CN1436810A - Synthetic resin applied as dielectric material in high-density printed circuti board - Google Patents
Synthetic resin applied as dielectric material in high-density printed circuti board Download PDFInfo
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- CN1436810A CN1436810A CN 02103181 CN02103181A CN1436810A CN 1436810 A CN1436810 A CN 1436810A CN 02103181 CN02103181 CN 02103181 CN 02103181 A CN02103181 A CN 02103181A CN 1436810 A CN1436810 A CN 1436810A
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Abstract
The synthetic resin applied as dielectric material in high-density printed circuit board is one multi-functional radical epoxy resin with amine hardening agent possessing multi-functional radical bridging performance and toughener to modify the epoxy resin. When painted onto proper copper foil precisely, may be obtained film with thickness precision within 2%, controllable electric impedance characteristic and excellent machinability for electrically drilling.
Description
Technical field
The invention relates to a kind of synthetic resins that is applied to the dielectric materials of high-density printed circuit board, refer in particular to the polyfunctional epoxy resin that has in a kind of amine type hardeners with multiple functional radical bridge formation characteristic and the molecule more than two or two, utilize toughness to pay agent and cooperate suitable reaction with Resins, epoxy to reach the purpose of upgrading.
Background technology
Along with the variation trend of following electronic product, on form, be tending towards compact, on function, then require high-performance, high function, high-speedization, therefore, on high-density structure packing technique, also must meet this demand; Printed circuit board (PCB) is the mother of electronic product, so more and more strictness of the demand of the development of its process technique (being the demand of high-density designs such as lightweight, thin typeization, graph thinning, apertureization); The circuit substrate of the portable product that PBGA substrate that the present utmost point attracts attention and usage quantity increase day by day, as mobile telephone, notebook computer, e-dictionary, pcmcia card etc., will use a large amount of high-density base boards, but the density of conventional substrate is not enough, though on processing procedure, constantly improve as process apparatus such as drilling machine, etching machines, but still can only accomplish 4mil line-spacing and 6mil via, so can't reach the demand, and following narrow pin is apart from the restriction of IC structure installing meter; Therefore the high-density base board with fine rule, aperture just arises at the historic moment, and wishes to replace the processing procedure of traditional multilayer pressing substrate; Layer increasing method (build-up) basal plate making process technology can effectively reduce the through hole area occupied, reach the high-density requirement of fine rule, aperture easily;
At present, on traditional PCB, add one to multiple several layers fine rule layer, it is the effective again way of a kind of economy, the middle layer of this type is traditional FR-4 substrate, successively is superimposed with dielectric layer and Copper Foil then, and all the PCB substrate than traditional is tiny with the aperture for this circuit that is superimposed with, and layer thickness also dwindles relatively, so density increases and the thickness attenuation, so the circuit of one deck is equivalent to the most layer lines of conventional substrate road, its relative price will be more cheap than conventional substrate; Therefore the extensive application of Layer increasing method printed circuit board (PCB) process technique will cause the revolutionary variation in following high-density printed circuit board market.
In recent years, united states, japan and other countries is in the development of high density circuit board process technique, existing pretty good application achievements: the addition that adds circuit technology, Ibiden as the surperficial lamination of IBM increases the heavy distribution technique of film of a layer technology, IBM Endicott, the cross laminates technology of IBM Austin, the holostrome gap guide hole basal plate making process technology of Matsushita Electric Industries etc., all is to reach one of means of densification.These build-up technology have the part employing of minority large scale circuit plate factory at home, and existing commercialization production; And the electronic packaging development trend of next generation will be to develop towards functional base plate, a large amount of passive components is integrated (Integration) in circuit card, to dwindle the volume of product, reduce element and IC, element and interelement transmission range, adapt to high frequency, high speed demand.The main gordian technique of Layer increasing method printed circuit board (PCB) processing procedure is the line design of high-density base board, the micropore processing procedure of on-mechanical boring and the exploitation of high-performance dielectric materials.
In addition, dielectric materials in the tradition multilager base plate processing procedure is a conventional film, and this kind film contains glass fibre and can't carry out effective Laser drill, can only use machine drilling, but the aperture is minimum to 10mil, can't reach and increase a layer processing procedure printed circuit board (PCB) demand, also just can't satisfy the technological trend of present high-density electronic packaging.
Summary of the invention
How a kind of synthetic resins that is applied to the dielectric materials of high-density printed circuit board to be proposed at the problems referred to above, not only can accurate be coated on the suitable Copper Foil material, obtain the high film of thickness accuracy, be not to use for a long time the person eagerly to look forward to always, the inventor is based on the research of engaging in related products for many years, exploitation and sell practical experience, through research and design and special topic discussion in many ways, work out the synthetic resins with dielectric materials of no glass fibre of the present invention finally.
