CN1246412C - Flexible printing circuit board adhesive - Google Patents
Flexible printing circuit board adhesive Download PDFInfo
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- CN1246412C CN1246412C CN 01131066 CN01131066A CN1246412C CN 1246412 C CN1246412 C CN 1246412C CN 01131066 CN01131066 CN 01131066 CN 01131066 A CN01131066 A CN 01131066A CN 1246412 C CN1246412 C CN 1246412C
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Abstract
The present invention provides adhesive for a flexible printed circuit board, which is a composition comprises the following components: (a) epoxy resin, (b) a curing accelerant, (c) nitrile rubber contaning carboxyl groups and (d) inorganic filler, wherein the weight ratio of the curing accelerant to the epoxy resin is from 0.008:1 to 0.03:1; the curing accelerant has one structural formula in two formulae, wherein E represents sulfur, nitrogen or phosphorus; Ar represents an aromatic ring; R1 represents identical or different substituted or non-substituted monovalent alkyl groups, hydroxyl groups, alkoxyl groups, nitro groups, cyano groups or halogen atoms; R2 and R3 respectively represent hydrogen atoms or methyl groups; R4 represents identical or different substituted or non-substituted monovalent alkyl groups; R5 represents substituted or non-substituted pyridinium groups; a represents an integral number from 0 to 2; b represents 2 or 3; the weight ratio of the nitrile rubber to the epoxy resin is from 1:5 to 10:1; the nitrile rubber is carboxyl group terminal group acrylonitrile bivinyl rubber divinyl rubber; the weight ratio of the inorganic filler to the epoxy resin is form 1:2 to 2:1; the inorganic filler is aluminum hydroxide.
Description
Technical field
The present invention relates to a kind ofly have high glass tansition temperature (Tg) and than the tackiness agent of long pot life, it is the composition that comprises compositions such as Resins, epoxy, hardening accelerator, carboxylic nitrile rubber and mineral filler, is mainly used in flexible print wiring board.Use the present invention, can improve the range of application and the operation processibility of flexible print wiring board.
Background technology
(Flexiblc Printed Circuit FPC) is called flexible printed circuit again to flexible print wiring board, because of having the characteristic of pliability and bendability, so can carry out tridimensional three-dimensional wiring with product available space size and shape.Various in recent years high technology equipments, as products such as photographic camera, Kamera, stereo set, disk drive, printer and mobil phones, the trend of short, little four general orientation development is arranged gradually towards light, thin, so flexible print wiring board becomes one of wherein indispensable assembly.
The structure of flexible print wiring board can be divided into five major parts basically: protection film, Copper Foil, substrate film, surface treatment and supporting material wherein are again the primary structure of flexible print wiring board with the first three items.The joint of this three part will utilize adhesive coated to glue together therebetween, and therefore, the thermotolerance of tackiness agent and stability in storage just become the principal element of decision flexible print wiring board quality.Because the heat that printed circuit board (PCB) is produced when practice and temperature, the humidity of Working environment, all can influence the usefulness and the stability in storage of tackiness agent itself, therefore, the R﹠D direction of tackiness agent is just wished to higher glass tansition temperature, and at room temperature long aspects such as shelf lives development.
Taiwan patent announcement number No. 279255 (application number 84105059) discloses the epoxy resin composition that uses an encapsulated semiconductor, this patent is the improvement at semiconductor packaging, but not at the application of flexible print wiring board manufacture method, and be the snap cure of convenient packaged material, this Resins, epoxy must contain the releasing agent as silicone oil, fluorine type hardening accelerator, wax, fluid paraffin wax, stearic metal-salt etc.
United States Patent (USP) the 5th, 162 discloses a flexible print wiring board and used tackiness agent thereof No. 140, but the sclerosis that its employed tackiness agent may contain promotes that (catalysis) agent composition is the salt of lewis acid, but not the hexafluoro-antimonic acid salt.United States Patent (USP) the 5th, 260, No. 130 also teaching can be used for the tackiness agent of flexible print wiring board, this tackiness agent is except that comprising the stiffening agent, its hardening accelerator then is the boron fluoride of zinc, tin or nickel, also the not use of teaching hexafluoro-antimonic acid salt.
