CN102121108B - Compound OSP treating agent for lead-free printed circuit board - Google Patents
Compound OSP treating agent for lead-free printed circuit board Download PDFInfo
- Publication number
- CN102121108B CN102121108B CN2011100433555A CN201110043355A CN102121108B CN 102121108 B CN102121108 B CN 102121108B CN 2011100433555 A CN2011100433555 A CN 2011100433555A CN 201110043355 A CN201110043355 A CN 201110043355A CN 102121108 B CN102121108 B CN 102121108B
- Authority
- CN
- China
- Prior art keywords
- osp
- circuit board
- printed circuit
- treatment agent
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004987 o-phenylenediamines Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/05—Patterning and lithography; Masks; Details of resist
- H05K2203/0562—Details of resist
- H05K2203/0591—Organic non-polymeric coating, e.g. for inhibiting corrosion thereby preserving solderability
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax or thiol
- H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
本发明涉及无铅印制电路板用复配OSP处理剂，用于印制电路板铜面形成优良可焊性保护膜。它公开了作为成膜活性成分是一个复配的咪唑化合物，即由二氟代苄基苯并咪唑和2,4位二芳基取代的咪唑化合物组成。所述二氟代苄基苯并咪唑为新的有机化合物，用量比例为0.01～0.1wt%，所述2,4位二芳基取代咪唑的用量比例为0.1～1.0wt%。本发明的处理剂不含溴、铅、汞等有害物质，绿色环保，符合欧盟RoHS标准和REACH法规，在印制电路板形成的OSP膜对铜焊盘有非常出色的保护功能，其抗氧化、抗变色和可焊性能力优良，克服内存插槽孔上锡不良的问题。所述二氟代苄基苯并咪唑结构通式如下：。The invention relates to a compound OSP treatment agent for a lead-free printed circuit board, which is used for forming a protective film with excellent solderability on the copper surface of the printed circuit board. It discloses that the film-forming active ingredient is a complex imidazole compound, which is composed of difluorobenzylbenzimidazole and imidazole compound substituted by 2 and 4-position diaryl groups. The difluorobenzylbenzimidazole is a new organic compound, and the usage ratio is 0.01-0.1 wt%, and the usage ratio of the 2,4-position diaryl-substituted imidazole is 0.1-1.0 wt%. The treatment agent of the present invention does not contain bromine, lead, mercury and other harmful substances, is green and environmentally friendly, and complies with EU RoHS standards and REACH regulations. The OSP film formed on the printed circuit board has a very good protective function for copper pads, and its oxidation resistance , Anti-discoloration and excellent solderability, overcome the problem of poor tin on the memory slot hole. The general structural formula of the difluorobenzylbenzimidazole is as follows:.
Description
Technical field
The present invention relates to a kind of copper face OSP treatment agent that is applicable to printed circuit board multiple high temp leadless welding and preparation method thereof, be used for copper face and form good weldability protective membrane, have that normal temperature is antirust, advantages such as high-temperature oxidation resistant and energy-conserving and environment-protective.
Background technology
When printed circuit board (pcb) at high temperature carried out components and parts welding (referring in particular to unleaded Reflow Soldering), the protection copper pad is avoided high temperature oxidation, kept its weldability was very important.If copper face oxidation or other pollution is arranged before welding can cause the welding effect of solder joint poor after the welding, shearing resistance is low, the danger that not only has solder joint to come off, even can cause components and parts in use to take place overheated and burn.Traditional method is to adopt hot air leveling technology (HASL) to protect bond pad copper in PCB manufacturing and assembling process, to avoid polluting and oxidation.But traditional HASL technology exists some significantly not enough: 1) pad unfairness is prone to when causing the SMT paster depart from, and causes dislocation or short circuit; Temperatures involved when 2) receiving the HASL technological operation, printed circuit board are prone to take place plate face warpage under thermal shocking; 3) the HASL high temperature thermal shocking causes the fine rule Louis to break to form opening circuit, then be easy to generate bridge joint so that short circuit between the lead of thin space; 4) be prone to form crystalline compound between scolder and the copper, be prone to crisp; High temperature and noise when 5) operating are unfavorable for environmental protection, also have fire alarm hidden danger simultaneously; 6) be applicable to that lead welding connects, do not met international unleaded trend; 7) production cost is higher.Under this background, an urgent demand of PCB industry adopts new technology to substitute traditional hot air flattening technology, and OSP wherein (organic weldable protective agent) technology is a kind of excellent selection.
OSP (Organic Solderability Preservative, organic weldable protective agent) is water-soluble organosilicon prepolymer solder flux again, and domestic more popular address is the copper face inhibitor, is a kind of product of unleaded, water-soluble, environmental protection.This technology is through being immersed in the naked copper printed circuit board in the OSP treatment solution; To utilize complex reaction optionally to form a layer thickness on PCB copper surface be the hydrophobic nature organic membrane of 0.2 ~ 0.5mm, avoided pcb board after storing transportation and SMT/SMD before the copper face oxidation and on causing tin bad.This layer organic protective film can not only be avoided bond pad copper oxidation under the welding hot environment; And in the SMT/SMD process, can and make fresh copper face expose out, thereby guarantee that the fused solder system can spread out on the copper surface easily and accomplish the welding alloy reaction with copper by the rapid dissolving of soldering flux.These technological characteristics are: 1) surface is evenly smooth, and thickness 0.2 ~ 0.5mm is very suitable for the manufacturing of SMT attachment process and thin wire, thin space pcb board; 2) aqueous solution operation, safety and environmental protection, and service temperature is low, generally is lower than 60 ℃, thus can not cause substrate warp, and avoided the high temperature, noise and the disaster hidden-trouble that produce in the production process; 3) soft being prone to of rete welded, and be good with the soldering flux compatibility, and can bear the Reflow Soldering thermal shocking more than 3 times; 4) do not have IMC to form between OSP film and the bond pad copper, scolder and copper directly weld when allowing welding, so solder joint is firm especially, and shearing resistance is very high; 5) add the energy consumption in man-hour seldom, overall operation cost is than hot blast leveling (HASL) technology low 25 ~ 50%; 6) preservation period can reach 1 year, and is easy to reprocess.
