CN102146558A - Pretreatment liquid for electroless plating - Google Patents
Pretreatment liquid for electroless plating Download PDFInfo
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- CN102146558A CN102146558A CN2010102143459A CN201010214345A CN102146558A CN 102146558 A CN102146558 A CN 102146558A CN 2010102143459 A CN2010102143459 A CN 2010102143459A CN 201010214345 A CN201010214345 A CN 201010214345A CN 102146558 A CN102146558 A CN 102146558A
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- resin base
- pretreatment fluid
- electroless plating
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/26—Roughening, e.g. by etching using organic liquids
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- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
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- 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
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/422—Plated through-holes or plated via connections characterised by electroless plating method; pretreatment therefor
-
- 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
- H05K2203/03—Metal processing
- H05K2203/0392—Pretreatment of metal, e.g. before finish plating, etching
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- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
The invention aims to provide a pretreatment liquid used in a wet method. When the metal plating is conducted on a resin substrate and a resin substrate having glass, a coating having a good adhesion to a surface that is not quite rough can be generated without conducting adherence based on a dry method to promote pretreatment or to generate a metal layer. The invention also provides a surface processing method suitable for the pretreatment liquid, a metal coating generating method and a producing method of a printing line substrate. The invention provides a pretreatment liquid which is used for the electroless plating of the resin substrate surface and has a cationic polymer, water and a bifluoride compound salt in 5-200g/L. The bifluoride compound salt is a conditioning agent.
Description
The present invention relates to a kind of pretreatment fluid that is used for non-electrolytic metal plating, especially for the resin base of pre-treatment printed wiring substrate, and the manufacture method that is used for the printed wiring substrate.
Being electrically connected usually between layer in the printed wiring substrate and the layer realizes by the meticulous hole that sees through that is known as through hole.As a kind of method that forms electrically-conductive layer in this through hole (woven fiber glass/resin part) the inside, usually use wet method contain pretreatment fluid (conditioning agent) pre-treatment of cats product in use after, use in this wet method to comprise that containing palladium forms coating as the electroless plating coating method of the catalyzer of main component.In addition, utilizing the Layer increasing method (bulid-up process) of High Performance Insulation resin material to be used in the high-performance semiconductor package substrates is in the high density printed circuit substrate of representative, additive process, semi-additive process particularly, as the formation method of circuit, wherein use the electroless plating copper coin as Seed Layer.
In order to improve the adhesivity of resin base and electrically-conductive layer in the wet method, contain after solvent implements the expansion step of resin as the treatment solution of main ingredient in use, use to comprise that containing permanganate carries out the alligatoring step as the treatment solution of main ingredient and come oxidation and decompose resin to form coarse profile.Utilize neutralization procedure subsequently, remove demanganize,, form anchor thorn (anchor) with by a series of scrubbing/alligatoring step.Use pre-treatment and the electroless plating by catalysis transmission (catalyst imparting) step to cover and handle the regulating step that carries out subsequently, and form the adherent electrically-conductive layer.Cover catalyzer as electroless plating, the palladium with excellent catalytic activity is used widely.By solvent impregnated resin substrate in catalyst solution (SnPd colloidal mixture), the SnPd colloidal mixture is attracted on the surface of resin base.Promotor is handled and have been activated catalyzer, and covers processing by electroless plating form electrically-conductive layer on the resin base surface.
But when the roughness decline on resin base surface and the adhesive power between substrate and the metal level descended, the coating that obtains excellent bonds in the adhesion process that mainly depends on the set effect was difficult.In addition, the acid in the pretreatment fluid, alkali and cats product, the type of resin material etc. influences adhesive power widely.Be accompanied by the improvement of IC unicircuit piece performance, the signal speed of increase and frequency especially influence high-performance semiconductor encapsulation, and are seeking the miniaturization of circuit in the package substrates and having the circuit on flat surface.But the traditional non-electrolytic copper solution and coating method in semi-additive process be difficult to form good adhesion at following lip-deep electrically-conductive layer, this surface coarse inadequately and its be conditional to the flat degree that material surface energy becomes.Based on background information, intensive need be developed surface treatment method and electroless plating coating method, and this electroless plating applies can give substrate and the excellent cohesive strength of metal interlevel and resin material and resin surface roughness do not influence its result.
