CN101279526A - Method for manufacturing high heat-resistant copper-clad panel - Google Patents
Method for manufacturing high heat-resistant copper-clad panel Download PDFInfo
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- CN101279526A CN101279526A CNA2007100392347A CN200710039234A CN101279526A CN 101279526 A CN101279526 A CN 101279526A CN A2007100392347 A CNA2007100392347 A CN A2007100392347A CN 200710039234 A CN200710039234 A CN 200710039234A CN 101279526 A CN101279526 A CN 101279526A
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- prepreg
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Abstract
The invention relates to a method for manufacturing a high heat-resistance overlapping copper clad, which has the steps that the liquid cement is prepared; the following components are mixed in the mass ratio: bromide bisphenol A resin accounts for 1333.3, high-purity electronic grade phenolic resin accounts for 63.5 to 66.5, dimethyl imidazole accounts for 0.025 to 0.04, propylene glycol monomethyl ether accounts for 28.0 to 34.0; the glue is added: the electronic grade glass cloth is dipped with the liquid cement in the steeping vet and then is put into an oven with the temperature ranging from 150 DEG C to 210 DEG C for baking; then the prepreg is obtained after cooling and the prepreg is cut into the slice according to the required size and gathered: the a certain amount of slice-shaped pregregs are folded into pellet according to the requirement for thickness of the plate and then the two sides of the pellet are paved with a copper foil with a thickness ranging from 1/2OZ to 3OZ and pressed; a certain amount of well-gathered plates are laminated with the stainless steel plates with one corresponding to one up and down, and then are put into a vacuum press for pressing at the temperature ranging from 100 to 200 DEG C; the holding temperature of pressing arranges from 190 to 200 DEG C and the time for holding temperature is no less than 60 minutes. The high heat-resistant overlapping copper plate prepared in the method can be applied to the lead-free welding process.
Description
Technical field
The present invention relates to a kind of copper-clad plate, relate in particular to the manufacture method of this copper-clad plate.
Background technology
Enhancing day by day along with human environmental consciousness, the use of heavy metal more and more is controlled and forbids, European Union has just proposed two instructions at the beginning of 2003: 1., " using harmful substance instruction (RoHS) " about restriction in the electric appliance and electronic product and 2., " instructing (WEEE) " about scrapping the electric appliance and electronic product.Clearly in the instruction will ban use of metallic lead in the electric appliance and electronic product.In formal enforcement on July 1st, 2006, their enforcement indicates that world's electron trade will enter the pb-free solder epoch in these two instructions.
The fusing point of Pb-free solder is generally high about 30 ℃ than traditional leypewter at present, and the eutectic point of traditional leypewter (Sn63/Pb37) is 183 ℃, and the eutectic point of at present representative SAC (Sn96.5/Ag3/Cu0.5) is 217 ℃.Temperature in actual welding, the temperature potential of SAC scolder must be than the high 20-30 of Sn/Pb scolder ℃.
Solder temperature ground improves, and has brought two big hidden danger for the FR-4 substrate, and the firstth, hole copper ruptures, and it two is substrate layerings.
1. hole copper breakage problem:
Behind the basal plate heated, Z-shaft size deformation rate depends on the thermal coefficient of expansion (CTE) before and after heating temperature scope, Tg and the Tg, promptly
δ=α
1* (Tg-T
1)+α
2* (T
2-Tg) (formula 1)
δ: the Z-shaft size deformation rate behind the basal plate heated
α
1: the thermal coefficient of expansion before the Tg
α
2: the thermal coefficient of expansion behind the Tg
T
1: the initial temperature of basal plate heated
T
2: the end temp of basal plate heated
Because the raising of welding temperature, i.e. T
2Rising, common FR-4 plate still keeps the CTE value before and after the original T g, and the Tg of common FR-4 plate is generally at 130 ℃-140 ℃, that have an effect in the temperature elevation process so is CTE behind the Tg, and the CTE behind the general Tg is about 4 times before the Tg, cause the Z-direction of principal axis size distortion that causes because of the variation that heats up big, be easy to cause copper facing fracture in the hole.
2. lamination problem:
Adopt dicyandiamide as curing agent in the common FR-4 plate resin system, because the poor heat resistance high temperature of dicyandiamide self easily decomposes, when common FR-4 plate ran into the high-temperature process of long period, substrate was easy to layering, brought fatal harm to sheet material.
Be subjected to extensive discussion for the exploitation applicable to the high heat-resistant copper-clad panel of pb-free solder, present many clients still adopt common FR-4 plate to deal with leadless process, bring so inevitably than the highland percent defective always.From formula 1 as can be known, because α
2Will be much larger than α
1So, improve the deformation rate that Tg can reduce sheet material.
