JP2009235565A - Solution for and method of treating surface of copper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stable, less-turbidity solution for stably treating the surface of copper, and to provide a method for copper surface treatment by contact with the solution. <P>SOLUTION: The solution contains a tin compound, a fluorine compound and a complexing agent, and has the pH of ≤5. The concentration of a free fluorine based on the whole solution is within the range of ≥0.1 ppm but ≤100 ppm. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a copper surface treatment liquid and a surface treatment method, a copper-clad material, a multilayer wiring board, and a wiring board. More specifically, a stable copper surface treatment solution with less turbidity, a copper surface treatment method for bringing the surface treatment solution into contact with the surface treatment solution, and a copper-coated surface treated by the surface treatment method in order to perform a stable surface treatment. The present invention relates to a material, a multilayer wiring board, and a wiring board.

  Conventionally, a general multilayer wiring board (build-up wiring board) is manufactured by laminating and pressing an inner layer substrate having a conductive layer made of copper on the surface portion with another inner layer substrate with an insulating material such as resin interposed therebetween. ing. The conductive layers are electrically connected by a through hole called a through hole whose hole wall is plated with copper.

  Here, the copper used for the surface portion of the inner layer substrate as the wiring of the multilayer wiring substrate is required to have adhesiveness with an insulating material such as a resin. Therefore, in order to improve the adhesion between the copper surface used for the surface portion of the inner layer substrate and an insulating material such as a resin, a copper surface treatment is generally performed.

  Examples of the copper surface treatment method include a method of roughening the copper surface by etching the copper surface with copper chloride, sulfuric acid / hydrogen peroxide, etc., and attaching an uneven oxide film to the copper surface. It is done. According to this method, the concavo-convex-shaped oxide film is difficult to insulate with an insulating material such as a resin, and an anchor effect is produced, thereby improving the adhesion between copper and an insulating material such as a resin. As another method for improving the adhesion between copper and an insulating material such as a resin, a method of treating the roughened copper surface with tin, a silane coupling agent or the like has been developed (for example, a patent). References 1-3).

  In order to cope with recent downsizing and thinning of electronic devices and electronic parts, it is required to make the multilayer wiring board thinner. Furthermore, in order to cope with the recent increase in frequency and density of electronic devices and electronic parts, it is required to make the wiring of the multilayer wiring board finer (finer).

  Further, when the surface of copper used for the surface portion of the multilayer wiring board is rough, there is a problem that a surface current flows through the multilayer wiring board, resulting in electrical loss and signal delay.

  Therefore, as a method of replacing the method using the roughening treatment such as etching, a method of forming a tin film by tin plating or the like on the surface of copper used for the surface portion of the inner layer substrate is shown (for example, (See Patent Documents 4 to 9). In particular, Patent Document 9 discloses a method in which borohydrofluoric acid or the like is used as an acid in order to adjust the pH to form a surface having excellent adhesion.

JP 10-289838 A (released on October 27, 1998) JP 2000-340948 A (published December 8, 2000) JP 10-256736 A (published on September 25, 1998) JP-A-4-233793 (published on August 21, 1992) JP-A-1-109796 (published on April 26, 1991) JP 7-170064 A (published July 4, 1995) Japanese Patent No. 3135516 (Japanese Patent Laid-Open No. 10-46359, published on Feb. 17, 1998) JP 2003-201585 A (published July 18, 2003) JP 2005-23301 A (published January 27, 2005)

  However, the copper surface treatment methods disclosed in Patent Documents 1 to 3 have hardly been put into practical use because the performance, particularly the adhesion between copper and an insulating material such as a resin, is insufficient. Furthermore, in these methods, since the roughening treatment dissolves copper, the copper width is reduced, and it becomes difficult to refine the copper-clad material surface-treated by these methods, and the electrical loss increases. Furthermore, in these methods, since an oxide film grows with a change with time after the roughening treatment, passivation becomes insufficient, and the performance deteriorates in all cases. Therefore, a rust prevention treatment as a post treatment is generally performed.

  Moreover, in the copper surface treatment methods shown in Patent Documents 4 to 9, in the copper surface treatment liquid, turbidity derived from precipitation of tin is likely to occur, and the solution itself becomes unstable, and as a result, stable. There is a problem that the surface treatment cannot be performed.

  In particular, in the copper surface treatment method disclosed in Patent Document 9, an acid such as borohydrofluoric acid is used to adjust the pH, but the present technology cannot suppress the precipitation of tin. This is because the addition of high concentration of borohydrofluoric acid may impair the stability of the surface treatment solution, and a large amount of free fluorine may be generated from the high concentration of borohydrofluoric acid, thereby hindering the copper surface treatment reaction. Because there is. Moreover, since wastewater treatment becomes difficult, use of a boron-containing compound is also not preferable.

  The present invention has been made in view of the above-described conventional problems, and its purpose is to provide a stable copper surface treatment solution with less turbidity and a copper contact with the surface treatment solution in order to perform stable surface treatment. The object is to provide a surface treatment method.

  As a result of intensive studies in view of the above problems, the present inventors have included a tin compound, a fluorine compound, and a complexing agent (chelating agent) in the copper surface treatment liquid, and the concentration of free fluorine with respect to the entire surface treatment liquid is set to 0. By setting the pH within the range of 1 ppm or more and 100 ppm or less and the pH of the surface treatment liquid to 5 or less, the tin compound is stably present in the surface treatment liquid, and the surface treatment liquid is less turbid and stable. The inventors have found that the present invention has been completed and completed the present invention.

  That is, the copper surface treatment liquid of the present invention contains a tin compound, a fluorine compound, and a complexing agent in order to solve the above problems, and the concentration of free fluorine with respect to the entire surface treatment liquid is 0.1 ppm. As described above, it is within the range of 100 ppm or less, and the pH of the surface treatment solution is 5 or less.

  According to the above invention, the copper surface treatment liquid of the present invention contains a tin compound and a fluorine compound, and is adjusted so that the pH of the surface treatment liquid is 5 or less. The tin ions dissociated from the above are stably present by the action of fluorine liberated from the fluorine compound, resulting in a stable solution with little turbidity. Furthermore, since the copper surface treatment liquid of the present invention becomes a stable solution with less turbidity, a uniform tin film can be formed on the surface of copper, and the adhesion between copper and an insulating material such as a resin is improved. be able to.

  Furthermore, since the copper surface treatment solution of the present invention has a free fluorine concentration within the range of 0.1 ppm or more and 100 ppm or less with respect to the entire surface treatment solution, an appropriate amount of free fluorine for stabilizing tin ions is present. It will be. As a result, the copper surface treatment liquid of the present invention has sufficient tin ions and free fluorine, and becomes a stable solution with much less turbidity.

  Furthermore, since the copper surface treatment liquid of the present invention contains a complexing agent, the complexing agent forms a complex with copper and the potential on the surface of the copper is lowered, so that it is easily reduced and tin is precipitated. It becomes easy to do. Furthermore, the surface treatment liquid may improve the uniformity of the tin film by chelating copper in which the complexing agent is dissolved.

  In the copper surface treatment liquid of the present invention, the molar ratio of fluorine released from the fluorine compound to tin ions dissociated from the tin compound is preferably in the range of 1 or more and 20 or less.

  Thereby, the copper surface treatment liquid of the present invention is sufficiently stabilized by the fluorine released from the tin and the fluorine compound in the surface treatment liquid, and becomes a stable solution with less turbidity.

  The copper surface treatment liquid of the present invention preferably contains at least thiourea or a derivative thereof as the complexing agent.

  Thereby, since the copper surface treatment liquid of the present invention contains thiourea or a derivative thereof, thiourea or a derivative thereof mainly functions as a complexing agent, and forms a complex with copper to form a copper surface. Reduce the potential to improve the reduction. Furthermore, thiourea or a derivative thereof also acts as a secondary reducing agent, and can promote a reaction for forming a tin film on the surface of copper.

  The copper surface treatment solution of the present invention preferably further contains a silane coupling agent.

  As a result, the copper surface treatment liquid of the present invention coexists when the tin compound and the silane coupling agent perform the surface treatment, so that the silane compound is deposited (attached) while forming a tin film on the copper surface. ). That is, the copper surface treatment liquid of the present invention can co-precipitate tin and a silane compound on the surface of copper. Therefore, due to the action of both the tin film having good adhesion with an insulating material such as a resin and the silane compound having an adhesive functional group with an insulating material such as a resin, the copper surface treatment liquid of the present invention is Sufficient adhesion between copper and an insulating material such as resin can be imparted.