In references 1, among the unexamined Japanese patent application 2003-338683, disclosed a kind of manufacture method of circuit substrate, wherein form the metal level of appointed thickness: make comprising and contain for example SiO by following steps
2The surface with conductor pattern on the resin layer of the electric insulation resin of the particulate additive of particle etc. is for example stood wetting ability such as plasma treatment and is improved and handle, be present in this particulate additive that the above-mentioned conductor pattern mentioned forms near surface and handle by this resin layer being contacted with the hydrofluoric acid compound solution to remove subsequently, and implement then that electroless plating covers and electrolytic coating to implement glass etching.But the method described in this references 1 needs plasma treatment, ozonize and Corona discharge Treatment to wait to produce water-wetted surface, because of needs install especially.
In references 2, among the domestic bulletin H06-505770 of Japanese Patent, described a kind of before implementing washing in the described substrate, be used for cleaning and modulating the solution of (condition) non metallic substrate, it contains the sodium polyphosphate of (a) about 10g/L～50g/L, (b) sodium-EDTA of 0～about 5g/L, (c) Tripotassium phosphate of about 5g/L～20g/L, (d) ANTAROX of 0.5g/L～about 2g/L
TMBL300, (e) SYNPERONIC of 0～about 2g/L
TMNP-10, (f) the quaternary ammonium compound of about 1g/L～5g/L, and (g) bifluoride (hydrogen of 0～about 2g/L based on imdazole derivatives?) ammonium, and with mineral acid with pH regulator into about 1.0～4.0.But this references 2 is not paid close attention to adhesive power at all, even and add the bifluoride hydrogen ammonium of these references 2 described amounts, as after described in the comparative example, it does not obtain enough adhesive powers yet.
In references 3, among the unexamined Japanese patent application 2002-38197, to have described a kind of design and be used for removing the composition of polymeric material from substrate, said composition contains one or more glycol ethers, water, fluoride salt and optional additive.But this references 3 is not described the manufacture method of pretreatment fluid of the present invention and printed wiring substrate.
The purpose of this invention is to provide a kind of when the metal electroless plating covers resin base, be used for the pretreatment fluid that electroless plating covers, so that can obtain well to adhere on this resin base the metal plating on the uneven surface not too, do not promote preprocessing process or form metal level and do not need to implement dry adhesion, and a kind of manufacture method of using the surface treatment method of the above-mentioned pretreatment fluid of mentioning, a kind of metal plating formation method and a kind of printed wiring substrate is provided.
The inventor finds, can solve problem recited above by the difluoro compound salt that has cationic polymers, water and specified amount in pretreatment fluid, and finish the present invention based on this discovery.
The application's invention provides a kind of pretreatment fluid, its lip-deep electroless plating that is designed in resin base is covered, and it is characterized in that containing the difluoro compound salt of anionic polymer, water and 5g/L～200g/L.The preferably at least a salt of forming group by bifluoride hydrogen ammonium, bifluoride hydrogen potassium and sodium hydrogen difluoride that is selected from of this difluoro compound salt.This pretreatment fluid can further contain nonionogenic tenside and/or sequestrant.And the above-mentioned resin base of mentioning can be the resin base that is used in the printed wiring substrate, and the resin base that is used for this printed wiring substrate can contain a plurality of through holes, a plurality of blind hole or the two all has.In addition, the application's invention also provides a kind of manufacture method of printed wiring substrate, and it is included in the enforcement electroless plating and covered the Cheng Qian, uses the above-mentioned pretreatment fluid of mentioning to handle this resin base surface.In addition, the application's invention also provides a kind of method that forms metal plating on resin base, it comprises following steps: contact the step on the surface of process resin substrate by making this resin base and the above-mentioned pretreatment fluid of mentioning, make catalyzer be adsorbed on the step on the surface of this resin base by this resin base of having handled with pre-treatment is contacted with catalyst solution, and make this resin base of having adsorbed catalyzer stand the step that electroless plating covers processing.
