 | Production method of copper-clad plate |
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