WO2010010716A1

WO2010010716A1 - Agent and method for treating copper surface

Info

Publication number: WO2010010716A1
Application number: PCT/JP2009/003492
Authority: WO
Inventors: 印部俊雄; 宇都宮朗; 西田真也
Original assignee: 日本ペイント株式会社
Priority date: 2008-07-25
Filing date: 2009-07-24
Publication date: 2010-01-28
Also published as: JP4621293B2; JPWO2010010716A1

Abstract

Disclosed is an agent for treating a copper surface, which is capable of processing the copper surface into a flat and smooth surface without increasing the number of processing steps and without subjecting the copper surface to a roughening treatment such as etching. The agent for treating a copper surface is also capable of maintaining adhesion between copper and an insulating material such as a resin. A method for treating a copper surface is also disclosed. The agent for treating a copper surface contains a tin compound, a complexing agent and a water-soluble or water-dispersible polymer. The water-soluble or water-dispersible polymer has at least one kind of functional group which is selected from the group consisting of an amino group, an epoxy group, a thiol group, a carboxyl group, a sulfonic acid group, a hydroxyl group, a phosphoric acid group, an imino group and a silanol group.

Description

Copper surface treatment agent and surface treatment method

The present invention relates to a copper surface treatment agent and a surface treatment method. More specifically, the present invention relates to a copper surface treatment agent and a surface treatment method capable of treating a copper surface in a smooth (flat) state without roughening such as etching.

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). Reference 1 to 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).

Also, when the copper surface used for the surface portion of the multilayer wiring board is rough, there is a problem that 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). Furthermore, in order to adjust pH and improve the adhesiveness between copper and an insulating material such as a resin, a method of adding an acid and a reaction accelerator simultaneously with a tin compound is disclosed (for example, Patent Documents 5 and 10). reference). Furthermore, in order to improve the adhesion between copper and an insulating material such as resin, a method of forming a metal layer having high adhesion with an insulating material such as resin by adding a copper salt to the surface of copper is shown. (For example, see Patent Document 10).

Japanese Patent Publication “Japanese Patent Laid-Open No. 10-289838 (published on Oct. 27, 1998)” Japanese Patent Publication “JP 2000-340948 A (published on Dec. 8, 2000)” Japanese Patent Publication “Japanese Patent Laid-Open No. 10-256736 (published on September 25, 1998)” Japanese Patent Publication “JP-A-4-233793 (published on August 21, 1992)” Japanese Patent Publication “Japanese Patent Laid-Open No. 2005-23301 (published January 27, 2005)” Japanese Patent Publication “Japanese Laid-Open Patent Publication No. 1-109796 (published on April 26, 1989)” Japanese Patent Publication “Japanese Laid-Open Patent Publication No. 7-170064 (published July 4, 1995)” Japanese Patent Publication “Patent No. 3135516 (Japanese Patent Laid-Open No. 10-46359, published on Feb. 17, 1998)” Japanese Patent Publication “Japanese Patent Laid-Open No. 2003-201585” (published July 18, 2003) Japanese Patent Publication “Japanese Patent Laid-Open No. 2008-109111 (published May 8, 2008)”

However, none of the copper surface treatment methods disclosed in Patent Documents 1 to 3 have been put to practical use because performance, particularly adhesion between copper and an insulating material such as 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.

Also, in the copper surface treatment methods disclosed in Patent Documents 5 to 9, since the copper surface is tin-plated and then treated with nitric acid, a silane coupling agent, etc., 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.

In addition, in the copper surface treatment method disclosed in Patent Documents 5 and 10, an acid and a reaction accelerator are added to the copper surface simultaneously with the tin compound, but the tin compound, the acid (pH), the reaction accelerator, There is a problem that sufficient adhesion between copper and an insulating material such as resin cannot be maintained as compared with a method of roughening the surface of copper, such as etching.

In addition, the copper surface treatment method disclosed in Patent Document 10 has a problem in that sufficient adhesion cannot be maintained, and it is difficult to uniformly adhere a metal layer to the copper surface. Since the coating is also coated, there is a problem that there is a concern about inhibition of plating property, electric conductivity, etc. during mounting.

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 investigations in view of the above problems, the present inventors, as a surface treatment agent used for copper surface treatment, contain a tin compound, a complexing agent, a water-soluble polymer or a water-dispersible polymer, The water-soluble polymer or water-dispersible polymer is at least one function selected from the group consisting of an amino group, an epoxy group, a thiol group, a carboxyl group, a sulfonic acid group, a hydroxyl group, a phosphoric acid group, an imino group, and a silanol group. By having a group, the water-soluble polymer or water-dispersible polymer forms a cross-linked structure with tin deposited on the copper surface and is embraced in the tin, and the functional group is insulated with a resin or the like. As a result, it was found that sufficient adhesion between copper and an insulating material such as resin can be maintained, and the present invention was completed.

That is, the copper surface treatment agent of the present invention contains a tin compound, a complexing agent, and a water-soluble polymer or a water-dispersible polymer in order to solve the above-mentioned problems. The water-dispersible polymer has at least one functional group selected from the group consisting of an amino group, an epoxy group, a thiol group, a carboxyl group, a sulfonic acid group, a hydroxyl group, a phosphoric acid group, an imino group, and a silanol group. It is said.

According to the above invention, the copper surface treatment agent of the present invention contains the tin compound and the water-soluble polymer or the water-dispersible polymer at the respective concentrations, and thus has the functional group. A water-soluble polymer or a water-dispersible polymer forms a crosslinked structure with tin deposited on the copper surface and adheres to the tin. Furthermore, in the copper surface treating agent of the present invention, the functional group is bonded to an insulating material such as a resin by hydrogen bonding or covalent bonding, and is in close contact with the insulating material. In addition, since the copper surface treatment agent of the present invention contains a complexing agent, when the surface treatment agent is used in a solution, the complexing agent forms a complex with copper to form a copper surface. 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. As a result, the copper surface treating agent of the present invention can provide sufficient adhesion between copper and an insulating material such as a resin.

The copper surface treating agent of the present invention preferably contains at least polyacrylic acid, polymaleic acid, polyitaconic acid or acrylic acid copolymer, or a derivative thereof as the water-soluble polymer.

Thereby, the copper surface treating 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 water-soluble polymer or water-dispersible polymer preferably has a molecular weight in the range of 2,000 or more and 10,000,000 or less.

As a result, the water-soluble polymer or water-dispersible polymer contained in the copper surface treatment agent of the present invention is likely to precipitate, and the workability is improved without increasing the viscosity of the surface treatment agent. .

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

Thereby, it is considered that the copper surface treatment agent of the present invention can uniformly and stably form a film containing an alloy of copper and tin on the surface of copper by the buffering action of metal ions.

