CN1181223C - Metallization method of bimaleimide resin-glass fibre composite material - Google Patents
Metallization method of bimaleimide resin-glass fibre composite material Download PDFInfo
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- CN1181223C CN1181223C CNB031299954A CN03129995A CN1181223C CN 1181223 C CN1181223 C CN 1181223C CN B031299954 A CNB031299954 A CN B031299954A CN 03129995 A CN03129995 A CN 03129995A CN 1181223 C CN1181223 C CN 1181223C
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Abstract
The present invention discloses a method for metallizing thermosetting resin bismaleimide resin-glass fiber composite material, which belongs to surface metallizing technology of non-metallic composite material. The method comprises material surface preprocessing and a process that an electroplating solution is plated on copper, nickel, gold or tin-lead alloy; the material surface preprocessing comprises processing procedures of oil removal, cleaning, pre-corrosion processing, alcohol processing, etching, sensitization, activation, recovery and chemical copper plating of material surfaces. The present invention is characterized in that etching processing is completed by the steps of acid processing, water washing, acid processing, water washing, nitration, combined soda processing, acid washing, etc. The present invention has the advantages of simple preparation processes and easy operation; besides, various waste solutions are easily processed, and a metal plating layer and a basal body have a favorable bonding state.
Description
Technical field
The present invention relates to a kind of method for metallising of thermosetting resin bimaleimide resin-glass fiber compound material, belong to the surface metalation technology of nonmetallic composite.
Background technology
Resin or plastics through surface metalation mainly are used to the alternative metals material, thereby can reduce the weight of total system significantly.All be not isolator usually, therefore have very high resistance, do not have shielding effect for irradiation of electromagnetic waves simultaneously through metallized resin.So the resin material of in electronics, electric power and consumer electronic device, using, often need be at coating surface one deck electroconductibility good metal coating of material.
Improving the sticking power between metallization coating and the resin matrix, is one of important technology in the resin metallic metallization processes.Through exploration for many years, the research of the surface metal metallization processes of many thermoplastic resins has obtained success.For example the plating pre-treatment of ABS resin is the determine bonding force problem of coating and matrix of principal solution with the coarsening technique of high chromic acid content or high sulfuric acid type solution mainly; The plating pre-treatment of the resin of thermoplastic polyimide class, mainly contain two big class methods, a class is alkaline purification, and relevant patent has U.S.Patent 6,063,445, U.S.Patent 5,441,770, soak resin surface for a long time with the certain density KOH or the NaOH aqueous solution, to reach the purpose of surface coarsening, this method is mainly used in the plating pre-treatment of the resin film of polyimide; Another kind of is acid treatment, and relevant patent has U.S.Patent 4,959,121, and its method is the surface with dense nitric acid, hydrochloric acid erosion material, to reach the purpose of alligatoring.
Summary of the invention
The object of the present invention is to provide a kind of method for metallising of thermosetting resin bimaleimide resin-glass fiber compound material.This method preparation process is simple, has the good binding state between metal plating and the matrix.
The present invention is the method for metallising of thermosetting resin bismaleimides-glass fiber compound material of being realized by following technical proposals.This method comprises the process to the pre-treatment of material surface and employing chemical bronze plating liquid plated copper.Described pre-treatment comprises cleans, loses in advance operations such as processing, pure processing, etching, sensitization, activation and reduction to the oil removing of material surface; It is at ambient temperature that pre-erosion is handled, and sample is immersed in the N-N DIMETHYL FORMAMIDE aqueous solution of 400～600g/L, keeps 50～60 minutes; Alcohol handle be sample that erosion is in advance handled to immerse concentration after washing be 400～600mL/L, temperature is in 40～50 ℃ the ethanolic soln, to keep 1～2 minute; Etching processing is finished through following steps: at first the sample that will handle through alcohol at room temperature immerses mass concentration and is 85～98% H after washing
2SO
4Kept in the solution 1～2 minute, sample is again through after the washing, at room temperature immerses mass concentration and be in 20～30% the HF solution to keep 5～10 minutes, and sample is again through after the washing, at room temperature immerses mass concentration and be 35～50% HNO
3Kept in the solution 3～5 minutes, sample is again through after the washing, immerses temperature and be 70～75 ℃, mass concentration and be 10～15% KMnO
4With mass concentration be in the mixing solutions of 30～40% KOH, kept 5～10 minutes, last, sample soaked 2～4 minutes in room temperature, mass concentration are 22～30% HCl solution after washing; Consisting of of the sensitized solution of sensitization process using: SnCl
2H
2O, 10～20g/L; Mass concentration is 37% hydrochloric acid, 40～50mL/L; The processing condition of sensitization are: the residence time in the sensitizing solution that sample at room temperature leaves standstill is 6～10 minutes.Consisting of of activation solution: PdCl
2, 0.25～1.5g/L; Mass concentration is 37% hydrochloric acid, 1～2mL/L; H
3BO
3, 15～20g/L; The condition of activating process is: the time that stops in the activation solution that sample at room temperature leaves standstill is 5～10 minutes.The reduction treatment process is that through the sample of activation treatment, the NaH that contains 40～60g/L is promptly immersed in washing a little
2PO
2H
2In the reduced liquid of O, at room temperature kept 3～5 minutes.The solution composition of electroless copper and processing condition are: CuSO
45H
2O, 15～20g/L; NaKC
4H
4O
64H
2O, 4～8g/L; Na
2EDTA, 16～20g/L; NaOH, 14～16g/L; Mass concentration is 37% formaldehyde CH
2O, 14～16mL/L; α-α dipyridyl, 28～30mg/L; The pH value is 12～13; At room temperature, plating time is 30 minutes.
