CN100562211C - Polybutadiene thermosetting resin printed circuit carrier plate is formed and method for making - Google Patents
Polybutadiene thermosetting resin printed circuit carrier plate is formed and method for making Download PDFInfo
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- CN100562211C CN100562211C CNB2006100994722A CN200610099472A CN100562211C CN 100562211 C CN100562211 C CN 100562211C CN B2006100994722 A CNB2006100994722 A CN B2006100994722A CN 200610099472 A CN200610099472 A CN 200610099472A CN 100562211 C CN100562211 C CN 100562211C
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Abstract
A kind of high-performance printed circuit carrier plate material, comprise the HMW polybutadiene of a high-vinyl-content and low molecular weight polybutadiene resin and have the cyclic olefins of two and two above vinyl double bonds and/or have acrylic acid, acrylontrile and polymerization thermosetting resin composition that the high molecular polymer of butadiene polymerization gained combines that its content accounts for 20～35wt% of total composition; Glass fabric reinforcement material accounts for 10～30wt%; The inorganic particulate filler accounts for 25～50wt%; Metallic coagents accounts for 1～10wt%; The bromine incombustible agent accounts for 10～30wt%.Above-mentioned prescription is made film with solvent dilution after the impregnation, under 170～220 ℃, and 20～50Kg/cm
2Pressing under the pressure, the circuit support plate composition that can obtain having excellent properties.
Description
Technical field
The present invention is relevant a kind of printed circuit carrier plate material, is main material with polybutadiene (polybutadiene) thermosetting resin, adds peroxide cure initiator or crosslinking agent etc. to form the insulating barrier on the copper clad laminate.And for meeting the processing procedure needs, selectivity adds the inorganic particulate filler (as silica) and the metal promoter (Metallic coagent) of high surface.So can make the film of making almost not have stickiness, allow the operator be easy to handle, and this low-viscosity feature help automated process, and can be suitable for the operation of general hot press.Made film among the present invention wherein, its viscosity is quite low, but can not cause slip when its viscosity is in pressing under the normal temperature.Be added with unique Metallic coagent during resin of the present invention is formed, can improve peel strength, be best suited for high-frequency electronic circuit support plate.
Background technology
Be that main material for example adds made circuit support plate such as adhesive-bonded fabric reinforcement material, particle filler, curing initiator, brominated incombustible agent with polybutadiene in the past:
United States Patent (USP) 4,241, the composition of the circuit support plate of mentioning in 132, (Ricon 150,70wt%1,2-addition polybutadiene rubber to comprise the polybutadiene polymer, sartomer) and fibrous reinforcement material, for example fiber of forming by polypropylene (polypropylene).And in this insulation compositing formula, the dielectric constant of its resin or fissipation factor need and the fibrous reinforcement material matches.Its shortcoming is:
1. the polybutadiene of Shi Yonging, its ethene (Vinyl) base is not enough, the substrate intensity difference.
2. there is not flame retardancy.
United States Patent (USP) 4,997, the composition of the circuit support plate of mentioning in 702 except that epoxy resin, also comprises inorganic filler or fibrous reinforcement material, accounts for 20～70wt% of total composition.Wherein fiber comprises glass or polymer fiber, and filler comprises clay or mineral matter (as silica) particle filler.Also have distinct disadvantage to be:
1. use epoxy resin to make substrate, (Dk, Df) is poor for its electrical properties, the hydroscopicity height.
2. use adhesive-bonded fabric, substrate intensity is relatively poor.
United States Patent (USP) 5,223, the circuit support plate thermosetting of describing in 568 is formed, and comprising:
A. be that liquid and molecular weight are less than 5,000 polybutadiene or polyisoprene (polyisoprene) resin in room temperature
B. butadiene (butadiene) or isoprene (isoprene) solid polymer that aggregates into polybutadiene or polyisoprene resin crosslinks
C. during hot setting, temperature is greater than 250 ℃, and is lower than the thermal cracking temperature of composition.
Though though circuit carrier plate material rerum natura of mentioning network not in this invention, but still following shortcoming is still arranged:
1. need hot setting (hot pressing temperature＞250 ℃).Because of traditional circuit support plate manufacturing equipment often is present in the restriction of 180 ℃ of temperature, and brominated incombustible agent also can not bear 250 ℃ of high temperature, can decompose under this high temperature or chemical cracking infringement material property.
2. the made film viscosity of its polybutadiene or polyisoprene resin is big, and the pressing operation of continuous and automatic circuit support plate is difficulty very.
United States Patent (USP) 6,048, institute's substrate of carrying is formed in 807, comprising:
A.10～the 75vol.% thermosetting resin forms, and wherein comprises molecular weight less than 5,000 polybutadiene or polyisoprene resin, and contain the unsaturated di-block polymer of butadiene;
B. vinyl propylene (ethylene propylene MW＜50 that are less than 14vol.%, 000) liquid rubber can be terpolymer or its combination of the diene (diene) (as dicyclopentadiene or ethylidene norbornene) of ethylene propylene co-polymer (copolymer) or ehtylene propylene;
C. particle filler; And
D. weave cotton cloth
Its shortcoming is:
1. the circuit support plate must just can obtain with HTHP (300 ℃, more than the 500psi) processing procedure, and brominated incombustible agent can decompose or chemical cracking no flame retardancy under this high temperature.
2. proportion of filler accounts for more than the 50wt%, even reaches 70wt%.With regard to existing most of equipment, difficult treatment during impregnation, and the abrasion of drill point are very big when circuit support plate boring processing procedure, increase the processing difficulties degree of its processing procedure simultaneously.