In the copper surface treatment agent of the present invention, the metal compound is a copper compound, and the ratio of the concentration of the copper compound to the concentration of the tin compound is in the range of 0.2 to 2.0. Is preferred.

Thereby, since the copper surface treating agent of the present invention contains a copper compound, copper ions are generated. As a result, the reaction between the copper ion and the tin compound proceeds.

Therefore, the copper surface treatment agent of the present invention can form a film (crystal) containing an alloy of copper and tin on the copper surface. Since the tin film in the said film is excellent in adhesiveness with insulating materials, such as resin, the copper surface treating agent of this invention can improve the adhesiveness between copper and insulating materials, such as resin.

In the copper surface treatment agent of the present invention, the concentration of the tin compound relative to the entire surface treatment agent is preferably in the range of 50 ppm or more and 10,000 ppm or less.

Thereby, the copper surface treatment agent of the present invention can easily form a film containing an alloy of copper and tin on the copper surface, and can further improve the adhesion between the copper and an insulating material such as a resin. it can.

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

Thereby, the copper surface treatment agent of the present invention promotes the function of the complexing agent by adjusting the pH in the solution of the surface treatment agent, and tin is likely to precipitate.

The copper surface treatment agent of the present invention preferably contains at least sulfuric acid, nitric acid, hydrochloric acid, methanesulfonic acid or phosphoric acid as the pH adjuster.

Thereby, the copper surface treatment agent of the present invention contains a strong acid, and facilitates the dissolution of copper.

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

Thereby, in the copper surface treatment agent of the present invention, the action of the complexing agent is activated by decreasing the pH value in the solution of the surface treatment agent, and the precipitation amount of tin increases.

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

Thus, 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 of treating the surface of the copper with tin and then treating with nitric acid, a silane coupling agent, or the like. 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.

Further, the copper surface treatment method of the present invention is at least one pretreatment selected from the group consisting of pickling treatment, roughening treatment, chemical conversion treatment, rust prevention treatment, oxidation treatment, reduction treatment, and degreasing treatment on the copper surface. After the treatment, it is preferable to contact the surface treatment agent.

Thereby, the copper surface treatment method of the present invention can remove dirt, oxides, etc. on the copper surface by pickling treatment and degreasing treatment, roughening treatment, chemical conversion treatment, rust prevention treatment, oxidation treatment, reduction. The treatment can improve the chemical conversion on the copper surface, improve the copper performance, and the like.

In the copper surface treatment method of the present invention, it is preferable that the surface treatment agent or the post-treatment agent is brought into contact with the copper surface after the tin compound is brought into contact therewith.

Thus, the copper surface treatment method of the present invention can form a tin film on the copper surface with the tin compound, and the tin film can further improve the adhesion between copper and an insulating material such as a resin. it can.

Further, the coating of the copper surface of the present invention is formed by the surface treatment method of the copper, by weight of tin in the coating of the copper surface is 1 mg / m ² or more, in the range of 2,000 mg / m ² or less, the Of the composition on the outermost surface of the film, the molar ratio of copper to tin is preferably in the range of 0.2 or more and 10 or less.

Thereby, since the film on the copper surface of the present invention contains an alloy of copper and tin or the like, the adhesion between the copper and an insulating material such as a resin can be maintained.

The copper-clad material of the present invention is preferably surface-treated by the above-described 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.

As described above, the copper surface treating agent of the present invention contains a tin compound, a complexing agent, and a water-soluble polymer or water-dispersible polymer, and the water-soluble polymer or water-dispersible polymer described above. Have at least one functional group selected from the group consisting of an amino group, an epoxy group, a thiol group, a carboxyl group, a sulfonic acid group, a hydroxyl group, a phosphoric acid group, an imino group, and a silanol group.

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

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.

(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 water-soluble or water-dispersible polymer. It is. 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 may contain a fluorine compound. Furthermore, the copper surface treatment agent of the present invention preferably contains a pH adjuster. Furthermore, the copper surface treating agent of the present invention preferably contains a metal compound. Furthermore, the copper surface treatment agent of the present invention preferably contains a rust inhibitor.

The copper surface treatment 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 treatment 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, stannous sulfate is particularly preferred because it does not adversely affect copper etching.

The concentration of the tin compound with respect to the whole surface treatment agent (the whole solution of the surface treatment agent) is 10 ppm to 100,000 ppm, preferably 20 ppm to 100,000 ppm, more preferably 50 ppm to 10,000 ppm, more preferably It is 500 ppm or more and 10,000 ppm or less, and particularly preferably 500 ppm or more and 3,000 ppm or less. 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 100,000 ppm, a large amount of tin is deposited on the surface of copper, the tin film may cohesively break, and it is difficult to form a tin film on the surface of copper because the solution stability is poor. This is not preferable.

<Water-soluble polymer or water-dispersible polymer>
The copper surface treatment agent of the present invention has at least one functional group selected from the group consisting of amino groups, epoxy groups, thiol groups, carboxyl groups, sulfonic acid groups, hydroxyl groups, phosphoric acid groups, imino groups, and silanol groups. It contains a water-soluble polymer or a water-dispersible polymer. Examples of the water-soluble polymer or water-dispersible polymer include aminosilane, mercaptosilane, polyacrylic acid, acrylic resin, phenol resin, epoxy resin, and polyamine resin. Among them, water-soluble acrylic resins containing carboxyl groups are difficult to inhibit the film crystal properties, have excellent aqueous solution stability, and easily co-deposit with tin by coordination or hydrogen bonding with tin compounds. Is preferred. Examples of the water-soluble acrylic resin containing a carboxyl group include polyacrylic acid, polymaleic acid, polyitaconic acid or an acrylic acid copolymer, or derivatives thereof. A water-soluble acrylic resin having a carboxyl group and a functional group other than a carboxyl group is more preferable because it easily forms a crosslink by heat with an insulator. Examples of water-soluble acrylic resins having a carboxyl group and a functional group other than a carboxyl group include acid monomers such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylic Copolymerization with acrylic monomers such as 2-hydroxyethyl acid, hydroxypropyl acrylate, acrylamide, N-methylolacrylamide, glycidyl methacrylate, acrylonitrile, 3-methacryloxypropylmethyldimethoxysilane, 2-acrylamido-2-methylpropanesulfonic acid Coalescence is desirable. Among these, a copolymer using 2-hydroxyethyl acrylate, acrylamide, and N-methylol acrylamide as an acrylic monomer containing a functional group other than a carboxyl group is more desirable. In addition, the acrylic monomer containing functional groups other than an acid monomer and a carboxyl group may be used alone, or one or both may be used in combination of a plurality of monomers.

Further, it is preferable to contain at least mercaptosilane or a derivative thereof for the reason of extremely improving the adhesion between copper and an insulating material such as an epoxy resin. Furthermore, it is more preferable to contain at least a mercaptosilane condensate because silane is likely to precipitate.

