CN1460730A - 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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- CN1460730A CN1460730A CN 03129995 CN03129995A CN1460730A CN 1460730 A CN1460730 A CN 1460730A CN 03129995 CN03129995 CN 03129995 CN 03129995 A CN03129995 A CN 03129995A CN 1460730 A CN1460730 A CN 1460730A
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Abstract
The metallization method of thermosetting resin bimaleimide resin-glass fibre composite material includes pretreatment of material surface and process of plating copper or plating nickel or plating gold or plating tin-lead alloy, and the described pretreatment includes the procedures of degreasing, cleaning, pre-etching, alcohol treatment, etching, activating, reducting and chemically-plating. The etching treatment is implemented by means of acid treatment, water washing, more acid treatment, water washing, nitrating, mixed alcali treatment and acid washing. Between metal cladding layer and base body they have good combined 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 realized by following technical proposals, the method for metallising of thermosetting resin bismaleimides-glass fiber compound material.This method comprises the pre-treatment of material surface and adopts the electroplate liquid plated copper or the process of nickel or gold or tinsel.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; 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; Consisting of of the sensitized solution of sensitization process using: SnCl
2H
2O, 10～20g/L; Hydrochloric acid (37%), 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, 0.25～1.5g/L; Hydrochloric acid (37%), 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; Formaldehyde CH
2O (37%), 14～16mL/L; α-α dipyridyl, 28～30mg/L; The pH value is 12～13; At room temperature, plating time is 30 minutes.It is characterized in that etching processing is finished through following steps: at first the sample that will handle through alcohol at room temperature immerses 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 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 concentration and be 35～50% HNO
3Kept in the solution 3～5 minutes, sample is again through after the washing, and to immerse temperature be 70～75 ℃, contain 10～15%KMnO
4In the mixing solutions that contains 30～40%KOH, kept 5～10 minutes, last, sample soaked 2～4 minutes in room temperature, concentration are 22～30% HCl solution after washing.
Through above-mentioned pretreated material, can adopt common electroplate liquid as required, further copper electroplating layer or nickel dam or golden layer 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, solderable coating can also be further electroplated on surface at this matrix material metallization coating, as nickel, tinsel etc., make this material can be used to prepare high-intensity electrical connector, also can be used for manufacturing radar reflector, radome, electromagnetic shielding base plate etc.
Embodiment
Testing used body material is QY8911-II type bimaleimide resin-glass fiber compound material, wherein the glass fibre that is adopted is a KH550 type alkali-free short glass fiber (length is less than 2mm), in the matrix material, the part by weight of resin and glass fibre is: 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; NaCO
3, 30g/L; Na
3PO
4, 25g/L; The OP emulsion, 2g/L; Temperature is 50 ℃, 30 minutes time.Lose processing then at ambient temperature in advance, promptly sample is immersed in the N-N DIMETHYL FORMAMIDE aqueous solution of 500g/L, kept 60 minutes; It is that the sample that erosion is in advance handled is put into concentration after washing be that 500mL/L, temperature are 40 ℃ ethanolic soln that alcohol is handled, and keeps 2 minutes; Etching processing need be finished through following steps: at first the sample room temperature immersion concentration after washing that will handle through alcohol is 98% H
2SO
4Kept in the solution 1 minute, it is to keep 8 minutes in 25% the HF solution that sample room temperature through washing after immerses concentration, and sample is again through washing, and room temperature immersion concentration is 40% HNO then
3Kept 5 minutes in the solution, through washing, immerse temperature then is 70 ℃ to sample, contains 12%KMnO again
4In the mixing solutions that contains 35%KOH, kept 8 minutes, last, sample soaked 3 minutes in room temperature, 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; Hydrochloric acid (37%), 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, 1g/L; Hydrochloric acid (37%), 1.5mL/L; H
3BO
3, 20g/L; The activating process condition 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; Formaldehyde CH
2O (37%), 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 consists of:
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 (1)
1. the method for metallising of a bimaleimide resin-glass fiber compound material, this method comprises to the pre-treatment of material surface and adopts the electroplate liquid plated copper or the process of nickel or gold or tinsel that described pre-treatment comprises the operation of the oil removing cleaning to material surface, pre-erosion processing, pure processing, etching, sensitization, activation, reduction and electroless 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; Consisting of of the sensitized solution of sensitization process using: SnCl
2H
2O, 10～20g/L; Hydrochloric acid (37%), 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, 0.25～1.5g/L; Hydrochloric acid (37%), 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; Formaldehyde CH
2O (37%), 14～16mL/L; α-α dipyridyl, 28～30mg/L; The pH value is 12～13; At room temperature, plating time is 30 minutes, it is characterized in that: etching processing is finished through following steps: at first the sample that will handle through alcohol at room temperature immerses concentration and is 85～98% H after washing
2SO
4Kept in the solution 1～2 minute, sample at room temperature immerses 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 concentration and be 35～50% HNO
3Kept in the solution 3～5 minutes, sample is again through after the washing, and to immerse temperature be 70～75 ℃, contain 10～15%KMnO
4In the mixing solutions that contains 30～40%KOH, kept 5～10 minutes, last, sample soaked 2～4 minutes in room temperature, concentration are 22～30% HCl solution after washing.
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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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031299954A CN1181223C (en) | 2003-06-06 | 2003-06-06 | Metallization method of bimaleimide resin-glass fibre composite material |
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| Publication Number | Publication Date |
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| CN1460730A true CN1460730A (en) | 2003-12-10 |
| CN1181223C CN1181223C (en) | 2004-12-22 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104513402A (en) * | 2013-09-29 | 2015-04-15 | 深圳光启创新技术有限公司 | Preparation method of resin fiber composite material and resin fiber composite material |
| CN105348752A (en) * | 2009-11-18 | 2016-02-24 | 帝斯曼知识产权资产管理有限公司 | RF filter housing |
| 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 |
Families Citing this family (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 |
-
2003
- 2003-06-06 CN CNB031299954A patent/CN1181223C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348752A (en) * | 2009-11-18 | 2016-02-24 | 帝斯曼知识产权资产管理有限公司 | RF filter housing |
| CN104513402A (en) * | 2013-09-29 | 2015-04-15 | 深圳光启创新技术有限公司 | Preparation method of resin fiber composite material and resin fiber composite material |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1181223C (en) | 2004-12-22 |
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