The OSP technical development experienced so far the three major types material and five generation azole development.The three major types material is meant that three kinds of rosin based (Rosin), reactive resin class (Active Resin) and azoles (Azole) once appearred in the used host chemical type of OSP technology.That use is the widest at present is azole OSP, and azole OSP has passed through the improvement in about 5 generations, and this five generation abbreviates BTA respectively as, IA, BIA, SBA and newer APA according to the female structure of encircling of its azole.Early stage BTA class and IA class are responsive to humidity, in stock's life-span very short (only 3 months), can not bear heating for multiple times, and need stronger soldering flux, so performance is not so good.The technical specialist of united states, japan and other countries is through updating the azole structure; The OSP protective membrane is constantly increased in the performance of aspects such as wet fastness, high temperature resistance and weldability; BTA class OSP from the first-generation develops into current widely used APA class OSP; Thereby during this period, the patent documentation of a lot of relevant OSP Technologies has appearred.People's such as Ishiko USP 5 for example; 658; 611 for the manufacturing of PCB provides the combination of a kind of aqueous surface-treating agent, contains benzimidizole derivatives, and to regulate the pH value with the hydrochloride of heavy metal ion such as copper, manganese, zinc (content is no more than 50ppm) be 1 ~ 5.Wherein, the active principle benzimidizole derivatives can be represented its chemical structure with following general formula:
In the formula; X be one be selected from that alkyl, halo are amino, lower dialkyl is amino, the group of lower alkoxy, cyanic acid, ethanoyl, benzoyl-, formamyl, carboxyl, lower alkoxycarbonyl and nitro; Carbonatoms is 1-7, and n and p are the integer of 0-4, and m is 1 integral multiple.
People's such as Kinoshita USP 5; 173,130 disclose a kind of copper surface treatment method, comprise the copper face immersion is contained in benzimidazole compound and a kind of organic acid aqueous solution; This compound has the alkyl of at least 3 carbon atoms on 2, general structure is following:
In the formula, the R representative has the alkyl of 3 carbon atoms at least.
People's such as Hirao USP 5,498,301 and 5,560,785 have been adopted 2-Aryimidazole compound to improve the thermotolerance and the wet fastness of OSP film as active ingredient, and general structure is following:
In the formula, R is Wasserstoffatoms or methyl, and R1 and R2 are Wasserstoffatoms, low alkyl group or halogen atom, and R3 and R4 are Wasserstoffatoms, low alkyl group, halogen atom, lower alkoxy, low-grade alkyl amino, cyanic acid or nitro.
In the European patent EP 0791671 disclosed surface treatment agent prescription of Hirao; The aqueous solution, title complex and the iron ion that contain imidazolium compounds or benzimidazole compound; They think that this treatment agent can optionally only form chemical rete on the copper surface, and can film forming at other metals such as Au surface.
People's such as Adams USP 5,362,334 discloses a kind of metal surface treating liquid, and principal constituent benzimidazole compound wherein has halogenophenyl, halogeno-benzyl or halogenated ethyl phenyl on 2.And in USP 5,376, the 189 disclosed aqueous surface treatment solutions of Kukanskis, benzimidazole compound has connected a carboxyl or sulfonic group directly or indirectly, and general structure is following:
The Wengenroth Karl F of U.S. Enthone company has then creatively used a kind of precoating technology in patent US6524644; Substituted benzimidazole compound beyond containing 2 in the pretreatment fluid; Cooperate with the organic weldable sanitas; Also can make OSP only at the copper surface deposition, and can not pollute golden face.
The people such as the great man of virtue and ability of horizontal tail of Japan Shikoku Chem have then proposed to increase in the OSP prescription innovation way of the glyconic acid compound of 0.01 ~ 50wt% in patent CN101448978.
Research in China personnel have also done some effort to the improvement of OSP technology, like people such as Huang Yan adding has antioxygenation in the OSP prescription the calixarene kind compound and the sulfo-calixarene kind compound (number of patent application 200910058833.2) of Sichuan University; The Yuan Jinan of Hunan rel electronics then is used as filmogen (number of patent application 200810031056.8) etc. with polybenzimidazole zinc class or derivatives thereof.
Although above so many technological improvement is arranged; Yet when the OSP disposable plates repeatedly torments down at unleaded Reflow Soldering pyritous, the OSP film still can wear out very soon; Last tin rate descends rapidly; The plug-in unit wave soldering technology of particularly after Reflow Soldering 2 ~ 3 times, carrying out, the scolder climb rate and the last tin rate in memory bank (DIMM) hole are difficult to meet the demands, and do not have which OSP supplier's of family product can satisfy requirement of client preferably at present.And many SMT assembling plant is all adopted neutral, cleaning-free scaling powder now, and the last tin problem in this dimm socket hole is particularly outstanding.Must employ strong active soldering flux and could incite somebody to action that aged OSP film pushes away away the completion welding smoothly.Yet strong active soldering flux can influence its long-term reliability and electric property especially to having adverse influence the work-ing life of circuit card.Under the situation of last resort, SMT producer is unwilling to use strong active scaling powder.
