JP5307117B2 - Copper surface treatment agent and surface treatment method - Google Patents

Abstract

Provided is a copper surface treatment agent comprising a tin compound, a complexing agent, and a silane coupling agent, and a surface treatment method whereby a copper surface can be treated so as to achieve a smooth state without performing a roughing process such as etching and close adhesion between the copper and an insulating material such as a resin can be maintained, without increasing the number of processing steps.

Description

  The present invention relates to a copper surface treatment agent and a surface treatment method, a copper-clad material, a multilayer wiring board, and a wiring board. More specifically, the copper surface treatment agent and surface treatment method capable of treating the copper surface in a smooth (flat) state without roughening such as etching, and the surface treatment method are used. The present invention relates to a copper-clad 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 Document 4). Furthermore, in order to improve the adhesion between copper and an insulating material such as resin, a method of treating with nitric acid, silane coupling agent, etc. after tin plating on the copper surface used for the surface part of the inner layer substrate is shown. (For example, see Patent Documents 5 to 9).
Japanese Patent Publication “Japanese Patent Laid-Open No. 10-289838 (Publication Date: October 27, 1998)” Japanese Patent Publication “JP 2000-340948 A (publication date: December 8, 2000)” Japanese Patent Publication “Japanese Patent Laid-Open No. 10-256736 (Publication Date: September 25, 1998)” Japanese Patent Publication “JP-A-4-233793 (Publication Date: August 21, 1992)” Japanese Patent Publication “Japanese Unexamined Patent Application Publication No. 2005-23301 (Publication Date: January 27, 2005)” Japanese Patent Publication “JP-A-1-109796 (Publication Date: April 26, 1989)” Japanese Patent Publication “Japanese Laid-Open Patent Publication No. 7-170064 (Publication Date: July 4, 1995)” Japanese Patent Publication “Japanese Patent No. 3135516 (Publication Date: JP 10-46359 A, Feb. 17, 1998)” Japanese Patent Publication “Japanese Patent Laid-Open No. 2003-201585 (Publication Date: July 18, 2003)”

  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.

  In addition, the copper surface treatment method disclosed in Patent Document 4 has a problem that the adhesion between copper and an insulating material such as a resin is not sufficient as compared with a method of roughening the surface of copper such as etching. Has a point.

  Moreover, in the copper surface treatment methods disclosed in Patent Documents 5 to 9, since the surface of the copper is tin-plated and then treated with nitric acid, a silane coupling agent, or the like, the number of treatment steps increases. Furthermore, these methods also have a problem that sufficient adhesion between copper and an insulating material such as a resin cannot be maintained as compared with a method of roughening the surface of copper such as etching.

  The present invention has been made in view of the above-described conventional problems, and its purpose is to process the surface of copper in a smooth state without increasing the number of processing steps and without performing roughening treatment such as etching. An object of the present invention is to provide a copper surface treatment agent and a surface treatment method capable of maintaining adhesion between copper and an insulating material such as a resin.

  As a result of intensive studies in view of the above problems, the present inventor, as a surface treatment agent used for copper surface treatment, contains a tin compound, a complexing agent (chelating agent), and a silane coupling agent in the surface treatment agent. Including the tin and the silane compound on the surface of copper and co-depositing them, it was found uniquely that it can maintain sufficient adhesion between copper and insulating materials such as resin, and the present invention was completed. I came to let you.

  That is, the copper surface treating agent of the present invention is characterized by containing a tin compound, a complexing agent, and a silane coupling agent in order to solve the above-mentioned problems.

  According to the above invention, since the tin compound and the silane coupling agent coexist when the surface treatment is performed, the silane compound can be deposited (attached) while forming a tin film on the copper surface. . That is, the copper surface treating agent of the present invention can co-precipitate tin and a silane coupling agent monomer or a silane coupling agent condensate 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 agent of the present invention is Sufficient adhesion between copper and an insulating material such as resin can be imparted. Furthermore, since the copper surface treating agent of the present invention contains a complexing agent, when the surface treating agent is used in a solution, the complexing agent forms a complex with copper, so that the surface of the copper is treated. Since the potential is low, it is easily reduced and tin is likely to precipitate. Furthermore, the solution of the surface treatment agent may improve the uniformity of the tin film by chelating copper in which the complexing agent is dissolved. Further, when a fluorine compound is included in the surface treatment agent, it is considered that tin ions are stabilized by free fluorine in the solution of the surface treatment agent, and the solution of the surface treatment agent is further stabilized with less turbidity. It can be a solution.

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

  Thereby, since the copper surface treating agent of the present invention contains thiourea or a derivative thereof, the thiourea or the derivative 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 depositing a silane compound while forming a tin film on the surface of copper.

  The copper surface treating agent of the present invention preferably further contains a fluorine compound or an organic acid.

  Thereby, when the copper surface treating agent of the present invention is used in a solution, tin ions are stabilized by fluorine or organic acid liberated from the fluorine compound. Although the mechanism of stabilization is not clear, it is considered that a stable solution with less turbidity may be obtained by forming a complex between tin ions and free fluorine or an organic acid. Furthermore, since the solution of the copper surface treatment agent of the present invention becomes a stable solution with little turbidity, a uniform tin film can be formed on the surface of copper, and adhesion between copper and an insulating material such as a resin can be improved. Can be improved.

  The copper surface treatment agent of the present invention preferably has a pH of 5 or less.

  Thereby, the copper surface treating agent of the present invention is easily stabilized.

  In the copper surface treating agent 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 treating agent of this invention. Furthermore, since the mercapto group reacts (crosslinks) with an insulating material such as an epoxy resin, adhesion to an insulating material such as an epoxy resin is improved if a silane coupling agent having a mercapto group is present on the copper surface. To do. In addition to mercapto groups, epoxy groups, amino groups, and the like react (crosslink) with insulating materials, so that adhesion to insulating materials such as epoxy resins is improved. 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 agent of the present invention, the silane coupling agent preferably contains a silane coupling agent condensate of a trimer or more.

  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 agent of the present invention can further improve the adhesion between copper and an insulating material such as a resin.

  In the copper surface treatment agent of the present invention, the ratio of the weight of the silane coupling agent to the weight of the tin compound is preferably in the range of 0.001 to 100. In the copper surface treatment agent of the present invention, the concentration of the tin compound with respect to the entire surface treatment agent (the entire solution of the surface treatment agent) is preferably in the range of 10 ppm to 200,000 ppm. In the copper surface treatment agent of the present invention, the concentration of the silane coupling agent with respect to the entire surface treatment agent is preferably in the range of 10 ppm to 100,000 ppm.

  The copper surface treatment agent of the present invention comprises a ratio of the weight of the silane coupling agent to a weight of the tin compound, a concentration of the tin compound with respect to the whole surface treatment agent (a whole solution of the surface treatment agent), and the surface treatment agent. When the concentration of the silane coupling agent relative to the whole is within the above range, tin and a silane compound can be more reliably co-deposited on the surface of copper. Therefore, the copper surface treatment agent of the present invention can more reliably realize the adhesion between copper and an insulating material such as a resin.