United States Patent (USP) 6,071, its circuit support plate is formed in 836 following several characteristics:
A. a high proportion of particle filler scope makes film almost not have viscosity and operation easily, is easy to processed;
B. electrical properties (dielectric constant, fissipation factor and dielectric strength) excellence has good thermal insulation and non-conductive characteristic;
C. for particle filler at high proportion, has only a spot of glass fabric reinforcement material, in order to improve the thermal coefficient of expansion of Z-direction;
D. the hot pressing process temperatures is lower than 250 ℃, avoids cracking; And
E. be added with silane, the then intensity that increases resin and Copper Foil and weave cotton cloth.
Though show that by above-mentioned data the character that its circuit support plate forms is quite excellent, but still still have following shortcoming to need further improvement:
1. peel strength is very poor, even add silane is arranged, and also is lower than 5lbf/inch;
2. no matter to water or to the hydroscopicity of toluene, all belong to higher;
3. proportion of filler accounts for more than the 50wt%, even 70wt% nearly, with regard to existing most of equipment, and difficult treatment during impregnation not only, and the abrasion of drill point are very big when PCB boring processing procedure, processing difficulties.
Except that United States Patent (USP), other technical literature also has mentions the application of polybutadiene on the circuit carrier plate material.N.Sawatari et al. for example, Ieee Transactions on ElectricalInsulation, Vol.EI-18, No.2, Apr.1983 publication, wherein relevant new fire proofing material 1, the 2-polybutadiene substrate just mentions 1, and 2-polybutadiene is in semi-cured state (B stage) operating difficulties, and being difficult to does not have stickiness, and be highly combustible, relatively poor with the Copper Foil property followed.Though the policy that document proposition addresses these problems, promptly in it is formed, use a large amount of HMW polybutadiene to eliminate outside the viscosity of B stage, also use a spot of low-molecular-weight upgrading polybutadiene resin to help the joint of Copper Foil and the flowability during the pressing.But do not mention the filler that uses any kind.Also having in European patent 0202488A2 with polybutadiene is the circuit support plate of main resin, wherein adds the brominated prepolymer of HMW (prepolymer), reduces polybutadiene film viscosity and flammable report.04,258,658 of Japan Patents add high-molecular weight compounds control viscosity in addition, and this kind compound mainly provides flame retardancy, and preferable Copper Foil property followed and thermal endurance.Do not mention and use other filler, but this circuit support plate still has than higher fissipation factor shortcoming.
Mention traditional polybutadiene resin in " 1 of electronics industry; 2-polybutadiene high performance resin (by R.E Drake; ANTEC 84pp.730-733; 1984) " and be made for the circuit substrate use, and clearly mention the reactive monomer report that solidifies usefulness with polybutadiene jointly.
U.K.Patent Applocation No.2172892 then mentions the general circuit support plate by styrene and the undersaturated pair of thermoplastic resin resin copolymer that key and polybutadiene formed.
Summary of the invention
In view of the pertinent literature of above-mentioned prior art report, the present invention mainly is that to improve with polybutadiene be electric, the chemistry and the heat-resistant quality of the support plate of circuit in the past of main material.Comprise its flame resistance, thermal coefficient of expansion, dielectric constant, fissipation factor, viscosity, bond strength and production cost, a kind of polybutadiene thermosetting resin circuit support plate constituent and method for making thereof of novelty is provided.
First purpose of the present invention provides carries out cross-linking reaction with a large amount of unsaturated ethylene thiazolinyls and generates the circuit support plate with good high temperature resistant rerum natura and form.
Second purpose of the present invention is the selection of the amount of filler and the kind that provide suitable, to generate the very low film of viscosity, is easy to the pressure programming operation, and the circuit support plate with the promptly lower dielectric constant of excellent electric character and fissipation factor is formed.
The 3rd purpose of the present invention provides a kind of circuit support plate that uses general Copper Foil also can reach the above peel strength of 4～5lbf/inch and forms.
The 4th purpose of the present invention provides a kind of circuit support plate lower than the copper clad laminate hydroscopicity of existing general use and forms.
The 5th purpose of the present invention provides a kind of temperature at lower (170～220 ℃) and carries out substrate heat compacting journey, avoids the thermal endurance of the cleaved destruction circuit of bromine incombustible agent support plate.
For achieving the above object, high performance circuit carrier plate material constituent provided by the invention comprises:
(1) thermosetting resin base material, the 20～35wt% that accounts for assembly wherein comprises:
(a) polybutadiene thermosetting resin of high-vinyl (more than the 70wt%), its molecular weight is MW=100, the above and MW=5 of 000g/mol, 000～10, two kinds of molecular weight ranges of 000g/mol mix; And
(b) a kind of cyclic olefins with above vinyl double bond more than two and two, and/or be the high molecular polymer with acrylic acid, acrylontrile and butadiene polymerization gained;
The glass fabric reinforcement material of (2) 10～30wt%;
The inorganic particulate filler of (3) 25～50wt%;
(4) 1～10wt% metal promoters (Metallic coagents); And
(5) 10～30wt% bromine incombustible agents
(6) and comprise peroxide sclerosis initiator
Constitute.
The constituent of described circuit carrier plate material, the shared preferred proportion of its thermosetting resin base material is 25～32wt%.
The ratio that the constituent of described circuit carrier plate material, its polybutadiene thermosetting resin account for the thermosetting resin base material is 40～90wt%.
The constituent of described circuit carrier plate material, its a kind of cyclic olefins with two and two above vinyl double bonds, and/or be that the ratio that high molecular polymer with acrylic acid, acrylontrile and butadiene accounts for the thermosetting resin base material is 10～60wt%.