Summary of the invention
The purpose of this invention is to provide a kind of copper face OSP treatment agent that can satisfy thermotolerance and this two aspect of weldableness; Its formed OSP film on printed circuit board has very outstanding defencive function to copper pad; Not only its anti-discolouring, resistance of oxidation are good; And can overcome the bad problem of last tin in above-mentioned DIMM hole, for vast PCB assembling plant provides a kind of effective terms of settlement.
The objective of the invention is to realize through following manner.
OSP treatment agent of the present invention, its essentially consist are to contain composite glyoxaline compound, organic acid, metallic compound, halogenide, buffer reagent and water.Wherein, glyoxaline compound is by new difluoro benzyl benzoglyoxaline and 2,4 composite forming of the substituted imidazolium compounds of diaryl.The general structure of difluoro benzyl benzoglyoxaline is following:
Compound (1): 2-(2, the 6-difluorobenzyl)-5-methyl isophthalic acid-H-benzoglyoxaline, 208 ℃ of fusing points (m.p.); Infrared IR (KBr), n/cm
-1: 3447.8 (w), 3025.0 (w), 2945.3 (w), 2867.1 (w), 1627.0 (w), 1485.3 (s), 1470.8 (s), 1456.2 (s), 1276.4 (s), 1015.8 (s), 802.0 (m), 785.7 (m);
1HNMR (300MHz, CDCl
3), δ (ppm): 4.3 (s, 2H), 6.8 ~ 7.1 (m, 3H), 7.2 ~ 7.4 (m, 3H), 2.5 (s, 3H); MS (APCI, m/Z, %): 258 (M
+, 61.9), 257 (21.2), 239 (100), 222 (5.8), 145 (3.1), 127 (9.3), 118 (6.4), 77 (5.9); Ultimate analysis (C
15H
12F
2N
2Theoretical value C 69.76, and H 4.68, and N 10.85, and F 14.71) measured value: C 69.73, H 4.76, and N 10.78, and F 14.70;
Compound (2): 2-(2, the 6-difluorobenzyl)-1-H-benzoglyoxaline, 243 ℃ of fusing points (m.p.); Infrared IR (KBr), n/cm
-1: 3448.1 (w), 3051.1 (w), 2950.3 (w), 2887.1 (w), 1628.8 (s), 1485.8 (s), 1471.2 (s), 1457.9 (s), 1288.9 (s), 1031.9 (s), 785.5 (m), 756.5 (m);
1HNMR (300MHz, CDCl
3), δ (ppm): 4.3 (s, 2H), 6.8 ~ 7.1 (m, 3H), 7.1 ~ 7.2 (m, 4H); MS (APCI, m/Z, %): 244 (M
+, 58.6), 243 (16.8), 225 (100), 127 (10.0), 112 (5.9), 77 (5.0); Ultimate analysis (C
14H
10F
2N
2Theoretical value C 68.85, and H 4.13, and N 11.47, and F 15.56) measured value: C 68.77, H 4.11, and N 11.46, and F 15.57;
Compound (3): 2-(3, the 4-difluorobenzyl)-1-H-benzoglyoxaline, 161 ℃ of fusing points (m.p.); Infrared IR (KBr), n/cm
-1: 3447.5 (w), 3083.8 (w), 2998.4 (w), 2737.3 (w), 1612.9 (w), 1537.7 (s), 1516.7 (s), 1456.2 (s), 1420.5 (s), 1282.8 (s), 766.0 (s), 747.6 (m);
1HNMR (300MHz, CDCl
3), δ (ppm): 4.2 (s, 2H), 6.9 ~ 7.1 (m, 3H), 7.2 ~ 7.6 (m, 4H); MS (APCI, m/Z, %): 244 (M
+, 95.5), 243 (100.0), 225 (6.4), 131 (10.5), 112 (5.1), 77 (4.3); Ultimate analysis (C
14H
10F
2N
2Theoretical value C 68.85, and H 4.13, and N 11.47, and F 15.56) measured value: C 68.73, H 4.21, and N 11.50, and F 15.56.
[0015]Through screening, we find that the difluoro benzyl benzoglyoxaline of above-mentioned three kinds of new textures has particular performances, is used in the OSP treatment agent formula and can plays an important role:
These three kinds of difluoro benzyl benzoglyoxalines all are the new organic cpds without reported in literature, and first Application is in the OSP prescription.Three's usage ratio is 0.01 ~ 0.1wt%, and preferred range is 0.05 ~ 0.08wt%, more preferably 0.07wt%.These difluoro benzyl benzoglyoxalines have the common constitutional features, and two fluorine atoms are promptly all arranged on the benzyl substituting group.Because fluorine atom combines relatively closely with phenyl ring, the bond energy of C-F covalent linkage is very high, has therefore strengthened the stability of compound and the resistance to elevated temperatures of OSP film greatly; And; The above two 2-(2, the 6-difluorobenzyl)-5-methyl isophthalic acid-H-benzoglyoxalines and 2-(2, the 6-difluorobenzyl)-1-H-benzoglyoxaline structurally also have symmetric two fluorine atoms; Just, further improved the fusing point and the stability of compound because of symmetric existence.Three's fusing point is respectively 208 ℃, 243 ℃ and 161 ℃, and not only fusing point is high, and decomposition temperature also correspondingly improves.Therefore, their adding can obviously improve the thermotolerance and the antioxidant effect of OSP film, makes the weldability of copper pad in storage, transportation and use, obtain better protection.
