CN102390145A - Environment-friendly copper clad laminate and preparation method thereof - Google Patents
Environment-friendly copper clad laminate and preparation method thereof Download PDFInfo
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- CN102390145A CN102390145A CN2011102248741A CN201110224874A CN102390145A CN 102390145 A CN102390145 A CN 102390145A CN 2011102248741 A CN2011102248741 A CN 2011102248741A CN 201110224874 A CN201110224874 A CN 201110224874A CN 102390145 A CN102390145 A CN 102390145A
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Abstract
The invention discloses an environment-friendly copper clad laminate and a preparation method thereof. A resin material in the laminate is an epoxy resin modified by a polyimide resin, and carbonate type aluminum magnesium hydrotalcite is added into a modified resin system. The preparation method for the environment-friendly copper clad laminate mainly comprises the following steps of: synthesizing the polyimide resin; and modifying the epoxy resin by using the polyimide resin, and preparing gelatinizing liquid by using the epoxy resin modified by the polyimide resin and the carbonate type aluminum magnesium hydrotalcite. The epoxy resin is modified by using the polyimide resin, so the crosslinking density of the environment-friendly copper clad laminate is much higher than that of the conventional epoxy resin; the environment-friendly copper clad laminate does not contain halogen or phosphorus, contains N, Al and Mg elements, and meets environmental protection requirements of European union restriction of hazardous substances (RoHS) and waste electrical and electronic equipment (WEEE) Directives; meanwhile, the heat resistance is also greatly improved, so that the environment-friendly copper clad laminate is more suitable for lead-free welding processes for printed circuit boards (PCB).
Description
Technical field
The invention belongs to copper-clad laminate (abbreviation copper-clad plate) technical field, be specifically related to the material behavior and the manufacture craft of copper-clad plate.
Background technology
The used for printed circuit copper-clad laminate all has fire-retardant characteristic, and traditional copper-clad plate is to adopt in the halogen series bromine (Br) as fire retardant mostly.FR-1 in the paper substrate plate, FR-2 series, the CEM-1 in the FR-4 in the glass fabricbase, FR-5 series and the composite base plate, CEM-3 series, these copper-clad plates all are to adopt brominated epoxy resin or add other bromide fire retardant.In recent years, along with the promulgation of the RoHS of European Union, WEEE environmental protection instruction, halogens was put among the electric equipment products banned substance because of its burning back generation nuisance dioxin.Therefore, the used fire retardant of non-halogen copper-clad plate turns to the phosphorous flame-retardant aspect, current generally use be phosphorous epoxy resin.Yet P elements also can produce harm to environment after burning, as makes soil acidification etc.
Also stipulated must not contain lead element in the electric equipment products in the RoHS instruction, the PCB welding material must be converted into lead-free solder by the original kupper solder that has so.The welding temperature of lead-free solder is higher 20～40 ℃ than the temperature that kupper solder is arranged, and therefore, the hear resistance of copper-clad plate also must satisfy the requirement of this high-temperature soldering, promptly has high heat decomposition temperature and heat-resisting quantity.Therefore, environmental protection PCB truly should be not halogen-containing, not phosphorous, not leaded, promptly wants copper-clad plate non-halogen non-phosphate pb-free solder compatible.
Summary of the invention
The object of the invention provides a kind of environment-friendly type copper-clad laminate and preparation method thereof, not only has the environmental protection characteristic of non-halogen non-phosphate, also has the resistance to elevated temperatures that is suitable for not having lead welding.
A kind of environment-friendly type copper-clad laminate is characterized in that: the resin material in the laminate is selected the polyimide resin modified epoxy for use, and adds carbonate type magnalium hydrotalcite in the epoxy-resin systems after modification.
A kind of method for preparing above-mentioned environment-friendly type copper-clad laminate is characterized in that, may further comprise the steps: the synthesis step of (1) polyimide resin; (2) make the polyimide resin modified epoxy, and with the step of carbonate type magnalium hydrotalcite mixing manufacture gluing glue; (3) the glass cloth gluing is made the step of prepreg; (4) with the step of prepreg and copper foil laminate, matching board and pressing; (5) tear the step of plate, sharp processing, check, packing open.
The synthetic of said polyimide resin comprises: (1) metered DMF is warming up to 60～70 ℃, stirs down to add DDM, stirs 10～15min and is dissolved to bright fully; Add BDM when (2) temperature rises to 80～90 ℃, stir also and heat up, behind 6～10min, during temperature recovery to 85～90 ℃, solution is bright; (3) be warming up to 125～130 ℃, and control constant temperature, behind this thermotonus 30～40min, vacuumize dehydration 3～5min; (4) the about 60～70min of constant temperature, sampling, GT:10 ± 1min/171 ℃ of controlling glue, the solids content 48～50% of glue; The mass ratio that feeds intake of DMF, DDM, BDM is 40～60%/9～12%/30～50% in the wherein above step.
