CN1493610A - Modified dimaleimide resin and its preparation method and application in cladding copper plate - Google Patents
Modified dimaleimide resin and its preparation method and application in cladding copper plate Download PDFInfo
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- CN1493610A CN1493610A CNA031345034A CN03134503A CN1493610A CN 1493610 A CN1493610 A CN 1493610A CN A031345034 A CNA031345034 A CN A031345034A CN 03134503 A CN03134503 A CN 03134503A CN 1493610 A CN1493610 A CN 1493610A
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Abstract
A modified bimaleimid resin is prepared from bimaleimide resin, allyl compound, epoxy resin, solidifying agent, and promoter. It can be used to prepare the substrate of copper coated board, which has high resistance to high temp (15-280 deg.C), low loss, high fire retarding performance and thermal and wet stability, and excellent mechanical performance. It can be used for computer, satellite communication equipment, mobile telephone, etc.
Description
One, technical field:
The present invention relates to field of compound material; Be a kind of modified bismaleimide resin and preparation method thereof and its application specifically as the copper-clad plate base material.
Two, technical background:
Since the last century the nineties, the development that with robot calculator, mobile telephone etc. is world's electronics and information industry of representative is maked rapid progress, the total amount of whole world electronic product is with the speed increase in every year about 13%, and electronic product has become the industry of current whole world maximum.Meanwhile, electronic product constantly develops to compactization, high performance and low-cost direction, and the circuit bank packing technique is also towards high-density, mini-development.This all requires must have more, higher, more excellent performance as the copper-clad plate of printed circuit board (PCB) base mateiral, mainly shows high heat resistance, high moisture-proof heat, low-k and aspects such as dielectric loss, high-dimensional stability and environmental protection; Carry out the importance and the urgent extensive concern in the world that caused of correlative study.
At present, the baseplate material that is applied to copper-clad plate preparation mainly contains thermosetting resin and thermoplastic resin two big classes.Thermosetting resin mainly contains Resins, epoxy and modified resin thereof, and the Resins, epoxy that is applied to wiring board mainly is FR-4, polyfunctional epoxy resin and modified epoxy etc., and they are matrix resins that present wiring board is produced, and output accounts for 97% of total amount.The advantage of epoxy resin board is technical maturity, stable performance, and shortcoming is that thermotolerance is not enough, and the second-order transition temperature of FR-4 is 130 ℃, and the second-order transition temperature of modified epoxy is 150～180 ℃, and dielectric properties are relatively poor, water-intake rate, moisture-proof poor heat stability etc.These drawbacks limit the application of Resins, epoxy in the high-performance plate.Thermoplastic resin mainly contains polyimide (PI), polytetrafluoroethylene (PTFE), polyphenylene oxide (PPO) etc.PI has high thermotolerance, Tg＞250 ℃, dielectric properties preferably, below 50MHz, specific inductivity is 4.1, and dielectric loss is 0.008, and its mechanical property, chemical resistant properties and size stability are also than more excellent, be a kind of resin, be mainly used in the production of flexible sheet at present with development potentiality.The shortcoming of PI is mold temperature and melt viscosity height (＞300 ℃), has influenced its application development, the domestic equipment that does not also have to produce at present the PI plate.The dielectric properties of PTFE are best in all resins, and it has very little and stable specific inductivity and dielectric loss in very wide range of frequency, and simultaneously, PTFE has excellent chemical resistant properties and environmental resistance.But because PTFE has high unreactiveness and minimum surface energy, in the time of in being applied to wiring board, it also exists many problems, and as second-order transition temperature very little (about 25 ℃ of Tg), thereby rigidity is very poor; Hot pressing temperature height (～400 ℃) is produced difficulty; Poor with the bonding force of Copper Foil, boring property is poor; Cost an arm and a leg etc.At present it only be applied to slightly some must with can not aerospace and military field in.The specific inductivity of PPO is 2.4-2.5, and dielectric loss is 0.001, and dielectric properties are only second to PTFE, good heat resistance (Tg is 210 ℃).But because it is thermoplastic resin, have creep properties, poor solvent resistance, and processing difficulties, thereby PPO also fails to enter into practical application at present, it is mainly used in modified epoxy in present stage, improves its thermotolerance.The thermotolerance height of bismaleimides (BMI) resin, dielectric properties, mechanical property are more excellent, but its mold temperature is higher, toughness is relatively poor, and these have all limited the application of BMI resin in high performance copper clad laminate.Therefore the BMI resin to be used in the copper-clad plate manufacturing and be gone, must carry out modification the BMI resin.