The water-soluble polymer or water-dispersible polymer has a molecular weight of 2,000 or more and 10,000,000 or less, preferably 20,000 or more and 7,000,000 or less, more preferably 200,000 or more and 5,000. , 000 or less. When the water-soluble polymer or water-dispersible polymer has a molecular weight of less than 2,000, it is difficult to precipitate, which is not preferable. On the other hand, if it exceeds 10,000,000, the viscosity of the surface treatment agent increases, so that workability is deteriorated, which is not preferable. In the present specification and the like, the molecular weight of the water-soluble polymer or water-dispersible polymer means the weight average molecular weight. The weight average molecular weight can be measured by a gel permeation chromatography (GPC) method using polystyrene as a standard.

The concentration of the water-soluble polymer or water-dispersible polymer with respect to the whole surface treatment agent (the whole solution of the surface treatment agent) is 10 ppm to 500,000 ppm, preferably 20 ppm to 100,000 ppm, more preferably 50 ppm or more. It is within the range of 3,000 ppm or less. If the concentration of the water-soluble polymer or water-dispersible polymer relative to the entire surface treatment agent is less than 10 ppm, it may not be deposited on the copper surface, which is not preferable. On the other hand, if it exceeds 500,000 ppm, crystal formation on the copper surface may be hindered, which is not preferable.

<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. It is preferable to contain at least thiourea for the purpose of easily forming 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 whole surface treatment agent (the whole solution of the surface treatment agent) is preferably 100 ppm or more and 500,000 ppm or less, more preferably 1,000 ppm or more and 300,000 ppm or less, and particularly preferably 10,000 ppm or more. Within the range of 150,000 ppm or less. If the concentration of the complexing agent relative to the entire surface treatment agent is less than 100 ppm, it is difficult to form a complex on the copper surface, which is not preferable. On the other hand, when it exceeds 500,000 ppm, the solubility of copper is deteriorated, and there is a possibility that the reaction of forming a tin film on the surface of copper may be inhibited, which is not preferable.

<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 100 ppm or more and 500,000 ppm or less, more preferably 1,000 ppm or more and 300,000 ppm or less, and particularly preferably 10,000 ppm or more and 150 or more. Within the range of 1,000 ppm or less. If the concentration of the reducing agent relative to the entire surface treatment agent is less than 100 ppm, a tin film may not be formed, which is not preferable. On the other hand, if it exceeds 500,000 ppm, it may be difficult to form a tin film on the surface of copper because tin is difficult to dissolve, which is not preferable.

<PH adjuster>
The copper surface treatment agent of the present invention preferably has a pH in the range of 0.1 or more and 5 or less, and therefore preferably contains a pH adjusting agent. The pH adjuster is not particularly limited as long as it is soluble in the solvent described later. 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, acrylic acid, and butyric acid; And organic acids such as alkane sulfonic acid such as acid and ethane sulfonic acid, and aromatic sulfonic acid such as benzene sulfonic acid, phenol sulfonic acid and cresol sulfonic acid. Among these, strong acids such as sulfuric acid, nitric acid, hydrochloric acid, methanesulfonic acid, and phosphoric acid are preferable because the pH can be adjusted to 5 or less.

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 500,000 ppm, more preferably 1,000 ppm to 300,000 ppm, and particularly preferably 10,000 ppm or more. It is in the range of 200,000 ppm or less. 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, which is not preferable. On the other hand, if it exceeds 500,000 ppm, the reaction of forming a tin film on the surface of copper may be inhibited, which is not preferable.

<Metal compound>
The copper surface treating agent of the present invention preferably contains a metal compound. Thereby, it is considered that the copper surface treatment agent of the present invention can uniformly and stably form a tin film on the surface of copper by the buffering action of metal ions. Examples of the metal compound include metal salts. Examples of metal compounds include silver compounds, aluminum compounds, zirconyl compounds, titanium compounds, calcium compounds, sodium compounds, magnesium compounds, strontium compounds, manganese compounds, vanadium compounds, yttrium compounds, niobium compounds, zinc compounds, and indium compounds. Silver compounds, iron compounds, palladium compounds, cobalt compounds, copper compounds and the like. Among these, silver compounds, palladium compounds, zinc compounds, cobalt compounds, and copper compounds are preferred because they are considered to be easily precipitated with tin and give a denser tin film. Among them, a copper compound is particularly preferable because an alloy with tin can be formed. These metal compounds can be used alone or in combination. When combining a plurality, it is preferable to use a combination of copper and silver or copper and palladium.

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, the effect cannot be expected, which is not preferable. On the other hand, if it exceeds 10,000 ppm, the reaction of forming a tin film on the surface of copper may be inhibited, which is not preferable.

<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.

The concentration of the rust inhibitor with respect to the entire surface treatment agent (the whole solution of the surface treatment agent) is preferably 10 ppm to 100,000 ppm, more preferably 20 ppm to 10,000 ppm, and particularly preferably 50 ppm to 3,000 ppm. Is within the range. When the concentration of the anticorrosive agent relative to the entire surface treatment agent is less than 10 ppm, the effect is not sufficient, which is not preferable. On the other hand, if it exceeds 100,000 ppm, the reaction of forming a tin film on the surface of copper may be inhibited, 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 forming a tin film on the surface of copper may be contained.

For example, the copper surface treating agent of the present invention may contain a fluorine compound. 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 in the range of 0.1 or more and 5 or less, tin ions are stably present, and a stable solution with less turbidity can be obtained. For this reason, hydrogen fluoride and sodium acid fluoride are preferred.

The concentration of the fluorine compound with respect to the entire surface treatment agent (the whole solution of the surface treatment agent) is preferably in the range of 10 ppm to 200,000 ppm, more preferably 25 ppm to 5000 ppm, and particularly preferably 100 ppm to 2000 ppm. . If the concentration of the fluorine compound 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 concentration of the fluorine compound with respect to the entire surface treatment agent is 5,000 ppm or less, the tin film formed on the copper surface may become thick, become porous (porous), etc. It is more preferable because it is not present.

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, if it exceeds 100 ppm, the reaction of forming a tin film on the surface of copper may be hindered, 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 treatment agent in 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.

<Ratio of tin compound concentration to copper compound concentration>
In the copper surface treatment agent of the present invention, the ratio of the copper compound concentration to the tin compound concentration is preferably in the range of 0.2 to 2.0, more preferably 0.4 to 1.2. Within the range, particularly preferably within the range of 0.7 to 1.0.