Main purpose of the present invention provides a kind of synthetic resins that is applied to the dielectric materials of high-density printed circuit board, is coated on the suitable Copper Foil material by precision, reaches to obtain thickness accuracy in ± 2% purpose with interior film thickness.
Secondary objective of the present invention provides a kind of synthetic resins that is applied to the dielectric materials of high-density printed circuit board, reaches the purpose of the electrical impedance characteristic of control material.
The 3rd purpose of the present invention provides a kind of synthetic resins that is applied to the dielectric materials of high-density printed circuit board, utilizes the made plank of synthetic resins pressing processing of the present invention, reaches to have the purpose that good electricity is penetrated the boring processibility.
The object of the present invention is achieved like this: a kind of synthetic resins that is applied to the dielectric materials of high-density printed circuit board, this dielectric insulation material can accurate rolling be coated on the Copper Foil, the mode of utilizing traditional printing circuit card hot pressing to make, the dielectric insulation resin is combined with traditional inner plating under 150 ℃-180 ℃ temperature, and the substrate of using this kind dielectric insulation material can be reached the demand of the high-density printed circuit board of new kenel.
The synthetic resins that is applied to the dielectric materials of high-density printed circuit board of the present invention consists predominantly of, Resins, epoxy 10-40 parts by weight, stiffening agent 5-25 parts by weight, toughness are paid agent 10-30 parts by weight and incombustible agent 10-30 parts by weight, at first, Resins, epoxy and toughness are paid agent and are carried out toughness reinforcing upgrading earlier, make the functional group and the toughness of Resins, epoxy pay agent generation part bond, main chain has enough toughness, again stiffening agent and incombustible agent is added wherein evenly stirring afterwards.
The thickness of dielectric insulation film is between 25-150 μ m, can utilize existing printed circuit board (PCB) processing procedure with the insulating film material hot pressing on the traditional printing circuit card, hot pressing temperature is at 150-180 ℃, selection by Resins, epoxy and stiffening agent kind, reach Resins, epoxy and toughness and pay the control of the reaction (temperature of reaction and time) of agent, the epoxy equivalent (weight) that makes Resins, epoxy is between 150-8000, the reaction of Resins, epoxy and stiffening agent is in order to make Resins, epoxy form the interlinkage structure, produce bigger molecular weight, to adapt to the intensity of film; For the rolling of film, the reaction of must flexible in the prescription paying agent exists, to add obdurability; Film also must reach difficult combustion grade, so add incombustible agent.
Resins, epoxy can be selected the pattern of Diglycidyl (Diglycidyl ether), and its epoxy equivalent (weight) is 150-8000, and its structural formula is as follows:
Wherein R can be following shown in one of them of structure:
Wherein a is 1-4, and b is 0-4.
Stiffening agent is to select multifunctional fundamental mode stiffening agent, and its structure is as follows:
Wherein R1 is one of them of following structure:
R2 is the alkyl of carbon number 1-10.
This stiffening agent also can be one of them of following structure:
Or
Flame retardant is one of them of the aluminium hydroxide that is selected from halogen, nitride, trimeric cyanamide, brominated epoxy resin, phosphide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, 3 crystal water, above derivative compound and above mixture;
Or be one of them of following structure:
Tetrabromo-benzene dihydroxyphenyl propane (Tetrabromo bisphenol A; TBBA)
Dibromo-isobutyl ethyl glycol (Dibromoneo phentyl glycol)
Triphen phenolic group phosphoric acid ester (Triphenyl phosphate; TPP)
Trimethylbenzene phenolic group phosphoric acid ester ((Tricresyl phosphate)
Tolyl-hexichol phenolic group phosphoric acid ester Cresyl diphenyl phosphate
This toughness is paid agent and is selected from the butadiene-acrylonitrile that carboxyl is a clearing end (CarboxyTerminated Butadene acrylonitrile; CTBN), amino is butadiene-acrylonitrile (the Amine-Terminates Butadiene acrylontirile of clearing end; ATBN) or p-nitrobenzoic acid.
Describe in detail below in conjunction with preferred embodiment and cooperation manufacturing flow chart.
Description of drawings
Fig. 1 is the prepolymerized schematic flow sheet of synthetic resins of the present invention;
Fig. 2 is the application flow synoptic diagram of synthetic resins of the present invention.
Embodiment
Consult Fig. 1, prepolymerized schematic flow sheet for synthetic resins of the present invention, the manufacture method of the synthetic resins of the dielectric materials that is applied to high-density printed circuit board of the present invention, main Resins, epoxy 20 and the toughness of adding is paid agent 10 and is stirred the mixture and 30 carry out prepolymerization, then add stiffening agent 40 and participate in reaction, make synthetic resin 60 with incombustible agent 50.