The constituent of described circuit carrier plate material, its contain high-vinyl-content polybutadiene thermosetting resin 1, the 2-addition contents of ethylene is preferably more than 80wt%.
The constituent of described circuit carrier plate material, its MW=100, the above and MW=5 of 000g/mol, 000～10, the proportion of two kinds of resins of 000g/mol is 40: 80 to 60: 20.
The constituent of described circuit carrier plate material, the preferable ratio of its glass fabric reinforcement material is 10～20wt%.
The constituent of described circuit carrier plate material, the preferable ratio of its inorganic particulate filler is 30～45wt%.
The constituent of described circuit carrier plate material, the preferable ratio of its Metallic coagents is 1～5wt%.
The constituent of described circuit carrier plate material, its Metallic coagents is selected from alkali metal group, alkaline earth or zinc element and acrylic acid reacts formed complex compound.
The constituent of described circuit carrier plate material, it is preferably metallic diacrylate or metallicdimethacrylate.
The constituent of described circuit carrier plate material, its inorganic particulate filler is selected from titanium dioxide, barium titanate, strontium titanates or silica.
The constituent of described circuit carrier plate material, its preferable inorganic particulate filler is selected from the silica after unbodied silica or the sintering processes.
The constituent of described circuit carrier plate material, the preferable ratio of its bromine incombustible agent is 15～25wt%.
The constituent of described circuit carrier plate material, its preferable bromine incombustible agent is selected from ethylenebistetrabromophthalimide, tetradecabromodiphenoxy benzene or dexabromodiphenoxy oxide.
The present invention makes the method for high performance circuit carrier plate material constituent, gets:
(1) thermosetting resin base material accounts for 20～35wt% of assembly, wherein contains:
(a) polybutadiene thermosetting resin of high-vinyl-content (more than the 70wt%), its molecular weight is MW=100, the above and MW=5 of 000g/mol, 000～10, two kinds of molecular weight ranges of 000g/mol mix; And
(b) a kind of cyclic olefins with above vinyl double bond more than two and two, and/or be the high molecular polymer with acrylic acid, acrylontrile and butadiene polymerization gained;
The glass fabric reinforcement material of (2) 10～30wt%;
The inorganic particulate filler of (3) 25～50wt%;
(4) 1～10wt%Metallic coagents; And
(5) 10～30wt% bromine incombustible agents;
(6) and comprise the peroxide cure initiator
With above-mentioned batching with solvent dilution to suitable viscosity, at 170～220 ℃ temperature and 20～50kg/cm
2Carried out pressing plate generative circuit support plate under the scope of pressure.
Described circuit support plate method for making, its glass fabric after 130 ℃ of semi-solid preparations are film 5～8 in storehouse its coat Copper Foil up and down and carry out hot pressing, its optimum temperature is that 195 ℃ of pressure are 30kg/cm
2
The present invention contains the polybutadiene thermosetting resin of high-vinyl-content in above-mentioned compositing formula.This resinoid contains 1 more than 85% of total composition, and the 2-addition vinyl can provide a large amount of unsaturated ethylene thiazolinyls to carry out cross-linking reaction, can form the highest crosslink density after curing.So can provide the circuit support plate good high-temperature stability.
Another technical characterictic of the present invention is that its prescription is formed via the suitable amount of filler and the selection of filling kind, make that varnish (varnish) viscosity is not high to be easy to impregnation, and behind semi-solid preparation, film layers and interlayer almost do not have viscosity, not only be easy to pressing, and improve Z axle thermal coefficient of expansion and dielectric property (for example fissipation factor), reduce the processing procedure cost.The most important thing is to be used in known existing substrate heat compacting journey, and can be applicable to the hot pressing processing procedure of lower temperature.
Except that above-mentioned technical characterictic, of paramount importance technical characterictic is among the present invention;
1. add the peel strength of 1 to 10wt%Metallic coagents increase resin and metal, can reach the purpose that enhancing resin and metal are followed intensity thus;
2. the curing temperature during hot pressing is low, and its hot pressing temperature can be carried out in 170～220 ℃ scope usually.Low-temperature setting not only can be avoided the brominated incombustible agent cracking that adds, and can be used in general circuit loading plate manufacturing process equipment again.Can use an amount of organic peroxide, for example dicumyl peroxide (DCP) and t-butyl perbenzoate peroxide (TBPB) in lower curing temperature simultaneously.
Embodiment
Below will be used for resin base material of the present invention, filler, Metallic coagents, crosslinking agent, glass cloth, incombustible agent and peroxide cure initiator and its source, be described in detail successively.
One, resin base material
The employed resin base material of circuit carrier plate material of the present invention is that a thermosetting resin is formed, and comprises (1) polybutadiene resin; And (2) are a kind of has the cyclic olefins of two or two above vinyl double bonds and/or a high molecular polymer that (3) have acrylic acid (acrylic acid), acrylonitrile (acrylonitrile), butadiene (butadiene) polymerization gained, during curing participate in cross-linking reaction.
(1) Polybutadiene resin wherein, in room temperature may be solid or liquid, but one is decided to be a HMW hard resin (MW=100, more than the 000g/mol) and low-molecular-weight liquid resin (MW=5,000～10, blending thing 000g/mol), and its 1, the 2-addition contents of ethylene is more than 70wt%, and is then better more than the 90wt%.Required a large amount of unsaturated ethylene thiazolinyls when the polybutadiene resin of its high-vinyl-content can provide curing cross-linked, and when crosslinked, can increase bridge formation density, provide the circuit support plate to have a good high-temperature stability.Best high molecular weight resin is that RB is resin such as RB810, RB820 and RB830, and 1,2 addition polybutadiene hard resin greater than 90wt% is arranged.The RB series plastics is commercial can be obtained from Japanese Japan Synthetic Rubber company.And low-molecular-weight liquid resin such as Ricon153 and Ricon154 resin (Sartomer company product) or resins such as B3000 and B1000 preferable (Nippon Soda company product).