  In the copper surface treatment liquid of the present invention, the silane coupling agent preferably has a mercapto group, an epoxy group or an amino group.

  Thereby, since the mercapto group tends to adsorb | suck to copper, the silane coupling agent becomes easy to co-precipitate with tin with the copper surface treatment liquid of this invention. Furthermore, since the mercapto group can react with an insulating material such as an epoxy resin, if a silane coupling agent having a mercapto group is present on the surface of copper, the adhesion with an insulating material such as an epoxy resin is improved. In addition to mercapto groups, epoxy groups, amino groups, and the like can react with insulating materials, thereby improving adhesion with insulating materials such as epoxy resins. Further, as other functional groups, silanol groups and alkoxyl groups of the silane coupling agent are adsorbed on the tin oxide.

  In the copper surface treatment liquid of the present invention, the silane coupling agent preferably contains a trimer or higher silane coupling agent condensate.

  Thereby, the silane coupling agent condensate of a trimer or more has an advantage that the silane coupling agent is easily precipitated as compared with the monomer of the silane coupling agent. Therefore, the copper surface treatment liquid of the present invention can further improve the adhesion between copper and an insulating material such as a resin.

  In the copper surface treatment liquid of the present invention, the weight ratio of the silane coupling agent to the weight of the tin compound is preferably within a range of 0.001 or more and 100 or less. In the copper surface treatment liquid of the present invention, the concentration of the silane coupling agent with respect to the entire surface treatment liquid is preferably in the range of 10 ppm to 100,000 ppm.

  The copper surface treatment liquid of the present invention is such that the ratio of the weight of the silane coupling agent to the weight of the tin compound and the concentration of the silane coupling agent with respect to the entire surface treatment liquid are within the above range. It is possible to more reliably co-precipitate tin and a silane compound on the surface. Therefore, the copper surface treatment liquid of the present invention can more reliably realize the adhesion between copper and an insulating material such as a resin.

  The copper surface treatment liquid of the present invention preferably further contains a reducing agent.

  Thereby, the copper surface treatment liquid of the present invention can promote the reaction of forming a tin film on the surface of copper.

  The copper surface treatment liquid of the present invention preferably further contains a rust inhibitor. In the copper surface treatment liquid of the present invention, the rust inhibitor is preferably at least one compound selected from tetrazole, triazole, imidazole, and thiol.

  Thereby, the copper surface treatment liquid of the present invention improves the adhesion between copper and an insulating material such as a resin, and the copper performance hardly changes even if it is stored for a long time after the surface treatment.

  The copper surface treatment liquid of the present invention preferably further contains a metal compound. Further, in the copper surface treatment liquid of the present invention, the metal compound is preferably a compound containing at least one metal selected from silver, palladium, gold, platinum, and copper.

  Thereby, it is thought that the copper surface treatment liquid of the present invention can form a tin film uniformly and stably on the surface of copper by the buffering action of metal ions.

  In the copper surface treatment method of the present invention, the surface treatment liquid is preferably brought into contact with the copper surface.

  Thereby, since the surface treatment method of the copper of this invention makes a stable surface treatment liquid with less turbidity contact the surface of copper, a tin film can be stably formed on the surface of copper.

  Moreover, the copper surface treatment method of the present invention comprises at least one pretreatment selected from pickling treatment, roughening treatment (unevenness treatment), rust prevention treatment, oxidation treatment, surface conditioning treatment, and degreasing treatment on the copper surface. Then, the surface treatment liquid is preferably contacted.

  Thereby, the copper surface treatment method of the present invention can remove stains, oxides, etc. on the copper surface by pickling treatment and degreasing treatment, and by roughening treatment, rust prevention treatment, oxidation treatment, surface conditioning treatment. It is possible to further improve the chemical conversion on the copper surface and the performance of copper.

  In the copper surface treatment method of the present invention, the surface treatment solution is preferably brought into contact with the copper surface, and then a rust preventive agent, a resin, or a silane coupling agent is brought into contact therewith.

  Thereby, since the rust preventive agent, resin, or silane compound precipitates on the surface of copper, the copper surface treatment method of the present invention can further improve the adhesion between copper and an insulating material such as resin. .

  Moreover, it is preferable that the copper clad material of this invention is surface-treated by the said copper surface treatment method. Furthermore, the multilayer wiring board of the present invention preferably includes the copper-clad material. Furthermore, the wiring board of the present invention preferably includes the copper-clad material in the outermost layer.

  The copper surface treatment method of the present invention is a method capable of stably forming a tin film on the surface of copper. Since the copper-clad material, multilayer wiring board and wiring board of the present invention are surface-treated by the above-described copper surface treatment method, the multilayer wiring board can be reduced in size, thickness, frequency, density, etc. Suitable for

  As described above, the copper surface treatment liquid of the present invention contains a tin compound, a fluorine compound, and a complexing agent, and the concentration of free fluorine with respect to the entire surface treatment liquid is 0.1 ppm or more and 100 ppm or less. Within the range, the pH of the surface treatment solution is 5 or less.

  Therefore, the copper surface treatment liquid of the present invention has the effect of providing a stable copper surface treatment liquid with less turbidity and a copper surface treatment method for bringing the surface treatment liquid into contact with the surface treatment liquid in order to perform a stable surface treatment. Play.

  Hereinafter, the present invention will be described in detail. However, the scope of the present invention is not limited to these descriptions, and other than the following examples, the present invention can be appropriately modified and implemented without departing from the spirit of the present invention. It is. Specifically, the present invention is not limited to the following embodiments, and various modifications are possible within the scope of the claims. That is, embodiments obtained by combining technical means appropriately modified within the scope of the claims are also included in the technical scope of the present invention. In this specification and the like, for convenience, “weight ppm” is simply referred to as “ppm”, and “weight%” is simply referred to as “%”.

(I) Substance to be surface-treated with copper surface treatment liquid in the present invention The substance to be surface-treated with a copper surface treatment liquid in the present invention is not particularly limited as long as it contains 50% or more of copper. That is, as long as it contains 50% or more of copper, it is included in the present invention even if a substance other than copper is included. Examples thereof include copper alone, copper alloy material containing copper, surface-treated copper such as chromate, and plated copper.

  As copper in the present invention, specifically, foil (electrolytic copper foil, rolled copper foil), plating film (electroless copper plating film, electrolysis) used for electronic parts such as electronic boards and lead frames, ornaments, building materials, etc. Copper plating film), wires, rods, tubes, plates, and the like can be used for various purposes. The said copper may contain other elements according to the objective, such as brass, bronze, white copper, arsenic copper, silicon copper, titanium copper, chromium copper. In the case of a copper wiring through which a high-frequency electrical signal flows in recent years, the copper surface is preferably a smooth surface having an average roughness of 0.1 μm or less.

  In the present invention, examples of the insulating material such as a resin that adheres to copper include thermosetting resins such as epoxy resin, phenol resin, polyimide, polyurethane, bismaleimide / triazine resin, modified polyphenylene ether, and cyanate ester. These resins may be modified with functional groups, and may be reinforced with glass fibers, aramid fibers, other fibers, and the like. For example, in printed circuit board applications in the build-up process, excellent adhesion can be secured even for inner layer insulating materials, prepregs, outer layer solder resists, and both insulating materials.

(II) Materials used for the copper surface treatment liquid in the present invention The copper surface treatment liquid of the present invention contains a tin compound, a fluorine compound, and a complexing agent. Furthermore, the copper surface treatment liquid of the present invention preferably contains a silane coupling agent. Furthermore, the copper surface treatment liquid of the present invention preferably contains a reducing agent. Furthermore, the copper surface treatment liquid of the present invention preferably contains a metal compound. Moreover, the copper surface treatment liquid of the present invention may contain an acid / alkali pH adjuster, if necessary.

  The copper surface treatment liquid of the present invention may contain a substance other than the above substances (hereinafter referred to as “other substances”) as long as the properties of the surface treatment liquid are not impaired. It does not specifically limit as a method of including another substance.