Consult shown in Figure 2ly, be the schematic flow sheet of the application of synthetic resins of the present invention; After synthetic resin 70 of the present invention is made, utilize accurate coating 72 that resin is coated rolling on the sodium Copper Foil, and process baking oven for heating 74 makes solvent evaporates, form the film of B-stage, its thickness is between 25-150 μ m, the dielectric insulation thin-film material of rolling is finished product 78 utilizing existing printed circuit board (PCB) to be processed into mode hot pressing 76 under 150-180 ℃ temperature environment on interior layer printed circuit board.
Further specify below in conjunction with specific embodiment.
Embodiment 1
Use 5 liters, 4 mouthfuls reactor, the stirring rod of 3 impellers adds 1710g Resins, epoxy (Dislycidylether of bisphenol A; DGEBA, Epon828, Shell Chemical Co.), 1207g toughness pays phenyl methyl acetate solvent (the phenyl methyl acetate of agent CTBN and 800g; PMA), be warming up to 90 ℃ of reactions and stirred 6 hours, add 300g4 again, and 4 '-diamino benzene sulfonic acid (4,4 '-Diamminodiphenolsulfone; DDS) continue reaction 2 hours, add tetrabromo-benzene dihydroxyphenyl propane (the Tetrabromo bisphenolA of 643g again; TBBA), make synthetic resins product of the present invention after stirring.
Embodiment 2
Use 5 liters, 4 mouthfuls reactor, the stirring rod of 3 impellers adds 1710g Resins, epoxy (Dislycidyl ether of bisphenol A; DGEBA, Epon828, Shell Chemical Co.), 145.8g DGEBA (Epon1009, Shell Chemical Co.), 1638g toughness pay phenyl methyl acetate solvent (the phenyl methyl acetate of agent CTBN and 1000g; PMA), be warming up to 90 ℃ of reactions and stirred 6 hours, add 356.4g4 again, and 4 '-diamino benzene sulfonic acid (4,4 '-Diamminodiphenolmethene; MDA) continue reaction 2 hours, add tetrabromo-benzene dihydroxyphenyl propane (the Tetrabromobisphenol A of 903.8g again; TBBA), after stirring, make synthetic resins product of the present invention.
Embodiment 3
Use 5 liters, 4 mouthfuls reactor, 3 impeller stirring rod add 1710g Resins, epoxy (Dislycidylether of bisphenol A; DGEBA, Epon828, Shell Chemical Co.), 29.3g ECN1299 (CIBA Co.), 1242g toughness is paid phenyl methyl acetate solvent (the phenylmethyl acetate of agent CTBN and 800g; PMA), be warming up to 90 ℃ of reactions and stirred 6 hours, add 167g4 again, and 4 '-diamino benzene sulfonic acid (4,4 '-Diaminodiphenyl sulfone; DDS) continue reaction 2 hours, add tetrabromo-benzene dihydroxyphenyl propane (the Tetrabromo bisphenol A of 565g again; TBBA) stir after, make synthetic resins product of the present invention.
Comparative example
Use 5 liters, 4 mouthfuls reactor, 3 impeller stirring rod add 1800g Resins, epoxy (Dislycidyl ether of bisphenol A; DGEBA, Epon828, Shell ChemicalCo.), 630g4, and 4 '-diamino benzene sulfonic acid (4,4 '-Diaminodiphenyl sulfone; DDS) with phenyl methyl acetate solvent (the phenyl methyl acetate of 720g; PMA), 1017g toughness is paid agent CTBN, the tetrabromo-benzene dihydroxyphenyl propane of 630g (Tetrabromo bisphenol A; TBBA) obtain the synthetic resins product after stirring under.
The addition of the foregoing description and comparative example and the physicals of resultant are listed as follows: table 1 is the interpolation weight of each embodiment and comparative example
Table 2 is the physicals of each embodiment and comparative example
| ??????Tg(℃) | ???150 | ????158 | ???168 | ?????145 |
| ????CTE(ppm/℃) | ???115 | ????116 | ???102 | ?????108 |
| Stripping strength (lbs/in) | ???7.3 | ????6.6 | ???6.2 | ?????5.2 |
| Water-intake rate (%) | ???1.3 | ????1.2 | ???1.2 | ?????1.5 |
Wherein: ◎ is splendid, zero for still can, △ is for slightly poor,
* for operating, water-absorbent is under room temperature soaked 24 hours.
In sum, the invention relates to a kind of synthetic resins that is applied to the dielectric materials of high-density printed circuit board, refer in particular to the polyfunctional epoxy resin that has in a kind of amine type hardeners with multiple functional radical bridge formation characteristic and the molecule more than two or two, and utilize toughness to pay agent to cooperate suitable reaction with Resins, epoxy, to reach the purpose of upgrading.Therefore the present invention has novelty, creativeness and practicality.