Another kind of thermosetting resin (2) is for to have the vinyl double bond cyclic olefins more than two and two and/or to have acrylic acid, acrylonitrile and the high molecular polymer of butadiene polymerization gained.The cyclic olefins that wherein has two or two above vinyl double bonds can utilize vinyl double bond to carry out outside the cross-linking reaction, and the cyclic olefins on its strand also can reduce hydroscopicity and dielectric constant and dielectric loss, this type of cyclic olefins is containing alkene (metallocene) metal solvent, and is synthetic by monomer reactions such as vinyl, bornylene and vinyl bornylenes:
(a) cyclic olefine copolymer (COC-A) is synthetic:
With highly purified bornylene (NB, norbornene) 4.01kg, ENB (5-Ethylidene-2-norbornene) 2.27kg and 2.59kg toluene are inserted in the reaction under high pressure groove, are warming up to the 10wt% accelerator (MAO/ toluene) and 6 * 10 that injects 0.2kg after 100 ℃
-5Behind the metallocene catalyst of kg, feed ethene (800ml/min) and hydrogen (50ml/min) gaseous mixture, at 18kg/cm
2Begin to carry out polymerization reaction under the pressure.The back adding dilution with toluene that reaction is finished is filtered with in the hydrochloric acid and back to solid 10wt%, gets filtrate and adds in a large amount of acetone, promptly get cycloolefin co-polymer (COC-A) after the solid oven dry that sedimentation is separated out, its molecular weight Mw=41,000g/mol, Tg=125 ℃.
(b) cyclic olefine copolymer (COC-B) is synthetic:
To react in high temperature behind the DCPD adding 1-Hexene, can get Butyl-NB, insert in the reaction under high pressure groove with highly purified Butyl-NB 2kg, NB (norbornene) 1kg, ENB (5-etheylidene-2-norbornene) 2kg and 1kg toluene, be warming up to 100 ℃ of 10wt% accelerators (MAO/ toluene) and 2 * 10 that inject 0.08kg
-5Behind the metallocene catalyst of kg, feed ethene (800ml/min) and hydrogen (50ml/min) gaseous mixture, at 10kg/cm
2Begin to carry out polymerization reaction under the pressure.The back adding dilution with toluene that reaction is finished is filtered with in the hydrochloric acid and back to solid 10wt%, gets filtrate and adds in a large amount of acetone, promptly gets cycloolefin co-polymer (COC-B) after the solid oven dry that sedimentation is separated out.Its molecular weight Mw=66,000g/mol, Tg=123 ℃.
(c) cyclic olefine copolymer (COC-C) is synthetic:
The Hexyl-NB that adds the synthetic long-chain of 1-octene with DCPD, insert in the reaction under high pressure groove with highly purified Hexyl-NB2.2kg, ENB (5-etheylidene-2-norbornrne) 2.8kg and 1kg toluene, be warming up to the 10wt% accelerator (MAO/ toluene) and 2 * 10 that injects 0.08kg after 100 ℃
-5Behind the metallocene catalyst of kg, feed ethene (800ml/min) and hydrogen (50ml/min) gaseous mixture, at 10kg/cm
2Begin to carry out polymerization reaction under the pressure.The back adding dilution with toluene that reaction is finished is filtered with in the hydrochloric acid and back to solid 10wt%, gets filtrate and adds in a large amount of acetone, can obtain cycloolefin co-polymer (COC-C) after the solid oven dry that sedimentation is separated out.Its molecular weight Mw=70,500g/mol, Tg=107 ℃.
And the high molecular polymer of another resin (3) acrylic acid, acrylonitrile and butadiene polymerization gained in addition then can increase the intensity of following of resin and Copper Foil.Carboxyl terminatedbutadiene acrylonitrile rubber series (as CTBN1300 * 8, CTBN1300 * 13, CTBN1300 * 31 etc.) for example, commercial can the acquisition from Noveon company.
Two, particle-filled material
Particle filler used in the present invention comprises that titanium dioxide, barium titanate, strontium titanates, silica (comprise amorphous silica and sintering processes after silica) account for 25～50wt% of total composition, and best ratio is between 30～45wt%.They can be used alone or in combination in processing procedure.Wherein Zui Jia filler is an amorphous silica, selects the high surface area person of tool as far as possible, as the silica behind the sintering.Because of the high surface person reduce aspect the stickiness more effective than the amorphous silica (being generally 10 μ m) of standard.Wherein silica is sintering silica AEROSIL200 later preferably, can obtain from Degussa company, is characterized in having about 200m
2The surface area of/g and the particle size of 12nm.Other also has CE44I (10micron amorphous Silica, CE Minerals), FB-35 (Fused Silica, Denka), Minsil 5 (Fused Silica, Minco), Min-sil 20 (Fused Slica, Minco), Novacite325 (Natural crystalline silica, Minerals), (Fused Silica HarbisonWalker) waits filler to GP7I.