Above-mentioned prior art all less than at the glass tansition temperature of flexible print wiring board tackiness agent or the improvement between the shelf lives, only belongs to connected prior art, so all and in herein for your guidance.
The present invention be directed to the achievement in research that flexible print wiring board demand is already done, it comprises Resins, epoxy, hardening accelerator, carboxylic nitrile rubber and mineral filler.Use hexafluoro antimonate to be hardening accelerator, the present invention can provide the tackiness agent of long pot life (greater than 50 days) under high glass tansition temperature of tool (140 ℃-170 ℃) and the room temperature, meets with the problem that causes the applicability variation of circuit card because of the tackiness agent unstable is too high in the use so can solve present mulch film.
Summary of the invention
The invention provides one and be used for flexible print wiring board, and have the tackiness agent of high glass tansition temperature and long pot life, it comprises Resins, epoxy, the hexafluoro antimonate as hardening accelerator, carboxylic nitrile rubber and mineral filler.
The object of the present invention is to provide a kind of tackiness agent that is applied to flexible print wiring board, it has high heat resistance, that is high glass tansition temperature, and long pot life under the room temperature, but and advantage such as snap cure simultaneously.This tackiness agent is the composition that contains following composition:
(A) a kind of Resins, epoxy;
(B) a kind of hardening accelerator, its content is 0.008: 1 to 0.03: 1 for the weight ratio with this Resins, epoxy, it has the structural formula of one of following two general formulas:
Wherein E is sulphur, nitrogen or phosphorus; Ar is an aromatic nucleus; R
1Be identical or different replacement or unsubstituted monovalence alkyl, hydroxyl, alkoxyl group, nitro, cyano group or halogen atom; R
2And R
3Be respectively hydrogen atom or methyl; R
4For replacing or unsubstituted monovalence alkyl; R
5For replacing or unsubstituted pyridine base: a is 0 to 2 integer: b is 2 or 3;
(c) carboxylic nitrile rubber: its content is 1: 5 to 10: 1 for the weight ratio with this Resins, epoxy, and is the carboxyl end groups acrylonitrile butadiene rubber; And
(d) mineral filler, its content are and the weight ratio of Resins, epoxy 1: 2 to 2: 1, and are aluminium hydroxide.
Wherein, composition (A) can be the Resins, epoxy of any molecular structure, as long as it has two or more epoxy constructions as oxyethane in each monomer molecule.
Among the present invention, Resins, epoxy can use separately, or is used in combination by the Resins, epoxy more than two kinds.In addition, being used for composition of the present invention (A) is generally under (1) normal temperature and is liquid curable epoxy, or (2) normal temperature is the liquid liquid curable Resins, epoxy and the mixture of solid-state curable epoxy down, and the latter can be diluted to liquid state with it by thinner at normal temperatures.At this, so-called " normal temperature is down for liquid " means this Resins, epoxy to have flowability and comprises so-called semisolid in the time of 25 ℃ to 40 ℃.
Indication (1) normal temperature for liquid curable epoxy, comprises molecular-weight average about 500 or bisphenol A-type liquid-state epoxy resin still less down; Bis-phenol fluorine type Resins, epoxy; Molecular-weight average about 570 or phenol phenolic resin varnish type epoxy resin still less; Cycloaliphatic epoxy resin, as 1,2-epoxy ethyl-3,4-epoxy cyclohexane, 3,4-epoxycyclohexyl carboxylic acid-3,4-epoxy hexyl methyl and two (3,4-epoxy-6-methyl cyclohexane ylmethyl) hexanodioic acids; The Racemic glycidol ether type epoxy is as hexahydrobenzene dioctyl phthalate 2-glycidyl ether-ether; 3-methyl-hexahydrobenzene dioctyl phthalate 2-glycidyl ether-ether and six hydrogen terephthalic acid 2-glycidyl ether-ethers; Glycidyl amine type epoxy resin is as two (aminomethyl) hexanaphthenes of 2-glycidyl aniline, 2-glycidyl Tolylamine, three-glycidyl-right-amido benzene, four Racemic glycidols-m-xylenedimaine and four Racemic glycidols; With glycolylurea type Resins, epoxy, as 1,3-diglycidyl-5-ethyl glycolylurea.