Below all be to have explained that theoretically new texture difluoro benzyl benzoglyoxaline makes the outstanding basic reason of OSP treatment agent formula performance.But from practice, the difluoro benzyl benzoglyoxaline must carry out compositely with 2,4 substituted imidazoles of diaryl, just can give full play to its unique effect, treatment agent formula is really had surmount the technological performance of existing OSP.2,4 composite diaryl substituted imidazole compounds have following general formula:
In the formula, R1 and R2 are Wasserstoffatoms, fluorine atom or ethanoyl, and R3 and R4 are Wasserstoffatoms, fluorine atom, ethanoyl or low-grade alkyl amino
The exemplary that is fit to the diaryl substituted imidazole compound of embodiment of the present invention comprises: 2, and 4-phenylbenzene-1H-imidazoles, 2-phenyl-4-(4-fluorophenyl)-1H-imidazoles; 2-phenyl-4-(4-acetyl phenyl)-1H-imidazoles, 2-(4-fluorophenyl)-4-phenyl-1H-imidazoles, 2-(4-acetyl phenyl)-4-phenyl-1H-imidazoles; 2-(4-first aminophenyl)-4-phenyl-1H-imidazoles, 2-(4-second aminophenyl)-4-phenyl-1H-imidazoles, 2-(4-fluorophenyl)-4-(4-fluorophenyl) imidazoles; 2-(4-fluorophenyl)-4-(4-acetyl phenyl) imidazoles, 2-(4-acetyl phenyl)-4-(4-fluorophenyl) imidazoles, 2-(4-acetyl phenyl)-4-(4-acetyl phenyl) imidazoles; 2-(4-first aminophenyl)-4-(4-fluorophenyl) imidazoles, 2-(4-first aminophenyl)-4-(4-acetyl phenyl) imidazoles, 2-(4-second aminophenyl)-4-(4-fluorophenyl) imidazoles; 2-(4-second aminophenyl)-4-(4-acetyl phenyl) imidazoles; 2-(2-fluoro-4-acetyl phenyl)-4-phenylimidazole, 2-phenyl-4-(2-fluoro-4-acetyl phenyl) imidazoles, 2-(4-first aminophenyl)-4-(2-fluoro-4-acetyl phenyl) imidazoles; 2-(2-fluoro-4-first aminophenyl)-4-(4-acetyl phenyl) imidazoles; 2-(4-second aminophenyl)-4-(2-fluoro-4-acetyl phenyl) imidazoles, 2-(2-fluoro-4-acetyl phenyl)-4-(4-fluorophenyl) imidazoles, 2-(2-fluoro-4-acetyl phenyl)
-4-(4-acetyl phenyl) imidazoles, 2-(2,4-diformazan aminophenyl)-4-phenylimidazole; 2-phenyl-4-(2,4 difluorobenzene base) imidazoles, 2-(2; The 4-difluorophenyl)-and the 4-phenylimidazole, 2-(2-fluoro-4-second aminophenyl)-4-(2-fluoro-4-second aminophenyl) imidazoles, 2-(2-acetyl phenyl)-4-(4-fluorophenyl) imidazoles; 2-(4-fluorophenyl)-4-(2-acetyl phenyl) imidazoles, 2-(4-first aminophenyl)-4-(2,4 difluorobenzene base) imidazoles etc.
Be embodiment of the present invention, the ratio of 2,4 substituted imidazolium compoundss of diaryl in prescription is 0.1 ~ 1.0wt%, and preferred range is 0.3 ~ 0.6wt%, more preferably 0.5wt%.
The OSP treatment agent formula also must be with organic acid as solvent.Organic acid can be selected formic acid, acetate, NSC 7300, trichoroacetic acid(TCA), propionic acid, levulinie acid, oxalic acid, propanedioic acid, Succinic Acid, hexanodioic acid, tosic acid, methylsulfonic acid, positive enanthic acid etc. for use.These organic acids can use separately, or two kinds or more kinds of combination use, and ratio is 1 ~ 20wt%, preferred 5 ~ 15wt%, more preferably 10wt%.
The used metallic compound of filling a prescription can be selected any have water miscible mantoquita or molysite for use, like Tubercuprose, cupric chloride, copper sulfate, neutralized verdigris, cupric oxalate, cupric bromide, cupric phosphate, and iron(ic)chloride, iron acetate, iron protochloride, iron bromide, ferric sulfate etc.These metallic compounds can use separately, or two kinds or more kinds of combination use, and the add-on in treatment agent is set at 0.01 ~ 1.0wt%, preferred 0.05 ~ 0.5wt%.
For improving rate of film build and welding characteristic; Treatment agent of the present invention also need add halogenide; Like Sodium Fluoride, Potassium monofluoride, Neutral ammonium fluoride, potassiumiodide, ammonium iodide, hydroiodic acid HI, zinc iodide, iodopropionic acid etc., they can use separately, or two kinds or more kinds of combination use; Consumption in treatment agent is set at 0.01 ~ 1.0wt%, preferred 0.05 ~ 0.5wt%.