<Tin compounds>
The copper surface treatment liquid of the present invention contains a tin compound. Although it will not specifically limit as a tin compound if it is soluble with respect to the solvent mentioned later, Salts with an acid are preferable from the solubility. For example, stannous sulfate, stannic sulfate, stannous borofluoride, stannous fluoride, stannic fluoride, stannous nitrate, stannic nitrate, stannous chloride, stannic chloride, Examples thereof include stannous salts such as stannous formate, stannic formate, stannous acetate, and stannic acetate, and stannic salts. Among them, stannous salt is preferable because of the high formation rate of tin film, and it is highly stable in a solution with a solvent to be described later, so that a uniform tin film can be formed. Tin salts are preferred. Furthermore, stannic sulfate is particularly preferred because it does not adversely affect copper etching.

  The concentration of the tin compound with respect to the entire surface treatment liquid is preferably in the range of 10 ppm to 200,000 ppm, more preferably 25 ppm to 10,000 ppm, and particularly preferably 100 ppm to 2,000 ppm. If the concentration of the tin compound with respect to the entire surface treatment liquid is less than 10 ppm, the adhesion with an insulating material such as copper and resin may be lowered, which is not preferable. On the other hand, if it exceeds 200,000 ppm, a large amount of tin is deposited on the copper surface, the tin coating may cohesively break, and it is difficult to form a tin coating on the copper surface because of poor solution stability. This is not preferable.

<Fluorine compound>
The copper surface treatment liquid of the present invention contains a fluorine compound. Examples of the fluorine compound include hydrogen fluoride, acidic sodium fluoride, acidic ammonium fluoride, sodium fluoride, ammonium fluoride, and hydrogen silicofluoride. Among them, hydrogen fluoride and sodium acid fluoride are preferred because tin is easily stabilized in the surface treatment solution having a pH of 5 or less and can be made into a stable solution with less turbidity. In addition, it is preferable that the said fluorine compound does not contain boron from a viewpoint of considering an environment.

  The concentration of the fluorine compound relative to the entire surface treatment liquid is preferably in the range of 10 ppm to 200,000 ppm, more preferably 25 ppm to 5,000 ppm, and particularly preferably 100 ppm to 2,000 ppm. If the concentration of the fluorine compound relative to the entire surface treatment liquid is less than 10 ppm, the amount of free fluorine may not be sufficient to stabilize tin ions, which is not preferable. On the other hand, if it exceeds 200,000 ppm, the reaction of forming a tin film on the surface of copper may be inhibited, which is not preferable. If the concentration of the fluorine compound relative to the entire surface treatment liquid is 5,000 ppm or less, the tin film formed on the copper surface may become thicker or become porous (porous) or the like. It is more preferable because it is not present.

  The molar ratio of fluorine liberated from the fluorine compound to tin ions dissociated from the tin compound is preferably in the range of 1 to 20, more preferably in the range of 3 to 9, most preferably 6. It is. The mechanism by which free fluorine stabilizes tin ions is not clear, but it is thought that tin ions and free fluorine form a complex, and the complex exists stably, resulting in a uniform solution with less turbidity.

  If the molar ratio of the free fluorine to the tin ion is less than 1, there is a possibility that the stabilization of tin may be insufficient, which is not preferable. On the other hand, if it exceeds 20, the surface treatment solution may impair the stability, which is not preferable.

  The ratio of the tin ion dissociated from the tin compound and the fluorine ion dissociated from the fluorine compound is determined by measuring the amount of tin by ICP (Inductively Coupled Plasma) analysis, atomic absorption analysis, etc., and measuring the concentration of free fluorine by an ion meter. It can be derived by measuring.

  The concentration of the free fluorine with respect to the entire surface treatment liquid is in the range of 0.1 ppm to 100 ppm, preferably 1 ppm to 50 ppm, particularly preferably 2 ppm to 20 ppm. If the concentration of the free fluorine with respect to the entire surface treatment liquid is less than 0.1 ppm, the amount of free fluorine for stabilizing tin may be insufficient, which is not preferable. On the other hand, if it exceeds 100 ppm, the reaction of forming a tin film on the surface of copper may be hindered, which is not preferable. Here, the concentration of free fluorine is the concentration of fluorine ions measured using a general ion electrode.

  Here, free fluorine (fluorine ion) will be described below. Free fluorine is present in the copper surface treatment liquid of the present invention. In order to allow the free fluorine to exist, a fluorine compound is included in the surface treatment liquid. The free fluorine has an action of improving the stability of the tin compound in the surface treatment liquid. Furthermore, the free fluorine also has an action of promoting the reaction of the tin compound with respect to copper which is the target of the surface treatment with the surface treatment liquid.

  Further, tin contained in the tin compound in the surface treatment liquid of the present invention can be stably present in the surface treatment liquid by forming a complex with fluorine in the surface treatment liquid. ing. By this action, even if the surface of the copper is continuously replenished with the above surface treatment solution as appropriate, the replenished tin compound locally forms a film due to the presence of free fluorine at a concentration above a certain level. There is nothing to do. Therefore, the copper surface treatment liquid of the present invention can form an optimum amount of tin film on copper by specifying the concentration of free fluorine, and can perform a stable surface treatment.

<Complexing agent>
The copper surface treatment liquid of the present invention contains a complexing agent. Here, the complexing agent as used in the present specification means coordination with copper to form a chelate, lowering the potential of the copper surface, making it easy to reduce, and providing an insulating material adhesion layer such as a resin on the tin surface. It means something that is easy to form. Examples of the complexing agent include thiourea derivatives such as thiourea, ethylenethiourea, diethylthiourea, and dibutylthiourea, thiosulfuric acid, and cyanides. Among these, thiourea, diethylthiourea, and dibutylthiourea are preferable because they can easily form a complex with copper and can further easily form a tin film because the potential of the copper surface is lowered. Some complexing agents also work as a reducing agent, which will be described later. Among them, thiourea also functions as a reducing agent which will be described later.

  The concentration of the complexing agent with respect to the entire surface treatment liquid is preferably in the range of 0.01% to 50%, more preferably 0.1% to 30%, and particularly preferably 1% to 15%. is there. If the concentration of the complexing agent relative to the entire surface treatment liquid is less than 0.01%, it may be difficult to form a complex on the copper surface, which is not preferable. On the other hand, if it exceeds 50%, the reaction for forming a tin film on the surface of copper may be inhibited, which is not preferable.

<Silane coupling agent>
The copper surface treatment liquid of the present invention preferably contains a silane coupling agent. The silane coupling agent is not particularly limited as long as it is soluble in the solvent described later. Examples of the silane coupling agent include mercaptosilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane, vinylsilanes such as vinyltrichlorosilane, vinyltrimethoxysilane and vinyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, epoxyglycan such as 3-glycidoxypropyltriethoxysilane, p-styryltri Stylylsilane such as methoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyltri Methacryloxysilane such as toxisilane, Acryloxysilane such as 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-amino Propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3 -Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, and other aminosilanes, 3-ureidopropyltriethoxysilane Such as ureidosilane, Chloropropyl silanes such as Russia trimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, etc. Surufidoshiran, isocyanate silanes such as 3-isocyanate propyl triethoxysilane, mixtures thereof and the like.

  In addition, since it easily adsorbs to copper, it easily co-precipitates with tin, and a silane coupling agent having a mercapto group, such as mercaptosilane, is preferable because it has excellent adhesion to an insulating material such as an epoxy resin. Amino silane, epoxy silane, and isocyanate silane are preferable because they are easily cross-linked with each other. For example, silane coupling agents having amino groups and silane cups having epoxy groups are preferred because they are excellent in compatibility with various insulating materials. A mixture with a ring agent and a cocondensate (for example, a cocondensate of aminosilane and epoxysilane) are preferred. Moreover, the silane coupling agent which has an alkoxyl group, silanol, etc. are also preferable. Among them, a silane coupling agent having a mercapto group is particularly preferable because the adhesion between copper and an insulating material such as an epoxy resin is extremely improved.

  Further, the copper surface treatment liquid of the present invention contains a silane coupling agent condensate of a trimer or more because it has an advantage of being easily precipitated as compared with a silane coupling agent monomer. It is preferable.

Here, the condensation rate of the silane coupling agent when forming the silane coupling agent condensate is expressed by the following formula (1).
z = x / (x + y) × 100 (1)
[In formula (1), x represents the molar ratio of the silane coupling agent condensate (a dimer or higher silane coupling agent), y represents the molar ratio of the silane coupling agent monomer, and z represents silane. Represents the condensation rate (%) of the coupling agent].

