KR20100082854A - Base processing agent for metal material and method for processing base for metal material - Google Patents

Abstract

Disclosed is a low-cost base processing agent for metal materials, which enables to improve adhesion, particularly adhesion at high temperatures between a metal material and a resin such as a prepreg without roughening the metal material surface. This base processing agent for metal materials does not use a substance such as hexavalent chromium which can be a cause for environmental contamination, and places little burden on the environment. Also disclosed is an environmentally advantageous method for processing a base for a metal material, which uses such a base processing agent and has excellent productivity. Further disclosed are a metal material having a base-processed coating film which is obtained by the base processing method, and a laminated member. Specifically disclosed is a base processing agent for metal materials, which contains at least one compound and at least one elastomer. The at least one compound is selected from the group consisting of compounds having one or more benzene nuclei and two or more functional groups selected from the group consisting of a hydroxy group, a carboxy group and an amino group and directly bonded to a carbon atom of the benzene nucleus, and thiourea derivatives.

Description

Base processing agent for metal material and method for processing base for metal material

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a base material treating agent for metal materials for forming a bottom coating film on a surface of a metal material, a method for treating a metal material using the same, a metal material with a bottom coating film, and a laminated member.

Various industrial materials are used for industrial products, and in addition to corrosion resistance and adhesion, various surface treatments are often performed to impart functionalities such as heat resistance, hydrophilicity, and sliding properties.

Generally, in order to improve the adhesiveness of a metal material and resin, the method of roughening a metal base surface mechanically by a blast etc. and forming what is called an anchor is used conventionally.

However, such machining generally tends to be poor in productivity and high in cost, and the precision of the electronic and electrical components is often impaired by fine particles generated during processing.

Therefore, in recent years, some chemical surface treatment is often performed on the surface of a metal material for the purpose of improving the adhesiveness by anchor effect and chemical affinity with resin.

For example, as surface treatment for improving adhesiveness, Patent Documents 1 and 2 disclose methods for improving the adhesiveness by performing chromate treatment on the surface of a metal material.

Moreover, in patent document 3, the method of forming the special chromium compound layer which has many fine flaky protrusions on the surface using the electrolytic method is described.

However, these methods all use a hexavalent chromium compound that is harmful to the surface treatment liquid, and it is considered that hexavalent chromium is contained in the film formed on the surface of the metal substrate, which is undesirable for the environment.

In addition, on the basis of the ELV directive in effect in October 2000 and the RoHS directive in effect in February 2003, use is particularly limited in electronic and electrical equipment and automobile parts.

Therefore, the research and development of the surface treatment of metal materials for the purpose of improving adhesiveness with resin, without using a hexavalent chromium compound is performed.

On the other hand, among metal materials, it is known that copper materials, such as copper and a copper alloy, have high electrical conductivity and a heat radiation characteristic as one of the characteristics. Copper materials make use of this feature and are widely used in electronic and electrical components such as printed wiring boards, lead frames, and LSIs, for example.

In the member used for an electronic and electronic component, many joining parts of a copper material and resin exist. These require adhesion between the copper material and the resin in a state where heat is applied. Specifically, thermosetting resins such as epoxy resins, polyimide resins, and thermoplastic resins having a high molding temperature are used on copper materials because of their excellent thermal stability, chemical stability, insulating properties, and the like. When molding, the entire part may need to be exposed to high temperatures of 150-350 ° C. In addition, soldering is used when mounting active components such as semiconductor elements and passive components such as LCRs. However, solder solder cannot be used due to environmental problems.

In such a situation, when the adhesion between the copper material and the resin is inferior, the moisture adsorbed on the surface of the copper material and the water absorbed by the adhesive interface of the resin in the manufacturing process expand, particularly at high temperatures. It may promote the peeling at the interface, and also cause the copper pattern to swell and damage the internal corrosion resistance, or in some cases the resin may break, resulting in breakage of the wiring pattern.