For keeping the stable of solution, also to suitably add some buffer reagents in the prescription, like ammonia, DL-Lactic acid ammonium salt, ammonium acetate, monoethanolamine, diethylamine, triethylamine, diethylolamine, trolamine, dimethylethanolamine, diethylethanolamine, isopropyl alcohol amine etc.
Before using OSP treatment agent of the present invention, need do following pre-treatment to printed circuit board:
Oil removing is washed little erosion washing pickling washing DI washing and is blotted
Then pcb board is immersed in this treatment agent solution of 35 ~ 45 ℃, handled 50 ~ 70 seconds,, can form the thick one deck OSP organic weldable protective membrane of 0.2 ~ 0.5mm on the copper surface again through washing, drying.
With existing OSP compared with techniques, technical superiority of the present invention is:
1) the OSP film of copper face formation is finer and close, bright, and resistance toheat is better;
2) after lead-free high-temperature Reflow Soldering repeatedly, basic nondiscoloration of OSP film or variable color are very slight;
3) repeatedly carry out wave soldering again after the Reflow Soldering, tin property is good on the DIMM hole, and the climb rate is high;
4) various soldering fluxs and the tin cream compatibility with commercially available is good;
5) treatment agent does not contain hazardous substance, and meets international standards such as RoHS of European Union and REACH.
Embodiment
1) the preparation feedback formula of difluoro benzyl benzimidazole compound is following:
With O-Phenylene Diamine or substituted o-phenylenediamine is starting raw material, in the solution that itself and organic solvent form, adds fluorine-containing organic acid, adds organic acid again or mineral acid is made dewatering agent, is heated to more than 100 ℃ reaction more than 4 hours.After reaction solution was cooled to room temperature, decompression steamed organic solvent.It is about 8 that residuum uses alkaline matter to be neutralized to PH.The solid that filtration is separated out is thick product.Thick product promptly gets product with the mixed solvent recrystallization of alcohol with water, and yield is 90-95%.The concrete physical data of three new compounds is following:
Compound (1): 208 ℃ of fusing points (m.p.); Infrared IR (KBr), n/cm
-1: 3447.8 (w), 3025.0 (w), 2945.3 (w), 2867.1 (w), 1627.0 (w), 1485.3 (s), 1470.8 (s), 1456.2 (s), 1276.4 (s), 1015.8 (s), 802.0 (m), 785.7 (m);
1HNMR (300MHz, CDCl
3), δ (ppm): 4.3 (s, 2H), 6.8 ~ 7.1 (m, 3H), 7.2 ~ 7.4 (m, 3H), 2.5 (s, 3H); MS (APCI, m/Z, %): 258 (M
+, 61.9), 257 (21.2), 239 (100), 222 (5.8), 145 (3.1), 127 (9.3), 118 (6.4), 77 (5.9); Ultimate analysis (C
15H
12F
2N
2Theoretical value C 69.76, and H 4.68, and N 10.85, and F 14.71) measured value: C 69.73, H 4.76, and N 10.78, and F 14.70;
Compound (2): 243 ℃ of fusing points (m.p.); Infrared IR (KBr), n/cm
-1: 3448.1 (w), 3051.1 (w), 2950.3 (w), 2887.1 (w), 1628.8 (s), 1485.8 (s), 1471.2 (s), 1457.9 (s), 1288.9 (s), 1031.9 (s), 785.5 (m), 756.5 (m);
1HNMR (300MHz, CDCl
3), δ (ppm): 4.3 (s, 2H), 6.8 ~ 7.1 (m, 3H), 7.1 ~ 7.2 (m, 4H); MS (APCI, m/Z, %): 244 (M
+, 58.6), 243 (16.8), 225 (100), 127 (10.0), 112 (5.9), 77 (5.0); Ultimate analysis (C
14H
10F
2N
2Theoretical value C 68.85, and H 4.13, and N 11.47, and F 15.56) measured value: C 68.77, H 4.11, and N 11.46, and F 15.57;
Compound (3): 161 ℃ of fusing points (m.p.); Infrared IR (KBr), n/cm
-1: 3447.5 (w), 3083.8 (w), 2998.4 (w), 2737.3 (w), 1612.9 (w), 1537.7 (s), 1516.7 (s), 1456.2 (s), 1420.5 (s), 1282.8 (s), 766.0 (s), 747.6 (m);
1HNMR (300MHz, CDCl
3), δ (ppm): 4.2 (s, 2H), 6.9 ~ 7.1 (m, 3H), 7.2 ~ 7.6 (m, 4H); MS (APCI, m/Z, %): 244 (M
+, 95.5), 243 (100.0), 225 (6.4), 131 (10.5), 112 (5.1), 77 (4.3); Ultimate analysis (C
14H
10F
2N
2Theoretical value C 68.85, and H 4.13, and N 11.47, and F 15.56) measured value: C 68.73, H 4.21, and N 11.50, and F 15.56;
2) the difluoro benzyl benzimidazole compound that obtains is mixed with corresponding OSP treatment agent by following embodiment and comparative example, describes in detail and embodiment of the present invention.Be noted that the present invention is confined to following embodiment.
Embodiment 1]
The component of the OSP treatment agent of embodiment 1 and the weight percent of each component are seen table 1.
Press the part by weight of table 1, earlier with 0.1% 2,4-diphenyl-imidazole and 0.01% 2-(2; The 6-difluorobenzyl)-5-methyl isophthalic acid-H-benzoglyoxaline is dissolved in 5% the acetate; All pour in the deionized water after the dissolving fully, add 0.3% Tubercuprose, 0.01% Potassium monofluoride and 0.01% DL-Lactic acid ammonium salt again, after the stirring and dissolving; Regulate pH value to 3.7 with ammoniacal liquor, make the OSP treatment agent thus.