Three, metal promoter (Metallic coagent)
The metal promoter that the present invention uses (Metallic coagent) reacts formed complex compound as alkali metal group, alkaline earth or zinc element and acrylic acid, this type of reagent is generally metallicdiacrylate (as SR633, SR636, SR638, SR705, SR706), and metallicdimethacrylate (as SR634, SR708), with metallic monomethacrylate (SR709) etc., produce by Sartomer company.In the curing process of processing procedure, because the reaction of Metallic coagent is higher, can react with the peroxide cure initiator earlier, formation contains free radical (Free Radical) compound, contain two key resins with polybutadiene resin or other again and carry out cross-linking reaction, make each strand all contain acrylate, therefore just can reach the purpose that enhancing resin and Copper Foil are followed intensity.
Four, crosslinking agent
For improving the degree of cross linking of thermosetting resin, crosslinking agent of the present invention comprises:
Triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, divinylbenzene or its combination.
Five, glass cloth
Glass cloth used in the present invention accounts for 10～30wt% of assembly, and the glass cloth that uses the South Asia Plastics Company to produce is the reinforcement material, according to the glass cloth kind of substrate requirement use different-thickness, and its specification such as following table:
Six, incombustible agent
Incombustible agent used in the present invention is an incombustible agent based on bromine, and consumption is 10～30wt%.Preferable brominated incombustible agent as:
Saytex?BT?93W(ethylene?bistetrabromophthalimide)、
Saytex 120 (tetradecabromodiphenoxy benzene) or
Saytex?102(decabromo?diphenoxy?oxide)。
Seven, solidify initiator
Add the radically curing initiator and can quicken cross-linking reaction, when composition of the present invention was heated, initiator was decomposed to form free radical, initial afterwards cross-linking polymerization.Radically curing initiator preferably, as organic peroxide, dicumyl peroxide (DCP), t-butylperbenzoate (TBPB) and t-butylperoxy hexyne-3 is the curing agent of using always, general consumption is between 0.2～3wt%.
Embodiment
Mentioned its material that is adopted of trial-production circuit support plate of the embodiment of the invention except that above-mentioned three kinds of synthetic cyclic olefine copolymers, all the other materials such as following table:
Material specification and source that the circuit support plate is formed
Embodiment 1
Get the HMW polybutadiene rubber RB810 of 104.3 weight portions, the divinol rubber Ricon154 of 63.6 weight portions is with the cyclic olefine copolymer (COC-A) of 85.9 weight portions and the mixing and stirring such as CTBN1300 * 8 of 12.5 weight portions; Mix the SARET633 of 13.3 weight portions then, and add the silica filler (FB-35) of 429.5 weight portions, be after incombustible agent (SAYTEX8010), 8 weight portion crosslinking agents (TAIC), 8 weight portions curing initiators (DCP) evenly mix, with 163.2 weight portion bromines again with South Asia glass cloth (1080woven glass) impregnation of 111.7 weight portions.After 130 ℃ of semi-solid preparations were film, with 8 film storehouses, it coated with South Asia 1oz Copper Foil up and down, at 30kg/cm
2(426psi), circuit carrier plate material constituent was made in hot pressing in 3 hours under 195 ℃ of conditions, and its rerum natura metric data such as table one are listed.
Embodiment 2
Improve the RB810 that the COC-A consumption replaces part, promptly get the RB810 of 61.3 weight portions, the Ricon154 of 63.6 weight portions is again with the COC-A of 128.9 weight portions and the CTBN1300 of 12.5 weight portions * 8 mixing and stirring; Mix 13.3 weight portion SARET 633 then and add the FB-35 filler of 429.5 weight portions, again with 163.2 weight portion SAYTEX8010,8 weight portion TAIC, 8 weight portion DCP mixing and stirring after, with the 1080woven glass impregnation of 111.7 weight portions.After 130 ℃ of semi-solid preparations were film, with 8 film storehouses, it coated with South Asia 1oz Copper Foil up and down, at 30kg/cm
2(426psi), circuit carrier plate material constituent was made in hot pressing in 3 hours under 195 ℃ of conditions, and its rerum natura metric data such as table one are listed.
Embodiment 3
Reduce the COC-A consumption and to increase the RB810 replacement, promptly get the RB810 of 147.2 weight portions, the Ricon154 of 63.6 weight portions is with the COC-A of 43.0 weight portions and the CTBN1300 of 12.5 weight portions * 8 mixing and stirring; Mix 13.3 weight portion SARET 633 then and add the FB-35 filler of 429.5 weight portions, again with 163.2 weight portion SAYTEX8010,8 weight portion TAIC, 8 weight portion DCP mixing and stirring after, with the 1080woven glass impregnation of 111.7 weight portions.After 130 ℃ of semi-solid preparations were film, with 8 film storehouses, it coated with South Asia 1oz Copper Foil up and down, at 30kg/cm
2(426psi), circuit carrier plate material constituent was made in hot pressing in 3 hours under 195 ℃ of conditions, and its rerum natura metric data such as table one are listed.
Embodiment 4
The Ricon154 resin is replaced with Ricon153, promptly get the RB810 of 104.3 weight portions, the Ricon153 of 63.6 weight portions is with the COC-A of 85.9 weight portions and the CTBN1300 of 12.5 weight portions * 8 mixing and stirring; Mix 13.3 weight portion SARET 633 then and add the FB-35 filler of 429.5 weight portions, again with 163.2 weight portion SAYTEX8010,8 weight portion TAIC, 8 weight portion DCP mixing and stirring after, with the 1080woven glass impregnation of 111.7 weight portions.After 130 ℃ of semi-solid preparations were film, with 8 film storehouses, it coated with South Asia 1oz Copper Foil up and down, at 30kg/cm
2(426psi), circuit carrier plate material constituent was made in hot pressing in 3 hours under 195 ℃ of conditions, and its rerum natura metric data such as table one are listed.