In addition, an oxide film, which is vulnerable to the interface between the copper material and the resin, is formed during heating, and the cohesive failure causes adhesion deterioration, or easily diffuses into the polyimide resin or Si single crystal, resulting in deterioration of electrical properties. These measures are also required when the copper material is used for the wiring material.

Even in the case of the copper oxide treatment called "blackening treatment", which is known as a chemical surface treatment of a copper material which does not use a hexavalent chromium compound, the initial adhesion cannot be maintained at the time of heating, and the adhesion at the initial stage of adhesion is good. However, there is a problem that the bond strength is lowered over time because the durability is poor. In addition, in the case of blackening process, it melt | dissolves easily in hydrochloric acid etc. For this reason, in the plating process of through-hole connection at the time of manufacture of a printed wiring board, the problem that the so-called pink ring etc. which generate | occur | produce the copper oxide around a hole melt-erodes by the acid in a plating bath also arises. It is pointed out.

Moreover, in recent years, the densification of a printed wiring board and the high speed of a signal are calculated | required, and the thinning and narrowing of copper wiring are progressing.

Therefore, among chemical surface treatments, the surface roughening technique has a limitation in the formation of fine patterns, and in the device used in the high frequency band of GHz or higher, the skin effect is increased, so that the transmission loss increases when the surface is harmonized. Therefore, the development of surface treatment that improves the adhesion with the resin only by chemical affinity without harmonizing the surface is urgently desired.

However, as a chemical surface treatment without surface roughening known at the present time, a coating type treatment using a silane coupling agent is known, but a practical level of adhesive strength has not been obtained.

As described above, conventionally, in order to improve the adhesion between the metal material and the resin such as prepreg, a method of etching the surface of the metal material or forming a film by reaction on the surface of the metal substrate such as chromate treatment or copper oxide treatment A chemical treatment method has been proposed.

To summarize the problems of these prior arts, first, in the conventional etching method or chemical treatment method, a large amount of non-renewable waste liquid is generated during the treatment process or during the cleaning process of the surface of the metal material required after etching or after chemical treatment. Therefore, the environmental load is large and unfavorable in terms of environmental protection. Moreover, with the increase of the number of processes, such as a washing | cleaning process, a manufacturing procedure became complicated and productivity was low. In particular, in the chemical treatment method, since the reaction time is required to some extent, the process itself takes a long time, which leads to a further decrease in productivity. Furthermore, the apparatus needs to be enlarged, which is undesirable in terms of cost.

In addition, as another problem, as described above, the surface of the metal material after the surface treatment is harmonized, and the transmission loss when a high frequency current flows during fabrication of the circuit increases, and as described in Patent Document 4, the microcircuit is described. Was difficult to form. Furthermore, in the case of using a printed wiring board or the like, if the surface of the metal substrate is rough, it is necessary to thicken the prepregs to be laminated in order to alleviate the roughness, which is uneconomical.

Patent Document 1: Japanese Patent Application Laid-Open No. 9-209167

Patent Document 2: Japanese Patent Application Laid-Open No. 9-172125

Patent Document 3: Japanese Patent Application Laid-Open No. 2000-183235

Patent Document 4: Japanese Patent Application Laid-Open No. 7-314603

In view of the present situation as described above, the present invention improves the adhesion between the metal material and the resin such as prepreg, especially at high temperatures, without sacrificing the surface of the metal material. It does not use materials that cause environmental pollution, such as chromium, and has a low environmental load, a low-cost base treatment agent for low cost metal materials, a high productivity using the same, and an environmental treatment method for metal materials which is advantageous in terms of environment. An object of the present invention is to provide a metal material with a base treatment film and a laminated member obtained by the base treatment method.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors used the base material for metal materials containing a compound and / or thiourea derivative which has a benzene nucleus and a predetermined functional group, and a predetermined elastomer, It discovered that what was excellent in adhesiveness, especially adhesiveness under high temperature, was completed, and this invention was completed.

That is, this invention provides the following (1)-(12).