Be the liquid liquid curable Resins, epoxy and the mixture of solid-state curable epoxy down as for (2) normal temperature, wherein be liquid Resins, epoxy as in the previous paragraph, and normal temperature is solid-state curable epoxy down, after through the thinner dilution, it is used also to can be the present invention, as bis-phenol fluorine type Resins, epoxy, phenol phenolic resin varnish type epoxy resin, cycloaliphatic epoxy resin, Racemic glycidol ether type epoxy, glycidyl amine type epoxy resin, three hydrazine type Resins, epoxy and glycolylurea type Resins, epoxy.Thinner as used herein is to be used for dissolving or central dispersion epoxy resins, and keeps its flowability, so that any thinner that possesses this kind function all can be the present invention is used.
Composition (B) is then shown in general formula (I) or general formula (II):
Wherein E, Ar, R
1, R
2, R
3, R
4, R
5, a and b definition seen before and stated.What must emphasize is, composition (B) is an aromatic nucleus Ar via-C (R
2R
3)-be connected to sulphur, nitrogen or the equiatomic hexafluoro antimonate of phosphorus.This aromatic nucleus Ar can be phenyl ring, naphthalene nucleus, anthracene nucleus or pinane ring, wherein is preferably phenyl ring, and is more synthetic because of it.
Aromatic nucleus Ar can be not and to replace or through one or two R
1Replace.R
1Can be the straight or branched alkyl, as methyl, ethyl, propyl group, butyl, amyl group, octyl group, decyl, dodecyl and tetradecyl; Cycloalkyl is as cyclohexyl; Aryl is as phenyl and naphthyl; Alkaryl is as tolyl and xylyl; Aralkyl is as benzyl and 2-phenyl-ethyl; Thiazolinyl, as vinyl, allyl group and butenyl; The monovalence alkyl that replaces is as methyl fluoride; Hydroxyl; Alkoxyl group is as methoxyl group, oxyethyl group, propoxy-and tert.-butoxy; Nitro; Cyano group; And halogen atom, as fluorine, chlorine, bromine and iodine.If use than low activity De phosphonium salt and pyridinium salt, preferred R
1Be electron-withdrawing group or halogen atom, can get high solidification rate.Can optionally select R for use
1The position that is added, however when Ar was phenyl ring, preferred positions was 2-position and/or 4-position, to be convenient to synthetic this compound.Special excellent R
1Therefore be the group of large volume, special excellent position is the 4-position, can more can not generate steric barrier and reduces activity.
R
2And R
3Be respectively hydrogen atom or methyl, hydrogen atom preferably is so that synthetic easily this compound.When increasing catalytic activity, R at least
2And R
3One of should be methyl.
R
4Can be the straight or branched alkyl, as methyl, ethyl, propyl group, butyl, amyl group, octyl group, decyl, dodecyl and tetradecyl; Cycloalkyl is as cyclohexyl; Aromatic base, as phenyl and bitter edible plant base: alkaryl, as tolyl and xylyl; Aralkyl is as benzyl and 2-phenyl-ethyl; Thiazolinyl is as vinyl, propenyl and butenyl; The monovalence alkyl that replaces is as hydroxyphenyl; Methoxyphenyl, phenelyl, benzonitrile base, fluorophenyl, acetyl oxygen phenyl, propionyl phenyl, methoxy carbonyl phenyl and ethoxy carbonyl phenyl.
R
5Can be replacement or unsubstituted pyridine base, as pyridine, 2-or 4-picoline, 2,4-lutidine, 2-or 4-cyanopyridine, 2-or 4-methoxy carbonyl pyridine and 2-or 4-ethoxy carbonyl pyridine.Nucleophilic group preferably is as the cyano group of 2-position or 4-position.