When using pretreatment fluid of the present invention as being used for the pretreatment fluid that electroless plating covers, when coming electroless plating to cover resin base, when with the pretreatment fluid of the present invention that uses the difluoro compound salt do not contain specified amount or the situation of not using pretreatment fluid of the present invention relatively the time, its advantage is to cover the metal plating that is obtained by this electroless plating very well to adhere on this resin base, even this resin base surface is not very coarse.
Fig. 1: when this photo has shown the pretreatment fluid of preparation in using embodiment 11, the covering power of chemical copper in the through hole (throwing power);
Fig. 2: when this photo has shown the pretreatment fluid of preparation in using embodiment 12, the covering power of chemical copper in the through hole; And
Fig. 3: when this photo has shown the pretreatment fluid of preparation in using embodiment 13, the covering power of chemical copper in the through hole.
Unless offer some clarification in addition, otherwise abbreviation as used in this specification has following implication: g=gram, the mg=milligram, ℃=degree centigrade, m=rice, L=liter, mL=milliliter, dm
2=square decimeter, mole=mole, and N=newton.All numerical ranges comprise endpoint value, and can be with combined in any order.
Pretreatment fluid of the present invention is the plating pretreatment fluid, and it also is known as conditioning agent sometimes, and it is characterized in that containing the difluoro compound salt of anionic polymer, water and 5g/L～200g/L.
Difluoro compound salt is the compound that contains FHF-, its can be in molecule electrolytic separation.The cationic components that constitutes this difluoro compound salt has no particular limits.More particularly, bifluoride hydrogen ammonium (NH
4FHF), bifluoride hydrogen potassium (KFHF) and sodium hydrogen difluoride (NaFHF) etc. can be used as this difluoro compound salt.The scope that pretreatment fluid of the present invention contains difluoro compound salt is 5g/L～200g/L, preferred 5g/L～50g/L, more preferably 7.5g/L～15g/L or 0.09mol/L～3.5mole/L, preferred 0.09mole/L～0.9mole/L or more preferably 0.13mole/L～0.26mole/L.When existence was less than the difluoro compound salt of 5g/L, this selection was not preferred, because as subsequently described in the comparative example, can not obtain enough adhesive powers.In addition, when this salt of existing greater than 200g/L, this selection is not preferred, because when dissolving nonionogenic tenside etc. in this pretreatment fluid, nonionogenic tenside etc. are to be difficult to dissolved.
Pretreatment fluid of the present invention contains cationic polymers as basic constituent.This cationic polymers is also referred to as cats product (surfactant) sometimes, its be a kind of in water electrolytic separation become organic cations surfactant (surface activation agent).In preprocessing solution, during this cationic polymers plays on the surface of resin base and electric charge and the effect that adds electric charge.The molecular weight of this cationic polymers preferably about 300～1000.As the example of preferred cationic polymkeric substance, can use poly-(two amido dimethyl) ammonium salt, poly-(poly (dially dialkyl) base) ammonium salt, polymeric quaternary ammonium compound for example gather (vinyl pyridine) quaternary salt etc., polyacrylamide, poly-(ethyleneimine) etc.In these, especially preferably poly-(diallyl dimethyl) ammonium chloride, poly-(diallyl dimethyl) ammonium chloride/acrylamide copolymer, and poly-(ethyleneimine).
Join the preferred 0.5g/L～2.0g/L of cationic polymers or more preferably 0.5g/L～1.0g/L in the pretreatment fluid.
As the example that is present in the water in the pretreatment fluid of the present invention, can use distilled water and deionized water etc.
Pretreatment fluid of the present invention can further contain nonionogenic tenside.Nonionogenic tenside is also referred to as the non-ionic surface activator sometimes, and it is the surfactant that does not represent ion characteristic in water.In pretreatment fluid, this nonsurfactant plays the effect of cationic polymers dispersion agent, and it has reduced the surface tension of pretreatment fluid.Preferred example as this nonionogenic tenside, can use for example poly-(ethylene oxide) alkyl oxide of poly-(ethylene oxide) derivative, poly-(ethylene oxide) octyl phenyl ether, poly-(ethylene oxide) nonylplenyl ether etc., poly-(ethylene glycol) and alkyl alcohol ethoxylate.Join the preferred 1g/L～10g/L of nonionogenic tenside and more preferably 1g/L～5g/L in the pretreatment fluid.