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

  Thereby, the copper surface treating agent of this invention can accelerate | stimulate the reaction which precipitates a silane compound, forming a tin membrane | film | coat on the surface of copper.

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

  Thereby, the copper surface treating agent 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 agent of the present invention preferably further contains a metal compound. Furthermore, the metal compound is preferably a compound containing at least one metal selected from silver, palladium, gold, platinum, and copper.

  Thereby, it is considered that the copper surface treatment agent 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 copper surface treatment agent is preferably brought into contact with the copper surface. Furthermore, in the copper surface treatment method of the present invention, the copper surface treatment agent is preferably brought into contact with the copper surface without roughening the copper surface.

  As a result, the copper surface treatment method of the present invention can reduce the number of treatment steps by one step compared to the surface treatment method in which the surface of copper is tin-plated and then treated with nitric acid, a silane coupling agent, or the like. The process reduction not only reduces the process cost, but also reduces the wastewater treatment, the management risk of the subsequent process, and the risk of lowering the reliability of the plating process of the next process. In addition, since the copper surface treatment method of the present invention can ensure sufficient adhesion without roughening the surface of the copper, such as etching, the surface of the copper can be treated in a smooth state. As a result, the copper surface treatment method of the present invention is suitable for dealing with downsizing, thinning, high frequency, high density and the like of a multilayer wiring board.

  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 agent may be 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, after the surface treatment agent is brought into contact with the copper surface, at least one of a rust inhibitor, a resin, a silane coupling agent, and a titanium alkoxide is brought into contact. Is preferred.

  As a result, the copper surface treatment method of the present invention further improves the adhesion between copper and an insulating material such as a resin because a rust inhibitor, resin, silane compound or titanium alkoxide is deposited on the surface of copper. Can do.

  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.

  As a result, the copper-clad material, multilayer wiring board, and wiring board of the present invention are made of copper and resin, etc., compared with the copper-clad material, multilayer wiring board, and wiring board surface-treated by the conventional copper surface treatment method. It becomes possible to maintain sufficient adhesion with the insulating material.

  Other objects, features, and advantages of the present invention will be fully understood from the following description. The advantages of the present invention will become apparent from the following description with reference to the accompanying drawings.

It is a figure which shows the SEM external appearance of the copper surface-treated by the copper surface treatment method in this invention. It is a figure which shows the copper SEM appearance surface-treated by the conventional copper surface treatment method. It is a figure which shows the copper SEM appearance surface-treated by the conventional copper surface treatment method.

  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) Substances Surface-treated with Copper Surface Treatment Agent in the Present Invention The substance surface-treated with the copper surface treatment agent 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 Copper Surface Treatment Agent in the Present Invention The copper surface treatment agent of the present invention contains a tin compound, a complexing agent, and a silane coupling agent. Further, the copper surface treatment agent of the present invention preferably contains a fluorine compound. Furthermore, the copper surface treating agent of the present invention preferably contains a reducing agent. Furthermore, the copper surface treating agent of the present invention preferably contains a metal compound. Moreover, the copper surface treating agent of the present invention may contain an acid / alkali pH adjuster, if necessary.

  The copper surface treating agent 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 treating agent are not impaired. It does not specifically limit as a method of including another substance.

<Tin compounds>
The copper surface treating agent 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 agent (the entire solution of the surface treatment agent) is preferably 10 ppm to 200,000 ppm, more preferably 25 ppm to 10,000 ppm, and particularly preferably 100 ppm to 2,000 ppm. Within range. If the concentration of the tin compound relative to the entire surface treatment agent 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.

<Silane coupling agent>
The copper surface treating agent of the present invention 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. For example, aminosilane, 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 silanes having epoxy groups are preferable because of excellent compatibility with various insulating materials. A mixture with a coupling agent or a cocondensate (for example, a cocondensate of aminosilane and epoxysilane) is preferred. Also, a silane coupling agent having an alkoxyl group, such as silanol and trisilanol, is preferable because of its excellent adhesion to the insulating material. 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 agent 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 whole surface treatment agent (the whole solution of the surface treatment agent) is preferably 10 ppm to 100,000 ppm, more preferably 100 ppm to 5,000 ppm, and particularly preferably 200 ppm to 2,000 ppm. Within the following range. If the concentration of the silane coupling agent with respect to the entire surface treatment agent is less than 10 ppm, the adhesion with the insulating material such as the tin film and the resin may decrease, which is not preferable. 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.

<Complexing agent>
The copper surface treating agent 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 them, when the surface treatment agent is used in a solution, it can be made a stable solution with less turbidity, and more easily forms a complex with copper, and further lowers the potential on the surface of copper. Thiourea is preferred because it can easily form a tin film. 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 agent (the whole solution of the surface treatment agent) is preferably 0.01% to 50%, more preferably 0.1% to 30%, and particularly preferably 1%. It is in the range of 15% or less. If the concentration of the complexing agent relative to the entire surface treatment agent is less than 0.01%, it is difficult to form a complex on the copper surface, which is not preferable. On the other hand, if it exceeds 50%, the solubility of copper is deteriorated, and there is a possibility that the reaction of depositing the silane compound while forming a tin film on the surface of copper may be hindered.

<Reducing agent>
The copper surface treating agent 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 whole surface treatment agent (the whole solution of the surface treatment agent) is preferably 0.01% or more and 50% or less, more preferably 0.1% or more and 30% or less, and particularly preferably 1% or more. It is in the range of 15% or less. If the concentration of the reducing agent relative to the entire surface treatment agent 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 it is difficult to dissolve tin, which is not preferable.

<Fluorine compounds, organic acids>
The copper surface treating agent of the present invention preferably contains a fluorine compound or an organic acid. Examples of the fluorine compound include hydrogen fluoride, borohydrofluoric acid, acidic sodium fluoride, acidic ammonium fluoride, sodium fluoride, ammonium fluoride, and hydrogen silicofluoride. Among these, when the surface treatment agent is used in a solution and the pH is 5 or less, tin ions are stably present, and it is possible to obtain a stable solution with less turbidity. Sodium fluoride is preferred. The organic acid is preferably isethionic acid, methanesulfonic acid, styrenesulfonic acid, or phosphonic acid.

  The total concentration of the fluorine compound and the organic acid with respect to the entire surface treatment agent (the entire solution of the surface treatment agent) is preferably 10 ppm to 200,000 ppm, more preferably 25 ppm to 5000 ppm, and particularly preferably 100 ppm to 2000 ppm. Is within the range. If the total concentration of the fluorine compound and the organic acid relative to the entire surface treatment agent is less than 10 ppm, tin ions may be difficult to stabilize, 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 total concentration of the fluorine compound and the organic acid with respect to the entire surface treatment agent is 5,000 ppm or less, the tin film formed on the surface of the copper becomes thick and becomes porous (porous). Since there is no possibility of becoming uniform, it is more preferable.

  The concentration of free fluorine derived from the fluorine compound with respect to the whole surface treatment agent (the whole solution of the surface treatment agent) is preferably 0.1 ppm to 100 ppm, more preferably 1 ppm to 50 ppm, and particularly preferably 2 ppm to 20 ppm. Is within the range. If the concentration of free fluorine in the fluorine compound relative to the entire surface treatment agent is less than 0.1 ppm, tin ions may not be stably present, which is not preferable. On the other hand, when it exceeds 100 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. The concentration of free fluorine can be measured with an ordinary ion meter as the amount of fluorine ions.