How to address this problem is the technical problem that engineers and technicians will solve.
Summary of the invention
The technical issues that need to address of the present invention have provided a kind of manufacture method of high heat-resistant copper-clad panel, are intended to solve the above problems.
In order to solve the problems of the technologies described above, the present invention realizes by following steps:
The allotment glue; Each component in the glue is carried out proportioning by following prescription with the quality share:
Brominated bisphenol A resin 133.3, high-purity electron level phenolic resins 63.5-66.5, methylimidazole 0.025-0.04, propylene glycol monomethyl ether 28.0-34.0;
Gluing; The electron level glass cloth toasts in 150 ℃ of-210 ℃ of baking ovens through entering temperature behind the impregnated glue of steeping vat, obtains prepreg through cooling again; Prepreg is cut into sheet by needed size;
Folded joining; According to the sheet metal thickness needs, the sheet prepreg of some is built up pellet, apply Copper Foil on the two sides of this pellet then; Copper thickness is between 1/2OZ-3OZ;
Compacting; The folded sheet material for preparing of some is corresponding one to one superimposed up and down with corrosion resistant plate, send vacuum press then to, between 100 ℃-200 ℃, to suppress, 190 ℃-200 ℃ of the holding temperature scopes of compacting, temperature retention time are no less than 60 minutes.
Compared with prior art, the invention has the beneficial effects as follows: sheet material more common FR-4 on hear resistance is significantly improved, and can be used for the pb-free solder processing procedure.
The specific embodiment
Below in conjunction with the specific embodiment the present invention is described in further detail:
The present invention is from improving sheet material Tg and using curing agent two aspects instead and start with and solve above-mentioned two big hidden danger.
The present invention realizes by following steps:
The allotment glue; Each component in the glue is carried out proportioning by following prescription with the quality share:
Brominated bisphenol A resin 133.3, high-purity electron level phenolic resins 63.5-66.5, methylimidazole 0.025-0.04, propylene glycol monomethyl ether 28.0-34.0;
Gluing; The electron level glass cloth toasts in 150 ℃ of-210 ℃ of baking ovens through entering temperature behind the impregnated glue of steeping vat, obtains prepreg through cooling again; Prepreg is cut into sheet by needed size; The basic parameter scope of prepreg is:
Resin content: 40-64%
Gel time: 70-100 second
Mobile: 18-35%
Folded joining; According to the sheet metal thickness needs, the sheet prepreg of some is built up pellet, apply Copper Foil on the two sides of this pellet then; Copper thickness is between 1/2OZ-3OZ;
Compacting; The folded sheet material for preparing of some is corresponding one to one superimposed up and down with corrosion resistant plate, send vacuum press then to, between 100 ℃-200 ℃, to suppress, 190 ℃-200 ℃ of the holding temperature scopes of compacting, temperature retention time are no less than 60 minutes.
The raw material source that relates among the present invention:
Brominated bisphenol A epoxy resin: the GEBR-558MK75 of Hongchang Electronic Material Inustry Co., Ltd., Guangzhou
High-purity electron level phenolic resins: the GERH-832K65 of Hongchang Electronic Material Inustry Co., Ltd., Guangzhou; The BN120A70 of Changchun Artificial Resin Factory Co. Ltd.