Pretreatment fluid of the present invention can further contain sequestrant.Sequestrant is to contain a plurality of reagent that combine the ligating atom that forms inner complex with metal ion, and it plays the effect that forms inner complex in pretreatment fluid with the metal ion that is dissolved in this treatment soln.As the preferred example of this sequestrant, can use for example single carbinolamine of monoalkylamine (monalkylamines), monoethanolamine, single Propanolamine, Yi Bingchunan etc.; Dialkylamine; Trialkylamine is trolamine, three butanolamines etc. for example; Ammonia (ammonia) and ethylenediamine tetraacetic acid (EDTA) (EDTA).In these, preferred especially monoethanolamine, three butanolamines, Yi Bingchunan and ammonia.The pH of pretreatment fluid is according to the type and the number change of this sequestrant now.Join the preferred 2.0g/L～20g/L of sequestrant and more preferably 2.0g/L～15g/L in the pretreatment fluid.
Can be as required, in pretreatment fluid of the present invention, add common additive for example pH regulator agent etc. as other optional components.
The pretreatment fluid that pretreatment fluid of the present invention covers as the electroless plating of implementing the resin base surface.This resin base contains resin as constituting a kind of of component, and the structured material of substrate, shape and size etc. have no particular limits, as long as electroless plating covers and can take place in its surface.For example, the printed wiring substrate can be used as this resin base.The printed wiring substrate can contain woven fiber glass/resin part.In addition, the printed wiring substrate can contain a plurality of meticulous holes that see through that are known as through hole (through hole), a plurality ofly be known as the meticulous non-of blind hole (blind vias) and see through the hole, or the two has.The mean diameter of through hole and blind hole without limits.But the mean diameter of through hole generally is 0.2mm～0.9mm, and the mean diameter of blind hole generally is 50 μ m～100 μ m.In addition, be in the high density printed circuit substrate of representative with the high-performance semiconductor package substrates, functional dielectric resin material substrate is as this resin base.Among the present invention, the interior side-wall surface that is present in the hole on the resin base also is comprised in " surface " lining of resin base.For example, the interior side-wall surface as the hole of through hole and blind hole that is present in the printed wiring substrate is comprised in " surface " of printed wiring substrate.
As the resin that is used for constituting resin base, can use Resins, epoxy, cyanate ester resin, bismaleimide-triazine resin, polyimide, ABS, poly-(phenyl ether), polysulfones, fluoro-resin, polycarbonate, polyacetal, poly-(phenylate), polypropylene, liquid crystalline polymers etc.Can only use a kind of resin to constitute this resin base, perhaps this resin base can be other materials by resin and non-resin, for example, and glass fibre, glasscloth, other inorganicss and paper etc., the composite substrate of formation.
Electroless plating coating method of the present invention is a kind ofly to use reductive agent in plating bath, and does not add electric energy in plating bath, allow metal deposition at the solution and coating method on the surface of catalytic activation, and it is a kind of usually by method known in those skilled in the art.For example, the electroless plating coating method can comprise following steps: contact with catalyst solution by the resin base that will treat plating and make catalyzer be adsorbed on the step on the surface of this resin base, and cover processing forms metal plating thus on this resin base step by making this resin base of having adsorbed catalyzer stand electroless plating.In addition, the electroless plating coating method can comprise the step of so-called decontamination, is used at adsorptive catalyst step and/or the alligatoring step on this resin base surface of alligatoring, soft etching step and oil removing and clean resin base before using the cleaning step etc. of acid.The known common treatment soln of technical field under the sour step of present above-mentioned decontamination step, alligatoring step, soft etching step and use acid can be used.