  Here, free fluorine (fluorine ion) will be described below. It is preferable that free fluorine exists in the solution of the copper surface treating agent of the present invention. In order to allow the free fluorine to exist, a fluorine compound is included in the surface treatment agent. The said free fluorine has the effect | action which improves the stability of the tin compound in the solution of the said surface treating agent. Furthermore, the free fluorine also has an action of promoting the reaction of the tin compound with respect to copper which is a target of the surface treatment with the solution of the surface treatment agent.

<Rust preventive>
The copper surface treatment agent 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 treating agent of the present invention preferably contains a metal compound. Examples of the metal compound include metal salts. Examples of metal compounds 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. Among these, silver compounds are more preferable from the viewpoints of reduction in resistance value in electrical reliability such as adsorption between fine wires, removal of a film necessary for plating pretreatment, rust prevention of copper as a base material, and cost.

  The concentration of the metal compound relative to the whole surface treatment agent (the whole solution of the surface treatment agent) is preferably 1 ppm to 10,000 ppm, more preferably 10 ppm to 2,000 ppm, and particularly preferably 100 ppm to 1,000 ppm. Within range. If the concentration of the metal compound relative to the entire surface treatment agent 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 agent of the present invention may contain an acid / alkali pH adjuster, if necessary. Here, the copper surface treatment agent of the present invention preferably 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 adjusting agent with respect to the whole surface treatment agent (the whole solution of the surface treatment agent) is preferably 10 ppm to 10,000 ppm, more preferably 50 ppm to 2,000 ppm, and particularly preferably 100 ppm to 1,000 ppm. Is within the range. If the concentration of the pH adjuster relative to the entire surface treatment agent is less than 10 ppm, the tin compound is difficult to dissolve, and it is difficult to form a complex with tin, 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 agent 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 promoting 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 depositing the silane compound while 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, and rust inhibitors, and any compound can be used as long as it has a functional group that is in close contact with the insulating material. Moreover, these can also be used in combination. Examples of the functional group in close contact with the insulating material include an epoxy group, a silanol group, an imide group, an isocyanate group, a carboxyl group, a phosphone group, a carbonyl group, and a mercapto group. 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.

(III) Manufacturing Method of Copper Surface Treatment Agent in the Present Invention The copper surface treatment agent 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 treating agent of the present invention is not particularly limited. Moreover, the said substance may be mixed at once, and may be divided and mixed.

(IV) Solution containing copper surface treatment agent in the present invention In the copper surface treatment method in the present invention, the surface treatment agent is preferably brought into contact with the surface of copper as a solution. The solution is composed of the surface treatment agent as a solute and a solvent. The solvent used in the present invention is not particularly limited as long as it can dissolve the surface treatment agent. 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 is determined depending on the temperature of the solution, the components of the surface treatment agent, etc., and is not particularly limited. However, for environmental reasons, it is preferably 0% or more and 10% or less, more preferably Is in the range of 0% to 1%, particularly preferably 0% to 0.1%.

  Here, since the present invention is also intended to perform a stable surface treatment of copper, the concentration of the surface treatment agent in the solution may be low. Therefore, the copper surface treating agent in the present invention is superior to the conventional copper surface treating agent in that the surface of the copper is not roughened by etching or the like.

(V) The surface treatment method of copper in this invention The surface treatment method of copper of this invention is a method of making the said surface treating agent contact the surface of copper. Furthermore, in the copper surface treatment method of the present invention, the surface treatment agent may be brought into contact with the copper surface without roughening the copper surface.

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

  The temperature at which the surface treatment agent is brought into contact with the surface of copper is not particularly limited depending on the components of the surface treatment agent, 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 ° C. or more and 40 ° C. or less.

  The time for which the surface treatment agent is brought into contact with the surface of copper is not particularly limited depending on the components of the surface treatment agent, 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 agent into contact with the copper surface. In the copper surface treatment method of the present invention, after the surface treatment agent is brought into contact with the copper surface, the copper treatment may be further performed with the surface treatment agent or the like. 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 agent may be brought into contact with the copper surface, and then heat treatment or the like may be performed.

(VI) Copper-clad material in the present invention The copper-clad material of the present invention is surface-treated by the above-described 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.

(VII) Multilayer Wiring Board in the Present Invention The multilayer wiring board (build-up wiring board) of the present invention is provided with 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 sample was immersed in a concentration of 1%) at 30 ° C. for 60 seconds, and then washed with tap water.

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

<Components of predetermined surface treatment agent>
The predetermined surface treatment agent includes tin sulfate as a tin compound (concentration of tin sulfate relative to the entire surface treatment agent: 25 ppm, reagent) and thiourea as a complexing agent (concentration of thiourea relative to the entire surface treatment agent: 5-mercaptopropyltrimethoxysilane diluted to 5% as a silane coupling agent (concentration of 3-mercaptopropyltrimethoxysilane with respect to the entire surface treatment agent: 1000 ppm, manufactured by Shin-Etsu Chemical Co., Ltd., Product name: “KBM-803”). Thereafter, sodium hydroxide was added to adjust the pH of the solution containing the surface treatment agent to 3.

<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) 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”.

(2) SEM appearance of electrolytic copper foil after copper surface treatment The external 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”.

  1 and 2 show the SEM appearance of copper in Example 1. FIG. As shown in FIG. 1, the copper which surface-treated with the copper surface treating agent of this invention was a state without an unevenness | corrugation. FIG. 2 shows the SEM appearance of copper after surface treatment with a sulfuric acid / hydrogen peroxide aqueous solution (conventional copper surface treatment agent) as a pretreatment.

(3) The 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-rays (product of Shimadzu Corporation, product) Name: “XRF1700”), and measured as the amount of tin element or silane element.

(4) Adhesiveness 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.

(5) Evaluation results of the above physical properties The evaluation results of the above physical properties are that 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 “◯”, the copper The amount of tin film on the electrolytic copper foil after the surface treatment of 35 mg / m ² , the amount of the silane compound film on the electrolytic copper foil after the surface treatment of copper is 0.3 mg / m ² , and the electrolytic 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 foil was 0.80 kN / m.

[Example 2]
Except that the tin compound contained in the specified surface treatment agent was changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm). 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 tin film of the electrolytic copper foil after the copper surface treatment The amount of the silane compound of the electrolytic copper foil after the surface treatment of copper is 137 mg / m ² , the amount of the silane compound is 0.4 mg / m ² , and the copper foil in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment Adhesion with an insulating material such as a resin was 1.00 kN / m.

Example 3
The tin compound contained in the specified surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm). The same operation as in Example 1 was performed except that hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment agent: 500 ppm, reagent) was added to the agent.

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 tin film of the electrolytic copper foil after the copper surface treatment Copper foil in a multilayer wiring board having an amount of 110 mg / m ² , a coating amount of the silane compound of the electrolytic copper foil after copper surface treatment is 0.4 mg / m ² , and an electrolytic copper foil after copper surface treatment; Adhesion with an insulating material such as resin was 1.10 kN / m.