Get the printed circuit board test film, size is 115mm ' 100mm.
Concrete size such as the pad in the test film, DIMM hole and PTH aperture and information are following:
Plate type: FR-4 type epoxy resin;
DIMM aperture: 0.6mm, 0.8mm, 1.0mm and 1.2mm;
PTH pore aperture: 0.4mm; Oversized hole: 2.99mm;
Pilot hole (not having heavy copper): 2.00mm;
Finished product thickness of slab: 1.53-1.58mm;
Copper is thick in the hole: 26mm; Total copper is thick: 37.9mm;
Soldering-resistance layer S/M Thickness:18.9um;
C/S live width: 0.23-0.24mm; S/S live width: 0.23-0.24mm;
PAD size: 0.5mm * 0.6mm, 1.5mm * 1.5mm, 7mm * 7mm
This test film was soaked 30 seconds in degreaser (45 ℃), wash 3 times after, in micro-etching agent (30 ℃), soaked 40 seconds; After washing 3 times, in 2% aqueous acetic acid, cleaned 20 seconds, wash 2 times after again with DI water cleaning 1 time; Blotting the back soaked 60 seconds in 40 ℃ OSP treatment agent solution; Blot the back with DI washing 3 times, drying promptly gets the test pcb board of OSP thickness at 0.35mm.
Embodiment 3]
The component of the OSP treatment agent of embodiment 3 and the weight percent of each component are seen table 1.
Press the part by weight of table 1; Earlier 2-(3, the 4-the difluorobenzyl)-1-H-benzoglyoxaline of 2-(4-first aminophenyl)-4-phenyl-1H-imidazoles of 0.3% and 0.05% is dissolved in 8% the NSC 7300, all pours in the deionized water after the dissolving fully; Add 0.7% neutralized verdigris, 0.05% hydroiodic acid HI and 0.01% ammonium acetate again; After the stirring and dissolving, regulate pH value to 3.5, make the OSP treatment agent thus with ammoniacal liquor.
Above-mentioned printed circuit board test film was soaked 30 seconds in degreaser (45 ℃), wash 3 times after, in micro-etching agent (30 ℃), soaked 40 seconds; After washing 3 times, in 2% aqueous acetic acid, cleaned 20 seconds, wash 2 times after again with DI water cleaning 1 time; Blotting the back soaked 60 seconds in 40 ℃ OSP treatment agent solution; Blot the back with DI washing 3 times, drying promptly gets the test pcb board of OSP thickness at 0.25mm.
Embodiment 5]
The component of the OSP treatment agent of embodiment 5 and the weight percent of each component are seen table 1.
Press the part by weight of table 1; Earlier 2-(2, the 6-the difluorobenzyl)-1-H-benzoglyoxaline of 2-(4-acetyl phenyl)-4-(4-fluorophenyl) imidazoles of 0.5% and 0.05% is dissolved in 10% the Succinic Acid, all pours in the deionized water after the dissolving fully; Add 1.0% ferric sulfate, 0.1% iodopropionic acid and 0.01% monoethanolamine again; After the stirring and dissolving, regulate pH value to 3.6, make the OSP treatment agent thus with ammoniacal liquor.
Above-mentioned printed circuit board test film was soaked 30 seconds in degreaser (45 ℃), wash 3 times after, in micro-etching agent (30 ℃), soaked 40 seconds; After washing 3 times, in 2% aqueous acetic acid, cleaned 20 seconds, wash 2 times after again with DI water cleaning 1 time; Blotting the back soaked 60 seconds in 40 ℃ OSP treatment agent solution; Blot the back with DI washing 3 times, drying promptly gets the test pcb board of OSP thickness at 0.29mm.
Embodiment 6]
The component of the OSP treatment agent of embodiment 6 and the weight percent of each component are seen table 1.
Press the part by weight of table 1; Earlier 2-(3, the 4-the difluorobenzyl)-1-H-benzoglyoxaline of 2-(4-first aminophenyl)-4-(4-acetyl phenyl) imidazoles of 0.6% and 0.07% is dissolved in 12% the methylsulfonic acid, all pours in the deionized water after the dissolving fully; Add 0.01% Tubercuprose, 0.3% Potassium monofluoride and 0.01% diethylamine again; After the stirring and dissolving, regulate pH value to 3.75, make the OSP treatment agent thus with ammoniacal liquor.
Above-mentioned printed circuit board test film was soaked 30 seconds in degreaser (45 ℃), wash 3 times after, in micro-etching agent (30 ℃), soaked 40 seconds; After washing 3 times, in 2% aqueous acetic acid, cleaned 20 seconds, wash 2 times after again with DI water cleaning 1 time; Blotting the back soaked 60 seconds in 40 ℃ OSP treatment agent solution; Blot the back with DI washing 3 times, drying promptly gets the test pcb board of OSP thickness at 0.47mm.
Embodiment 8]
The component of the OSP treatment agent of embodiment 8 and the weight percent of each component are seen table 1.
Press the part by weight of table 1; Earlier 2-(2, the 6-the difluorobenzyl)-1-H-benzoglyoxaline of 2-(2-fluoro-4-first aminophenyl)-4-(4-acetyl phenyl) imidazoles of 0.8% and 0.05% is dissolved in 14% the formic acid, all pours in the deionized water after the dissolving fully; Add 0.05% neutralized verdigris, 0.7% hydroiodic acid HI and 0.01% trolamine again; After the stirring and dissolving, regulate pH value to 3.56, make the OSP treatment agent thus with ammoniacal liquor.