Among the present invention, phrase " pretreatment fluid that covers with the electroless plating that acts on the resin base surface " means pretreatment fluid of the present invention, catalyzer is adsorbed onto in the step before the step on resin base surface in the electroless plating coating method, is used as treatment solution and comes the process resin substrate.For example, when in the electroless plating coating method, implementing extra for example decontamination step of step, alligatoring step, soft etching step and/or acid pickling step etc., before the optional step of these steps and/or any stage afterwards, pretreatment fluid of the present invention is used as preprocessing solution.
In another embodiment of the present invention, provide a kind of resin base surface treatment method, wherein used pretreatment fluid of the present invention to come the surface of process resin substrate.Be used for the surface treatment method of the present invention of resin base, make resin base go for " using preprocessing solution of the present invention to come the surface of process resin " with the optional approach that this pretreatment fluid contacts, as long as after the electroless plating of the resin base that obtains by described treating processes covers processing, the metal plating that obtains on this resin base has at last produced beneficial effect of the present invention and has got final product.For example be immersed in this pretreatment fluid, or on the resin base of handling, spray this preprocessing solution, implement to use the processing on surface of the resin base of pretreatment fluid of the present invention by the resin base that will handle.The resin base of using resin base surface treatment method of the present invention to handle has no particular limits, as long as resin base is carried out electroless plating subsequently and covered processing.This resin base can be a kind of by implementing the resin base that decontamination step described above, alligatoring step, soft etching step and/or acid pickling step etc. obtain, and perhaps can be not implement the resin base that these steps obtain.
In another embodiment of the present invention, provide a kind of method that forms metal plating on resin base, it may further comprise the steps:
Make resin base contact the step of handling this resin base surface with pretreatment fluid of the present invention,
This resin base of having handled with preprocessing solution is contacted with catalyst solution make catalyzer be adsorbed on the step on the surface of this resin base, and,
Make this resin base of having adsorbed catalyzer carry out the step that electroless plating covers processing.
Sometimes, before catalyzer is adsorbed on the step on resin base surface with the resin base surface by with the inventive method in preprocessing solution of the present invention contact the process resin substrate surface to carry out decontamination step described above, alligatoring step, soft etching step and/or acid pickling step etc. before or after with the step that forms the metal plating on the resin base.In addition, sometimes, can implement the promotor of activated catalyst in catalyzer absorption back and handle.
By after with pretreatment fluid pre-treatment of the present invention, with for example resin base of printed wiring substrate, be immersed in the catalyst solution, so that catalyzer is attracted to this resin base surface, handle activated catalyst and on this resin base surface, implement electroless plating by optional promotor and cover processing, can form and have excellent close-burning electrically-conductive layer.In this case, the preferred catalyzer with excellent catalytic activity that uses covers catalyzer as this electroless plating, and, for example, can use the catalyzer that contains palladium.
Among the present invention, electroless plating covers and can cover copper, nickel or copper-nickel alloy at electroless plating, is not limited to these metals though this electroless plating covers.
Example as the electroless plating copper that utilizes the surface treatment method that uses pretreatment fluid of the present invention can use following method.
At first, pretreatment fluid of the present invention described above is heated to 45 ℃, and resin base is immersed in wherein 5 minutes, carry out surface adjustment, catalyzer is applied on the surface of pending material.On 30 ℃ of surfaces of using soft these resin base of etching of Sodium Persulfate one minute, pickled surface one minute and remove the residue salt (smut salt) that produces by etching under the room temperature then.Flood pending material subsequently, for example, in the gluey catalytic solution of 45 ℃ SnPd, flood 4 minutes so that catalyzer is applied on the surface of this pending material.Then Sn etc. is removed, and by in will this pending material soaking accelerator solution at room temperature, Pd being metallized in catalyzer activation step in 5 minutes.By being covered by the enterprising normal electroless plating that works of the pending material of catalyzer activated, for example, cover 20 minutes by 25 ℃ of electroless platings, on this resin base, form the copper layer.
Then, by the embodiment and the comparative example that exemplify the present invention is described in more detail.The adhesion strength in following examples and the comparative example and the assessment of surfaceness are as follows.