Note that the molar ratio of the silane coupling agent condensate or a silane coupling Zaitan monomers can be derived using the ^{29 Si-NMR.} Specifically, a silane coupling agent condensate is one in which a silicon atom in a silane coupling agent is bonded to another silicon atom through an oxygen atom, and the silicon atom is bonded to another silicon through an oxygen atom. The mole ratio of the silane coupling agent condensate or the silane coupling agent monomer can be derived by using a silane coupling agent monomer that is not bonded to an atom.

  The concentration of the silane coupling agent with respect to the entire surface treatment liquid is preferably in the range of 10 ppm to 100,000 ppm, more preferably 100 ppm to 5,000 ppm, and particularly preferably 200 ppm to 2,000 ppm. If the concentration of the silane coupling agent with respect to the entire surface treatment liquid is less than 10 ppm, the adhesion with an insulating material such as the tin film and resin is liable to be unfavorable. On the other hand, if it exceeds 100,000 ppm, the silane compound may be adsorbed on the copper surface and it may be difficult to precipitate tin, which is not preferable.

  The ratio of the weight of the silane coupling agent to the weight of the tin compound is preferably 0.001 or more and 100 or less, more preferably 0.00 because the balance between the formation of the tin film and the precipitation of the silane compound is good. The range is from 01 to 10, particularly preferably from 0.02 to 1.

<Reducing agent>
The copper surface treatment liquid of the present invention preferably contains a reducing agent. Examples of the reducing agent include thiourea, diethylthiourea, potassium borohydride, dimethylaminoborane, sodium hypophosphite, hydrazine, formaldehyde and the like. Among them, it is preferable to contain at least thiourea because it is easy to add a tin compound and to form a tin film made of tin alone, tin oxide, or the like.

  The concentration of the reducing agent with respect to the entire surface treatment liquid is preferably in the range of 0.01% to 50%, more preferably 0.1% to 30%, and particularly preferably 1% to 15%. . If the concentration of the reducing agent relative to the entire surface treatment liquid is less than 0.01%, the tin film may not be formed, which is not preferable. On the other hand, if it exceeds 50%, it is difficult to form a tin film on the surface of copper because tin is difficult to dissolve in copper, which is not preferable.

<Rust preventive>
The copper surface treatment liquid of the present invention preferably contains a rust inhibitor. Examples of the rust preventive include aminotetrazole, methyl mercaptotetrazole, benzotriazole, carboxybenzotriazole, aminomercaptotriazole, imidazole, methylimidazole, triazine thiol, trimercaptotriazine or a salt thereof, or a similar compound thereof; mercaptosilane Thioglycolic acid; thioglycerol; guanylthiourea; thioureas; Among them, tetrazole, triazole, imidazole, and thiol rust preventives are preferred because they have both a rust preventive function on the copper surface and chemical conversion.

<Metal compound>
The copper surface treatment liquid of the present invention preferably contains a metal compound. Examples of the metal compound include metal salts. Examples of the metal compound include aluminum compounds, zirconyl compounds, titanium compounds, calcium compounds, sodium compounds, magnesium compounds, strontium compounds, manganese compounds, vanadium compounds, yttrium compounds, niobium compounds, zinc compounds, indium compounds, silver compounds. , Iron compounds, palladium compounds, cobalt compounds, copper compounds, nickel compounds and the like. Among these, silver compounds, palladium compounds, gold compounds, platinum compounds, and copper compounds are preferred because they are considered to easily co-precipitate with tin and give a denser tin film.

  The concentration of the metal compound with respect to the entire surface treatment liquid is preferably in the range of 1 ppm to 10,000 ppm, more preferably 10 ppm to 2,000 ppm, and particularly preferably 100 ppm to 1,000 ppm. If the concentration of the metal compound relative to the entire surface treatment liquid is less than 1 ppm, it may be difficult to form a complex with fluorine, which is not preferable. On the other hand, if it exceeds 10,000 ppm, there is a possibility of inhibiting the reaction of depositing the silane compound while forming a tin film on the surface of copper, which is not preferable.

<PH adjuster>
The copper surface treatment liquid of the present invention may contain an acid / alkali pH adjuster, if necessary. Here, the copper surface treatment solution of the present invention has a pH of 5 or less. As the acid pH adjuster, at least one acid selected from inorganic acids and organic acids can be used. Examples of the acid that can be used in the present invention include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, borofluoric acid, and phosphoric acid; carboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid, methanesulfonic acid, and ethane. And organic acids such as alkane sulfonic acids such as sulfonic acid, aromatic sulfonic acids such as benzene sulfonic acid, phenol sulfonic acid, and cresol sulfonic acid. Among them, sulfuric acid is preferable because of the speed of forming an adhesion layer with an insulating material such as a resin and the solubility of a tin compound.

  The concentration of the pH adjuster with respect to the entire surface treatment liquid is preferably in the range of 10 ppm to 10,000 ppm, more preferably 50 ppm to 2,000 ppm, and particularly preferably 100 ppm to 1000 ppm. When the concentration of the pH adjusting agent relative to the entire surface treatment liquid is less than 10 ppm, the tin compound is difficult to dissolve, and stabilization of tin ions by free fluorine may be insufficient, which is not preferable. On the other hand, if it exceeds 10,000 ppm, there is a possibility of inhibiting the reaction of depositing the silane compound while forming a tin film on the surface of copper, which is not preferable.

<Other substances>
The copper surface treatment liquid of the present invention is a surfactant for forming a uniform adhesion layer with an insulating material such as a resin, a polymerization initiator for accelerating the formation of an adhesion layer with an insulating material such as a resin, etc. If necessary, various additives that do not inhibit the reaction of forming a tin film on the surface of copper may be contained.

<Post-treatment agent>
Examples of the post-treatment agent include silane coupling agents, titanium alkoxides, resins, rust inhibitors, and the like, and any compound can be used alone or in combination as long as it has a functional group that is in close contact with the insulating material. Examples of functional groups that are in close contact with the insulating material include epoxy groups, silanol groups, imide groups, isocyanate groups, carboxyl groups, phosphone groups, carbonyl groups, amino groups, and mercapto groups. The resin has only to have the above functional group, and examples thereof include polyacrylic acid, alklu resins such as derivatives thereof, epoxy resins, polyallylamine and the like. The concentration when these post-treatment agents are used is preferably within the range of 10 ppm or more and 20,000 ppm or less.

<Solvent>
The copper surface treatment liquid in the present invention is composed of the above-mentioned substance as a solute and a solvent. The solvent used in the present invention is not particularly limited as long as it can dissolve the above substances. For example, water, and organic solvents such as benzene, toluene, xylene, n-heptane, n-hexane, cyclohexane, n-octane and other hydrocarbons; dichloromethane, dichloroethane, carbon tetrachloride, chloroform, chlorobenzene, dichlorobenzene and tri And halogenated hydrocarbons such as chlorobenzene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethers such as tetrahydrofuran, diethyl ether, dioxane and methyl cellosolve; alcohols such as methanol, ethanol and methoxypropanol; The said solvent may be used independently and may mix and use 2 or more types suitably. The water is preferably water from which ionic substances and impurities such as ion-exchanged water, pure water, and ultrapure water have been removed.

  The concentration of the organic solvent in the solution depends on the temperature of the solution, the components of the substance and the like and is not particularly limited, but is preferably 0% or more and 10% or less, more preferably 0 for reasons of environmental consideration. % To 1%, particularly preferably in the range of 0% to 0.1%.

  Here, since this invention aims at performing the stable surface treatment of copper, the density | concentration of the said substance in the said solution may be low concentration. Therefore, the copper surface treatment liquid in the present invention is superior to the conventional copper surface treatment liquid in that the copper surface is not subjected to roughening treatment such as etching.

(III) Manufacturing Method of Copper Surface Treatment Liquid in the Present Invention The copper surface treatment liquid of the present invention is mixed by a conventionally known mixing method / mixing apparatus. The order of mixing the substances contained in the copper surface treatment liquid of the present invention is not particularly limited. Moreover, the said substance may be mixed at once, and may be divided and mixed.

(IV) Copper surface treatment method of the present invention The copper surface treatment method of the present invention is a method of bringing the surface treatment solution into contact with the surface of copper. In the copper surface treatment method of the present invention, the silane coupling agent may be further contacted after the surface treatment liquid is brought into contact with the copper surface.