Three, summary of the invention:
The object of the present invention is to provide a kind of modified bismaleimide resin that has high temperature resistant, low dielectric characteristics, can be directly used in the preparation of high temperature resistant copper-clad plate.
Another object of the present invention is to provide a kind of preparation method of modified bismaleimide resin.
Another object of the present invention is to provide of the application of a kind of modified bismaleimide resin as high temperature resistant copper-clad plate base material.
For achieving the above object, the technical solution used in the present invention is:
A kind of modified bismaleimide resin, what it was special goes out to be: the composition and the proportioning of described modified bismaleimide resin are as follows: (b is a weight unit)
Bimaleimide resin 100b allylic cpd 50-90b
Resins, epoxy 0-300b solidifying agent 0-12b
Promotor 0-4b
Above-mentioned bimaleimide resin is 4,4 '-dimaleoyl imino ditane, 4,4 '-dimaleoyl imino phenyl ether, 4, one or more mixtures of 4 '-dimaleoyl imino sulfobenzide.
One or more mixtures of above-mentioned allylic cpd diallyl bisphenol, diallyl bisphenol S, chavicol.
Above-mentioned Resins, epoxy is one or more mixtures of halogen-containing Resins, epoxy, novolac epoxy, bisphenol A type epoxy resin.
Above-mentioned solidifying agent is one or more mixtures of triethylamine, xylidine, triethylene tetramine, Dyhard RU 100, boron trifluoride mono aminoethane.
Above-mentioned promotor is one or more mixtures of imidazoles, glyoxal ethyline, 2-methyl-4-ethyl imidazol(e).
A kind of preparation method of modified bismaleimide resin, what it was special goes out to be:
Take by weighing raw material according to above-mentioned weight part, with the Resins, epoxy, allylic cpd and the bimaleimide resin that take by weighing in reaction flask, under oil bath heating, stirring, slowly be warming up to 120 ℃-150 ℃, treat the transparent back of resin solution clock reaction 30-60min, add the mixed solvent of the dimethyl formamide of 70 parts acetone and 30 parts, reduce to the modified bismaleimide resin solution that room temperature obtains homogeneous transparent;
Epoxy curing agent and promotor is stand-by, when needing to use, it is mixed with modified bismaleimide resin solution.
The application of a kind of modified bismaleimide resin in the copper-clad plate preparation, what it was special goes out to be:
Epoxy curing agent, promotor are dissolved in the glue of modified bismaleimide resin, stir, the uniform figure of glue brushes on the alkali-free glass cloth, at 150 ℃ of left and right sides air seasoning 5-10min, obtains prepreg; Prepreg is cut out deflashing, selects the place of surfacing, no spot to cut into the square of 100cm * 100cm, gets 8 and is superimposed together, and upper and lower surface is all put an onesize electrolytic copper foil, send in the hot pressing level and suppresses, promptly.
The technology of above-mentioned compacting is: pressing pressure is 2.5MPa, and 170 ℃ of pressurize 2h at 200 ℃ of pressurize 3h, are cooled to room temperature with press and take out, in 220 ℃ of aftertreatment 5h of baking oven.
The present invention is with respect to its major advantage of prior art:
Modified bismaleimide resin has good solubility, can be dissolved in the mixed solvent of acetone/dimethyl formamide, and the good stability of solution is deposited under the room temperature and do not had the physical chemical phenomenon generation half a year.It can carry out forming process with existing FR-4 technology.It can be used for high-technology fields such as high-speed computing machine, satellite communication device, mobile telephone.