(1) adhesion strength
The surface of the coating material that contains the copper coating that is obtained by electroless plating copper on resin base was at room temperature further cleaned 3 minutes with deionized water, and heat drying (120 ℃ of dryings 30 minutes).In sour sanitising agent (fluid temperature was flooding 2 minutes for 35 ℃), pickling is subsequently also used (ELECTROPOSIT with this surface impregnation that has plated the non-electrolytic copper layer on the material
TMEP100) carrying out electroless plating copper handles.The surface of this copper electroplating was at room temperature cleaned 3 minutes with deionized water and is dry down at high temperature (180 ℃ 60 minutes).The copper coating thickness that obtains is 20 μ m～25 μ m.This coating is cut into the wide bar of 1cm (strips), and according to printed wiring board measuring method JIS
TMC5012 uses INSTRON
TM5564 under delamination (pull up) speed of an angle of 90 degrees and 50mm/ minute, tests the adhesion strength of this coating to base resin.
(2) surfaceness (Ra)
With pending resin base be immersed in fluid temperature be 70 ℃～80 ℃ contain the resin inflation fluid (CIRCUPOSIT of solvent as main ingredient
TMMLB211) in 5～10 minutes, and subsequently by be immersed in fluid temperature be 70 ℃～80 ℃ contain the solution (CIRCUPOSIT of permanganate as main ingredient
TMMLB213) carried out alligatoring in 5～20 minutes.By being immersed in the neutralizing treatment liquid (CIRCUPOSIT of 45 ℃ of fluid temperatures
TMMLB216-5) in 5～10 minutes removing demanganize, and use surface finish measurement equipment WYKO NT 8000 to measure the surfaceness (Ra) of the resin base of these processing subsequently.
Embodiment 1-10
Use following resin base 1-3 as pending resin base.
Resin base
Resin base 1:Ra:590-630 (nm)
Resin base 2:Ra:480-500 (nm)
Resins, epoxy substrate 3:Ra:900-1000 (nm)
According to the ratio shown in the table 1, use the pre-treatment liquid storage (A) that contains cationic polymers, sequestrant, nonionogenic tenside and water that describes below and (D) and by adding bifluoride hydrogen ammonium prepare the pre-treatment bath of liquid as difluoro compound salt.Resin base 1-3 is by decontamination and use the permanganate alligatoring, and is impregnated in the pretreatment fluid shown in 45 ℃ the table 35 minutes.Use this substrate of the soft etching of Sodium Persulfate subsequently, and clean with acid.Use SnPd colloid mixture (CATAPOSIT subsequently
TM44 catalyzer) deposited catalyst, and use accelerator solution (ACCELERATOR
TM19E) activated catalyst.This substrate is submerged in 25 ℃ electroless plating copper liquid (CUPOSIT subsequently
TMNon-electrolytic copper plating took place 328 bronze medal mixing enriched materials) in 20 minutes.Carry out the electrolytic coating process subsequently, and this substrate stands the adhesive power test.Assessment result also is reported in the table 1.
The deposit pretreatment fluid
The solution that describes below (A)～(D) is all produced by ROHM AND HAAS Electronics Materials Co., Ltd (RohmandHaas Denshi Zairyo K.K.), and contains cationic polymers, sequestrant, nonionogenic tenside and water.
(A) regulate neutralizing agent 3320
(B) cleaning conditioning agent 231
(C)CIRCUPOSIT
TM860
(D) cleaning conditioning agent XP2285
Table 1
Embodiment 11-13
According to the ratio shown in the table 2, bifluoride hydrogen ammonium is added in the deposit preprocessing solution described above prepares the pre-treatment bath of liquid.Carry out the non-electrolytic copper plating as pending material except using resin base 4, according to the mode implementation and operation described in the embodiment 1, this resin base 4 is to obtain by using drill bit to go up a plurality of through holes of making diameter 0.9mm at the thick dual platen of 1.6mm (FR-4 that Hitachi Chemical Co., Ltd. (Hitachi Kasei Kogyo K.K) makes), this dual platen on the two sides of the Resins, epoxy that contains woven fiber glass all with the thick Copper Foil lamination of 18um.This through hole substrate is polished subsequently, and uses back side illumination method to check the covering power of chemical copper in the through hole.The results are shown among Fig. 1-3.