  The method for bringing the surface treatment solution into contact with the copper surface is not particularly limited. For example, a method of immersing copper in the surface treatment solution, a method of spraying the surface treatment solution on the surface of copper by spraying, a method of applying the surface treatment solution on the surface of copper, and the like can be mentioned. Moreover, the said surface treatment liquid may be made to contact at once, and may be divided and made to contact.

  The temperature at which the surface treatment liquid is brought into contact with the copper surface is not particularly limited depending on the components of the surface treatment liquid, but is preferably 10 ° C. or higher because of excellent reactivity. It is 60 ° C. or less, more preferably 20 ° C. or more and 50 ° C. or less, particularly preferably 30% or more and 40% or less.

  The time for which the surface treatment liquid is brought into contact with the copper surface is determined by the components of the surface treatment liquid and is not particularly limited, but is preferably 1 second or more and 600 seconds because of excellent reactivity. Hereinafter, it is more preferably in the range of 5 seconds to 300 seconds, particularly preferably 15 seconds to 120 seconds.

  The copper surface treatment method of the present invention may be pretreated with an acid or the like before bringing the surface treatment solution into contact with the copper surface. In the copper surface treatment method of the present invention, after the surface treatment liquid is brought into contact with the surface of copper, the surface treatment liquid, the silane coupling agent, or the like may be further post-treated. After the post-treatment, it may be washed with water and dried, or may be dried without washing. In the copper surface treatment method of the present invention, the surface treatment solution may be brought into contact with the copper surface, and then heat treatment or the like may be performed.

(V) Copper-clad material in this invention The copper-clad material of this invention is surface-treated by the said copper surface treatment method. Examples of the copper-clad material before the surface treatment by the copper surface treatment method include electronic parts such as general electronic substrates and lead frames, ornaments, and building materials. The copper-clad material of the present invention is not limited to those in which the entire surface of copper is surface-treated by the above-mentioned surface treatment method, and those in which a part of the surface of copper is surface-treated by the above-mentioned surface treatment method are also included in the present invention. include.

(VI) Multilayer Wiring Board in the Present Invention The multilayer wiring board (build-up wiring board) of the present invention comprises the above copper-clad material. The multilayer wiring board of the present invention is manufactured by a conventionally known method for manufacturing a multilayer wiring board. Specifically, an inner layer substrate having a conductive layer whose surface is made of copper is manufactured by being laminated and pressed with another inner layer substrate with an insulating material such as resin interposed therebetween. The multilayer wiring board (build-up wiring board) includes a batch lamination type build-up board and a sequential build-up type build-up board.

  The multilayer wiring board in the present invention includes an outer layer board and a single layer board provided with the copper-clad material in the outermost layer. The outer layer substrate includes a single-sided or double-sided outer layer substrate having the copper-clad material on one or both sides on the outermost layer surface.

  Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to these examples.

[Example 1]
<Copper surface treatment process>
A 35 μm thick electrolytic copper foil (Furukawa Circuit Foil, trade name: “F-WS foil”) diluted with tap water in sulfuric acid and hydrogen peroxide (sulfuric acid concentration 3%, hydrogen peroxide The film was immersed in a concentration of 1% at 30 ° C. for 60 seconds, washed with tap water, and dried.

  Next, the electrolytic copper foil subjected to the above treatment is immersed in a predetermined surface treatment solution (components and the like will be described later) at 40 ° C. for 60 seconds, washed with tap water, and then at 80 ° C. · 5 Dried for minutes.

<Components of predetermined surface treatment liquid, etc.>
In the predetermined surface treatment liquid, tin sulfate as a tin compound (concentration of tin sulfate with respect to the entire surface treatment liquid: 25 ppm, reagent) and hydrogen fluoride as a fluorine compound (concentration of hydrogen fluoride with respect to the entire surface treatment liquid) : 25 ppm, reagent) and thiourea as a complexing agent (thiourea concentration with respect to the entire surface treatment solution: 5%, reagent). Thereafter, sodium hydroxide was added to adjust the pH of the surface treatment solution to 3. The concentration of free fluorine with respect to the entire surface treatment solution was 6 ppm. The concentration of free fluorine was measured by (Fluorine ion meter, manufactured by Toa DKK Corporation, trade name: “IM-55G”).

<Multilayer wiring board manufacturing process>
In order to evaluate the adhesion between the obtained electrolytic copper foil and an insulating material such as a resin, build-up wiring board insulating materials (general-purpose prepreg, FR-4 manufactured by Matsushita Electric Works, Ltd.) are laminated on both surfaces of the electrolytic copper foil. 150 ° C. · 20 kg / m ² → 150 ° C. · 30 kg / m ² · 0.5 hours → 180 ° C. · 30 kg / m ² · 1.5 hours heating and laminating press, then 80 ° C. -It cooled on the conditions for 1.5 hours. Thereafter, the press was terminated, and cooling was performed at 20 ° C. for 20 minutes.

<Physical properties after surface treatment of copper>
(1) Tin precipitation (amount) in copper surface treatment solution
The tin precipitation (amount) in the copper surface treatment solution was measured visually. Specifically, after immersing 10 pieces of 100 mm × 70 mm copper foil in 1 L of the surface treatment liquid, the state where there was no tin precipitation was set as “◯”, and the state where there was tin precipitation was set as “x”. .

(2) The etching amount of the electrolytic copper foil after the copper surface treatment The etching amount of the electrolytic copper foil after the copper surface treatment was obtained by measuring the weight change before and after the etching with a precision balance. As a result, the state where the etching amount is less than 0.1 g / m ² is “◯”, the state where the etching amount is 0.1 g / m ² or more and 1 g / m ² or less is “Δ”, and the state exceeds 1 g / m ^2. Was marked “x”.

(3) SEM appearance of electrolytic copper foil after copper surface treatment The appearance of the electrolytic copper foil after copper surface treatment is determined by SEM (Scanning Electron Microscope, manufactured by JEOL Ltd., trade name: “JSM5310”). Was 1000 times and 5000 times and evaluated visually. As a result, the state without unevenness (flat) was set as “◯”, and the state with unevenness was set as “x”.

(4) Amount of tin / silane compound film on the electrolytic copper foil after copper surface treatment The amount of tin / silane compound film on the electrolytic copper foil after copper surface treatment was measured using fluorescent X-ray (Shimadzu Corporation, product) Name: “XRF1700”).

(5) Adhesion between copper foil and insulating material such as resin in multilayer wiring board provided with electrolytic copper foil after surface treatment of copper Adhesion between copper foil of multilayer wiring board and insulating material such as resin, The peel strength of the copper foil from the insulating material in the multilayer wiring board is 100 kg / m in load cell according to JIS C 6481 using a universal testing machine (manufactured by A & D Co., Ltd., trade name: “Tensilon”). ^2. Measurement was performed under conditions of a range of 2%, a crosshead speed of 50 mm / min, and a chart speed of 20 mm / min.

(6) Evaluation results of the above physical properties The evaluation results of the above physical properties are that the precipitation amount of tin in the copper surface treatment solution is “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment is “◯”, and the copper surface SEM appearance of electrolytic copper foil after treatment is “◯”, tin film amount of electrolytic copper foil after copper surface treatment is 45 mg / m ² , multilayer wiring board provided with electrolytic copper foil after copper surface treatment The adhesion between the copper foil and an insulating material such as resin was 0.60 kN / m.

[Example 2]
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). The hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment liquid: 25 ppm) was changed to hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment liquid: 500 ppm), and the concentration of free fluorine was changed from 6 ppm to 10 ppm. Except for this, the same operation as in Example 1 was performed.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” ”The amount of tin film on the electrolytic copper foil after the copper surface treatment is 156 mg / m ² , and the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment” The property was 0.60 kN / m.

Example 3
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment liquid: 25 ppm) was changed to hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment liquid: 500 ppm), and the complexing agent was thiourea (with respect to the entire surface treatment liquid) Example 1 except that the concentration of thiourea was changed from 5% to diethylthiourea (the concentration of diethylthiourea with respect to the entire surface treatment solution: 5%), and the concentration of free fluorine was changed from 6 ppm to 10 ppm. The operation was performed.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” "The adhesion amount of the copper foil and the insulating material such as a resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment is 34 mg / m < ² > after the copper surface treatment. The property was 0.60 kN / m.