Above-mentioned printed circuit board test film was soaked 30 seconds in degreaser (45 ℃), wash 3 times after, in micro-etching agent (30 ℃), soaked 40 seconds; After washing 3 times, in 2% aqueous acetic acid, cleaned 20 seconds, wash 2 times after again with DI water cleaning 1 time; Blotting the back soaked 60 seconds in 40 ℃ OSP treatment agent solution; Blot the back with DI washing 3 times, drying promptly gets the test pcb board of OSP thickness at 0.40mm.
Embodiment 10]
The component of the OSP treatment agent of embodiment 10 and the weight percent of each component are seen table 1.
Press the part by weight of table 1; Earlier 2-(3, the 4-the difluorobenzyl)-1-H-benzoglyoxaline of 2-(2-fluoro-4-second aminophenyl)-4-(2-fluoro-4-second aminophenyl) imidazoles of 1.0% and 0.1% is dissolved in 16% the oxalic acid, all pours in the deionized water after the dissolving fully; Add 0.1% iron(ic)chloride, 1.0% zinc iodide and 0.01% diethylethanolamine again; After the stirring and dissolving, regulate pH value to 3.9, make the OSP treatment agent thus with ammoniacal liquor.
Above-mentioned printed circuit board test film was soaked 30 seconds in degreaser (45 ℃), wash 3 times after, in micro-etching agent (30 ℃), soaked 40 seconds; After washing 3 times, in 2% aqueous acetic acid, cleaned 20 seconds, wash 2 times after again with DI water cleaning 1 time; Blotting the back soaked 60 seconds in 40 ℃ OSP treatment agent solution; Blot the back with DI washing 3 times, drying promptly gets the test pcb board of OSP thickness at 0.43mm.
Embodiment 2,4,7,9, comparative example 1 ~ 3]
According to preparing each OSP treatment agent of component proportions as shown in table 1 with embodiment 1 identical operations mode, press the application art of embodiment 1 again and handle the printed electronic circuit test film, obtain required OSP test piece.
Evaluation to OSP test film performance
One, the variable color evaluation of OSP film after the repeatedly unleaded Reflow Soldering
Regulate the dynamic temperature of hot air reflux brazier (LF-F730C of the peak company type of Shenzhen power) earlier by the unleaded Reflow Soldering temperature curve of the 5th page in this specification sheets; Wherein, Preheating temperature 150 ~ 200 ℃/130 seconds; Reflux temperature was greater than 220 ℃/50 ~ 60 seconds, and peak temperature is 255 ℃, chain speed 60 ~ 80 cm/min.After waiting the homo(io)thermism of each warm area, place stove to transmit respectively the OSP test film of embodiment and comparative example gained, simulation Reflow Soldering 1 ~ 3 time, the appearance color change situation of observing OSP film after each Reflow Soldering.
We are divided into six grades with the grade of variable color, specifically describe as follows:
Two, the last tin rate in DIMM hole is estimated after the repeatedly unleaded Reflow Soldering
OSP test film with embodiment and comparative example gained places the hot air reflux stove earlier, and simulation Reflow Soldering 1 ~ 3 time uses the crest welding plant to weld subsequently.Soldering flux is the RF800 (acid value 18 mg KOH/g, solid content 4.1%) that be sure of Ai Fa company, and scolder is a SAC305 tin bar of be sure oing Ai Fa company.The operating parameter of crest welder is provided with as follows:
For the test film of the welding of crest, climb the tin situation according to the scolder in its DIMM hole, the standard of setting qualified (or claiming acceptance) is: when scolder was climbed the top to the DIMM hole, it was qualified to be judged to; And when the climb altitude of scolder not pedal aperture high 80% the time, be judged to NG.Again with the number in qualified DIMM hole divided by total via count (400), promptly get the tin rate.
The comprehensive evaluation grade standard:
* wherein go up the tin rate and be meant tin rate on the last DIMM hole of Reflow Soldering
The comprehensive evaluation result such as the table 2 of embodiment and comparative example gained OSP test film:
Industrial applicibility
According to the present invention; A kind of copper face OSP treatment agent that is applicable to printed circuit board multiple high temp leadless welding can be provided, the copper pad of printed circuit board is had very outstanding defencive function, anti-oxidant strong with anti-tarnishing ability; Through the multiple high temp leadless Reflow Soldering; Still show the gratifying tin rate that goes up behind the circuit card DIMM hole wave soldering that protected by OSP film of the present invention, this is that the existing technology of all OSP institute is beyond one's reach at present, so can predict its tempting market application foreground.
In addition; According to the present invention, a kind of printed circuit board can be provided, wherein the protective membrane on the copper pad is to contact with OSP treatment agent of the present invention through the printed circuit board with naked copper to form; And a kind of method that is used to produce printed circuit board is provided; Promptly make copper face form the good organic protective film of one deck, use lead-free solder to carry out reflow soldering and crest welding then, accomplish the final finished manufacturing of circuit card through OSP treatment agent of the present invention is contacted with the printed circuit board of naked copper.