Table 2
Based on embodiment 11-13, pretreatment fluid of the present invention can use in the substrate that contains a plurality of through holes, when plating without any problem.
Embodiment 14-19
According to the ratio shown in the table 3, substitute the bifluoride hydrogen ammonium that uses the 11.4g/L (0.2mole/L) that shows among the embodiment 1 by the difluoro compound salt that adds separately, prepare the pre-treatment bath of liquid.Implement electroless plating copper according to the mode described in the embodiment 1.Test result separately is also shown in the table 3.
Table 3
Comparative example 1-16
Come by the compound separately shown in the interpolation table 4 that employed 11.4g/L (0.2mole/L) bifluoride hydrogen ammonium prepares the pre-treatment bath of liquid in the alternate embodiment 1, and implement electroless plating copper by the identical mode of describing among the embodiment 1.Test result has announcement equally in table 4.PH among the comparative example 13-16 uses sulfuric acid or sodium hydroxide to regulate now.
Table 4
The continuous table of table 4
Comparative example 17 and 18
Come in the alternate embodiment 1 employed 11.4g/L (0.2mole/L) bifluoride hydrogen ammonium to prepare preprocessing solution by the compound separately shown in the interpolation table 5 and bathe, and implement electroless plating copper by the identical mode of describing among the embodiment 1.Test result also is published in the table 5.After having added aforementioned compound, the present pH of deposit pretreatment fluid A is 3.93, and the pH of deposit pretreatment fluid D is 9.97.The pH of this pre-treatment bath of liquid uses sulfuric acid or sodium hydroxide to regulate.
Table 5
Result according to embodiment 1-19 is obtained when using pretreatment fluid of the present invention, regardless of the surfaceness of resin base and the kind of deposit pretreatment fluid, can both obtain excellent adhesive power.In addition, as the pretreatment fluid that has added bifluoride hydrogen ammonium and the embodiment (comparative example 1) that does not add bifluoride hydrogen ammonium and what add is that the embodiment (comparative example 9～12) of the compound of non-difluoro compound salt is relatively the time, according to the comparison of embodiment 1 with comparative example 1 and 9～12, excellent strength and adhesive power are outstanding.In addition, when the compound that adds non-difluoro compound salt in comparative example 13～18 replaces difluoro compound salt, can not obtain excellent adhesive power, even the pH of this pretreatment fluid is similar to those embodiment.In addition, according to the result's of the result of embodiment 5 and comparative example 7 comparison, and the result's of the result of embodiment 6 and comparative example 8 comparison, when the add-on of bifluoride hydrogen ammonium is less than 5g/L, find that adhesive power is poor.When using bifluoride hydrogen potassium or sodium hydrogen difluoride as difluoro compound salt, the stripping strength and the adhesive power of the excellence relevant with bifluoride hydrogen ammonium can not be obtained.
Claims (5)
1. pretreatment fluid, it is to be used for implementing the pretreatment fluid that electroless plating covers on the resin base surface, it is characterized in that containing the difluoro compound salt of cationic polymers, water and 5g/L～200g/L.
2. pretreatment fluid according to claim 1, wherein said difluoro compound salt are at least a salt that is selected from bifluoride hydrogen ammonium, bifluoride hydrogen potassium and sodium hydrogen difluoride.
3. pretreatment fluid according to claim 1 and 2 wherein also contains nonionogenic tenside and/or sequestrant.
4. according to any one pretreatment fluid described in the claim 1-3, wherein said resin base is to be used in to contain a plurality of through holes, a plurality of blind hole or resin base that the two all has in the printed wiring substrate.