Example 4
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 10,000 ppm), and fluorine compound Is changed from hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 10,000 ppm), and the concentration of free fluorine is changed from 6 ppm to 30 ppm. The same operation as Example 1 was performed except having changed into.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” "The amount of tin film on the electrolytic copper foil after the copper surface treatment is 1123 mg / m ² , and the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment" The property was 0.60 kN / m.

Example 5
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). The hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment liquid: 25 ppm) was changed to hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment liquid: 200 ppm), and the concentration of free fluorine was changed from 6 ppm to 5 ppm. Except for this, the same operation as in Example 1 was performed.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” The adhesion amount of the copper foil and the insulating material such as resin in the multilayer wiring board having the electrolytic copper foil after the copper surface treatment is 321 mg / m ² after the copper surface treatment. The property was 0.60 kN / m.

Example 6
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride to the entire surface treatment solution: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride to the entire surface treatment solution: 2,000 ppm), and change the concentration of free fluorine from 6 ppm to 100 ppm Except that, the same operation as in Example 1 was performed.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” The adhesion amount of the copper foil and the insulating material such as a resin in the multilayer wiring board having the electrolytic copper foil after the copper surface treatment is 21 mg / m ² after the copper surface treatment. The property was 0.60 kN / m.

Example 7
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment liquid: 50 ppm), change the pH of the surface treatment liquid to 1, The same operation as in Example 1 was performed except that the concentration of free fluorine was changed from 6 ppm to 3 ppm.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” The adhesion amount of the copper foil and the insulating material such as resin in the multilayer wiring board having the electrolytic copper foil after the copper surface treatment is 882 mg / m ² after the copper surface treatment. The property was 0.60 kN / m.

Example 8
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment liquid: 500 ppm), change the pH of the surface treatment liquid to 5, The same operation as in Example 1 was performed except that the concentration of free fluorine was changed from 6 ppm to 10 ppm.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” ”The adhesion amount of the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment is 19 mg / m ² after the surface treatment of the copper. The property was 0.60 kN / m.

Example 9
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride to the entire surface treatment solution: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride to the entire surface treatment solution: 500 ppm), and 5% with 50% ethanol as the silane coupling agent Diluted with 3-mercaptopropyltrimethoxysilane (concentration of 3-mercaptopropyltrimethoxysilane with respect to the entire surface treatment solution: 1000 ppm, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBM-803”), and free fluorine The same operation as in Example 1 was performed except that the concentration of 6 was changed from 6 ppm to 10 ppm. Was Tsu.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” ”, The amount of tin film on the electrolytic copper foil after the surface treatment of copper is 156 mg / m ² , the amount of film of the silane compound on the electrolytic copper foil after the surface treatment of copper is 0.4 mg / m ² , after the surface treatment of copper The adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil was 1.00 kN / m.

Example 10
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) was changed to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 500 ppm) and diluted to 30% as a silane coupling agent 3 -Mercaptopropyltrimethoxysilane (concentration of 3-mercaptopropyltrimethoxysilane with respect to the entire surface treatment solution: 1000 ppm) was added, and the same operation as in Example 1 was carried out except that the concentration of free fluorine was changed from 6 ppm to 10 ppm. Went.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” "coating weight of 91 mg / m 2 of tin of the electrolytic copper foil after the surface treatment of ^copper, the coating weight of 0.7 mg / m 2 of a silane compound of the electrolytic copper foil after the surface treatment of ^copper, after the surface treatment of copper The adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil was 1.10 kN / m.

Example 11
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride to the entire surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride to the entire surface treatment liquid: 500 ppm), and 3-mercaptopropyltrimethoxy as a silane coupling agent Add a mixture of silane and epoxysilane (trade name: “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) 1: 1 and diluted to 5% (concentration of the above mixture with respect to the entire surface treatment solution: 1000 ppm) The same operation as in Example 1 was performed except that the concentration of free fluorine was changed from 6 ppm to 10 ppm.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” "coating weight of 144 mg / m 2 of tin of the electrolytic copper foil after the surface treatment of ^copper, the coating weight of 1.0 mg / m 2 of a silane compound of the electrolytic copper foil after the surface treatment of ^copper, after the surface treatment of copper The adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil was 1.20 kN / m.

Example 12
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride to the entire surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride to the entire surface treatment liquid: 500 ppm), and 3-mercaptopropyltrimethoxy as a silane coupling agent Add a mixture of silane and aminosilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBM903”) 1: 1 and diluted to 5% (concentration of the above mixture with respect to the entire surface treatment solution: 1000 ppm), The same operation as in Example 1 was performed except that the concentration of free fluorine was changed from 6 ppm to 10 ppm.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” The amount of tin film on the electrolytic copper foil after copper surface treatment is 155 mg / m ² , the amount of silane compound film on the electrolytic copper foil after copper surface treatment is 1.2 mg / m ² , after the surface treatment of copper The adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil was 1.20 kN / m.

Example 13
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride to the entire surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride to the entire surface treatment liquid: 500 ppm), and 3-mercaptopropyltrimethoxy as a silane coupling agent Add a mixture of silane and isocyanate silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBE9007”) 1: 1 and diluted to 5% (the concentration of the above mixture with respect to the entire surface treatment solution: 1000 ppm). The same operation as in Example 1 except that the concentration of free fluorine was changed from 6 ppm to 10 ppm. I went.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” "coating weight of 127 mg / m 2 of tin of the electrolytic copper foil after the surface treatment of ^copper, the coating weight of 0.6 mg / m 2 of a silane compound of the electrolytic copper foil after the surface treatment of ^copper, after the surface treatment of copper The adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil was 1.10 kN / m.

Example 14
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) was changed to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 500 ppm), and epoxysilane and aminosilane as silane coupling agents were changed. Same as Example 1 except that a mixture mixed at 1: 1 and diluted to 5% (concentration of the above mixture with respect to the entire surface treatment solution: 1000 ppm) was added, and the concentration of free fluorine was changed from 6 ppm to 10 ppm. Was performed.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” ”, The amount of tin film on the electrolytic copper foil after the surface treatment of copper is 166 mg / m ² , the amount of film of the silane compound on the electrolytic copper foil after the surface treatment of copper is 1.2 mg / m ² , after the surface treatment of copper The adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil was 1.10 kN / m.

Example 15
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride to the whole surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride to the whole surface treatment liquid: 500 ppm), and aminotetrazole (the whole surface treatment liquid) Aminotetrazole concentration: 1000 ppm, reagent) was added, and the same operation as in Example 1 was performed except that the concentration of free fluorine was changed from 6 ppm to 10 ppm.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” ”The adhesion amount of the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment is 128 mg / m ² after the copper surface treatment. The property was 0.70 kN / m.

Example 16
The pickling of the electrolytic copper foil was changed from an aqueous solution of sulfuric acid and hydrogen peroxide to an aqueous solution of sulfuric acid (sulfuric acid concentration 3%), and the tin compound contained in the prescribed surface treatment solution was changed to tin sulfate (sulfuric acid for the entire surface treatment solution). The concentration of tin was changed from 25 ppm to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm), and the fluorine compound was changed from hydrogen fluoride (concentration of hydrogen fluoride relative to the entire surface treatment liquid: 25 ppm) to hydrogen fluoride. (The concentration of hydrogen fluoride with respect to the entire surface treatment solution: 500 ppm) The same operation as in Example 1 was performed except that the concentration of free fluorine was changed from 6 ppm to 10 ppm.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” ”The amount of tin film of the electrolytic copper foil after the copper surface treatment is 146 mg / m ² , and the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment” The property was 0.60 kN / m.

Example 17
Pickling electrolytic copper foil from sulfuric acid and hydrogen peroxide aqueous solution, sulfuric acid, hydrogen peroxide and aqueous solution of thioglycerol as rust inhibitor (sulfuric acid concentration 3%, hydrogen peroxide concentration 1%, thioglycerol The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). The fluorine compound was changed from hydrogen fluoride (concentration of hydrogen fluoride to the whole surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride to the whole surface treatment liquid: 500 ppm), and the concentration of free fluorine The same operation as in Example 1 was performed except that 6 was changed from 6 ppm to 10 ppm.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” ”The amount of tin film of the electrolytic copper foil after the copper surface treatment is 158 mg / m ² , and the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment” The property was 0.90 kN / m.