The above; it only is a preferred embodiment of the present invention; be not to be used for limiting scope of the invention process, all equalizations of doing according to the described shape of the present patent application claim, structure, feature and spirit change and modify, and all should be included within protection scope of the present invention.
Claims (27)
1, a kind of synthetic resins that is applied to the dielectric materials of high-density printed circuit board, it is characterized in that: it comprises following compositions in portion by weight:
Epoxy resin compound 10-40 part
Toughness is paid agent 10-30 part
Flame retardant 10-30 part
Stiffening agent 5-25 part.
2, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 1 is characterized in that: this epoxy resin compound is the Resins, epoxy of flame retardancy.
3, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 1, it is characterized in that: this molecular weight of epoxy resin is between 150-9000.
4, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 1 is characterized in that: this Resins, epoxy is the epoxy resin compound of plural at least multi-functional epoxy's base.
5, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 1 is characterized in that: this Resins, epoxy is the structural shape that contains Diglycidyl, and its chemical structural formula is:
6, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 5 is characterized in that: this R is following structure:
7, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 5 is characterized in that: this R is following structure:
8, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 5 is characterized in that: this R is following structure:
9, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 5 is characterized in that: this R is following structure:
10, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 5 is characterized in that: this R is following structure:
11, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 5 is characterized in that: this R is following structure:
12, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 5 is characterized in that: this R is following structure:
13, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 5 is characterized in that: this R is following structure:
14, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 5 is characterized in that: this R is following structure:
15, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 5 is characterized in that: this R is following structure:
16, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 5 is characterized in that: this R is following structure:
17, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 5 is characterized in that: this R is following structure:
Wherein a is 0-4, and b is 0-4.
18, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 1 is characterized in that: this stiffening agent is the stiffening agent with multifunctional fundamental mode.
19, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 18 is characterized in that: this multiple functional radical stiffening agent is selected from one of them of amine, amides or anhydrides stiffening agent with multiple functional radical chemical structure.
20, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 18, it is characterized in that: the structural formula of this stiffening agent is as follows:
Wherein the structure of R1 is:
R2 is the alkyl of carbon number 1-10
21, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 20 is characterized in that: this R1 is following structure:
22, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 20 is characterized in that: this R1 is following structure:
23, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 1 is characterized in that: this stiffening agent is the amino-benzene acid amides, and its structural formula is as follows:
24, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 1 is characterized in that: this stiffening agent is a diaminotoluene, and its structural formula is as follows:
25, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 1 is characterized in that: this incombustible agent is selected from aluminium hydroxide and/or its derivative of halogen, nitride, trimeric cyanamide, brominated epoxy resin, phosphide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, 3 crystal water.
26, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 1 is characterized in that: this incombustible agent is selected from tetrabromo-benzene dihydroxyphenyl propane, dibromo-isobutyl ethyl glycol, triphen phenolic group phosphoric acid ester, trimethylbenzene phenolic group phosphoric acid ester or tolyl-hexichol phenolic group phosphoric acid ester.
27, the synthetic resins that is applied to the dielectric materials of high-density printed circuit board according to claim 1 is characterized in that: this toughness is paid agent and is selected from butadiene-acrylonitrile that carboxyl is a clearing end, aminoly is the butadiene-acrylonitrile of clearing end or p-nitrobenzoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02103181 CN1436810A (en) | 2002-02-04 | 2002-02-04 | Synthetic resin applied as dielectric material in high-density printed circuti board |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02103181 CN1436810A (en) | 2002-02-04 | 2002-02-04 | Synthetic resin applied as dielectric material in high-density printed circuti board |
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| CN1436810A true CN1436810A (en) | 2003-08-20 |
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| CN 02103181 Pending CN1436810A (en) | 2002-02-04 | 2002-02-04 | Synthetic resin applied as dielectric material in high-density printed circuti board |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104902687A (en) * | 2015-06-18 | 2015-09-09 | 镇江华印电路板有限公司 | Anti-crack printed circuit board |
| CN104962037A (en) * | 2009-02-25 | 2015-10-07 | 松下电器产业株式会社 | Thermoconductive composition, heat dissipating plate, heat dissipating substrate and circuit module using thermoconductive composition, and process for production of thermoconductive composition |
-
2002
- 2002-02-04 CN CN 02103181 patent/CN1436810A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104962037A (en) * | 2009-02-25 | 2015-10-07 | 松下电器产业株式会社 | Thermoconductive composition, heat dissipating plate, heat dissipating substrate and circuit module using thermoconductive composition, and process for production of thermoconductive composition |
| CN104902687A (en) * | 2015-06-18 | 2015-09-09 | 镇江华印电路板有限公司 | Anti-crack printed circuit board |
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