Example 4
The tin compound contained in the specified surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm). Change from thiourea (concentration of thiourea to the entire surface treatment agent: 5%) to diethylthiourea (concentration of diethylthiourea to the entire surface treatment agent: 5%), and use hydrogen fluoride (surface treatment agent) as the prescribed surface treatment agent The same operation as in Example 1 was performed except that the concentration of hydrogen fluoride with respect to the whole: 500 ppm) was added.

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 tin film of the electrolytic copper foil after the copper surface treatment Copper foil in a multilayer wiring board having an amount of 35 mg / m ² , a coating amount of the silane compound of the electrolytic copper foil after copper surface treatment is 0.3 mg / m ² , and an electrolytic copper foil after copper surface treatment; The adhesion with an insulating material such as resin was 0.70 kN / m.

Example 5
The tin compound contained in the predetermined surface treatment agent is changed from tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 10,000 ppm). The same operation as in Example 1 was performed except that hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment agent: 10,000 ppm) was added to the surface treatment agent.

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 tin film of the electrolytic copper foil after the copper surface treatment amount 1024mg / m ^2, and the copper foil in the multilayer wiring board coating amount of the silane compound of the electrolytic copper foil after the surface treatment of the copper with an electrolytic copper foil after the 0.6 mg / m ^2, the surface treatment of copper The adhesion with an insulating material such as resin was 0.70 kN / m.

Example 6
The tin compound contained in the predetermined surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm), and a silane coupling agent 3-mercaptopropyltrimethoxysilane (concentration of 3-mercaptopropyltrimethoxysilane with respect to the whole surface treatment agent: 1000 ppm) diluted to 5% from 3-mercaptopropyltrimethoxysilane (to the whole surface treatment agent) Example 1 except that the concentration of 3-mercaptopropyltrimethoxysilane was changed to 200 ppm and hydrogen fluoride (the concentration of hydrogen fluoride with respect to the entire surface treatment agent: 500 ppm) was added to the predetermined surface treatment agent. The same operation 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 tin film of the electrolytic copper foil after the copper surface treatment The amount of 252 mg / m ² , the amount of the silane compound film on the electrolytic copper foil after copper surface treatment is 0.3 mg / m ² , and the copper foil in the multilayer wiring board provided with the electrolytic copper foil after copper surface treatment; Adhesion with an insulating material such as resin was 0.80 kN / m.

Example 7
The tin compound contained in the predetermined surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm), and a silane coupling agent 3-mercaptopropyltrimethoxysilane (concentration of 3-mercaptopropyltrimethoxysilane with respect to the whole surface treatment agent: 1000 ppm) diluted to 5% from 3-mercaptopropyltrimethoxysilane (to the whole surface treatment agent) Example 1 except that the concentration of 3-mercaptopropyltrimethoxysilane was changed to 5000 ppm and hydrogen fluoride (the concentration of hydrogen fluoride with respect to the entire surface treatment agent: 500 ppm) was added to the predetermined surface treatment agent. The same operation 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 tin film of the electrolytic copper foil after the copper surface treatment A copper foil in a multilayer wiring board having an amount of 17 mg / m ² , a coating amount of the silane compound of the electrolytic copper foil after copper surface treatment of 2.4 mg / m ² , and an electrolytic copper foil after the copper surface treatment; Adhesion with an insulating material such as resin was 1.20 kN / m.

Example 8
The tin compound contained in the specified surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm). The same operation as in Example 1 was performed except that hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment agent: 500 ppm) was added to the agent, and the pH of the solution containing the surface treatment agent was changed to 1. It was.

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 tin film of the electrolytic copper foil after the copper surface treatment amount 862 mg / m ^2, and the copper foil in the multilayer wiring board coating amount of the silane compound of the electrolytic copper foil after the surface treatment of the copper with an electrolytic copper foil after the 0.7 mg / m ^2, the surface treatment of copper Adhesion with an insulating material such as resin was 0.80 kN / m.

Example 9
The tin compound contained in the specified surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm). The same operation as in Example 1 was performed except that hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment agent: 500 ppm) was added to the agent, and the pH of the solution containing the surface treatment agent was changed to 5. It was.

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 tin film of the electrolytic copper foil after the copper surface treatment Copper foil in a multilayer wiring board having an amount of 19 mg / m ² , a coating amount of the silane compound of the electrolytic copper foil after copper surface treatment is 0.3 mg / m ² , and an electrolytic copper foil after copper surface treatment; Adhesion with an insulating material such as resin was 0.80 kN / m.

Example 10
The tin compound contained in the predetermined surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm), and a silane coupling agent 3-mercaptopropyltrimethoxysilane (concentration of 3-mercaptopropyltrimethoxysilane with respect to the whole surface treatment agent: 1000 ppm) diluted to 30% to 3-mercaptopropyltrimethoxysilane (with respect to the whole surface treatment agent) Example 1 except that the concentration of 3-mercaptopropyltrimethoxysilane was changed to 1000 ppm and hydrogen fluoride (the concentration of hydrogen fluoride with respect to the entire surface treatment agent: 500 ppm) was added to the predetermined surface treatment agent. The same operation 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 tin film of the electrolytic copper foil after the copper surface treatment Copper foil in a multilayer wiring board having an amount of 89 mg / m ² , a coating amount of the silane compound of the electrolytic copper foil after copper surface treatment is 0.7 mg / m ² , and an electrolytic copper foil after copper surface treatment; Adhesion with an insulating material such as resin was 1.10 kN / m.

Example 11
The tin compound contained in the predetermined surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm), and a silane coupling agent 3-mercaptopropyltrimethoxysilane diluted with 5% to 3-mercaptopropyltrimethoxysilane and epoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBM403”) mixed 1: 1 to 5% Except that it was changed to a diluted mixture (concentration of the above-mentioned mixture with respect to the whole surface treatment agent: 1000 ppm), and hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment agent: 500 ppm) was added to the predetermined surface treatment agent. 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 tin film of the electrolytic copper foil after the copper surface treatment Copper foil in a multilayer wiring board having an amount of 135 mg / m ² , a coating amount of the silane compound of the electrolytic copper foil after copper surface treatment is 1.0 mg / m ² , and an electrolytic copper foil after copper surface treatment; Adhesion with an insulating material such as resin was 1.20 kN / m.

Example 12
The tin compound contained in the predetermined surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm), and a silane coupling agent 3-mercaptopropyltrimethoxysilane diluted to 5% with 3-mercaptopropyltrimethoxysilane and aminosilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBM903”) in a ratio of 1: 1 to 5% Except for changing to a diluted mixture (concentration of the above mixture with respect to the entire surface treatment agent: 1000 ppm) and adding hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment agent: 500 ppm) to the predetermined surface treatment agent, 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 tin film of the electrolytic copper foil after the copper surface treatment The amount of 159 mg / m ² , the coating amount of the silane compound of the electrolytic copper foil after copper surface treatment is 1.2 mg / m ² , and the copper foil in the multilayer wiring board provided with the electrolytic copper foil after copper surface treatment; Adhesion with an insulating material such as resin was 1.20 kN / m.