Example 18
Pickling of electrolytic copper foil from aqueous solution of sulfuric acid and hydrogen peroxide to aqueous solution of palladium dichloride and cupric chloride (palladium dichloride concentration 0.03%, cupric chloride concentration 1%, pH 2) The tin compound contained in the specified surface treatment solution was changed from tin sulfate (concentration of tin sulfate to the entire surface treatment solution: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment solution: 500 ppm), and fluorine The compound was changed from hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 500 ppm), and the concentration of free fluorine was changed from 6 ppm to 10 ppm. The same operation as Example 1 was performed except having changed.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” ”The adhesion amount of the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment is 120 mg / m ² after the copper surface treatment. The property was 0.90 kN / m.

Example 19
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 500 ppm), change the concentration of free fluorine from 6 ppm to 10 ppm, The electrolytic copper foil immersed in the surface treatment liquid is treated with a post-treatment liquid containing 3-mercaptopropyltrimethoxysilane diluted to 5% (concentration of 3-mercaptopropyltrimethoxysilane with respect to the whole post-treatment liquid: 1000 ppm). Then, operation similar to Example 1 was performed except wash | cleaning with tap water.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” "coating weight of 142 mg / m 2 of tin of the electrolytic copper foil after the surface treatment of ^copper, the coating weight of 0.7 mg / m 2 of a silane compound of the electrolytic copper foil after the surface treatment of ^copper, after the surface treatment of copper The adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil was 1.20 kN / m.

Example 20
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 500 ppm), change the concentration of free fluorine from 6 ppm to 10 ppm, The electrolytic copper foil immersed in the surface treatment solution is treated with a post-treatment agent containing 3-mercaptopropyltrimethoxysilane diluted to 5% (concentration of 3-mercaptopropyltrimethoxysilane with respect to the whole post-treatment agent: 1000 ppm). Thereafter, the same operation as in Example 1 was performed, except that it was not washed with tap water.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” The amount of tin film on the electrolytic copper foil after copper surface treatment is 130 mg / m ² , and the amount of silane compound film on the electrolytic copper foil after copper surface treatment is 2.5 mg / m ² , after copper surface treatment The adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil was 1.30 kN / m.

Example 21
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 500 ppm), change the concentration of free fluorine from 6 ppm to 10 ppm, The same operation as in Example 1 was performed except that silver nitrate (concentration of silver nitrate relative to the entire surface treatment solution: 50 ppm, reagent) was added as a metal compound.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” The adhesion amount of the copper foil and the insulating material such as resin in the multilayer wiring board having the electrolytic copper foil after the copper surface treatment is 220 mg / m ² after the copper surface treatment. The property was 0.70 kN / m.

[Example 22]
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 500 ppm), change the concentration of free fluorine from 6 ppm to 10 ppm, The same operation as in Example 1 was performed except that palladium chloride as a metal compound (palladium chloride concentration with respect to the entire surface treatment solution: 50 ppm, reagent) was added.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” ”The adhesion amount of the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment is 203 mg / m ² after the copper surface treatment. The property was 0.70 kN / m.

Example 23
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 500 ppm), change the concentration of free fluorine from 6 ppm to 10 ppm, Post-treatment agent containing epoxy silane (trade name: “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted with 5% of the electrolytic copper foil immersed in the surface treatment solution, concentration of epoxy silane with respect to the whole post-treatment agent: 1000 ppm), and then the same operation as in Example 1 was performed except that it was not washed with tap water.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” ”The amount of tin film on the electrolytic copper foil after the copper surface treatment is 156 mg / m ² , and the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment” The property was 1.20 kN / m.

Example 24
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 500 ppm), change the concentration of free fluorine from 6 ppm to 10 ppm, Epoxysilane (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by adding silver nitrate as a metal compound (concentration of silver nitrate to the entire surface treatment solution: 50 ppm) and diluting the electrolytic copper foil immersed in the surface treatment solution to 5% : "KBM403") containing a post-treatment agent (epoxysilane concentration with respect to the whole post-treatment agent: 1000 ppm), After, except that no washing with tap water, experiment was carried out in the same manner as in Example 1.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” The adhesion amount of the copper foil and the insulating material such as resin in the multilayer wiring board having the electrolytic copper foil after the copper surface treatment is 221 mg / m ² after the copper surface treatment. The property was 1.30 kN / m.

Example 25
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 500 ppm), change the concentration of free fluorine from 6 ppm to 10 ppm, Post-treatment agent containing polyacrylic acid (manufactured by Nippon Pure Chemical Co., Ltd., molecular weight 20,000) diluted to 5% with the electrolytic copper foil immersed in the surface treatment solution (concentration of polyacrylic acid relative to the whole post-treatment agent: 1000 ppm), and then the same operation as in Example 1 was performed except that it was not washed with tap water.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” ”The amount of tin film on the electrolytic copper foil after the copper surface treatment is 156 mg / m ² , and the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment” The property was 1.20 kN / m.

Example 26
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 500 ppm), change the concentration of free fluorine from 6 ppm to 10 ppm, Polyacrylic acid (manufactured by Nippon Pure Chemical Co., Ltd., molecular weight 20,000) and epoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBM403”) diluted to 5% of an electrolytic copper foil immersed in the surface treatment solution ) Containing post-treatment agent (polyacrylic acid concentration with respect to the whole post-treatment agent: 1000 ppm, epoxy silane concentration: 1000 p) Was treated with m), then, except that no washing with tap water, experiment was carried out in the same manner as in Example 1.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” ”The amount of tin film on the electrolytic copper foil after the copper surface treatment is 156 mg / m ² , and the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment” The property was 1.30 kN / m.

Example 27
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 500 ppm), change the concentration of free fluorine from 6 ppm to 10 ppm, Post-treatment agent (titanium alkoxide for the entire post-treatment agent) containing titanium alkoxide (Matsumoto Fine Chemical Co., Ltd., trade name: “Orga Tx TC-400”) diluted to 5% with the electrolytic copper foil immersed in the surface treatment solution Example 1 except that the concentration was 1000 ppm) and was not washed with tap water. The operation was performed in the same manner.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” ”The amount of tin film on the electrolytic copper foil after the copper surface treatment is 156 mg / m ² , and the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment” The property was 1.20 kN / m.

[Comparative Example 1]
A process of immersing an electrolytic copper foil laminated with an electrolytic copper foil having a thickness of 35 μm in a hydrogen peroxide solution of sulfuric acid diluted to about 17% and a predetermined surface treatment liquid is a roughening process (unevenness process) such as etching. The same operation as Example 1 was performed except having changed.

  As a result, the SEM appearance of the electrolytic copper foil after the copper surface treatment is “x”, and the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment is It was 1.00 kN / m.

[Comparative Example 2]
Copper chloride (concentration of copper chloride with respect to the entire surface treatment solution: 1%) tin sulfate as a tin compound, hydrogen fluoride as a fluorine compound, and thiourea as a complexing agent contained in a predetermined surface treatment solution , Reagent), acetic acid (concentration of acetic acid with respect to the whole surface treatment solution: 10%, reagent) and aminotetrazole (concentration of aminotetrazole with respect to the whole surface treatment solution: 0.3%, reagent) The same operation as in Example 1 was performed.

  As a result, the etching amount of the electrolytic copper foil after the copper surface treatment is “×”, the SEM appearance of the electrolytic copper foil after the copper surface treatment is “×”, and the multilayer including the electrolytic copper foil after the copper surface treatment The adhesion between the copper foil and the insulating material such as resin on the wiring board was 0.40 kN / m.

[Comparative Example 3]
Tin sulfate as a tin compound, hydrogen fluoride as a fluorine compound, and thiourea as a complexing agent contained in a predetermined surface treatment solution, sulfuric acid (sulfuric acid concentration with respect to the entire surface treatment solution: 10%, reagent ), Hydrogen peroxide (concentration of hydrogen peroxide with respect to the whole surface treatment solution: 3%, reagent) and aminotetrazole (concentration of aminotetrazole with respect to the whole surface treatment solution: 0.3%) The same operation as in Example 1 was performed.

  As a result, the etching amount of the electrolytic copper foil after the copper surface treatment is “×”, the SEM appearance of the electrolytic copper foil after the copper surface treatment is “×”, and the multilayer including the electrolytic copper foil after the copper surface treatment The adhesion between the copper foil and the insulating material such as resin on the wiring board was 0.20 kN / m.