<Relationship between concentration of complexing agent and concentration of pH adjusting agent>
The copper surface treating agent of the present invention has a concentration of the complexing agent in the range of 20,000 ppm or more and less than 40,000 ppm with respect to the entire surface treating agent, and the pH adjusting agent with respect to the entire surface treating agent. The concentration may be 50,000 ppm or more. As a result, the concentration of the complexing agent can be lowered as the concentration of the pH adjusting agent is increased, so that the solubility of copper is improved and a film containing tin and copper is formed on the surface of copper. The reaction to form can be promoted.

(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, an organic solvent, etc. are mentioned. The copper surface treating agent in the present invention is superior to the conventional copper surface treating agent in that the copper surface is not subjected to roughening treatment such as etching.

(V) The surface treatment method of copper in this invention Moreover, the surface treatment method of copper of this invention is a method of making the said surface treating agent contact the surface of copper. 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. Among them, a method of immersing copper in a solution containing the surface treatment agent and performing strong stirring because the replacement of the solution containing the surface treatment agent on the copper surface is preferable is faster. A method of spraying a solution containing a treatment agent by spraying is preferred. In addition, when stirring the solution containing the said surface treating agent, it is preferable to stir within the range of 50 rpm or more and 3000 rpm or less, for example. 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. In the following, it is more preferably 5 seconds to 300 seconds, further preferably 15 seconds to 180 seconds, still more preferably 60 seconds to 180 seconds, and particularly preferably 60 seconds to 120 seconds.

The copper surface treatment method in the present invention is selected from pickling treatment, roughening treatment, chemical conversion treatment, rust prevention treatment, oxidation treatment, reduction treatment, and degreasing treatment before bringing the surface treatment agent into contact with the copper surface. At least one kind of pretreatment may be performed. In the copper surface treatment method of the present invention, the tin compound may be contacted before the surface treatment agent is brought 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. 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 a rust inhibitor, a pH adjuster, a post-treatment agent, or the like may be brought into contact therewith.

Examples of the post-treatment agent include silane coupling agents such as mercaptosilane, vinyl silane, epoxy silane, styryl silane, methacryloxy silane, acryloxy silane, amino silane, ureido silane, chloropropyl silane, sulfide silane, isocyanate silane, and the like. Preference is given to mixtures, silane coupling agent condensates and mixtures thereof, and water-soluble polymers having at least one functional group as described above. As the post-treatment method, after the chemical conversion treatment, the post-treatment agent may be contacted by spraying, dipping, coating, or the like, and then washed with water or dried without washing with water to form a coating film.

(VI) Copper Surface Film in the Present Invention The copper surface film in the present invention is formed by the above-described copper surface treatment method, and the weight of tin in the copper surface film is 1 mg / m ² or more and 2,000 mg / m ^2. The molar ratio of copper to tin on the outermost surface of the coating is preferably in the range of 0.2 or more and 10 or less, more preferably 0.2 or more and 2.0 or less.

Here, the outermost surface of the film means an extremely thin layer on the surface of the film, and specifically means a layer having a depth of about 10 nm from the surface of the film. The composition of tin or copper on the outermost surface of the film can be measured by narrow scan.

The weight of tin in the coating is preferably 1 mg / m ² or more and 2,000 mg / m ² or less, more preferably 20 mg / m ² or more and 2,000 mg / m ² or less, and even more preferably 50 mg / m ² or more and 1,500 mg. / M ² or less, particularly preferably in the range of 10 mg / m ² or more and 1,000 mg / m ² or less.

(VII) 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.

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

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

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Example 1]
<Copper surface treatment process>
An aqueous solution of sulfuric acid and hydrogen peroxide (3% sulfuric acid concentration, peroxidation) obtained by diluting 35 μm or 18 μm thick electrolytic copper foil (Furukawa Circuit Foil Co., Ltd., trade name: “F-WS foil”) with tap water After being immersed in hydrogen at a concentration of 1% at 30 ° C. for 60 seconds, it was 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 stannous sulfate as a tin compound (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm, reagent) and thiourea as a complexing agent (thio with respect to the whole surface treatment agent). Urea concentration: 50,000 ppm, reagent) and polyacrylic acid as a water-soluble polymer (molecular weight 2,000,000, concentration of polyacrylic acid relative to the entire surface treatment agent: 1,000 ppm, reagent) . Here, when the pH was measured with a pH meter (trade name “F-21” manufactured by Horiba, Ltd.), the pH was 3.

<Multilayer wiring board manufacturing process>
In order to evaluate the adhesion between the obtained electrolytic copper foil and an insulating material such as resin, build-up wiring board insulating materials [A material (manufactured by Matsushita Electric Works, FR-5), B material (Ajinomoto Co., insulation AGF-GX13 package) overlapping ^{the], 150 ℃ · 20kg / m} 2 → 150 ℃ · 30kg / m 2 · 0.5 hours ^{→ 180 ℃ · 30kg / m 2} · The laminate was pressed under heating for 1.5 hours, and then cooled under conditions of 80 ° C. and 1.5 hours. Thereafter, the press was terminated, and cooling was performed at 20 ° C. for 20 minutes. Further, the A material was measured with a 35 μm copper foil, and the B material was measured with an 18 μ copper foil because the insulating material had high adhesion.

<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 set as “◯”, the state where the etching amount is 0.1 g / m ² or more and 1 g / m ² or less is set as “Δ”, and the state exceeding 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”.

(3) Tin / carbon coating amount of electrolytic copper foil after copper surface treatment The amount of tin / carbon coating of electrolytic copper foil after copper surface treatment was measured by fluorescent X-ray (manufactured by Shimadzu Corporation, trade name: It was measured as the amount of tin element or carbon element by measurement according to “XRF1700”).

(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. When the A material was used as the insulating material, a copper foil having a thickness of 35 μm was used, and when the B material was used as the insulating material, a copper foil having a thickness of 18 μm was used.

(5) Evaluation results of the above physical properties Table 1 shows the evaluation results of the above physical properties.

[Example 2]
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) The same operation as Example 1 was performed except having changed into.

The evaluation results of the above physical properties are shown in Table 1. Here, when the pH was measured with a pH meter, the pH was 3.

Example 3
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) The same operation as in Example 1 was performed except that hydrogen fluoride as a fluorine compound (hydrogen fluoride concentration with respect to the entire surface treatment agent: 500 ppm, reagent) was added.

Example 4
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) And the complexing agent was changed from thiourea (concentration of thiourea to the entire surface treatment agent: 50,000 ppm) to diethylthiourea (concentration of diethylthiourea to the entire surface treatment agent: 50,000 ppm, reagent), and The same operation as in Example 1 was performed except that hydrogen fluoride as a fluorine compound (the concentration of hydrogen fluoride with respect to the entire surface treatment agent: 500 ppm) was added.