Modified bismaleimide resin is used as the copper-clad plate base material, advantage such as high temperature resistant (200 ℃～280 ℃), low-loss (tg＜0.012), good flame resistance, moisture-proof thermostability are excellent, comprehensive mechanical property excellence that it has.
Four, embodiment:
In the present invention, the composition and the proportioning of modified bismaleimide resin (BMI) are as follows: (b is a weight unit)
Bimaleimide resin 100b allylic cpd 50-90b
Resins, epoxy 0-300b solidifying agent 0-12b
Promotor 0-4b
In compositing formula, bismaleimides adopts: 4, and 4 '-dimaleoyl imino ditane, 4,4 '-dimaleoyl imino phenyl ether, 4, the mixture of one or several in 4 '-dimaleoyl imino sulfobenzide.It is existing industrial goods, can be produced by acetone method or hot closed loop method, if purity is lower, then need carries out recrystallization it is purified.
Allylic cpd mainly adopts: the mixture of one or several of diallyl bisphenol, diallyl bisphenol S or chavicol.
Resins, epoxy adopts one or several mixture of halogen-containing Resins, epoxy, novolac epoxy, bisphenol A type epoxy resin.
Novolac epoxy can be F-44, F-51, F-48, F-46, JF-45, JF-43 etc., and they are homemade industrialization product.The novolac epoxy of import type such as Epiclon N-740, EPN-1139, DEN-1139, DEN-431, Epiclon N-730, EPN-1138, DEN-438, Epikote-154, Epiclon N-73, ECN-1273, Epiclon N-665 etc. all can use.
Halogen-containing Resins, epoxy is mainly tetrabormated bisphenol A epoxide resin or tetrachloro bisphenol A epoxide resin.Usually mainly use tetrabormated bisphenol A epoxide resin such as BE-4, BE-1938, BE-2620, EX-40, EX-20 etc., in addition, tetrabormated bisphenol A epoxide resin such as Araldite-8047, DER-511, the Araldite-8011 etc. of import type also can use.
In order to improve manufacturability, can add a small amount of bisphenol A epoxide resin such as E-55, E-51, E-44, E-42, E-33, E-20 etc.
Epoxy curing agent can adopt: the mixture of one or several of triethylamine, xylidine, triethylene tetramine, Dyhard RU 100, boron trifluoride mono aminoethane.
Curing catalyst can adopt: the mixture of one or several of imidazoles, glyoxal ethyline, 2-methyl-4-ethyl imidazol(e).
In the resin system prescription, the consumption of allylic cpd is generally the 50-90% (weight ratio) of bimaleimide resin, and less than 50%, then the solvability of system and toughness are relatively poor as if consumption, if consumption is greater than 90%, then the thermotolerance of system and dielectric properties descend significantly.In addition, in resin system, the 2-4% of the consumption goods and materials amount of epoxy of solidifying agent, accelerator level is the 0.5-1% of amount of epoxy.
The preparation method of modified bismaleimide resin is as follows: take by weighing raw material according to above-mentioned weight part, with the Resins, epoxy that takes by weighing, allylic cpd and bimaleimide resin are in reaction flask, heat in oil bath, stir down and slowly be warming up to 120 ℃-150 ℃, treat the transparent back of resin solution clock reaction 30-60min, add 70 parts acetone and dimethyl formamide (acetone/dimethyl formamide of 30 parts, 70/30) mixed solvent, used solvent also can be acetone, butanone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, toluene, dimethylbenzene, trichloromethane, methylene dichloride, one or several mixture of alcoholic acid.Reduce to room temperature and obtain the modified bismaleimide resin solution of homogeneous transparent; Epoxy curing agent and promotor is stand-by, during use, it is mixed with modified bismaleimide resin solution, get final product.
During with the application of modified bismaleimide resin in copper-clad plate preparation, epoxy curing agent, promotor are dissolved in the glue of modified bismaleimide resin, stir, the uniform figure of glue brushes on the alkali-free glass cloth, at 150 ℃ of left and right sides air seasoning 5-10min, obtain prepreg; Prepreg is cut out deflashing, select the place of surfacing, no spot to cut into the square of 100cm * 100cm, getting 8 is superimposed together, upper and lower surface is all put an onesize electrolytic copper foil, send in the hot pressing level and suppresses, and the technology of compacting is: pressing pressure is 2.5MPa, 170 ℃ of pressurize 2h, at 200 ℃ of pressurize 3h, be cooled to room temperature with press and take out, in 220 ℃ of aftertreatment 5h of baking oven; Promptly.