Claims (5)
1. lead-free printed circuit board is with composite OSP treatment agent, and it comprises composite imidazolium compounds, organic acid, metallic compound; Halogenide, buffer reagent and water is characterized in that as the film forming activeconstituents be a composite imidazolium compounds; Promptly by difluoro benzyl benzoglyoxaline and 2; 4 substituted imidazolium compoundss of diaryl are formed, and said difluoro benzyl benzoglyoxaline is that usage ratio is 0.01～0.1wt%, and said 2; The usage ratio of 4 diaryl substituted imidazoles is 0.1～1.0wt%, and said difluoro benzyl benzimidazole structure general formula and physical constant are following:
Compound (1): 208 ℃ of fusing points (m.p.); Infrared IR (KBr), n/cm
-1: 3447.8 (w), 3025.0 (w), 2945.3 (w), 2867.1 (w), 1627.0 (w), 1485.3 (s), 1470.8 (s), 1456.2 (s), 1276.4 (s), 1015.8 (s), 802.0 (m), 785.7 (m);
1HNMR (300MHz, CDCl
3), δ (ppm): 4.3 (s, 2H), 6.8 ~ 7.1 (m, 3H), 7.2 ~ 7.4 (m, 3H), 2.5 (s, 3H); MS (APCI, m/Z, %): 258 (M
+, 61.9), 257 (21.2), 239 (100), 222 (5.8), 145 (3.1), 127 (9.3), 118 (6.4), 77 (5.9); Ultimate analysis (C
15H
12F
2N
2Theoretical value C 69.76, and H 4.68, and N 10.85, and F 14.71) measured value: C 69.73, H 4.76, and N 10.78, and F 14.70;
Compound (2): 243 ℃ of fusing points (m.p.); Infrared IR (KBr), n/cm
-1: 3448.1 (w), 3051.1 (w), 2950.3 (w), 2887.1 (w), 1628.8 (s), 1485.8 (s), 1471.2 (s), 1457.9 (s), 1288.9 (s), 1031.9 (s), 785.5 (m), 756.5 (m);
1HNMR (300MHz, CDCl
3), δ (ppm): 4.3 (s, 2H), 6.8 ~ 7.1 (m, 3H), 7.1 ~ 7.2 (m, 4H); MS (APCI, m/Z, %): 244 (M
+, 58.6), 243 (16.8), 225 (100), 127 (10.0), 112 (5.9), 77 (5.0); Ultimate analysis (C
14H
10F
2N
2Theoretical value C 68.85, and H 4.13, and N 11.47, and F 15.56) measured value: C 68.77, H 4.11, and N 11.46, and F 15.57;
Compound (3): 161 ℃ of fusing points (m.p.); Infrared IR (KBr), n/cm
-1: 3447.5 (w), 3083.8 (w), 2998.4 (w), 2737.3 (w), 1612.9 (w), 1537.7 (s), 1516.7 (s), 1456.2 (s), 1420.5 (s), 1282.8 (s), 766.0 (s), 747.6 (m);
1HNMR (300MHz, CDCl
3), δ (ppm): 4.2 (s, 2H), 6.9 ~ 7.1 (m, 3H), 7.2 ~ 7.6 (m, 4H); MS (APCI, m/Z, %): 244 (M
+, 95.5), 243 (100.0), 225 (6.4), 131 (10.5), 112 (5.1), 77 (4.3); Ultimate analysis (C
14H
10F
2N
2Theoretical value C 68.85, and H 4.13, and N 11.47, and F 15.56) measured value: C 68.73, H 4.21, and N 11.50, and F 15.56.
2. lead-free printed circuit board according to claim 1 is with composite OSP treatment agent, and the usage ratio that it is characterized in that described difluoro benzyl benzoglyoxaline is 0.05～0.08wt%.
3. lead-free printed circuit board according to claim 2 is with composite OSP treatment agent, and the usage ratio that it is characterized in that described difluoro benzyl benzoglyoxaline is 0.07wt%.
4. lead-free printed circuit board according to claim 1 is with composite OSP treatment agent, and the usage ratio that it is characterized in that described 2,4 substituted imidazolium compoundss of diaryl is 0.3～0.6wt%.
5. lead-free printed circuit board according to claim 4 is with composite OSP treatment agent, and the usage ratio that it is characterized in that described 2,4 substituted imidazolium compoundss of diaryl is 0.5wt%.
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| WO2015171628A1 (en) * | 2014-05-06 | 2015-11-12 | Gtx, Inc. | Compounds for treatment of cancer |
| CN106903455A (en) * | 2016-12-26 | 2017-06-30 | 长沙理工大学 | A kind of high temperature resistant organic solderability preservative and apply usage |
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| CN107971655B (en) * | 2018-01-23 | 2019-12-27 | 永星化工(上海)有限公司 | High-heat-resistance organic solder flux and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5173130A (en) * | 1989-11-13 | 1992-12-22 | Shikoku Chemicals Corporation | Process for surface treatment of copper and copper alloy |
| CN1391618A (en) * | 1999-08-26 | 2003-01-15 | 恩索恩－Omi公司 | Process for selective deposition of copper substrates |
| CN101448978A (en) * | 2006-05-19 | 2009-06-03 | 四国化成工业株式会社 | Metal surface treatment agent and use of same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5173130A (en) * | 1989-11-13 | 1992-12-22 | Shikoku Chemicals Corporation | Process for surface treatment of copper and copper alloy |
| CN1391618A (en) * | 1999-08-26 | 2003-01-15 | 恩索恩－Omi公司 | Process for selective deposition of copper substrates |
| CN101448978A (en) * | 2006-05-19 | 2009-06-03 | 四国化成工业株式会社 | Metal surface treatment agent and use of same |
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