Example 13
The tin compound contained in the predetermined surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm), and a silane coupling agent 3-mercaptopropyltrimethoxysilane diluted to 5% with 3-mercaptopropyltrimethoxysilane and isocyanate silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBE9007”) in a ratio of 1: 1 to 5% Except that it was changed to a diluted mixture (concentration of the above-mentioned mixture with respect to the whole surface treatment agent: 1000 ppm), and hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment agent: 500 ppm) was added to the predetermined surface treatment agent. 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 tin film of the electrolytic copper foil after the copper surface treatment Copper foil in a multilayer wiring board having an amount of 120 mg / m ² , a coating amount of the silane compound of the electrolytic copper foil after copper surface treatment is 0.6 mg / m ² , and an electrolytic copper foil after copper surface treatment; Adhesion with an insulating material such as resin was 1.10 kN / m.

Example 14
The tin compound contained in the predetermined surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm), and a silane coupling agent From 3-mercaptopropyltrimethoxysilane diluted to 5%, the mixture was changed to 5% by mixing epoxysilane and aminosilane 1: 1 (concentration of the above mixture with respect to the whole surface treatment agent: 1000 ppm), The same operation as in Example 1 was performed except that hydrogen fluoride (hydrogen fluoride concentration with respect to the entire surface treatment agent: 500 ppm) was added to the predetermined surface treatment agent.

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 tin film of the electrolytic copper foil after the copper surface treatment The amount of 163 mg / m ² , the coating amount of the silane compound of the electrolytic copper foil after the copper surface treatment is 1.2 mg / m ² , and the copper foil in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment Adhesion with an insulating material such as resin was 1.10 kN / m.

Example 15
The tin compound contained in the specified surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm). Sodium thiosulfate (concentration of sodium thiosulfate relative to the entire surface treatment agent: 1000 ppm, reagent) is added to the agent, and hydrogen fluoride (concentration of hydrogen fluoride relative to the entire surface treatment agent: 500 ppm) is added to the specified surface treatment agent Except that, 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 tin film of the electrolytic copper foil after the copper surface treatment amount 87 mg / m ^2, and the copper foil in the multilayer wiring board coating amount of the silane compound of the electrolytic copper foil after the surface treatment of the copper with an electrolytic copper foil after the 0.6 mg / m ^2, the surface treatment of copper Adhesion with an insulating material such as a resin was 1.00 kN / m.

Example 16
The tin compound contained in the specified surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm). Sodium hypophosphite (concentration of sodium hypophosphite with respect to the whole surface treatment agent: 1000 ppm, reagent) is added to the agent, and hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment agent: The same operation as in Example 1 was performed except that 500 ppm) was added.

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 tin film of the electrolytic copper foil after the copper surface treatment The copper foil in the multilayer wiring board provided with the amount of 113 mg / m ² , the coating amount of the silane compound of the electrolytic copper foil after the copper surface treatment is 0.5 mg / m ² , and the electrolytic copper foil after the copper surface treatment; Adhesion with an insulating material such as a resin was 1.00 kN / m.

Example 17
The tin compound contained in the specified surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm). Aluminum nitrate (concentration of aluminum nitrate relative to the entire surface treatment agent: 1000 ppm, reagent) was added to the agent, and hydrogen fluoride (concentration of hydrogen fluoride relative to the entire surface treatment agent: 500 ppm) was added to the specified surface treatment agent Except for this, 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 tin film of the electrolytic copper foil after the copper surface treatment amount 126 mg / m ^2, and the copper foil in the multilayer wiring board coating amount of the silane compound of the electrolytic copper foil having an electrolytic copper foil after the 0.4 mg / m ^2, the surface treatment of the copper after the surface treatment of copper Adhesion with an insulating material such as a resin was 1.00 kN / m.

Example 18
The tin compound contained in the specified surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm). Aminotetrazole (concentration of aminotetrazole with respect to the entire surface treatment agent: 1000 ppm, reagent) as a rust inhibitor is added to the agent, and hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment agent: 500 ppm) is added to the predetermined surface treatment agent. ) The same operation as in Example 1 was performed except that.

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 tin film of the electrolytic copper foil after the copper surface treatment A copper foil in a multilayer wiring board having an amount of 105 mg / m ² , a coating amount of the silane compound of the electrolytic copper foil after copper surface treatment is 0.4 mg / m ² , and an electrolytic copper foil after the copper surface treatment; Adhesion with an insulating material such as resin was 1.20 kN / m.

Example 19
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 specified surface treatment agent was changed to tin sulfate (sulfuric acid for the entire surface treatment agent). Changed from tin concentration: 25 ppm) to tin sulfate (concentration of tin sulfate with respect to the entire surface treatment agent: 500 ppm), and hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment agent: 500 ppm, reagent) ) The same operation as in Example 1 was performed except that.

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 tin film of the electrolytic copper foil after the copper surface treatment Copper foil in a multilayer wiring board having an amount of 123 mg / m ² , a coating amount of the silane compound of the electrolytic copper foil after copper surface treatment is 0.4 mg / m ² , and an electrolytic copper foil after copper surface treatment; Adhesion with an insulating material such as a resin was 1.00 kN / m.

Example 20
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 agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm). The same operation as in Example 1 was performed, except that hydrogen fluoride (hydrogen fluoride concentration with respect to the entire surface treatment agent: 500 ppm, reagent) was added to the predetermined surface treatment agent.

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 tin film of the electrolytic copper foil after the copper surface treatment Copper foil in a multilayer wiring board having an amount of 98 mg / m ² , a coating amount of the silane compound of the electrolytic copper foil after copper surface treatment is 0.4 mg / m ² , and an electrolytic copper foil after copper surface treatment; Adhesion with an insulating material such as a resin was 1.50 kN / m.

Example 21
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) Change the tin compound contained in the specified surface treatment agent from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm) The same operation as in Example 1 was performed except that hydrogen fluoride (concentration of hydrogen fluoride with respect to the entire surface treatment agent: 500 ppm, reagent) was added to the surface treatment agent.

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 tin film of the electrolytic copper foil after the copper surface treatment The amount of the silane compound of the electrolytic copper foil after the surface treatment of copper of 77 mg / m ² is 0.4 mg / m ² and the copper foil in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment; Adhesion with an insulating material such as a resin was 1.50 kN / m.

[Example 22]
The tin compound contained in the specified surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm). Hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment agent: 500 ppm) was added to the agent, and 3-mercaptopropyltrimethoxysilane diluted with 5% of the electrolytic copper foil immersed in the solution of the surface treatment agent was added. The same operation as in Example 1 was performed, except that it was treated with a post-treatment agent (concentration of 3-mercaptopropyltrimethoxysilane with respect to the whole post-treatment agent: 1000 ppm) and then washed with tap water.

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 tin film of the electrolytic copper foil after the copper surface treatment Copper foil in a multilayer wiring board having an amount of 137 mg / m ² , a coating amount of the silane compound of the electrolytic copper foil after copper surface treatment is 0.7 mg / m ² , and an electrolytic copper foil after copper surface treatment; Adhesion with an insulating material such as resin was 1.20 kN / m.