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

Example 6
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) The water-soluble polymer was changed from polyacrylic acid (molecular weight 2,000,000, concentration of polyacrylic acid to the whole surface treatment agent: 1,000 ppm) to polyacrylic acid (molecular weight 2,000,000, surface treatment agent). The operation was the same as in Example 1 except that the polyacrylic acid concentration relative to the whole was changed to 200 ppm) and hydrogen fluoride as a fluorine compound was further added (hydrogen fluoride concentration relative to the entire surface treatment agent: 500 ppm). Went.

Example 7
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) The water-soluble polymer was changed from polyacrylic acid (molecular weight 2,000,000, concentration of polyacrylic acid to the whole surface treatment agent: 1,000 ppm) to polyacrylic acid (molecular weight 2,000,000, surface treatment agent). The same as in Example 1, except that the polyacrylic acid concentration relative to the whole was changed to 5,000 ppm, and hydrogen fluoride as a fluorine compound (hydrogen fluoride concentration relative to the entire surface treatment agent: 500 ppm) was added. Was performed.

Example 8
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) In addition, hydrogen fluoride as a fluorine compound (hydrogen fluoride concentration relative to the entire surface treatment agent: 500 ppm) and sulfuric acid as a pH adjuster (sulfuric acid concentration relative to the entire surface treatment agent: 5,000 ppm) were added. Except that, the same operation as in Example 1 was performed.

The evaluation results of the above physical properties are shown in Table 1. Here, when the pH was measured with a pH meter, the pH was 1.

Example 9
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) Example 1 except that hydrogen fluoride as a fluorine compound (concentration of hydrogen fluoride with respect to the entire surface treatment agent: 500 ppm) was added and the pH was adjusted to 5.0 with sodium hydroxide. The same operation was performed.

The evaluation results of the above physical properties are shown in Table 1. Here, when the pH was measured with a pH meter, the pH was 5.

Example 10
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) The water-soluble polymer was changed from polyacrylic acid (molecular weight 2,000,000, concentration of polyacrylic acid to the whole surface treatment agent: 1,000 ppm) to polyacrylic acid (molecular weight 200,000, to the whole surface treatment agent). The concentration was changed to polyacrylic acid concentration: 1,000 ppm, reagent, and hydrogen fluoride as a fluorine compound (hydrogen fluoride concentration with respect to the entire surface treatment agent: 500 ppm) was added, as in Example 1. Was performed.

Example 11
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) The water-soluble polymer was changed from polyacrylic acid (molecular weight 2,000,000, concentration of polyacrylic acid to the whole surface treatment agent: 1,000 ppm) to polyacrylic acid (molecular weight 20,000, to the whole surface treatment agent). The concentration was changed to polyacrylic acid concentration: 1,000 ppm, reagent, and hydrogen fluoride as a fluorine compound (hydrogen fluoride concentration with respect to the entire surface treatment agent: 500 ppm) was added, as in Example 1. Was performed.

Example 12
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) The water-soluble polymer was changed from polyacrylic acid (molecular weight 2,000,000, concentration of polyacrylic acid to the whole surface treatment agent: 1,000 ppm) to a copolymer of acrylic acid and 2-hydroxyethyl acrylate (acrylic). The molar ratio of the acid to 2-hydroxyethyl acrylate was changed to 7: 3, the molecular weight was 200,000, and the concentration of the copolymer with respect to the whole surface treatment agent was 1,000 ppm. Further, hydrogen fluoride as a fluorine compound (surface treatment) The same operation as in Example 1 was performed except that the concentration of hydrogen fluoride with respect to the whole agent: 500 ppm) was added.

Example 13
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) The water-soluble polymer was changed from polyacrylic acid (molecular weight 2,000,000, concentration of polyacrylic acid to the whole surface treatment agent: 1,000 ppm) to amino-modified epoxy resin (amino-modified epoxy resin to the whole surface treatment agent) Concentration: 1,000 ppm, manufactured by ADEKA CORPORATION, trade name “ADEKA RESIN EP4100”), and further, hydrogen fluoride as a fluorine compound (concentration of hydrogen fluoride with respect to the whole surface treatment agent: 500 ppm) was added. The same operation as in Example 1 was performed.

Example 14
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) The water-soluble polymer was changed from polyacrylic acid (molecular weight 2,000,000, polyacrylic acid concentration to the whole surface treatment agent: 1,000 ppm) to epoxy silane (Shin-Etsu Chemical Co., Ltd.) as a water-soluble polymer. The product was changed to a 50% ethanol solution (product name: “KBM403”) (concentration of epoxysilane with respect to the entire surface treatment agent: 1,000 ppm), and hydrogen fluoride as a fluorine compound (hydrogen fluoride with respect to the entire surface treatment agent) The same operation as in Example 1 was performed except that 500 ppm) was added.

Example 15
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) The water-soluble polymer was changed from polyacrylic acid (molecular weight 2,000,000, concentration of polyacrylic acid to the entire surface treatment agent: 1,000 ppm) to 5% polyacrylic acid by epoxysilane (Shin-Etsu Chemical Co., Ltd.) A silane-modified polyacrylic acid (molecular weight 200,000, whole surface treatment agent) obtained by adding 1% by weight of a product made by the company, trade name: “KBM403”) and stirring for 30 minutes at room temperature to silane-modify polyacrylic acid. The concentration of silane-modified polyacrylic acid with respect to the surface is changed to 1,000 ppm, and hydrogen fluoride as a fluorine compound (for the entire surface treatment agent) The concentration of hydrogen fluoride that: except for the addition of 500 ppm), were subjected to the same procedure as in Example 1.

Example 16
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) contained in the predetermined surface treatment agent In addition, hydrogen fluoride as a fluorine compound (concentration of hydrogen fluoride with respect to the entire surface treatment agent: 500 ppm) and silver chloride as a metal compound (concentration of silver chloride with respect to the entire surface treatment agent: 20 ppm, reagent) Except that, the same operation as in Example 1 was performed.

Example 17
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) In addition, hydrogen fluoride as a fluorine compound (hydrogen fluoride concentration relative to the entire surface treatment agent: 500 ppm) and copper sulfate as a metal compound (copper sulfate concentration relative to the entire surface treatment agent: 100 ppm, reagent) added Except that, the same operation as in Example 1 was performed (the ratio of the concentration of the copper compound to the concentration of the tin compound in the surface treatment agent was 0.5).

Example 18
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 1, In addition, hydrogen fluoride as a fluorine compound (concentration of hydrogen fluoride with respect to the whole surface treatment agent: 1,000 ppm), copper sulfate as a metal compound (concentration of copper sulfate with respect to the whole surface treatment agent: 500 ppm) The same operation as in Example 1 was performed except that the concentration of the copper compound to the concentration of the tin compound in the surface treatment agent was 0.5.

Example 19
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 2, 000 ppm), hydrogen fluoride as a fluorine compound (hydrogen fluoride concentration relative to the entire surface treatment agent: 2,000 ppm), copper sulfate as a metal compound (copper sulfate concentration relative to the entire surface treatment agent: 1, (000 ppm) was added, except that the same operation as in Example 1 was performed (the ratio of the concentration of the copper compound to the concentration of the tin compound in the surface treatment agent was 0.5).