Methylimidazole: Ningxia Darong Chemical and Metallurgy Co., Ltd.'s methylimidazole
Propylene glycol monomethyl ether: Yida Chemical Co., Ltd.'s propylene glycol monomethyl ether
Embodiment 1:
| Brominated bisphenol A epoxy resin (g) | 133.3 |
| High-purity electron level phenolic resins (g) | 63.5 |
| Methylimidazole (g) | 0.030 |
| Propylene glycol monomethyl ether (g) | 30 |
| Prepreg resin content (%) | 41.5 |
| Prepreg gel time (S) | 80 |
| Tg, the DSC method (℃) | 174.6 |
| T-288 (minute) | 26 |
| Caloric deformation rate, 50 ℃-260 ℃ (%) | 3.0 |
Embodiment 2:
| Brominated bisphenol A epoxy resin (g) | 133.3 |
| High-purity electron level phenolic resins (g) | 66.5 |
| Methylimidazole (g) | 0.028 |
| Propylene glycol monomethyl ether (g) | 29 |
| Prepreg resin content (%) | 42.5 |
| Prepreg gel time (S) | 81 |
| Tg, the DSC method (℃) | 177.9 |
| T-288 (minute) | 28 |
| Caloric deformation rate, 50 ℃-260 ℃ (%) | 3.2 |
Embodiment 3:
| Brominated bisphenol A epoxy resin (g) | 133.3 |
| High-purity electron level phenolic resins (g) | 66.5 |
| Methylimidazole (g) | 0.035 |
| Propylene glycol monomethyl ether (g) | 34 |
| Prepreg resin content (%) | 42.5 |
| Prepreg gel time (S) | 72 |
| Tg, the DSC method (℃) | 176.2 |
| T-288 (minute) | 25 |
| Caloric deformation rate, 50 ℃-260 ℃ (%) | 3.3 |
Test result of the present invention is as follows:
| Pilot project | Range of results | Representative value |
| 1. peel strength pound/inch, minimum of a value A1/2 ounce copper foil accepting state thermal stress improve be exposed to mill solution under the temperature after | ≥6.0 ≥6.0 ≥4.0 ≥4.5 | 6.8-7.8 6.8-7.8 5.5-6.5 5.5-6.5 |
| 2. volume resistance, minimum of a value, M Ω .CM is improving under the temperature | ≥10 3 | 10 6 |
| 3. sheet resistance, minimum of a value, M Ω is improving under the temperature | ≥10 3 | 10 6 |
| 4. water imbibition, maximum (%) | ≤0.35 | 0.15-0.20 |
| 5. breakdown voltage, minimum of a value (KV), stepping | ≥40 | 65 |
| 6. bending strength, minimum of a value (kip/inch) warp-wise broadwise | ≥60 ≥50 | 68 58 |
| 7. arc resistance, minimum of a value, second | ≥60 | 80 |
| 8. anti-flammability | UL94V0 | UL94V0 |
| 9. solderability | Can weld | Can weld |
| 10. dielectric constant is under the 1MHZ | ≤5.4 | 4.6 |
| 11. loss angle tangent is under the 1MHZ | ≤0.035 | 0.018 |
| 12. bending and warpage, maximum (%) two-sided (sheet metal thickness is greater than 0.78mm) single face (sheet metal thickness is greater than 0.78mm) | ≤0.7 ≤1.0 | 0.15 0.30 |
| 13. thermal stress, 288 ℃, 20 seconds samples after the etching of etching sample not | NO DEFECT NO DEFECT | NO DEFECT NO DEFECT |
| 14. glass transition temperature, TG (DSC, ℃) | ≥170 | 178 |
| 15. heat decomposition temperature, TD (TGA, 10 ℃/Min), ℃ | ≥325 | 344 |
| 16. hear resistance T-260, minute T-288, minute | ≥30 ≥5 | 60 25 |
| 17. 50 ℃-260 ℃ of caloric deformation rates, % | ≤3.5 | 2.8-3.3 |
。
Claims (2)
1. the manufacture method of a high heat-resistant copper-clad panel, realize by following steps:
The allotment glue: each component in the glue is carried out proportioning by following prescription with the quality share:
Brominated bisphenol A resin 133.3, high-purity electron level phenolic resins 63.5-66.5, methylimidazole 0.025-0.04, propylene glycol monomethyl ether 28.0-34.0;
Gluing: the electron level glass cloth toasts in 150 ℃ of-210 ℃ of baking ovens through entering temperature behind the impregnated glue of steeping vat, obtains prepreg through cooling again; Prepreg is cut into sheet by needed size;
Folded joining: according to the sheet metal thickness needs, the sheet prepreg of some is built up pellet, apply Copper Foil on the two sides of this pellet then; Copper thickness is between 1/2OZ-3OZ;
Compacting: the folded sheet material for preparing and the corrosion resistant plate of some is corresponding one to one superimposed up and down, send vacuum press then to, between 100 ℃-200 ℃, to suppress, 190 ℃-200 ℃ of the holding temperature scopes of compacting, temperature retention time are no less than 60 minutes.