Comparative example 1
Do not add SARET 633.Get the RB810 of 105.7 weight portions, CTBN1300 * 8 mixing and stirring of the Ricon154 of 64.5 weight portions and 87.1 weight portion COC-A and 12.6 weight portions; The FB-35 filler that adds 435.3 weight portions, again with 165.4 weight portion SAYTEX8010,8.1 weight portion TAIC, 8.1 weight portion DCP mixing and stirring after, with the 1080woven glass impregnation of 113.2 weight portions.After 130 ℃ of semi-solid preparations were film, with 8 film storehouses, it coated with South Asia 1oz Copper Foil up and down, at 30kg/cm
2(426psi), circuit carrier plate material constituent was made in hot pressing in 3 hours under 195 ℃ of conditions, and its rerum natura metric data such as table one are listed.
Comparative example 2
Replace RB810 resin, CTBN1300 * 8 mixing and stirring of promptly getting Ricon153 and the 85.9 weight portion COC-A and 12.5 weight portions of 104.3 weight portions with Ricon153; Mix the SARET 633 of 163.2 weight portions then, and add the FB-35 filler of 429.5 weight portions, again with 163.2 weight portion SAYTEX8010,8 weight portion TAIC, 8 weight portion DCP mixing and stirring after, with the 1080woven glass impregnation of 111.7 weight portions.After 130 ℃ of semi-solid preparations were film, with 8 film storehouses, it coated with South Asia 1oz Copper Foil up and down, at 30kg/cm
2(426psi), circuit carrier plate material constituent was made in hot pressing in 3 hours under 195 ℃ of conditions, and its rerum natura metric data such as table one are listed.
Table one
Physical Property Analysis:
Increase the COC-A consumption and can improve degree of peeling off a little, and reduce hydroscopicity; Influence not quite when low molecular weight polybutadiene rubber Ricon153 (molecular weight Mn＜5000) replaces the Ricon154 resin in the prescription, if but replacement RB810 (molecular weight Mn＞5000) then can make the peel strength variation, and weldering WU thermal endurance is obviously not enough.As shown in Table 1, mix SARET 633 (consumption is the 5phr of thermosetting resin) and can improve peel strength, do not have its peel strength variation of adding.
Embodiment 5
Reduce amount of filler.Get the RB810 of 141.5 weight portions, the Ricon154 of 75.9 weight portions is with the COC-A of 85.4 weight portions and the CTBN1300 of 14.9 weight portions * 8 mixing and stirring; Mix 15.9 weight portion SARET 633 then and add the FB-35 filler of 341.6 weight portions, again with 194.7 weight portion SAYTEX8010,9.5 weight portion TAIC, 9.5 weight portion DCP mixing and stirring after, with the 1080woven glass impregnation of 111.0 weight portions.After 130 ℃ of semi-solid preparations were film, with 8 film storehouses, it coated with South Asia 1oz Copper Foil up and down, at 30kg/cm
2(426psi), circuit carrier plate material constituent was made in hot pressing in 3 hours under 195 ℃ of conditions, and its rerum natura metric data such as table two are listed.
Embodiment 6
Improve the RB810 that the COC-A consumption replaces part, promptly get the RB810 of 98.8 weight portions, the Ricon154 of 75.9 weight portions is with the COC-A of 128.1 weight portions and the CTBN1300 of 14.9 weight portions * 8 mixing and stirring; Mix 15.9 weight portion SARET 633 then and add the FB-35 filler of 341.6 weight portions, again with 194.7 weight portion SAYTEX8010,9.5 weight portion TAIC, 9.5 weight portion DCP mixing and stirring after, with the 1080woven glass impregnation of 111.0 weight portions.After 130 ℃ of semi-solid preparations were film, with 8 film storehouses, it coated with South Asia 1oz Copper Foil up and down, at 30kg/cm
2(426psi), circuit carrier plate material constituent was made in hot pressing in 3 hours under 195 ℃ of conditions, and its rerum natura metric data such as table two are listed.
Embodiment 7
Reduce the COC-A consumption and to increase the RB810 replacement, promptly get the RB810 of 184.2 weight portions, the Ricon154 of 75.9 weight portions is with the COC-A of 42.7 weight portions and the CTBN1300 of 14.9 weight portions * 8 mixing and stirring; Mix 15.9 weight portion SARET 633 then and add the FB-35 filler of 341.6 weight portions, again with 194.7 weight portion SAYTEX8010,9.5 weight portion TAIC, 9.5 weight portion DCP mixing and stirring after, with the 1080woven glass impregnation of 111.0 weight portions.After 130 ℃ of semi-solid preparations were film, with 8 film storehouses, it coated with South Asia 1oz Copper Foil up and down, at 30kg/cm
2(426psi), circuit carrier plate material constituent was made in hot pressing in 3 hours under 195 ℃ of conditions, and its rerum natura metric data such as table two are listed.
Embodiment 8
Replace the Ricon153 resin with the Ricon154 tree, promptly get the RB810 of 141.5 weight portions, the Ricon153 of 75.9 weight portions is with the COC-A of 85.4 weight portions and the CTBN1300 of 14.9 weight portions * 8 mixing and stirring; Mix 15.9 weight portion SARET 633 then and add the FB-35 filler of 341.6 weight portions, again with 194.7 weight portion SAYTEX8010,9.5 weight portion TAIC, 9.5 weight portion DCP mixing and stirring after, with the 1080woven glass impregnation of 111.0 weight portions.After 130 ℃ of semi-solid preparations were film, with 8 film storehouses, it coated with South Asia 1oz Copper Foil up and down, at 30kg/cm
2(426psi), circuit carrier plate material constituent was made in hot pressing in 3 hours under 195 ℃ of conditions, and its rerum natura metric data such as table two are listed.