Example 20
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 2, 000 ppm), hydrogen fluoride as a fluorine compound (hydrogen fluoride concentration relative to the entire surface treatment agent: 2,000 ppm), copper sulfate as a metal compound (copper sulfate concentration relative to the entire surface treatment agent: 1, 000 ppm), and the same operation as in Example 1 was carried out except that sulfuric acid as a pH adjuster (sulfuric acid concentration relative to the entire surface treatment agent: 5,000 ppm) was added (the tin compound in the surface treatment agent). The ratio of the concentration of the copper compound to the concentration was 0.5).

Example 21
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 5, 000 ppm), hydrogen fluoride as a fluorine compound (hydrogen fluoride concentration relative to the entire surface treatment agent: 5,000 ppm), copper sulfate as a metal compound (copper sulfate concentration relative to the entire surface treatment agent: 2, The same operation as in Example 1 was performed except that (500 ppm) was added (the ratio of the concentration of the copper compound to the concentration of the tin compound in the surface treatment agent was 0.5).

[Example 22]
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 1, 000ppm), hydrogen fluoride as fluorine compound (hydrogen fluoride concentration with respect to the entire surface treatment agent: 1,000ppm), copper sulfate as metal compound (concentration of copper sulfate with respect to the entire surface treatment agent: 200ppm) The same operation as in Example 1 was performed except that the concentration of the copper compound with respect to the concentration of the tin compound in the surface treatment agent was 0.2.

Example 23
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) The water-soluble polymer was changed from polyacrylic acid (molecular weight 2,000,000, concentration of polyacrylic acid to the entire surface treatment agent: 1,000 ppm) to polyacrylic acid (molecular weight 2,000, based on the whole surface treatment agent). The concentration was changed to polyacrylic acid concentration: 1,000 ppm, reagent, and hydrogen fluoride as a fluorine compound (hydrogen fluoride concentration with respect to the entire surface treatment agent: 500 ppm) was added, as in Example 1. Was performed.

Example 24
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 1, 000 ppm), hydrogen fluoride as a fluorine compound (hydrogen fluoride concentration relative to the entire surface treatment agent: 1,000 ppm), copper sulfate as a metal compound (copper sulfate concentration relative to the entire surface treatment agent: 2, 000 ppm), except that methanesulfonic acid (concentration of methanesulfonic acid with respect to the entire surface treatment agent: 100,000 ppm) as a pH adjuster was added (the surface treatment agent had the same operation). The ratio of the copper compound concentration to the tin compound concentration was 2).

The evaluation results of the above physical properties are shown in Table 1. Here, when the pH was measured with a pH meter, the pH was 0.5 or less.

Example 25
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 2, 000 ppm), the complexing agent was changed from thiourea (thiourea concentration to the entire surface treatment agent: 5%) to thiourea (thiourea concentration to the entire surface treatment agent: 3%), and a metal compound Example 1 except that copper sulfate (concentration of copper sulfate with respect to the entire surface treatment agent: 400 ppm) and sulfuric acid (concentration of sulfuric acid with respect to the entire surface treatment agent: 100,000 ppm) as a pH adjuster were added. (The ratio of the concentration of the copper compound to the concentration of the tin compound in the surface treatment agent was 0.2).

Example 26
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 2, 000 ppm), the complexing agent was changed from thiourea (thiourea concentration to the entire surface treatment agent: 5%) to thiourea (thiourea concentration to the entire surface treatment agent: 3%), and a metal compound Copper sulfate (concentration of copper sulfate relative to the entire surface treatment agent: 400 ppm) and silver nitrate (concentration of silver nitrate relative to the entire surface treatment agent: 100 ppm), sulfuric acid as a pH adjuster (concentration of sulfuric acid relative to the entire surface treatment agent: 100, 000 ppm) except that the same operation as in Example 1 was performed (the concentration of the copper compound relative to the concentration of the tin compound in the surface treatment agent). It was 0.2).

Example 27
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 2, 000 ppm), the complexing agent was changed from thiourea (thiourea concentration to the entire surface treatment agent: 5%) to thiourea (thiourea concentration to the entire surface treatment agent: 3%), and a metal compound Copper sulfate (concentration of copper sulfate with respect to the whole surface treatment agent: 400 ppm), sulfuric acid as pH adjuster (concentration of sulfuric acid with respect to the whole surface treatment agent: 100,000 ppm), sodium hypophosphite (surface) as a reducing agent The same operation as in Example 1 was performed except that sodium hypophosphite concentration (2,000 ppm) with respect to the entire treatment agent was added (the above-mentioned sulphate in the surface treatment agent). The concentration ratio of the copper compound to the concentration of compound was 0.2).

Example 28
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 2, 000 ppm), the complexing agent was changed from thiourea (thiourea concentration to the entire surface treatment agent: 5%) to thiourea (thiourea concentration to the entire surface treatment agent: 3%), and a metal compound Copper sulfate (concentration of copper sulfate with respect to the whole surface treatment agent: 400 ppm), sulfuric acid as pH adjuster (concentration of sulfuric acid with respect to the whole surface treatment agent: 100,000 ppm), thioglycerol (surface treatment agent) The same operation as in Example 1 was carried out except that the concentration of thioglycerol with respect to the whole was added (5,000 ppm) (the tin compound in the surface treatment agent) The ratio of the concentration of the copper compound to the concentration was 0.2).

Example 29
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 2, 000 ppm), the complexing agent was changed from thiourea (thiourea concentration to the entire surface treatment agent: 5%) to thiourea (thiourea concentration to the entire surface treatment agent: 3%), and a metal compound Except for adding copper sulfate (concentration of copper sulfate relative to the entire surface treatment agent: 400 ppm) and methanesulfonic acid as a pH adjuster (concentration of methanesulfonic acid relative to the entire surface treatment agent: 100,000 ppm) The same operation as in Example 1 was performed (the ratio of the copper compound concentration to the tin compound concentration in the surface treatment agent was 0.2).

Example 30
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 2, 000 ppm), the complexing agent was changed from thiourea (thiourea concentration to the entire surface treatment agent: 5%) to thiourea (thiourea concentration to the entire surface treatment agent: 3%), and a metal compound Copper sulfate (concentration of copper sulfate with respect to the entire surface treatment agent: 400 ppm), sulfuric acid as pH adjuster (concentration of sulfuric acid with respect to the entire surface treatment agent: 100,000 ppm), polyacrylic acid (molecular weight as a water-soluble polymer) The same operation as in Example 1 was performed except that 20,000 and the concentration of the polyacrylic acid with respect to the whole surface treatment agent: 1,000 ppm were added (Table). The ratio of the concentration of the copper compound to the concentration of the tin compound in the treatment agent was 0.2).