Composition (B) can be sulfonium salt, as hexafluoro-antimonic acid methyl (4-methoxy-benzyl) (1-menaphthyl) sulfonium salt, hexafluoro-antimonic acid methyl (4-hydroxybenzyl) benzyl sulfonium salt, hexafluoro-antimonic acid dimethyl benzyl sulfonium salt, hexafluoro-antimonic acid dimethyl (4-methyl-benzyl) sulfonium salt, hexafluoro-antimonic acid dimethyl (4-methoxy-benzyl) sulfonium salt, hexafluoro-antimonic acid dimethyl (4-ethoxy benzyl) sulfonium salt, hexafluoro-antimonic acid dimethyl (4-tert.-butoxy benzyl) sulfonium salt, hexafluoro-antimonic acid dimethyl (4-nitrobenzyl) sulfonium salt, hexafluoro-antimonic acid dimethyl (4-cyano group benzyl) sulfonium salt, hexafluoro-antimonic acid dimethyl (4-benzyl chloride base) sulfonium salt, hexafluoro-antimonic acid aminomethyl phenyl benzyl sulfonium salt, hexafluoro-antimonic acid (4-acrinyl)-benzyl sulfonium salt, hexafluoro-antimonic acid dimethyl (1-menaphthyl) sulfonium salt, hexafluoro-antimonic acid methyl (4-hydroxyl) (1-menaphthyl) sulfonium salt, hexafluoro-antimonic acid dimethyl (α aminomethyl phenyl) sulfonium salt etc.; Ammonium salt, as hexafluoro-antimonic acid trimethyl benzyl ammonium salt, hexafluoro-antimonic acid 3,5-dimethylphenyl benzyl ammonium salt, hexafluoro-antimonic acid 3,5-dimethylphenyl (4-nitre benzyl) ammonium salt, hexafluoro-antimonic acid (4-cyanobenzyl) ammonium salt, hexafluoro-antimonic acid (4-benzyl chloride base) ammonium salt etc.: phosphonium salt, as hexafluoro-antimonic acid triphenyl benzyl base phosphonium salt; Salt, as hexafluoro-antimonic acid triphenyl (4-nitrobenzyl) pyridinium salt, hexafluoro-antimonic acid (4-methyl-benzyl)-4-cyanogen pyridinium salt, hexafluoro-antimonic acid (4-tertiary butyl benzyl)-4-cyanogen pyridinium salt, hexafluoro-antimonic acid (4-methoxy-benzyl)-4-cyanogen pyridinium salt, hexafluoro-antimonic acid (4-benzyl chloride base)-4-cyanogen pyridinium salt, hexafluoro-antimonic acid (α-Jia Bianji)-4-cyanogen pyridinium salt, hexafluoro-antimonic acid benzyl-2-cyanogen pyridinium salt, hexafluoro-antimonic acid (α-Jia Bianji)-2-cyanogen pyridinium salt, hexafluoro-antimonic acid 4-oxygen carbonyl pyridine salt etc.
Composition (C) is carboxylic nitrile rubber, its be the copolymerization rubber of vinyl cyanide and divinyl and in molecule chain end by carboxylic acidization.Preferably, the nitrile of this carboxyl, rubber are the carboxyls that contains 2 to 8 weight %.For example, but be not limited to, can use the carboxyl end groups acrylonitrile butadiene rubber to be composition (C) in the present invention.
Composition (D) is mineral filler, and it can make the present invention that less shrinkage is arranged in solidification process, includes ground silica and spherical silica, thickness silica and precipitated silica; Aluminum oxide, titanium oxide, zirconium white, weisspiessglanz, aluminium hydroxide, lime carbonate, glass bead, boron nitride, aluminium carbide, aluminium nitride, powder such as aluminium nitride, silicon carbide, silicon nitride, nitro silicon carbide, titanium carbide, titanium nitride all can use.
In the present composition, composition (C) should be between 1/5 to 10/1 than the mixed weight ratio of composition (B), and if ratio is greater than 10/1, and then its thermotolerance of the tackiness agent of Sheng Chenging is with relatively poor, if ratio is less than 1/5, and then the bounding force of the tackiness agent of Sheng Chenging will be lower: preferably between 1/2 to 2/1.In addition, composition (B) mixes ratio with the weight of composition (A) should be between 0.05% to 10%, if be lower than 0.05%, then the solidification rate of the tackiness agent of Sheng Chenging will be lower, otherwise, if be higher than 10%, then the tackiness agent of Sheng Chenging is when uncured, less stable then presents relatively poor rerum natura after the curing, preferred ratio is between 0.8% to 3%.