Example 23
The tin compound contained in the specified surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm). Hydrogen fluoride (concentration of hydrogen fluoride with respect to the whole surface treatment agent: 500 ppm) was added to the agent, and 3-mercaptopropyltrimethoxysilane diluted with 5% of the electrolytic copper foil immersed in the solution of the surface treatment agent was added. The same operation as Example 1 was performed except that it was treated with the post-treatment agent (concentration of 3-mercaptopropyltrimethoxysilane with respect to the whole post-treatment agent: 1000 ppm) and then not washed with tap water.

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 tin film of the electrolytic copper foil after the copper surface treatment Copper foil in a multilayer wiring board having an amount of 137 mg / m ² , a coating amount of the silane compound of the electrolytic copper foil after copper surface treatment is 2.5 mg / m ² , and an electrolytic copper foil after copper surface treatment; Adhesion with an insulating material such as a resin was 1.50 kN / m.

Example 24
The tin compound contained in the predetermined surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm), and a silane coupling agent Other than changing 3-mercaptopropyltrimethoxysilane diluted to 5% to epoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBM-403”, concentration of epoxy silane with respect to the entire surface treatment agent: 1000 ppm) 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 tin film of the electrolytic copper foil after the copper surface treatment amount 158 mg / m ^2, and the copper foil in the multilayer wiring board coating amount of the silane compound of the electrolytic copper foil having an electrolytic copper foil after the 0.2 mg / m ^2, the surface treatment of the copper after the surface treatment of copper Adhesion with an insulating material such as resin was 0.80 kN / m.

Example 25
From tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm) contained in the predetermined surface treatment agent contained in the predetermined surface treatment agent From 3-mercaptopropyltrimethoxysilane diluted with 5% silane coupling agent to epoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBM-403”, concentration of epoxy silane with respect to the entire surface treatment agent : 1000 ppm), and the same operation as in Example 1 was performed except that methanesulfonic acid (concentration of methanesulfonic acid with respect to the whole surface treatment agent: 500 ppm, reagent) was added to the predetermined surface treatment agent.

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 tin film of the electrolytic copper foil after the copper surface treatment The amount of 192 mg / m ² , the coating amount of the silane compound of the electrolytic copper foil after the copper surface treatment is 0.2 mg / m ² , and the copper foil in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment; Adhesion with an insulating material such as resin was 0.80 kN / m.

Example 26
From tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm) contained in the predetermined surface treatment agent contained in the predetermined surface treatment agent From 3-mercaptopropyltrimethoxysilane diluted with 5% silane coupling agent to epoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBM-403”, concentration of epoxy silane with respect to the entire surface treatment agent : 1000 ppm), and the same operation as in Example 1 was performed except that silver nitrate (silver nitrate concentration with respect to the whole surface treatment agent: 50 ppm, reagent) was added to the predetermined surface treatment agent.

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 tin film of the electrolytic copper foil after the copper surface treatment The amount of 252 mg / m ² , the amount of the silane compound film on the electrolytic copper foil after copper surface treatment is 0.2 mg / m ² , and the copper foil in the multilayer wiring board provided with the electrolytic copper foil after copper surface treatment; The adhesion with an insulating material such as resin was 0.90 kN / m.

Example 27
From tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm) contained in the predetermined surface treatment agent contained in the predetermined surface treatment agent From 3-mercaptopropyltrimethoxysilane diluted with 5% silane coupling agent to epoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBM-403”, concentration of epoxy silane with respect to the entire surface treatment agent : 1000 ppm), and the same operation as in Example 1 was performed except that palladium chloride (palladium chloride concentration with respect to the whole surface treatment agent: 50 ppm, reagent) was added to the predetermined surface treatment agent.

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 tin film of the electrolytic copper foil after the copper surface treatment amount 213 mg / m ^2, and the copper foil in the multilayer wiring board coating amount of the silane compound of the electrolytic copper foil having an electrolytic copper foil after the 0.2 mg / m ^2, the surface treatment of the copper after the surface treatment of copper The adhesion with an insulating material such as resin was 0.90 kN / m.

Example 28
From tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm) contained in the predetermined surface treatment agent contained in the predetermined surface treatment agent From 3-mercaptopropyltrimethoxysilane diluted with 5% silane coupling agent to epoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBM-403”, concentration of epoxy silane with respect to the entire surface treatment agent : 1000 ppm), and a post-treatment agent containing epoxy silane (trade name: “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.) in which the electrolytic copper foil immersed in the surface treatment agent solution is diluted to 5%. (Epoxysilane concentration with respect to the entire post-treatment agent: 1000 ppm), and then not washed with tap water The procedure is as in Example 1.

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 tin film of the electrolytic copper foil after the copper surface treatment amount 158 mg / m ^2, and the copper foil in the multilayer wiring board coating amount of the silane compound of the electrolytic copper foil after the surface treatment of the copper with an electrolytic copper foil after the 2.3 mg / m ^2, the surface treatment of copper Adhesion with an insulating material such as resin was 1.20 kN / m.

Example 29
From tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm) contained in the predetermined surface treatment agent contained in the predetermined surface treatment agent And a post-treatment agent (post-treatment) containing epoxy silane (trade name: “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.) diluted to 5% of an electrolytic copper foil immersed in the surface treatment agent solution. The same operation as in Example 1 was performed except that the epoxy silane was treated with a concentration of 1000 ppm of the whole agent and then not washed with tap water.

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 tin film of the electrolytic copper foil after the copper surface treatment Copper foil in a multilayer wiring board having an amount of 137 mg / m ² , a coating amount of the silane compound of the electrolytic copper foil after copper surface treatment is 0.7 mg / m ² , and an electrolytic copper foil after copper surface treatment; Adhesion with an insulating material such as a resin was 1.40 kN / m.

Example 30
From tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm) contained in the predetermined surface treatment agent contained in the predetermined surface treatment agent From 3-mercaptopropyltrimethoxysilane diluted with 5% silane coupling agent to epoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBM-403”, concentration of epoxy silane with respect to the entire surface treatment agent : 1000 ppm), and a post-treatment agent (post-treatment) containing polyacrylic acid (manufactured by Nippon Pure Chemical Co., Ltd., molecular weight 20,000) diluted to 5% of the electrolytic copper foil immersed in the above-mentioned surface treatment agent solution Example 1 with the exception that the concentration of polyacrylic acid with respect to the entire agent: 1000 ppm) and then not washed with tap water. It was like operation.

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 tin film of the electrolytic copper foil after the copper surface treatment amount 158 mg / m ^2, and the copper foil in the multilayer wiring board coating amount of the silane compound of the electrolytic copper foil having an electrolytic copper foil after the 0.2 mg / m ^2, the surface treatment of the copper after the surface treatment of copper Adhesion with an insulating material such as resin was 1.20 kN / m.