Example 31
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 5, 000 ppm), the complexing agent was changed from thiourea (thiourea concentration to the entire surface treatment agent: 5%) to thiourea (thiourea concentration to the entire surface treatment agent: 3%), and a metal compound Example 1 except that copper sulfate (concentration of copper sulfate with respect to the whole surface treatment agent: 1,000 ppm) and sulfuric acid as a pH adjuster (concentration of sulfuric acid with respect to the whole surface treatment agent: 100,000 ppm) were added. (The ratio of the copper compound concentration to the tin compound concentration in the surface treatment agent was 0.2).

[Example 32]
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) The water-soluble polymer was changed from polyacrylic acid (molecular weight 2,000,000, polyacrylic acid concentration to the whole surface treatment agent: 1,000 ppm) to a copolymer of acrylic acid and acrylamide (acrylic acid and acrylamide The molar ratio was changed to 7: 3, the molecular weight was 200,000, the concentration of the copolymer with respect to the whole surface treatment agent: 1,000 ppm, and hydrogen fluoride as a fluorine compound (the concentration of hydrogen fluoride with respect to the whole surface treatment agent: 500 ppm) The same operation as in Example 1 was carried out except that was added.

[Comparative Example 1]
Copper chloride containing stannous sulfate as a tin compound, hydrogen fluoride as a fluorine compound, thiourea as a complexing agent, and polyacrylic acid as a water-soluble polymer contained in a predetermined surface treatment agent (Concentration of copper chloride with respect to the whole surface treatment agent: 10%, 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) The same operation as in Example 1 was performed, except that the change was made to. The evaluation results of the physical properties are shown in Table 1.

[Comparative Example 2]
Stannous sulfate as a tin compound, hydrogen fluoride as a fluorine compound, thiourea as a complexing agent, and polyacrylic acid as a water-soluble polymer contained in a predetermined surface treatment agent, sulfuric acid ( Concentration of sulfuric acid relative to the entire surface treatment agent: 10%, reagent), hydrogen peroxide (concentration of hydrogen peroxide relative to the entire surface treatment agent: 3%, reagent), and aminotetrazole (concentration of aminotetrazole relative to the entire surface treatment agent) : 0.3%) The same operation as in Example 1 was performed except that the change was made. The evaluation results of the physical properties are shown in Table 1.

[Comparative Example 3]
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) The same operation as in Example 1 was performed except that thiourea as a complexing agent was not added.

[Comparative Example 4]
Stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate relative to the entire surface treatment agent: 500 ppm) The same operation as in Example 1 was performed except that polyacrylic acid as a water-soluble polymer was not added.

[Comparative Example 5]
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 18, And the complexing agent is changed from thiourea (the concentration of thiourea to the entire surface treatment agent: 50,000 ppm) to thiourea (the concentration of thiourea to the entire surface treatment agent: 150,000 ppm), and Sulfuric acid (concentration of sulfuric acid relative to the entire surface treatment agent: 220,000 ppm), nickel sulfate (concentration of nickel sulfate relative to the entire surface treatment agent: 50,000 ppm), copper sulfate (concentration of copper sulfate relative to the entire surface treatment agent: 20,000 ppm) ), Diethylene glycol (concentration of diethylene glycol with respect to the entire surface treatment agent: 300,000 ppm) In addition, the same operation as in Example 1 was performed except that polyacrylic acid as a water-soluble polymer was not added (ratio of the concentration of the copper compound to the concentration of the tin compound in the surface treatment agent). Was 1.1).

[Comparative Example 6]
The tin compound contained in the predetermined surface treatment agent is changed from stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 25 ppm) to stannous sulfate (concentration of stannous sulfate with respect to the whole surface treatment agent: 18, And the complexing agent is changed from thiourea (the concentration of thiourea to the entire surface treatment agent: 50,000 ppm) to thiourea (the concentration of thiourea to the entire surface treatment agent: 150,000 ppm), and Sulfuric acid (concentration of sulfuric acid relative to the entire surface treatment agent: 220,000 ppm), nickel sulfate (concentration of nickel sulfate relative to the entire surface treatment agent: 50,000 ppm), copper sulfate (concentration of copper sulfate relative to the entire surface treatment agent: 20,000 ppm) ), Diethylene glycol (concentration of diethylene glycol with respect to the entire surface treatment agent: 300,000 ppm) In addition, polyacrylic acid as a water-soluble polymer was not added, and epoxy silane as a water-soluble polymer (concentration of epoxy silane with respect to the entire surface treatment agent: 10,000 ppm) was added as a post-treatment (washing with water) (The ratio of the concentration of the copper compound to the concentration of the tin compound in the surface treatment agent was 1.1).

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

When Example 1 and Example 2 are compared, in Example 2, compared with Example 1, by increasing the concentration of stannous sulfate as a tin compound contained in the predetermined surface treatment agent, As a result, the adhesion with an insulating material such as resin was improved.

When Example 3 and Example 2 are compared, in Example 3, compared with Example 2, the concentration of hydrogen fluoride as the fluorine compound is increased, whereby the adhesion between the copper foil and an insulating material such as a resin is increased. The result was improved.

Comparing Example 4 and Example 3, in Example 4, compared with Example 3, even when the complexing agent was changed from thiourea to diethylthiourea, sufficient copper foil and insulating material such as resin were sufficient. As a result, it was possible to maintain the adhesion.

When Example 5 is compared with Example 1, in Example 5, compared with Example 1, even if the concentration of stannous sulfate as a tin compound is significantly increased, copper foil and an insulating material such as a resin As a result, it was possible to maintain sufficient adhesion.

Comparing Example 6 and Example 3, in Example 6, compared to Example 3, even when the concentration of polyacrylic acid as a water-soluble polymer was lowered, the copper foil and an insulating material such as a resin As a result, sufficient adhesion could be maintained.

When Example 7 and Example 3 are compared, in Example 7, compared with Example 3, by increasing the concentration of polyacrylic acid as a water-soluble polymer, copper foil and an insulating material such as a resin As a result, the adhesion was improved.

Comparing Example 8 and Example 3, in Example 8, the adhesion between the copper foil and the insulating material such as resin is improved by adding sulfuric acid as a pH adjuster as compared with Example 3. It became the result.

Comparing Example 9 and Example 3, in Example 9, compared to Example 3, even when the pH is increased, sufficient adhesion between the copper foil and an insulating material such as a resin can be maintained. It became the result.

When Example 10, 11, 23 and Example 3 are compared, even if the molecular weight of the polyacrylic acid as a water-soluble polymer is made small in Example 10, 11, 23 compared with Example 3, it is copper foil. As a result, sufficient adhesion between the resin and an insulating material such as resin can be maintained.