The present invention does not contain solidifying agent, as novolac resin, amine type compound or anhydride compound, therefore general solidifying agent the curing that can cause inhomogeneous, toxicity or water absorbability, the present invention all can avoid.In addition, the present invention also can add additives such as fire retardant, flame-retardant additive, silane or titanium coupling agent, pigment, dyestuff if necessary.
Embodiment
The present invention will be further described with following example, but scope of the present invention is not limited to these examples.
In following embodiment or Comparative Examples, employed composition is respectively:
| Code name | English name | Chinese |
| A-1 | Bisphenol A Epoxy (Epon828) | Molecular weight is the liquid-state epoxy resin of electronic-grade dihydroxyphenyl propane-Epicholorohydrin type of 380 |
| A-2 | Brominatted Epoxy (Epon 5045) | The liquid-state epoxy resin of bromination electronic-grade dihydroxyphenyl propane-Epicholorohydrin type |
| A-3 | 3,4-epoxy cyclohexane carboxylic acid-3,4-epoxycyclohexyl | |
| B-1 | Hexafluoro-antimonic acid 3,5-dimethylphenyl (4-p-methoxy-phenyl) ammonium salt | |
| B-2 | Hexafluoro-antimonic acid methyl (4-methoxy-benzyl) (1-menaphthyl) sulfonium salt | |
| B-3 | Hexafluoro-antimonic acid methyl (4-hydroxybenzyl) benzyl sulfonium salt | |
| C | CTBN | The carboxyl end groups acrylonitrile butadiene rubber |
| D | Al(OH) 3 | Aluminium hydroxide |
| DICY | Two cyanogen diamide | |
| 2MI | 2 Methylimidazoles |
And in following example,
Earlier composition (A), composition (C) and composition (D) are mixed, add methylethyl acetone as solvent, utilize shredder to grind after, make dosing I; Composition (B) with after methylethyl acetone mixes, is made dosing II; Dosing I is mixed with dosing II, utilize shredder to grind after, promptly make binder solution III.
The binder solution III that configuration is finished, set test condition with Brooker LVT type viscosity measurements instrument (Brookfied (LVT type)), do viscosity test, its leaving standstill at room temperature time when tested viscosity reaches two times of initial stage viscosity of process be called " between the shelf lives " (Pot life).In addition, use the TMA-2940 of Du Pont type thermal analyzer (Du Pont TMA2940) to set test condition, the glass tansition temperature of test binder solution III.
Embodiment 1
Step 1: preparation dosing I
A-1 50g
A-2 50g
C 100g
D 20g
Methylethyl acetone (MEK) 210g,
Behind the blended, ground four hours with shredder.
Step 2: preparation dosing II (hardening accelerator)
B-1 2g
Methylethyl acetone (MEK) 12g
Step 3: dosing I is mixed with weight ratio with dosing II at 1: 1, ground one hour with shredder afterwards.Get the binder solution of weight percent 50%.
Embodiment 2
The step of preparation tackiness agent is identical with example 1, but the hardening accelerator among the dosing II is changed into hexafluoro-antimonic acid (four-methoxy-benzyl) (naphthyl methyl) sulfonium salt (B-2) of 2g.
Embodiment 3
The step of preparation tackiness agent is identical with example 1, but the hardening accelerator among the dosing II is changed into hexafluoro-antimonic acid methyl (four-hydroxybenzyl) the benzyl sulfonium salt (B-3) of 2g.
Embodiment 4
The step of preparation tackiness agent is identical with example 3, but changes the A-1 among the dosing I into 45g, and adds 5g A-3 composition.
Embodiment 5
The step of preparation tackiness agent is identical with example 1, but changes the hardening accelerator among the dosing II into the DICY (two cyanogen diamide) of 8g and the 2MI of 1g, and gained dosing general as a comparison case 1.
Embodiment 6
The step of preparation tackiness agent is identical with example 5, but changes the hardening accelerator among the dosing II into the DICY (two cyanogen diamide) of 8g and the C of 1g
11Z-2AZINE, the gained dosing will be as a comparison case 2.
Embodiment 7
The step of preparation tackiness agent is identical with example 5, but changes the hardening accelerator among the dosing II into the DICY (two cyanogen diamide) of 8g and the C of 3g
112-2AZINE, the gained dosing will be as a comparison case 3.