2. the manufacture method of high heat-resistant copper-clad panel according to claim 1, in the gluing step: the basic parameter scope of prepreg is:
Resin content: 40-64%
Gel time: 70-100 second
Mobile: 18-35%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100392347A CN101279526B (en) | 2007-04-06 | 2007-04-06 | Method for manufacturing high heat-resistant copper-clad panel |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100392347A CN101279526B (en) | 2007-04-06 | 2007-04-06 | Method for manufacturing high heat-resistant copper-clad panel |
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| Publication Number | Publication Date |
|---|---|
| CN101279526A true CN101279526A (en) | 2008-10-08 |
| CN101279526B CN101279526B (en) | 2011-10-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100392347A Active CN101279526B (en) | 2007-04-06 | 2007-04-06 | Method for manufacturing high heat-resistant copper-clad panel |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101808466A (en) * | 2010-03-24 | 2010-08-18 | 腾辉电子（苏州）有限公司 | Manufacturing method of copper-clad plate and glue solution for copper-clad plate |
| CN101905559A (en) * | 2010-07-08 | 2010-12-08 | 广东生益科技股份有限公司 | Method and device for controlling temperature of mirror steel plate after cleaning |
| CN101560287B (en) * | 2009-05-15 | 2011-03-02 | 联茂(无锡)电子科技有限公司 | Thermofixation plastic resin for accelerating thermofixation |
| CN102173173A (en) * | 2011-02-28 | 2011-09-07 | 浙江华正新材料股份有限公司 | Attraction material device and manufacturing method thereof |
| CN102275354A (en) * | 2011-06-10 | 2011-12-14 | 苏州生益科技有限公司 | Method for manufacturing tinsel laminate for improving thickness uniformity of insulating layer |
| CN103963414A (en) * | 2014-05-27 | 2014-08-06 | 铜陵浩荣华科复合基板有限公司 | Method for preparing halogen-free and lead-free high-flame-retardant Tg copper-clad laminate |
| CN104582248A (en) * | 2014-12-23 | 2015-04-29 | 广东生益科技股份有限公司 | FR4 reinforcement plate production method and FPC (flexible printed circuit) reinforcement method |
| CN106476408A (en) * | 2016-08-29 | 2017-03-08 | 上海国纪电子材料有限公司 | A kind of preparation method of P10 copper-clad plate |
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2007
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560287B (en) * | 2009-05-15 | 2011-03-02 | 联茂(无锡)电子科技有限公司 | Thermofixation plastic resin for accelerating thermofixation |
| CN101808466A (en) * | 2010-03-24 | 2010-08-18 | 腾辉电子（苏州）有限公司 | Manufacturing method of copper-clad plate and glue solution for copper-clad plate |
| CN101808466B (en) * | 2010-03-24 | 2011-09-28 | 腾辉电子（苏州）有限公司 | Manufacturing method of copper-clad plate and glue solution for copper-clad plate |
| CN101905559B (en) * | 2010-07-08 | 2013-06-12 | 广东生益科技股份有限公司 | Method and device for controlling temperature of mirror steel plate after cleaning |
| CN101905559A (en) * | 2010-07-08 | 2010-12-08 | 广东生益科技股份有限公司 | Method and device for controlling temperature of mirror steel plate after cleaning |
| CN102173173A (en) * | 2011-02-28 | 2011-09-07 | 浙江华正新材料股份有限公司 | Attraction material device and manufacturing method thereof |
| CN102173173B (en) * | 2011-02-28 | 2013-08-14 | 浙江华正新材料股份有限公司 | Attraction material device and manufacturing method thereof |
| CN102275354A (en) * | 2011-06-10 | 2011-12-14 | 苏州生益科技有限公司 | Method for manufacturing tinsel laminate for improving thickness uniformity of insulating layer |
| CN103963414A (en) * | 2014-05-27 | 2014-08-06 | 铜陵浩荣华科复合基板有限公司 | Method for preparing halogen-free and lead-free high-flame-retardant Tg copper-clad laminate |
| CN103963414B (en) * | 2014-05-27 | 2016-03-23 | 铜陵浩荣华科复合基板有限公司 | The fire-retardant High Tg CCL preparation method of a kind of halogen-free and lead-free |
| CN104582248A (en) * | 2014-12-23 | 2015-04-29 | 广东生益科技股份有限公司 | FR4 reinforcement plate production method and FPC (flexible printed circuit) reinforcement method |
| CN104582248B (en) * | 2014-12-23 | 2017-11-03 | 广东生益科技股份有限公司 | A kind of production method of FR4 stiffening plates and FPC reinforcement |
| CN106476408A (en) * | 2016-08-29 | 2017-03-08 | 上海国纪电子材料有限公司 | A kind of preparation method of P10 copper-clad plate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101279526B (en) | 2011-10-19 |
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Owner name: GDM TECHNOLOGY (ZHUHAI) CO., LTD. Free format text: FORMER OWNER: GOLDENMAX INTERNATIONAL TECHNOLOGY CO., LTD. Effective date: 20120203 |
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Effective date of registration: 20120203 Address after: 519040 Guangdong city of Zhuhai Province Qin stone industrial district Sanzao town Jinwan District Qin Shi Road No. 8 Patentee after: GOLDENMAX INTERNATIONAL TECHNOLOGY (ZHUHAI) LTD. Address before: 201600 Shanghai City Baosheng Industrial Zone Songjiang Road No. 33 Patentee before: Goldenmax International Technology Co., Ltd. |