In modified bismaleimide resin was applied to copper-clad plate preparation, the alkali-free glass cloth of electronic-grade that can adopt different thickness, specification was as strongthener, and it can also be quartz fabric.
Specific embodiment 1:
Take by weighing 4,4 '-dimaleoyl imino ditane 100g, diallyl bisphenol 50g, tetrabormated bisphenol A epoxide resin 350g puts into the 2000ml reaction flask, is heated to 140-150 ℃ of reaction 30min, be cooled to 100 ℃ and add acetone/dimethyl formamide (70/30) 500ml, reduce to room temperature and add Dyhard RU 100 10g, glyoxal ethyline 3.5g stirs.Above-mentioned glue is brushed on the EW210 woven fiber glass, treats that fugitive constituent＜5% back at 150 ℃ of air seasoning 10min, obtains prepreg.Prepreg is cut out deflashing, select the place of surfacing, no spot to cut into the square of 100cm * 100cm, getting 8 is superimposed together, upper and lower surface is all put an onesize electrolytic copper foil, send in the hot pressing level and suppresses, and pressing process is: pressing pressure is 2.5MPa, 170 ℃ of pressurize 2h, at 200 ℃ of pressurize 3h, be cooled to room temperature with press and take out, in 220 ℃ of aftertreatment 5h of baking oven.The fundamental property that obtains copper-clad plate reaches the requirement as table-1.Its special feature is that heat-drawn wire is 168 ℃, and second-order transition temperature is 182 ℃.
Specific embodiment 2:
Take by weighing 4,4 '-dimaleoyl imino ditane 100g, diallyl bisphenol 50g, tetrabormated bisphenol A epoxide resin 150g puts into the 2000ml reaction flask, is heated to 140-150 ℃ of reaction 20min, be cooled to 100 ℃ and add acetone/dimethyl formamide (70/30) 300ml, reduce to room temperature and add Dyhard RU 100 4.5g, glyoxal ethyline 1.5g stirs.Above-mentioned glue is brushed on the EW210 woven fiber glass, treats that fugitive constituent＜5% back at 150 ℃ of air seasoning 10min, obtains prepreg.Prepreg is cut out deflashing, select the place of surfacing, no spot to cut into the square of 100cm * 100cm, getting 8 is superimposed together, upper and lower surface is all put an onesize electrolytic copper foil, send in the hot pressing level and suppresses, and pressing process is: pressing pressure is 2.5MPa, 170 ℃ of pressurize 2h, at 200 ℃ of pressurize 3h, be cooled to room temperature with press and take out, in 220 ℃ of aftertreatment 5h of baking oven.The fundamental property that obtains copper-clad plate reaches the requirement as table-1.Its special feature is that heat-drawn wire is 185 ℃, and second-order transition temperature is 203 ℃.
Specific embodiment 3:
Take by weighing 4,4 '-dimaleoyl imino ditane 200g, diallyl bisphenol 120g, tetrabormated bisphenol A epoxide resin 140g puts into three mouthfuls of reaction flasks of 2000ml, is heated to 140-150 ℃ of reaction 23min, be cooled to 100 ℃ and add acetone/dimethyl formamide (70/30) 500ml, reduce to room temperature and add Dyhard RU 100 3.6g, glyoxal ethyline 1.2g stirs.Above-mentioned glue is brushed on the EW210 woven fiber glass, treats that fugitive constituent＜5% back at 150 ℃ of air seasoning 10min, obtains prepreg.Prepreg is cut out deflashing, select the place of surfacing, no spot to cut into the square of 100cm * 100cm, getting 8 is superimposed together, upper and lower surface is all put an onesize electrolytic copper foil, send in the hot pressing level and suppresses, and pressing process is: pressing pressure is 2.5MPa, 170 ℃ of pressurize 2h, at 200 ℃ of pressurize 3h, be cooled to room temperature with press and take out, in 220 ℃ of aftertreatment 5h of baking oven.The fundamental property that obtains copper-clad plate reaches the requirement as table-1.Its special feature is that heat-drawn wire is 210 ℃, and second-order transition temperature is 242 ℃.