Embodiment 8
Tackiness agent with embodiment 1 gained is an example.Earlier it is coated on the 25 μ m Kaptons, with the shiny surface pressing of Copper Foil, 170 ℃ of pressing-in temps, pressing pressure 20kg/cm
2, pressing time 10min, overflow glue 50-75 μ m, the thickness of tackiness agent is 30 μ m after the pressing.
Do viscosity test with Brookfied (LVT type), probe temperature is 25 ℃.Measure the glass tansition temperature with DuPont TMA 2940 in addition, test condition is 20 ℃/min for temperature rise rate under nitrogen.
Test result is as shown in the table:
| Shelf lives (Pot Life) (my god) | Tg(℃) | Kg/cm 2Bond strength | Number of flexings | ||
| ND (parallel coating direction) | TD (vertically being coated with direction) | ||||
| Embodiment 1 | 50 | 140 | 0.85 | 8163 | 10655 |
| Embodiment 2 | 90 | 150 | 0.91 | 12608 | 11333 |
| Embodiment 3 | 180 | 160 | 0.89 | 8455 | 9215 |
| Embodiment 4 | 60 | 170 | 0.87 | 10664 | 9906 |
| Comparative Examples 1 | 10 | 140 | 0.75 | 11196 | 13077 |
| Comparative Examples 2 | 20 | 88 | 0.83 | 8455 | 9215 |
| Comparative Examples 3 | 10 | 130 | 0.90 | 11338 | 11132 |
Through with the test result of Comparative Examples, and after the usefulness of the present adhesive therefor of industry compared, tackiness agent provided by the present invention had higher glass tansition temperature and long shelf lives really.
Claims (3)
1. binder composition, it comprises:
(a) a kind of Resins, epoxy is characterized in that its each monomer molecule contains the epoxy group(ing) more than at least two or two;
(b) a kind of hardening accelerator, its content is 0.008: 1 to 0.03: 1 for the weight ratio with this Resins, epoxy, it has the structural formula of one of following two general formulas:
Wherein E is sulphur, nitrogen or phosphorus; Ar is an aromatic nucleus; R
1Be monovalence alkyl identical or different replacement or unsubstituted, hydroxyl, alkoxyl group, nitro, cyano group or halogen atom; R
2With R
3Be respectively hydrogen atom or methyl; R
4Be that replace or unsubstituted monovalence alkyl; R
5For replacing or the unsubstituted pyridine base; A is 0 to 2 integer; B is 2 or 3;
(c) carboxylic nitrile rubber, its content is 1: 5 to 10: 1 for the weight ratio with this Resins, epoxy, and is the carboxyl end groups acrylonitrile butadiene rubber; And
(d) mineral filler, its content is 1: 2 to 2: 1 for the weight ratio with Resins, epoxy, and is aluminium hydroxide.
2. binder composition according to claim 1 is characterized in that it is to be used for flexible print wiring board.
3. binder composition according to claim 1 is characterized in that also adding fire retardant and flame-retardant additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01131066 CN1246412C (en) | 2001-09-10 | 2001-09-10 | Flexible printing circuit board adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01131066 CN1246412C (en) | 2001-09-10 | 2001-09-10 | Flexible printing circuit board adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1407049A CN1407049A (en) | 2003-04-02 |
| CN1246412C true CN1246412C (en) | 2006-03-22 |
Family
ID=4670339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01131066 Expired - Fee Related CN1246412C (en) | 2001-09-10 | 2001-09-10 | Flexible printing circuit board adhesive |
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| Country | Link |
|---|---|
| CN (1) | CN1246412C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1758157A1 (en) * | 2004-06-18 | 2007-02-28 | Hitachi Chemical Co., Ltd. | Resin paste for die bonding and its use |
| US20080199713A1 (en) * | 2004-07-14 | 2008-08-21 | David Murray James | Powder Coating Composition |
| CN101602925B (en) * | 2008-06-15 | 2012-09-26 | 比亚迪股份有限公司 | Halogen-free ethoxyline resin antiflaming bonding adhesive and adhesive film thereof |
| CN102689463A (en) * | 2012-05-28 | 2012-09-26 | 珠海亚泰电子科技有限公司 | Flexible copper-clad plate |
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2001
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| CN1407049A (en) | 2003-04-02 |
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