Through above-mentioned pretreated material, can adopt common electroplate liquid as required, further electro-coppering, nickel, gold or tinsel layer on the surface of above-mentioned chemical plating copper layer.
This method preparation process is simple, and easy handling, various waste liquids are easy to handle, and have the good binding state between metal plating and the matrix.Bismaleimides-glass fiber compound material through surface metalation can replace metalwork, has characteristics in light weight, that intensity is high, application is wide; In addition, this matrix material is through after the surface metalation, possessed electro-magnetic screen function and electrically contacted function, on the surface of this matrix material metallization coating, can also further electroplate solderable coating, as nickel, tinsel etc., make this material can be used to prepare high-intensity electrical connector, also can be used for making radar reflector, radome, electromagnetic shielding base plate etc.
Specific embodiments
Testing used body material is QY8911-II type bimaleimide resin-glass fiber compound material, wherein the glass fibre that is adopted is the KH550 type alkali-free short glass fiber of length less than 2mm, and the part by weight of resin and glass fibre is in the matrix material: portions of resin glass fibre=7: 3.
The metallization processes of matrix material carries out according to above-mentioned technical process.Matrix at first needs through sufficient oil removing and cleaning, and the composition and the processing condition of degreasing fluid are: NaOH, 25g/L; Na
2CO
3, 30g/L; Na
3PO
4, 25g/L; The OP emulsion, 2g/L; Temperature is 50 ℃, 30 minutes time.At room temperature lose processing then in advance, promptly sample is immersed in the N-N DIMETHYL FORMAMIDE aqueous solution of 500g/L, kept 60 minutes; It is that to immerse concentration after washing be that 500mL/L, temperature are in 40 ℃ the ethanolic soln, to keep 2 minutes for sample that erosion is in advance handled that alcohol is handled; Etching processing need be finished through following steps: at first the sample that will handle through alcohol at room temperature immerses mass concentration and is 98% H after washing
2SO
4Kept in the solution 1 minute, sample at room temperature immerses mass concentration and is in 25% the HF solution and kept 8 minutes after washing, and sample is again through after the washing, at room temperature immerses mass concentration and be 40% HNO
3Kept in the solution 5 minutes, sample is again through after the washing, immerses temperature and be 70 ℃, mass concentration and be 12% KMnO
4With mass concentration be in the mixing solutions of 35% KOH, kept 8 minutes, last, sample soaked 3 minutes in room temperature, mass concentration are 25% HCl solution after washing.Samples with water through etching processing is cleaned a little, promptly implements sensitization and activation treatment.Consisting of of sensitized solution: SnCl
2H
2O, 15g/L; Mass concentration is 37% hydrochloric acid, 45mL/L; The processing condition of sensitization are: under the room temperature, the residence time of sample in the sensitizing solution that leaves standstill is 8 minutes.Consisting of of activation solution: PdCl
2, 1g/L; Mass concentration is 37% hydrochloric acid, 1.5mL/L; H
3BO
3, 20g/L; The condition of activating process is: under the room temperature, the time that sample stops in the activation solution that leaves standstill is 5 minutes.Through the sample of activation treatment, washing is a little promptly immersed room temperature, is contained the NaH of 50g/L
2PO
2H
2Kept 3 minutes in the reduced liquid of O.After the quick washing of the sample of reduction processing, to immerse in the chemical copper plating solution, the solution composition of electroless copper is: CuSO
45H
2O, 18g/L; NaKC
4H
4O
64H
2O, 5g/L; Na
2EDTA, 18g/L; NaOH, 15g/L; Mass concentration is 37% formaldehyde CH
2O, 15mL/L; α-α dipyridyl, 28mg/L; The pH value is 12; Under the room temperature, plating time is 30 minutes.Sample through electroless copper is directly implemented common bright nickel plating, and the solution additive of bright nickel plating is the commercially available prod, and its plating bath is formed and technological specification is:
NiSO
4·7H
2O 280g/L
NiCl
2·6H
2O 40g/L
H
3BO
3 40g/L
LY993(A) 9mL/L
LY993(B) 0.2mL/L
LY993(C) 0.6mL/L
LY9810 2mL/L
pH 4
50 ℃ of temperature
Current density 5A/dm
2
In the electroplating process, the thickness that adopts voltameter control electroless nickel layer is greater than 50 μ m.Adopt thermal cycling test check coating and high base strength.Thermal cycle conditions and testing sequence that test is adopted are: the classification of (1) test conditions: upper cycling temperature is 75 ± 2 ℃; The circulation lower limit temperature is-40 ± 2 ℃.(2) loop cycle testing sequence: (a) in temperature is-40 ± 2 ℃ cryostat, placed 1 hour; (b) be to place 1 hour in 20 ± 5 ℃ the clean environment in temperature; (c) in being 75 ± 2 ℃ loft drier, temperature placed 1 hour; (d) be to place 1 hour in 20 ± 5 ℃ the clean environment in temperature.Repeat 4 tests according to the condition of above-mentioned cold cycling, the outward appearance of observation sample does not have the foaming, crackle of coating, the appearance of wrinkling, bad defective such as come off.