5. the manufacture method of a printed wiring substrate, it is included in before electroless plating covers, and uses among the claim 1-3 each described pretreatment fluid to handle described resin base surface.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-023481 | 2010-02-04 | ||
| JP2010023481A JP2011162806A (en) | 2010-02-04 | 2010-02-04 | Pretreatment liquid for electroless plating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102146558A true CN102146558A (en) | 2011-08-10 |
Family
ID=44421020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102143459A Pending CN102146558A (en) | 2010-02-04 | 2010-04-30 | Pretreatment liquid for electroless plating |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2011162806A (en) |
| KR (1) | KR20110090726A (en) |
| CN (1) | CN102146558A (en) |
| TW (1) | TW201127987A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI626989B (en) * | 2017-04-21 | 2018-06-21 | 國立中興大學 | Pretreatment of chemical copper plating and catalyst solution including cu(ii) complex and conditioner employed therein |
| CN108251874A (en) * | 2018-01-24 | 2018-07-06 | 永星化工(上海)有限公司 | Suitable for the preprocessing solution of coating metal layer on the functional resin composition of plating |
| CN109563623A (en) * | 2016-08-10 | 2019-04-02 | 上村工业株式会社 | The preparation method of the chemical plating pretreatment liquid and printed circuit board that are used simultaneously with reduction treatment |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8840967B2 (en) | 2006-10-11 | 2014-09-23 | Samsung Electro-Mechanics Co., Ltd. | Method for manufacturing printed circuit board including flame retardant insulation layer |
| JP5412550B2 (en) * | 2011-09-16 | 2014-02-12 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Method for manufacturing printed circuit board |
| KR101384025B1 (en) * | 2012-02-21 | 2014-04-09 | 주식회사 에이스테크놀로지 | Pre-treatment Solution for Plastic Plating and Plating Method Using the Same |
| JP6367606B2 (en) * | 2013-09-09 | 2018-08-01 | 上村工業株式会社 | Pretreatment agent for electroless plating, pretreatment method for printed wiring board using said pretreatment agent for electroless plating, and method for producing the same |
| CN106471001B (en) | 2014-08-01 | 2019-05-07 | 株式会社杰希优 | The purposes of silicone oligomer, its manufacturing method containing catalyst metals and the silicone oligomer containing catalyst metals |
| JP6540843B1 (en) * | 2018-03-06 | 2019-07-10 | 栗田工業株式会社 | Hydrophilization treatment method of polypropylene resin |
| JP6551563B1 (en) * | 2018-03-06 | 2019-07-31 | 栗田工業株式会社 | Pre-plating method for ABS resin surface, plating method for ABS resin surface, and ABS resin plating product |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935828A (en) * | 2008-10-31 | 2011-01-05 | 罗门哈斯电子材料有限公司 | Conditioner for electroless plating |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4325991A (en) * | 1981-01-05 | 1982-04-20 | Crown City Plating Co. | Electroless plating of polyesters |
| IL82764A0 (en) * | 1986-06-06 | 1987-12-20 | Advanced Plating Technology Ap | Selective plating process for the electrolytic coating of circuit boards |
-
2010
- 2010-02-04 JP JP2010023481A patent/JP2011162806A/en active Pending
- 2010-04-30 KR KR1020100040665A patent/KR20110090726A/en not_active Application Discontinuation
- 2010-04-30 CN CN2010102143459A patent/CN102146558A/en active Pending
- 2010-04-30 TW TW099113820A patent/TW201127987A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935828A (en) * | 2008-10-31 | 2011-01-05 | 罗门哈斯电子材料有限公司 | Conditioner for electroless plating |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109563623A (en) * | 2016-08-10 | 2019-04-02 | 上村工业株式会社 | The preparation method of the chemical plating pretreatment liquid and printed circuit board that are used simultaneously with reduction treatment |
| TWI626989B (en) * | 2017-04-21 | 2018-06-21 | 國立中興大學 | Pretreatment of chemical copper plating and catalyst solution including cu(ii) complex and conditioner employed therein |
| CN108251874A (en) * | 2018-01-24 | 2018-07-06 | 永星化工(上海)有限公司 | Suitable for the preprocessing solution of coating metal layer on the functional resin composition of plating |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110090726A (en) | 2011-08-10 |
| TW201127987A (en) | 2011-08-16 |
| JP2011162806A (en) | 2011-08-25 |
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Application publication date: 20110810 |