The salient features of table 1 modified BMI resin copper-clad plate
The performance project performance data
Specific inductivity (1MHz)＜4
Tangent of the dielectric loss angle value＞0.01
(1MHz)
Surface resistivity (Ω)＞2 * 10
13
Volume specific resistance (Ω m)＞1 * 10
12
Voltage breakdown (Kv)＞145
Arc resistance (s)＞165
Heat-drawn wire (℃)＞168
Second-order transition temperature (℃)＞180
Flexural strength (MPa)＞485
Tensile strength (MPa)＞300
Flame retardant resistance (UL94) V-0
Water-intake rate (%)＜2.5
Weldability can be welded
Copper Foil stripping strength (N/mm)＞1.4
Claims (9)
1, a kind of modified bismaleimide resin is characterized in that: the composition and the proportioning of described modified bismaleimide resin are as follows: (b is a weight unit)
Bimaleimide resin 100b allylic cpd 50-90b
Resins, epoxy 0-300b solidifying agent 0-12b
Promotor 0-4b
2, modified bismaleimide resin according to claim 1, it is characterized in that: described bimaleimide resin is 4,4 '-dimaleoyl imino ditane, 4,4 '-dimaleoyl imino phenyl ether, 4, one or more mixtures of 4 '-dimaleoyl imino sulfobenzide.
3, modified bismaleimide resin according to claim 1 is characterized in that: one or more mixtures of described allylic cpd diallyl bisphenol, diallyl bisphenol S, chavicol.
4, modified bismaleimide resin according to claim 1 is characterized in that: described Resins, epoxy is one or more mixtures of halogen-containing Resins, epoxy, novolac epoxy, bisphenol A type epoxy resin.
5, modified bismaleimide resin according to claim 1 is characterized in that: described solidifying agent is one or more mixtures of triethylamine, xylidine, triethylene tetramine, Dyhard RU 100, boron trifluoride mono aminoethane.
6, modified bismaleimide resin according to claim 1 is characterized in that: described promotor is one or more mixtures of imidazoles, glyoxal ethyline, 2-methyl-4-ethyl imidazol(e).
7, a kind of preparation method of modified bismaleimide resin is characterized in that:
Weight part according to claim 1 takes by weighing raw material, with the Resins, epoxy, allylic cpd and the bimaleimide resin that take by weighing in reaction flask, under oil bath heating, stirring, slowly be warming up to 120 ℃-150 ℃, treat the transparent back of resin solution clock reaction 30-60min, add the mixed solvent of the dimethyl formamide of 70 parts acetone and 30 parts, reduce to the modified bismaleimide resin solution that room temperature obtains homogeneous transparent;
Epoxy curing agent and promotor is stand-by, when needing to use, it is mixed with modified bismaleimide resin solution.
8, the application of a kind of modified bismaleimide resin in the copper-clad plate preparation is characterized in that:
Epoxy curing agent, promotor are dissolved in the glue of modified bismaleimide resin, stir, the uniform figure of glue brushes on the alkali-free glass cloth, at 150 ℃ of left and right sides air seasoning 5-10min, obtains prepreg; Prepreg is cut out deflashing, selects the place of surfacing, no spot to cut into the square of 100cm * 100cm, gets 8 and is superimposed together, and upper and lower surface is all put an onesize electrolytic copper foil, send in the hot pressing level and suppresses, promptly.
9, the application of modified bismaleimide resin according to claim 8 in the copper-clad plate preparation is characterized in that:
The technology of described compacting is: pressing pressure is 2.5MPa, and 170 ℃ of pressurize 2h at 200 ℃ of pressurize 3h, are cooled to room temperature with press and take out, in 220 ℃ of aftertreatment 5h of baking oven.
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