Comparative example 3
Do not add SARET 633.Get the RB810 of 143.8 weight portions, CTBN1300 * 8 mixing and stirring of the Ricon154 of 77.1 weight portions and 86.8 weight portion COC-A and 15.1 weight portions; The FB-35 filler that adds 347.1 weight portions, again with 197.9 weight portion SAYTEX8010,9.7 weight portion TAIC, 9.7 weight portion DCP mixing and stirring after, with the 1080woven glass impregnation of 112.8 weight portions.After 130 ℃ of semi-solid preparations were film, with 8 film storehouses, it coated with South Asia 1oz Copper Foil up and down, at 30kg/cm
2(426psi), circuit carrier plate material constituent was made in hot pressing in 3 hours under 195 ℃ of conditions, and its rerum natura metric data such as table two are listed.
Comparative example 4
Replace the RB810 resin with Ricon153, all the other steps are with embodiment 5.
Comparative example 5
The reduction proportion of filler is 25wt%, and the increase bromine is that the incombustible agent consumption makes circuit support plate base material can reach difficult combustion requirement.Get the RB810 of 164.1 weight portions, the Ricon154 of 88.1 weight portions is with the COC-A of 99.0 weight portions and the CTBN1300 of 16.6 weight portions * 8 mixing and stirring; Mix 18.4 weight portion SARET 633 then and add the FB-35 filler of 254.7 weight portions, again with 225.9 weight portion SAYTEX8010,11.1 weight portion TAIC, 11.1 weight portion DCP mixing and stirring after, with the 1080woven glass impregnation of 111.0 weight portions.After 130 ℃ of semi-solid preparations were film, with 8 film storehouses, it coated with South Asia 1oz Copper Foil up and down, at 30kg/cm
2(426psi), circuit carrier plate material constituent was made in hot pressing in 3 hours under 195 ℃ of conditions, and its rerum natura metric data such as table two are listed.
Table two
Physical Property Analysis:
Increase thermosetting resin consumption and raising SARET 633 usage ratio (consumption is the 5hr of thermosetting resin) can improve peel strength, and can reduce dielectric constant; But amount of filler is if be lower than total composition 30wt%, and then thermal endurance and flame retardancy all can variation.
Embodiment 9～16
Step is with embodiment 1～8, and the COC-A in just will forming changes COC-B into, and physical property measurement data that its circuit carrier plate material is formed such as table three and table four are listed.
Comparative example 6～10
Step is with comparative example 1～5, and the COC-A in just will forming changes COC-B into, and rerum natura metric data that the circuit carrier plate material is formed such as table three and table four are listed.
Table three
Table four
Embodiment 17～24
Step is with embodiment 1～8, and the COC-A in just will forming changes COC-C into, and physical property measurement data that its circuit carrier plate material is formed such as table five and table six are listed.
Comparative example 11～15
Step is with comparative example 1～5, and the COC-A in just will forming changes COC-C into, and physical property measurement data that its circuit carrier plate material is formed such as table five and table six are listed.
Table five
Table six
Physical Property Analysis:
Change the kind of the cyclic olefine copolymer in the thermosetting resin composition, very little to dielectric constant and fissipation factor influence, wherein COC-C is because of there being longer side chain, toughness is better than COC-B, more near rubber, the scolding tin thermal endurance is preferable in nature, and the COC-A of unprotected side chain is the poorest.But side chain is longer on the cyclic olefine copolymer, suction more easily, and peel strength also can reduce.
Effect of the present invention:
Each embodiment and the physical property measurement thereof above-mentioned by the present invention are worth knowing that the peel strength of (1) of the present invention copper clad laminate mainly is relevant with SARET 633 consumptions (5phr of thermosetting resin gross weight) and the amount of cyclic olefine copolymer, the two shared total proportion of composing is higher, and then its peel strength is just bigger.(2) dielectric property (Dk, Df) is subjected to having the greatest impact of thermosetting resin total amount, and the thermosetting resin ratio in the composition is higher, and Dk, Df are just lower, but hydroscopicity can increase.(3) consumption that increases cyclic olefine copolymer can reduce hydroscopicity, but its influence is more not remarkable.(4) high molecular weight resin (molecular weight Mn＞5 during scolding tin thermal endurance and thermosetting resin are formed, 000) ratio is relevant with the consumption of filler, at least to there be the above high molecular weight resin (as RB810, COC-A, COC-B, COC-C) of 15t% that excellent thermal endurance is just arranged in the thermosetting resin, and filler must account for total composition more than the 30wt%, and promptly the thermosetting resin consumption is no more than total composition 35wt%.(5) flame retardancy will meet the standard of UL-94V-0, mainly be to be that the ratio of incombustible agent and filler is relevant with bromine, because of the present invention is that the incombustible agent consumption is controlled at about bromine content 30wt% and (does not contain filler and woven glass) with bromine, therefore proportion of filler is if be lower than total composition 30wt%, flame retardancy variation then, and film can have bigger viscosity, is unfavorable for process operations.
As mentioned above, the present invention compares with general copper clad laminate, and circuit support plate of the present invention is formed and really had more excellent electrical properties, promptly has lower dielectric constant and a fissipation factor and a lower hydroscopicity.And aspect peel strength, use general Copper Foil just can reach 4～5lbf/inch, and use the 0.25lbf/inch of general Copper Foil PCB substrate to compare with other, character is improved a lot of.In addition, aspect thermal endurance, character is also better.Simultaneously when processing is solidified, hot pressing temperature need only 195 ℃, and must not do the back in high temperature (more than 250 ℃) again and solidify, and circuit support plate rerum natura is very excellent.