When Examples 12 and 32 are compared with Example 10, in Examples 12 and 32, as compared with Example 10, a water-soluble polymer having a carboxyl group and a functional group other than a carboxyl group is added as a water-soluble polymer. As a result, the adhesion between the copper foil and an insulating material such as resin was improved.

When Examples 13 and 14 are compared with Example 3, in Examples 13 and 14, even when a polymer that does not contain a carboxyl group other than polyacrylic acid is added as a water-soluble polymer, As a result, sufficient adhesion between the copper foil and an insulating material such as resin can be maintained.

Comparing Examples 15 to 17 and Example 3, compared to Example 3, Examples 15 to 17 can be obtained by adding a silane, a metal compound, etc. As a result, it was possible to maintain the adhesion.

Comparing Examples 18 to 22 and 24 with Example 3, in Examples 18 to 22 and 24, compared with Example 3, the addition of copper sulfate as a copper compound resulted in the addition of thiourea as a complexing agent. As a result, even when the concentration was low, sufficient adhesion between the copper foil and an insulating material such as resin could be maintained.

Comparing Example 25 and Example 20, in Example 25, compared to Example 20, the concentration of sulfuric acid as a pH adjuster was increased without adding a fluorine compound, and accordingly, thiourea as a complexing agent was added. As a result, it was possible to maintain sufficient adhesion between the copper foil and the insulating material such as resin.

When Example 26 and Example 25 are compared, in Example 26, the adhesion between copper foil and an insulating material such as a resin is improved by adding silver nitrate as a metal compound as compared with Example 25. Became.

Comparing Example 27 and Example 25, in Example 27, sodium hypophosphite as a reducing agent was added as compared with Example 25, so that sufficient adhesion between the copper foil and an insulating material such as a resin was achieved. As a result, it was possible to maintain sex.

Comparing Example 28 and Example 25, in Example 28, sufficient adhesion between the copper foil and an insulating material such as a resin can be obtained by adding thioglycerol as a rust inhibitor compared to Example 25. The result was that it could be maintained.

Comparing Example 29 and Example 25, compared with Example 25, in Example 29, methanesulfonic acid was added instead of sulfuric acid as a pH adjuster, so that copper foil and an insulating material such as a resin were used. As a result, sufficient adhesion could be maintained.

When Example 30 and Example 25 are compared, in Example 30, compared with Example 25, by adding polyacrylic acid as a water-soluble polymer, the adhesion between the copper foil and an insulating material such as a resin is improved. The result was improved.

When Example 31 and Example 25 are compared, in Example 31, the concentration of stannous sulfate as the tin compound is high by increasing the concentration of copper sulfate as the copper compound as compared with Example 25. As a result, sufficient adhesion between the copper foil and an insulating material such as resin can be maintained.

Comparing Comparative Examples 1 and 2 with Examples 1 to 32, Comparative Examples 1 and 2 did not use a surface treatment agent containing a tin compound or the like as compared with Examples 1 to 32, and roughened etching and the like. Since the treatment (unevenness treatment) was performed, the result was that unevenness was seen in the SEM appearance of the electrolytic copper foil after the copper surface treatment.

Comparing Comparative Example 3 and Example 2, in Comparative Example 3, the adhesiveness between the copper foil and the insulating material such as resin is reduced by not adding thiourea as a complexing agent as compared with Example 2. It became the result.

Comparing Comparative Example 4 and Example 2, in Comparative Example 4, the adhesion between the copper foil and an insulating material such as a resin is improved by not adding polyacrylic acid as a water-soluble polymer as compared with Example 2. The result was a decline.

Comparing Comparative Examples 5 and 6 with Example 1, in Comparative Examples 5 and 6, the concentration of stannous sulfate as a tin compound was significantly increased compared to Example 1, and copper sulfate ( As a result, the adhesion between the copper foil and an insulating material such as a resin is greatly reduced.

The specific embodiments and examples described above are merely to clarify the technical contents of the present invention, and should not be construed in a narrow sense as being limited to such specific examples. Various modifications can be made within the spirit of the present invention and the following claims.

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 roughening the surface of the copper, 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. 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. Specifically, the copper surface treatment agent and 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

Containing a tin compound, a complexing agent, a water-soluble polymer or a water-dispersible polymer,
The water-soluble polymer or water-dispersible polymer is at least one function selected from the group consisting of an amino group, an epoxy group, a thiol group, a carboxyl group, a sulfonic acid group, a hydroxyl group, a phosphoric acid group, an imino group, and a silanol group. A copper surface treatment agent comprising a group.
The copper surface treatment agent according to claim 1, wherein the water-soluble polymer contains at least polyacrylic acid, polymaleic acid, polyitaconic acid, an acrylic acid copolymer, or a derivative thereof.
The copper surface treatment agent according to claim 1 or 2, wherein the water-soluble polymer or water-dispersible polymer has a molecular weight in the range of 2,000 to 10,000,000.
The copper surface treatment agent according to any one of claims 1 to 3, further comprising a metal compound.
The metal compound is a copper compound;
5. The copper surface treatment agent according to claim 4, wherein a ratio of the copper compound concentration to the tin compound concentration is in a range of 0.2 or more and 2.0 or less.
The copper surface treatment agent according to claim 5, wherein the concentration of the tin compound with respect to the entire surface treatment agent is in the range of 50 ppm to 10,000 ppm.
The copper according to any one of claims 1 to 6, further comprising a pH adjusting agent, wherein the pH adjusting agent contains at least sulfuric acid, nitric acid, hydrochloric acid, methanesulfonic acid or phosphoric acid. Surface treatment agent.
The surface treatment agent for copper according to claim 7, wherein the pH is 5 or less.
A copper surface treatment method comprising contacting the copper surface treatment agent according to any one of claims 1 to 8 with a copper surface.
The surface treatment agent is contacted after at least one pretreatment selected from pickling treatment, roughening treatment, chemical conversion treatment, rust prevention treatment, oxidation treatment, reduction treatment, and degreasing treatment on the surface of copper. The copper surface treatment method according to claim 9.
11. The copper surface treatment method according to claim 9, wherein the surface treatment agent or the post-treatment agent is contacted after the tin compound is brought into contact with the copper surface.
A copper surface treatment method according to any one of claims 9 to 11,
The weight of tin in the film on the copper surface is in the range of 1 mg / m 2 or more and 2,000 mg / m 2 or less,
The copper surface coating, wherein the molar ratio of copper to tin in the composition on the outermost surface of the coating is in the range of 0.2 or more and 10 or less.
A copper-clad material that is surface-treated by the copper surface treatment method according to any one of claims 9 to 11.
A multilayer wiring board comprising the copper-clad material according to claim 13.
A wiring board comprising the copper clad material according to claim 13 in an outermost layer.