Example 31
From tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm) contained in the predetermined surface treatment agent contained in the predetermined surface treatment agent From 3-mercaptopropyltrimethoxysilane diluted with 5% silane coupling agent to epoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBM-403”, concentration of epoxy silane with respect to the entire surface treatment agent : 1000 ppm), and polyacrylic acid (manufactured by Nippon Pure Chemicals Co., Ltd., molecular weight 20,000) and epoxysilane (Shin-Etsu Chemical Co., Ltd.) diluted to 5% of an electrolytic copper foil immersed in the surface treatment solution. Post-treatment agent (trade name: “KBM-403” manufactured by company) (concentration of polyacrylic acid relative to the whole post-treatment agent: 10 0 ppm, the concentration of the epoxy silane: treated with 1000 ppm), then, except that no washing with tap water, experiment was carried out in the same manner as in Example 1.

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 tin film of the electrolytic copper foil after the copper surface treatment amount 158 mg / m ^2, and the copper foil in the multilayer wiring board coating amount of the silane compound of the electrolytic copper foil having an electrolytic copper foil after the 2.5 mg / m ^2, the surface treatment of the copper after the surface treatment of copper Adhesion with an insulating material such as resin was 1.20 kN / m.

[Example 32]
From tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm) contained in the predetermined surface treatment agent contained in the predetermined surface treatment agent From 3-mercaptopropyltrimethoxysilane diluted with 5% silane coupling agent to epoxy silane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “KBM-403”, concentration of epoxy silane with respect to the entire surface treatment agent : 1000 ppm), and after-treatment containing titanium alkoxide (trade name: “Orgatechs TC-400” manufactured by Matsumoto Fine Chemical Co., Ltd.) in which the electrolytic copper foil immersed in the surface treatment solution is diluted to 5%. Treatment with an agent (concentration of titanium alkoxide with respect to the whole aftertreatment agent: 1000 ppm) Except that no washing with road water, was subjected to the same procedure as in Example 1.

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 tin film of the electrolytic copper foil after the copper surface treatment amount 158 mg / m ^2, and the copper foil in the multilayer wiring board coating amount of the silane compound of the electrolytic copper foil having an electrolytic copper foil after the 0.2 mg / m ^2, the surface treatment of the copper after the surface treatment of copper Adhesion with an insulating material such as resin was 1.20 kN / m.

[Comparative Example 1]
A treatment in which an electrolytic copper foil having a thickness of 35 μm is immersed in an aqueous solution of sulfuric acid / hydrogen peroxide and a predetermined surface treatment agent is applied to an aqueous solution containing 4% copper chloride, 5% acetic acid, and 0.3% aminotetrazole. The same operation as Example 1 was performed except having changed into the etching roughening process (concavo-convex process) immersed for 60 seconds.

  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.

  FIG. 3 shows the SEM appearance of copper in Comparative Example 1. As shown in FIG. 3, the copper which surface-treated with the surface treating agent of the conventional copper had the unevenness | corrugation.

[Comparative Example 2]
Tin sulfate as a tin compound contained in a predetermined surface treatment agent, thiourea as a complexing agent, and 3-mercaptopropyltrimethoxysilane as a silane coupling agent are mixed with copper chloride (chlorination of the entire surface treatment agent). Copper concentration: 1%, reagent), acetic acid (concentration of acetic acid with respect to the whole surface treatment agent: 10%, reagent), and aminotetrazole (concentration of aminotetrazole with respect to the whole surface treatment agent: 0.3%, reagent) The same operation as Example 1 was performed except having changed into.

  As a result, the etching amount of the electrolytic copper foil after the copper surface treatment is “Δ”, the SEM appearance of the electrolytic copper foil after the copper surface treatment is “x”, 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 contained in a predetermined surface treatment agent, thiourea as a complexing agent, and 3-mercaptopropyltrimethoxysilane as a silane coupling agent are mixed with sulfuric acid (sulfuric acid relative to the whole surface treatment agent). Concentration: 10%, reagent), hydrogen peroxide (concentration of hydrogen peroxide with respect to the whole surface treatment agent: 3%, reagent), aminotetrazole (concentration of aminotetrazole with respect to the whole surface treatment agent: 0.3%), The same operation as Example 1 was performed except having changed into.

  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 agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm) as a complexing agent The same operation as in Example 1 was performed except that the thiourea was not included.

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 tin film of the electrolytic copper foil after the copper surface treatment amount 0 mg / m ^2, coating weight of 0 mg / m 2 of a silane compound of the electrolytic copper foil after the surface treatment of ^copper, a copper foil and a resin or the like in the multilayer wiring board with an electrolytic copper foil after the surface treatment of copper The adhesion with the insulating material was 0.00 kN / m.

[Comparative Example 5]
The tin compound contained in the predetermined surface treatment agent is changed from tin sulfate (concentration of tin sulfate to the entire surface treatment agent: 25 ppm) to tin sulfate (concentration of tin sulfate relative to the entire surface treatment agent: 500 ppm), and a silane coupling agent The same operation as in Example 1 was performed except that 3-mercaptopropyltrimethoxysilane was not included.

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 tin film of the electrolytic copper foil after the copper surface treatment The amount of 325 mg / m ² , the coating amount of the silane compound of the electrolytic copper foil after the copper surface treatment is 0 mg / m ² , the copper foil and the resin in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment, etc. The adhesion with the insulating material 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.

  Comparing Example 1 and Example 2, in Example 2, compared with Example 1, the concentration of tin sulfate as a tin compound was increased, thereby providing a multilayer wiring including an electrolytic copper foil after copper surface treatment As a result, the adhesion between the copper foil on the substrate and the insulating material such as resin was improved.

  Comparing Example 2 and Example 3, in Example 3, by including hydrogen fluoride as a fluorine compound as compared with Example 2, a multilayer wiring board provided with an electrolytic copper foil after copper surface treatment was used. As a result, the adhesion between the copper foil and the insulating material such as resin was improved.

  Comparing Example 3 and Example 4, in Example 4, compared with Example 3, thiourea as a complexing agent was changed to diethylthiourea, thereby providing an electrolytic copper foil after the surface treatment of copper. Although the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board was lowered, the result was that sufficient adhesion was maintained.

  When Example 3 and Example 5 are compared, in Example 5, the concentration of tin sulfate as a tin compound is significantly increased compared to Example 3, so that the tin of the electrolytic copper foil after copper surface treatment is increased. The amount of film is greatly increased, and although the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil is lowered, the result is that sufficient adhesion is maintained. It was.

  Comparing Example 3 with Examples 6 and 7, in Example 6, the concentration of 3-mercaptopropyltrimethoxysilane as a silane coupling agent was decreased as compared with Example 3, so that after the surface treatment 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 was reduced, but sufficient adhesion was maintained. On the other hand, in Example 7, compared with Example 3, the concentration of 3-mercaptopropyltrimethoxysilane as a silane coupling agent was increased, 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 an insulating material such as resin was improved.

  When Example 3 is compared with Examples 8 and 9, in Example 8, the pH of the solution of the surface treatment agent was lowered from 3 to 1 as compared with Example 3, so that the electrolytic copper foil after the surface treatment of copper was performed. The amount of tin film increases significantly, and although the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board provided with the electrolytic copper foil is reduced, sufficient adhesion is maintained. The result was. On the other hand, in Example 9, the copper foil in the multilayer wiring board provided with the electrolytic copper foil after the copper surface treatment was also increased by increasing the pH of the solution of the surface treatment agent from 3 to 5 as compared with Example 3. As a result, the adhesion with an insulating material such as resin was the same.