Though the present invention discloses as above with preferred embodiment, right its is not in order to limit the present invention, all any this technical staff that has the knack of, without departing from the spirit and scope of the present invention, when doing to change and retouching, technology of the present invention and interest field are defined with claim of the present invention and are as the criterion.
Claims (17)
1, a kind of high performance circuit carrier plate material constituent comprises:
(1) thermosetting resin base material accounts for 20～35wt% of assembly, wherein comprises:
(a) the above polybutadiene thermosetting resin of high-vinyl 70wt%, its molecular weight is weight average molecular weight=100, above and weight average molecular weight=5,000～10 of 000g/mol, two kinds of molecular weight ranges of 000g/mol mix; And
(b) a kind of cyclic olefins with two and two above vinyl double bonds, and/or be the high molecular polymer with acrylic acid, acrylonitrile and polymerizing butadiene gained;
The glass fabric reinforcement material of (2) 10～30wt%;
The inorganic particulate filler of (3) 25～50wt%;
(4) 1～10wt% metal promoters;
(5) 10～30wt% bromine incombustible agents; And
(6) comprise peroxide sclerosis initiator
Constitute;
The polybutadiene thermosetting resin composition consists of the blending thing of HMW hard resin and low-molecular-weight liquid resin, and 1,2-addition reaction contents of ethylene is more than 70wt%.
2, circuit carrier plate material constituent as claimed in claim 1, the shared ratio of its thermosetting resin base material is 25～32wt%.
3, circuit carrier plate material constituent as claimed in claim 2, the ratio that its polybutadiene thermosetting resin accounts for the thermosetting resin base material is 40～90wt%.
4, circuit carrier plate material constituent as claimed in claim 2, its a kind of cyclic olefins with two and two above vinyl double bonds, and/or be that the ratio that high molecular polymer with acrylic acid, acrylonitrile and butadiene accounts for the thermosetting resin base material is 10～60wt%.
5, circuit carrier plate material constituent as claimed in claim 2, its contain high-vinyl-content polybutadiene thermosetting resin 1,2-addition reaction contents of ethylene is more than the 80wt%.
6, circuit carrier plate material constituent as claimed in claim 1, in its polybutadiene thermosetting resin, its weight average molecular weight=100, above and weight average molecular weight=5 of 000g/mol, 000～10, the proportion of two kinds of resins of 000g/mol is 40: 80 to 60: 20.
7, circuit carrier plate material constituent as claimed in claim 1, the ratio of its glass fabric reinforcement material is 10～20wt%.
8, circuit carrier plate material constituent as claimed in claim 1, the ratio of its inorganic particulate filler is 30～45wt%.
9, circuit carrier plate material constituent as claimed in claim 1, the ratio of its metal promoter is 1～5wt%.
10, circuit carrier plate material constituent as claimed in claim 9, its metal promoter is selected from alkali metal group, alkaline earth or zinc element and acrylic acid reacts formed complex compound.
11, circuit carrier plate material constituent as claimed in claim 10, its metal promoter is diacrylate slaine or dimethylacrylate slaine.
12, circuit carrier plate material constituent as claimed in claim 1, its inorganic particulate filler is selected from titanium dioxide, barium titanate, strontium titanates or silica.
13, circuit carrier plate material constituent as claimed in claim 12, its preferable inorganic particulate filler is selected from the silica after unbodied silica or the sintering processes.
14, circuit carrier plate material constituent as claimed in claim 1, the ratio of its bromine incombustible agent is 15～25wt%.
15, circuit carrier plate material constituent as claimed in claim 14, its bromine incombustible agent is selected from 1, two (tetrabromo phthalimide) ethane of 2-, ten tetrabromo two (phenoxy group) benzene or deca-BDEs.
16, a kind of manufacture method of circuit support plate, with metal promoter with the described circuit carrier plate material of claim 1 constituent with solvent dilution to suitable viscosity, at 170～220 ℃ temperature and 20～50kg/cm
2Carry out pressing plate generative circuit support plate under the scope of pressure.
17, circuit support plate manufacture method as claimed in claim 16, its glass fabric after 130 ℃ of semi-solid preparations are film 5～8 in storehouse its coat Copper Foil up and down and carry out hot pressing, its temperature is 195 ℃, pressure is 30kg/cm
2
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| TWI513747B (en) * | 2011-06-13 | 2015-12-21 | Nanya Plastics Corp | A high frequency copper foil substrate and the composite material used |
| CN104698750A (en) * | 2013-12-04 | 2015-06-10 | 乐凯华光印刷科技有限公司 | Photosensitive composition for photopolymerization type lithographic plate |
| CN105130274B (en) * | 2015-07-15 | 2017-07-21 | 中国电子科技集团公司第四十六研究所 | A kind of microwave composite medium substrate of high thermal stability and preparation method thereof |
| CN105130423B (en) * | 2015-07-15 | 2017-05-24 | 中国电子科技集团公司第四十六研究所 | Preparation technology of microwave composite dielectric substrate based on barium titanate-type ceramic powder |
| TWI614325B (en) * | 2015-12-07 | 2018-02-11 | 臻鼎科技股份有限公司 | Resin composition, film and circuit board using the same |
| CN108148332A (en) * | 2016-12-02 | 2018-06-12 | 臻鼎科技股份有限公司 | The film and circuit board of resin combination and the application resin combination |
| CN113121943B (en) | 2019-12-31 | 2022-11-29 | 广东生益科技股份有限公司 | Thermosetting resin composition, and prepreg, laminated board and printed wiring board using thermosetting resin composition |
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