Saidly make the gluing glue through polyimide resin and carbonate type magnalium hydrotalcite and comprise: the said polyimide resin that (1) will measure adds the DMF that measures, heat temperature raising to 50～60 ℃; (2) add Fj-43 type novolac epoxy resin, the E-20 type epoxy resin stirring and dissolving of pulverizing, dissolving fully behind 40～50min; (3) add E-51 type epoxy resin again, stir 30～40min, be cooled to room temperature; (4) add the carbonate type magnalium hydrotalcite that measures, dispersed with stirring, slaking 4～6h; The glue of polyimide resin, Fj-43 type novolac epoxy resin, E-20 type epoxy resin, E-51 type epoxy resin, DMF, the carbonate type magnalium hydrotalcite mass ratio that feeds intake is in the wherein above step: 40～55%/1～3%/10～18%/1～3%/10～18%/15～20%.
Environment-friendly type copper-clad laminate provided by the invention; Since used the polyimide resin modified epoxy, high more a lot, not halogen-containing, not phosphorous than the cross linking of epoxy resin density of routine; Contain N, Al, Mg element, reached the environmental requirement of RoHS of European Union and WEEE instruction; Hear resistance also is able to very big improvement simultaneously, is more suitable for being fit to the pb-free solder technology of PCB.
Description of drawings
The technological process of production figure that Fig. 1 provides for the embodiment of the invention.
The specific embodiment
Keynote idea of the present invention be in the used resin material of copper-clad plate, add environmental protection more, have the N element and the Al element of anti-flaming function simultaneously, it is cooperated according to a certain percentage, utilize its cooperative effect each other, reach flame retardant effect.
Resin material in the copper-clad plate that provides based on above-mentioned thought present embodiment is selected polyimide resin for use, with modified epoxy, and then add carbonate type magnalium hydrotalcite, make to form N, AL, Mg (OH)
2Composite flame retardant system, heat resistance is also effectively guaranteed simultaneously.
Wherein, polyimide resin has outstanding heat resistance, and contains the N element, and N content is about 9.0%, has certain anti-flammability.In addition, said carbonate type magnalium hydrotalcite is called for short LDHs, and chemical formula is: [Mg
6Al
2(OH)
16CO
3] 4H
2O wherein contains the hydrate of Al, Mg, is called for short the magnalium hydrotalcite again.That the magnalium hydrotalcite has is nontoxic, the characteristics of low cigarette, high performance-price ratio, can be used as the preferred inorganic combustion inhibitor of present embodiment.
The manufacturing process of the copper-clad plate that present embodiment provides is following:
One, material.
4,4 '-dimaleoyl imino diphenyl-methane (BDM), chemical formula is following:
Two amido diphenyl-methanes (DDM), chemical formula is following:
The E type epoxy resin of E-51 type;
The E type epoxy resin of E-20 type;
The orthoresol phenolic aldehyde epoxy of Fj-43 type;
Dimethyl formamide (DMF);
Carbonate type magnalium hydrotalcite: particle diameter 5 μ m;
7628 type glass fabrics;
Electrolytic copper foil.
Two, polyimide resin is synthetic.
Material therefor and measure as shown in the table:
| Material | Mass ratio feeds intake |
| BDM | 895 |
| DDM | 198 |
| DMF | 1093 |
(1) metered DMF is warming up to 70 ℃, stirs down to add DDM, stirs 10min and is dissolved to bright fully.
Add BDM when (2) temperature rises to 80 ℃, stir also and heat up, behind the 6min, during temperature recovery to 85 ℃, solution is bright.
(3) be warming up to 125～130 ℃, and control constant temperature, behind this thermotonus 30min, vacuumize dehydration 5min.(this dehydration purpose does not have moisture content to produce just in order to slough the moisture content of the absorption in the material in the course of reaction)
(4) about the about 60～70min of constant temperature, sampling, GT:10 ± 1min/171 ℃ of controlling glue, the solids content of glue about 50%.
Three, the making of gluing glue.
| Material | The glue mass ratio that feeds intake |
| Polyimide resin | 200 |
| Fj-43 | 8 |
| E-20 | 50 |
| E-51 | 8 |
| DMF | 55 |
| Hydrotalcite | 71 |
The above-mentioned synthetic polyimides glue that (1) will measure adds the DMF of metering, heat temperature raising to 50～60 ℃.
(2) add Fj-43, the E-20 stirring and dissolving of pulverizing, dissolving fully behind about 40min;
(3) add E-51 again, stir 30min, be cooled to room temperature.
(4) add the hydrotalcite that measures, dispersed with stirring, slaking 4h.
Four, the glass cloth gluing is made the process of prepreg: 7628 glass are distributed in gluing on the fall shaft hlue spreader, afterwards oven dry.Controlled condition comprises: gluing speed: 12m/min; Oven temperature: 200 ℃; Prepreg GT control: 80～100s/171 ℃; Prepreg indicated weight: 3.6～3.8g/m2 (specifically adjusting) according to the thickness of making sheet material; The RF:18 of prepreg～24%.