  When Example 3 and Examples 10-14 are compared, in Examples 10-14, 3-mercaptopropyltrimethoxysilane as a silane coupling agent is compared with Example 3 in comparison with other silane coupling agents (two kinds of silane coupling agents). By changing to a mixture of silane coupling agents, 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 was improved. .

  Comparing Example 3 with Examples 15 and 17, in Examples 15 and 17, the multilayer wiring board provided with the electrolytic copper foil after the surface treatment of copper also includes a metal compound as compared with Example 3. As a result, the adhesion between the copper foil and the insulating material such as resin was equal.

  Comparing Example 3 and Example 16, the copper foil in the multilayer wiring board provided with the electrolytic copper foil after the surface treatment of copper in Example 16 also includes a reducing agent as compared with Example 3; As a result, the adhesion with an insulating material such as resin was the same.

  When Example 3 and Example 18 are compared, in Example 18, by including a rust preventive agent compared to Example 3, the copper foil in the multilayer wiring board provided with the electrolytic copper foil after the surface treatment of copper and As a result, the adhesion with an insulating material such as resin was improved.

  Comparing Example 3 and Example 19, in Example 19, the multilayer wiring board provided with the electrolytic copper foil after the surface treatment of copper was obtained by not including hydrogen peroxide in the pickling as compared with Example 3. As a result, the adhesion between the copper foil and the insulating material such as resin was the same.

  When Example 3 and Example 20 are compared, in Example 20, the anti-corrosion agent is included in the pickling as compared with Example 3, 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.

  When Example 3 and Example 21 are compared, in Example 21, compared with Example 3, by performing noble metal treatment during pickling, a multilayer wiring board provided with an electrolytic copper foil after copper surface treatment As a result, the adhesion between the copper foil and the insulating material such as resin was improved.

  When Example 3 is compared with Examples 22 and 23, the surface treatment of copper is performed in Examples 22 and 23 by post-treatment with 3-mercaptopropyltrimethoxysilane as a silane coupling agent as compared with Example 3. 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 later was improved. In particular, in Example 23, the adhesion between the copper foil and the insulating material such as resin in the multilayer wiring board was further improved by not washing with tap water after the post-treatment.

  Comparing Example 2 and Examples 24-27, in Examples 24-27, by changing 3-mercaptopropyltrimethoxysilane as an silane coupling agent to epoxy silane, compared to Example 2, copper Although the adhesiveness 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 was lowered, the sufficient adhesiveness was maintained. In Examples 26 and 27 among Examples 24 to 27, the adhesion was improved by adding a metal compound containing Ag or Pd.

  Comparing Example 2 with Examples 28 to 32, Examples 28 to 32 were 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 1-32 and Comparative Examples 1-3 are compared, in Comparative Examples 1-3, a surface treatment agent containing a tin compound and a silane coupling agent is not used as compared with Examples 1-32, and etching is performed. Since the roughening process (unevenness | corrugation process), etc. are 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 the tin and silane compounds of the electrolytic copper foil after copper surface treatment The film was not formed, 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 was lost.

  When Example 2 and Comparative Example 5 are compared with each other, Comparative Example 5 does not contain 3-mercaptopropyltrimethoxysilane as a silane coupling agent as compared with Example 2, so that the electrolytic copper foil after copper surface treatment The film of the silane compound was not formed, 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 was reduced.

  As described above, the copper surface treatment agent of the present invention contains a tin compound, a complexing agent, and a silane coupling agent.

  Therefore, the copper surface treatment agent of the present invention can treat the surface of the copper in a smooth state without increasing the number of treatment steps, without roughening treatment such as etching, and copper and resin. There exists an effect that the adhesiveness between insulating materials can be maintained.

  The specific embodiments or examples made in the detailed description section of the invention are merely to clarify the technical contents of the present invention, and are limited to such specific examples and are interpreted in a narrow sense. It should be understood that the invention can be practiced with various modifications within the spirit of the invention and within the scope of the following claims.

  Since the copper surface treatment agent and surface treatment method of the present invention can maintain the adhesion between copper and an insulating material such as a resin without subjecting the copper surface to a roughening treatment such as etching, It is possible to cope with higher frequency and higher density of electronic devices and electronic parts. 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 treating agent of the present invention performs adhesion and rust prevention (passivation) at the same time, the production process of electronic devices and electronic parts 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 agent 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 (21)

  A copper surface treatment agent comprising a tin compound, a complexing agent, and a silane coupling agent.   The copper surface treatment agent according to claim 1, wherein the complexing agent contains at least thiourea or a derivative thereof.   The copper surface treatment agent according to claim 1 or 2, further comprising a fluorine compound or an organic acid.   The copper surface treatment agent according to claim 3, wherein the pH is 5 or less.   The copper surface treatment agent according to any one of claims 1 to 4, wherein the silane coupling agent has a mercapto group, an epoxy group, or an amino group.   The copper surface treatment agent according to any one of claims 1 to 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, 7. The method according to any one of claims 1 to 6, Copper surface treatment agent.   The copper surface according to any one of claims 1 to 7, wherein a concentration of the tin compound with respect to the entire surface treatment agent is within a range of 10 ppm or more and 200,000 ppm or less. Processing agent.   The copper according to any one of claims 1 to 8, wherein a concentration of the silane coupling agent with respect to the entire surface treatment agent is within a range of 10 ppm or more and 100,000 ppm or less. Surface treatment agent.   Furthermore, the reducing agent is contained, The copper surface treating agent of any one of Claim 1-9 characterized by the above-mentioned.   Furthermore, a rust preventive agent is contained, The surface treating agent of copper of any one of the Claims 1-10 characterized by the above-mentioned.   The copper surface treatment agent according to claim 11, wherein the rust inhibitor is at least one compound selected from tetrazole, triazole, imidazole, and thiol.   The copper surface treatment agent according to any one of claims 1 to 12, further comprising a metal compound.   14. The copper surface treatment agent according to claim 13, wherein the metal compound is a compound containing at least one metal selected from Ag, Pd, Au, Pt, and Cu.   A copper surface treatment method, wherein the copper surface treatment agent according to any one of claims 1 to 14 is brought into contact with the copper surface.   The copper surface treatment, wherein the copper surface treatment agent according to any one of claims 1 to 14 is brought into contact with the surface of the copper without roughening the surface of the copper. Method.   16. The surface treatment agent according to claim 15, wherein the surface treatment agent 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. The surface treatment method of copper as described in the item.   The rust preventive agent, the resin or the silane coupling agent is brought into contact with the surface of the copper after the surface treatment agent is brought into contact with the surface of the copper, according to any one of claims 15 to 17. Copper surface treatment method.   A copper-clad material characterized by being surface-treated by the copper surface treatment method according to any one of claims 15 to 18.   A multilayer wiring board comprising the copper clad material according to claim 19.   A wiring board comprising the copper clad material according to claim 19 in an outermost layer.