[Comparative Example 4]
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Change from hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 500 ppm), change the concentration of free fluorine from 6 ppm to 10 ppm, The same operation as in Example 1 was performed except that thiourea as a complexing agent was not included.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” "The amount of tin film on the electrolytic copper foil after the copper surface treatment is 0 mg / m ² , and the adhesion between the copper foil and the insulating material such as resin on the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment" The property was 0.00 kN / m.

[Comparative Example 5]
The tin compound contained in the predetermined surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). The same operation as in Example 1 was performed except that hydrogen fluoride was not included.

As a result, the precipitation amount of tin in the copper surface treatment solution was “×”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” ”The amount of tin film on the electrolytic copper foil after the copper surface treatment is 325 mg / m ² , and the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment” The property was 0.30 kN / m.

[Comparative Example 6]
The tin compound contained in the specified surface treatment liquid is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment liquid: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment liquid: 500 ppm). Hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 25 ppm) was changed to hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment liquid: 10,000 ppm), and the concentration of free fluorine was changed from 6 ppm to 1,000 ppm. The same operation as Example 1 was performed except having changed into.

As a result, the precipitation amount of tin in the copper surface treatment solution was “◯”, the etching amount of the electrolytic copper foil after the copper surface treatment was “◯”, and the SEM appearance of the electrolytic copper foil after the copper surface treatment was “◯” The adhesion amount of the copper foil and the insulating material such as resin in the multilayer wiring board having the electrolytic copper foil after the copper surface treatment is 15 mg / m ² after the copper surface treatment. The property was 0.30 kN / m.

(Summary of Examples)
Table 1 summarizes the evaluation results of the above physical properties after the surface treatment of copper.

  When Examples 1-8 are compared with Examples 9-14, 19, and 20, Examples 9-14, 19, and 20 include a silane coupling agent as compared with Examples 1-8, thereby increasing the surface of copper. As a result, the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the treatment was improved.

  When Example 2 and Example 15 are compared, in Example 15, the copper foil in the multilayer wiring board provided with the electrolytic copper foil after the surface treatment of copper is obtained by including a rust preventive agent as compared with Example 2. As a result, the adhesion with an insulating material such as resin was improved.

  When Example 2 is compared with Example 16, the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment in Example 16 can be obtained by not including hydrogen peroxide in the pickling as compared with Example 2. As a result, the adhesion between the copper foil and the insulating material such as resin was the same.

  When Example 2 and Example 17 are compared, in Example 17, the anti-corrosion agent is included in the pickling as compared with Example 2, so that the multilayered wiring board provided with the electrolytic copper foil after the copper surface treatment is used. As a result, the adhesion between the copper foil and an insulating material such as resin was improved.

  Comparing Example 2 and Example 18, in Example 18, compared with Example 2, the precious metal treatment was performed at the time of pickling, so that the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment was used. As a result, the adhesion between the copper foil and the insulating material such as resin was improved.

  When Example 2 is compared with Examples 21 and 22, Examples 21 and 22 include an electrolytic copper foil after surface treatment of copper by including a metal compound containing Ag or Pd as compared with Example 2. As a result, the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board was improved.

  When Example 2 is compared with Examples 23 to 27, Examples 23 to 27 are post-treated with epoxy silane, polyacrylic acid or titanium alkoxide as a rust inhibitor, resin or silane coupling agent, as compared with Example 2. As a result, the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil after the surface treatment of copper was improved.

  When Examples 1-27 are compared with Comparative Examples 1-3, Comparative Examples 1-3 does not use a surface treatment solution containing a tin compound and a fluorine compound as compared with Examples 1-27. Since the roughening process (unevenness | corrugation process) is performed, it became a result that an unevenness | corrugation was seen in the SEM external appearance of the electrolytic copper foil after the surface treatment of copper.

  When Example 2 and Comparative Example 4 are compared, Comparative Example 4 does not contain thiourea as a complexing agent as compared with Example 2, so that a tin film is formed on the electrolytic copper foil after the copper surface treatment. As a result, the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil was lost.

  When Example 2 and Comparative Example 5 are compared, since Comparative Example 5 does not contain hydrogen fluoride as a fluorine compound as compared with Example 2, the result is that the amount of tin precipitated in the copper surface treatment liquid increases. Became.

  When Example 2 and Comparative Example 6 are compared, in Comparative Example 6, since the concentration of the fluorine compound and free fluorine is higher than in Example 2, the amount of tin film on the electrolytic copper foil after copper surface treatment is reduced. As a result, the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil decreased.

  Since the copper surface treatment liquid of the present invention is stable with little turbidity so as to perform stable surface treatment, a tin film can be stably formed on the surface of copper. As a result, the tin film formed on the copper surface can maintain the adhesion between copper and an insulating material such as a resin without roughening such as etching. For this reason, the copper surface treatment liquid and surface treatment method of the present invention can cope with the recent increase in frequency and density of electronic devices and electronic components. Moreover, in the conventional roughening process (unevenness | corrugation process), since the oxide film grew after the process and the function as an electronic device / electronic component is not exhibited, in many cases, the rust prevention process was performed as a post-process. In addition, since the copper etching is performed by several microns, a large wastewater treatment cost is required. Since the copper surface treatment liquid of the present invention performs adhesion and rust prevention (passivation) at the same time, the production process of electronic devices and electronic components can be reduced as compared with the conventional roughening treatment. Furthermore, since the dissolution of copper can be suppressed to 1/10 or less of the conventional amount in the film formation process, the wastewater treatment load is greatly reduced. Specifically, the copper surface treatment liquid and the surface treatment method of the present invention are used for various electronic devices and electronic parts such as printed wiring boards, semiconductor mounting products, liquid crystal devices, and electroluminescence having fine (fine) wiring. It is possible.

Claims (19)

Containing a tin compound, a fluorine compound, and a complexing agent,
The concentration of free fluorine with respect to the entire surface treatment liquid is in the range of 0.1 ppm to 100 ppm,
A copper surface treatment solution, wherein the surface treatment solution has a pH of 5 or less.   2. The copper surface treatment solution according to claim 1, wherein a molar ratio of fluorine liberated from the fluorine compound to tin ions dissociated from the tin compound is in a range of 1 or more and 20 or less.   The copper surface treatment solution according to claim 1, wherein the complexing agent contains at least thiourea or a derivative thereof.   Furthermore, the silane coupling agent is contained, The copper surface-treatment liquid of any one of Claims 1-3 characterized by the above-mentioned.   The copper surface treatment solution according to claim 4, wherein the silane coupling agent has a mercapto group, an epoxy group, or an amino group.   The copper surface treatment solution according to claim 4 or 5, wherein the silane coupling agent contains a trimer or higher silane coupling agent condensate.   The ratio of the weight of the silane coupling agent to the weight of the tin compound is in the range of 0.001 or more and 100 or less, The copper surface treatment according to any one of claims 4 to 6, liquid.   The copper surface treatment solution according to any one of claims 4 to 7, wherein the concentration of the silane coupling agent with respect to the entire surface treatment solution is in the range of 10 ppm to 100,000 ppm.   Furthermore, a reducing agent is contained, The copper surface-treatment liquid of any one of Claims 1-8 characterized by the above-mentioned.   Furthermore, a rust preventive agent is contained, The copper surface treatment liquid of any one of Claims 1-9 characterized by the above-mentioned.   The copper surface treatment solution according to claim 10, wherein the rust inhibitor is at least one compound selected from tetrazole, triazole, imidazole, and thiol.   The copper surface treatment solution according to claim 1, further comprising a metal compound.   13. The copper surface treatment solution according to claim 12, wherein the metal compound is a compound containing at least one metal selected from silver, palladium, gold, platinum, and copper.   A copper surface treatment method comprising contacting the copper surface treatment liquid according to any one of claims 1 to 13 with a copper surface.   The surface treatment solution is contacted after at least one pretreatment selected from pickling treatment, roughening treatment, rust prevention treatment, oxidation treatment, and degreasing treatment on the surface of copper. Copper surface treatment method.   The copper surface treatment method according to claim 14 or 15, wherein after the surface treatment liquid is brought into contact with the copper surface, a rust preventive agent, a resin or a silane coupling agent is brought into contact therewith.   A copper-clad material, which is surface-treated by the copper surface treatment method according to any one of claims 14 to 16.   A multilayer wiring board comprising the copper-clad material according to claim 17.   A wiring board comprising the copper clad material according to claim 17 in an outermost layer.