Five, lamination, matching board, pressing process: by the prepreg of the superimposed corresponding number of technology thickness requirement, need 8 like 1.6mm, 1.2mm needs 6, and 1.0mm needs 5; Be covered with electrolytic copper foil, in press, suppress.Controlled condition comprises: press temperature: 200 ℃/2h; Pressure: vacuum press: 30kg/cm2.
Six, tear plate, sharp processing, check, packing open.
Each item performance test results of the copper foil covered plate that following epi-position is made according to above embodiment:
In the test data: T288, Tg, three indexs of Td are enough to reflect the hear resistance that this sheet material is good and the adaptability of pb-free solder; Content of halogen also embodies the environmental protection characteristic of sheet material.
Claims (4)
1. environment-friendly type copper-clad laminate, it is characterized in that: the resin material in the laminate is selected the polyimide resin modified epoxy for use, and adds carbonate type magnalium hydrotalcite in the epoxy-resin systems after modification.
2. a method for preparing above-mentioned environment-friendly type copper-clad laminate is characterized in that, may further comprise the steps: the synthesis step of (1) polyimide resin; (2) make the polyimide resin modified epoxy, and with the step of carbonate type magnalium hydrotalcite mixing manufacture gluing glue; (3) the glass cloth gluing is made the step of prepreg; (4) with the step of prepreg and copper foil laminate, matching board and pressing; (5) tear the step of plate, sharp processing, check, packing open.
3. the preparation method of environment-friendly type copper-clad laminate according to claim 2; It is characterized in that: the synthetic of said polyimide resin comprises: (1) metered DMF is warming up to 60～70 ℃; Stir adding DDM down, stir 10～15min and be dissolved to bright fully; Add BDM when (2) temperature rises to 80～90 ℃, stir also and heat up, behind 6～10min, during temperature recovery to 85～90 ℃, solution is bright; (3) be warming up to 125～130 ℃, and control constant temperature, behind this thermotonus 30～40min, vacuumize dehydration 3～5min; (4) the about 60～70min of constant temperature, sampling, GT:10 ± 1min/171 ℃ of controlling glue, the solids content 48～50% of glue; The mass ratio that feeds intake of DMF, DDM, BDM is 40～60%/9～12%/30～50% in the wherein above step.
4. the preparation method of environment-friendly type copper-clad laminate according to claim 3; It is characterized in that: saidly make the gluing glue through polyimide resin and carbonate type magnalium hydrotalcite and comprise: the said polyimide resin that (1) will measure; The DMF that adds metering, heat temperature raising to 50～60 ℃; (2) add Fj-43 type novolac epoxy resin, the E-20 type epoxy resin stirring and dissolving of pulverizing, dissolving fully behind 40～50min; (3) add E-51 type epoxy resin again, stir 30～40min, be cooled to room temperature; (4) add the carbonate type magnalium hydrotalcite that measures, dispersed with stirring, slaking 4～6h; The glue of polyimide resin, Fj-43 type novolac epoxy resin, E-20 type epoxy resin, E-51 type epoxy resin, DMF, the carbonate type magnalium hydrotalcite mass ratio that feeds intake is in the wherein above step:
40～55％/1～3％/10～18％/1～3％/10～18％/15～20％。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897395A (en) * | 2014-03-28 | 2014-07-02 | 哈尔滨工程大学 | Preparation method of hydrotalcite and polyimide composite foam material |
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| CN1868735A (en) * | 2006-04-13 | 2006-11-29 | 上海南亚覆铜箔板有限公司 | Non-halogen epoxide glass cloth base copper coated foil plate and its preparation method |
| KR100665388B1 (en) * | 2005-11-11 | 2007-01-04 | 곽봉주 | Flexible epoxy resin composites and epoxy copper clad laminates using the same |
| JP3906547B2 (en) * | 1998-02-13 | 2007-04-18 | 松下電工株式会社 | Copper-clad laminate, multilayer laminate |
| CN101654005A (en) * | 2008-08-22 | 2010-02-24 | 金安国纪科技股份有限公司 | Method for manufacturing halogen-free FR-4 copper-clad laminate |
-
2011
- 2011-08-05 CN CN201110224874.1A patent/CN102390145B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3906547B2 (en) * | 1998-02-13 | 2007-04-18 | 松下電工株式会社 | Copper-clad laminate, multilayer laminate |
| KR100665388B1 (en) * | 2005-11-11 | 2007-01-04 | 곽봉주 | Flexible epoxy resin composites and epoxy copper clad laminates using the same |
| CN1868735A (en) * | 2006-04-13 | 2006-11-29 | 上海南亚覆铜箔板有限公司 | Non-halogen epoxide glass cloth base copper coated foil plate and its preparation method |
| CN101654005A (en) * | 2008-08-22 | 2010-02-24 | 金安国纪科技股份有限公司 | Method for manufacturing halogen-free FR-4 copper-clad laminate |
Non-Patent Citations (2)
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| 《印制电路信息》 20070310 辜信实 "三无"环保型覆铜板的开发 , * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897395A (en) * | 2014-03-28 | 2014-07-02 | 哈尔滨工程大学 | Preparation method of hydrotalcite and polyimide composite foam material |
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