Claims (2)
1. the method for metallising of a bimaleimide resin-glass fiber compound material, this method comprises that described pre-treatment comprises the operation that the oil removing of material surface is cleaned, lost processing, pure processing, etching, sensitization, activation, reduction and electroless copper in advance to the process of the pre-treatment of material surface and employing chemical bronze plating liquid plated copper; It is at ambient temperature that pre-erosion is handled, and sample is immersed in the N-N DIMETHYL FORMAMIDE aqueous solution of 400～600g/L, keeps 50～60 minutes; Alcohol handle be sample that erosion is in advance handled to enter concentration after washing be 400～600mL/L, temperature is in 40～50 ℃ the ethanolic soln, to keep 1～2 minute; Etching processing is finished through following steps: at first the sample that will handle through alcohol at room temperature immerses mass concentration and is 85～98% H after washing
2SO
4Kept in the solution 1～2 minute, sample at room temperature immerses mass concentration and is in 20～30% the HF solution and kept 5～10 minutes again after washing, and sample is again through after the washing, at room temperature immerses mass concentration and be 35～50% HNO
3Kept in the solution 3～5 minutes, sample is again through after the washing, immerses temperature and be 70～75 ℃, mass concentration and be 10～15% KMnO
4With mass concentration be in the mixing solutions of 30～40% KOH, kept 5～10 minutes, last, sample soaked 2～4 minutes in room temperature, mass concentration are 22～30% HCl solution after washing; Consisting of of the sensitized solution of sensitization process using: SnCl
2H
2O, 10～20g/L; The quality percentage composition is 37% hydrochloric acid, 40～50mL/L; The processing condition of sensitization are: the residence time in the sensitizing solution that sample at room temperature leaves standstill is 6～10 minutes, the consisting of of activation solution: PdCl
2, 0.25～1.5g/L; The quality percentage composition is 37% hydrochloric acid, 1～2mL/L; H
3BO
3, 15～20g/L; The activating process condition is: the time that stops in the activation solution that sample at room temperature leaves standstill is 5～10 minutes, and the reduction treatment process is that through the sample of activation treatment, the NaH that contains 40～60g/L is promptly immersed in washing a little
2PO
2H
2At room temperature kept in the reduced liquid of O 3～5 minutes, the solution composition of electroless copper and processing condition are: CuSO
45H
2O, 15～20g/L; NaKC
4H
4O
64H
2O, 4～8g/L; Na
2EDTA, 16～20g/L; NaOH, 14～16g/L; Mass concentration is 37% formaldehyde CH
2O, 14～16mL/L; α-α dipyridyl, 28～30mg/L; The pH value is 12～13; At room temperature, plating time is 30 minutes.
2. by the method for metallising of the described bimaleimide resin-glass fiber compound material of claim 1, it is characterized in that behind electroless copper, can carry out the plating of copper, nickel, gold or tinsel.
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|---|---|---|---|
| CNB031299954A CN1181223C (en) | 2003-06-06 | 2003-06-06 | Metallization method of bimaleimide resin-glass fibre composite material |
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|---|---|---|---|
| CNB031299954A CN1181223C (en) | 2003-06-06 | 2003-06-06 | Metallization method of bimaleimide resin-glass fibre composite material |
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| CN1181223C true CN1181223C (en) | 2004-12-22 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302080B (en) * | 2007-05-10 | 2011-06-15 | 西北工业大学 | Pretreatment method of chemical plating conductive magneto-conductive glass fibre |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9203130B2 (en) * | 2009-11-18 | 2015-12-01 | Dsm Ip Assets B.V. | RF filter housing |
| CN104513402B (en) * | 2013-09-29 | 2017-11-03 | 深圳光启创新技术有限公司 | The preparation method and resin fibre composite of resin fibre composite |
| CN114986792A (en) * | 2022-05-27 | 2022-09-02 | 中国第一汽车股份有限公司 | Composite molding method of metal and resin |
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2003
- 2003-06-06 CN CNB031299954A patent/CN1181223C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302080B (en) * | 2007-05-10 | 2011-06-15 | 西北工业大学 | Pretreatment method of chemical plating conductive magneto-conductive glass fibre |
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| Publication number | Publication date |
|---|---|
| CN1460730A (en) | 2003-12-10 |
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