(1) Compound (A-1) and thiourea derivatives selected from the group consisting of at least one benzene nucleus, a hydroxyl group, a carboxyl group and an amino group, and having at least two functional groups directly bonded to the carbon atoms constituting the benzene nucleus ( A ground treatment agent for metal materials containing at least one compound (A) selected from the group consisting of A-2) and at least one elastomer (B).

(2) The base treatment agent for metal materials as described in (1) which further contains 1 or more types of oxidizing agents (C).

(3) The oxidizing agent (C) is a nitric acid compound, a sulfuric acid compound, a halogen acid compound, a Group IV element compound having an oxidation number of 4 or 5, a Group VIA element compound having a oxidation number of 6, a copper (II) compound, iron ( III) A base material for metal materials as described in (2) which is 1 or more types chosen from the group which consists of a compound and an organic peroxide.

(4) The compound (A-1) is a cyclic organic compound represented by the following formula (1) or (2), a polycondensate of the cyclic organic compound, or a copolymer of the cyclic organic compound and another polymerizable compound. The base treatment agent for metal materials in any one of (1)-(3).

In Formula 1, X ¹ to X ⁶ each independently represent a hydrogen atom or a functional group, and two or more of X ¹ to X ⁶ represent a functional group selected from the group consisting of a hydroxyl group, a carboxy group and an amino group.

In formula (2), Y ¹ to Y ⁸ each independently represent a hydrogen atom or a functional group, and two or more of Y ¹ to Y ⁸ each represent a functional group selected from the group consisting of a hydroxyl group, a carboxy group and an amino group.)

(5) The base treatment agent for metal materials according to any one of (1) to (4), wherein the thiourea derivative (A-2) is a compound represented by the following general formula (3).

In Formula 3, Z ¹ and Z ² each independently represent an alkyl group, an aryl group, an alkoxycarbonyl group, an amino group, an alkylamino group, an allylamino group, an acetylamino group, a hydroxyethylamino group, an N-benzoylamino group, a cyclohexylamino group, a phenylamino group, Tolylamino group, naphthylamino group, phenylazo group, guanylamino group, nicotine group, hydrazino group, phenylhydrazino group, thiocarbamoyl group, or thiocarbamoylamino group.)

(6) The base treatment agent for a metal material according to any one of (1) to (5), wherein the thiourea derivative (A-2) is a compound represented by the following general formula (4).

(In formula, R <^1> , R <^2> , R <^3> and R <^4> show a hydrogen atom, an alkyl group, an alkenyl group, or a hydroxyalkyl group each independently.)

(7) A metal material with an undercoat obtained by treating a metal material using the undertreatment agent for a metal material according to any one of (1) to (6), wherein the metal material is formed on the surface layer on the metal material side of the undercoat. A metal material with an undercoat, in which a metal atom derived is concentrated and a part of said metal atom exists in a metal state.

(8) A metal material with an undercoat obtained by treating a metal material using the undertreatment agent for a metal material according to any one of (2) to (6), wherein the metal material is formed on the surface layer on the metal material side of the undercoat. Derived metal atoms are concentrated, a portion of the metal atoms are present in a metal state,

The base film-coated metal material, wherein at least one metal atom selected from the group consisting of vanadium, niobium, tantalum, molybdenum, and tungsten is concentrated on the surface layer on the metal material side of the base film.

(9) an application step of applying the base treatment agent for a metal material according to any one of (1) to (6) to the metal material surface;

After the coating step, drying without washing with water to form a base film

The method of treating the base material of the metal material having a.

(11) The base material treating method of metal material as described in (9) which has the process of performing the metal plating which consists of Ni and / or Co on the surface of a metal material, and wash | cleans before an application | coating process by electrolytic or electroless system.

(11) A metal material with an undercoat obtained by treating the metal material by the method for treating the metal material according to (9) or (10).

The laminated member which has the metal material with an undercoat as described in (7), (8), or (11), and the resin layer provided on the undercoat.

Advantageous Effects of Invention The present invention makes it possible to improve the adhesion between a metal material and a resin such as prepreg, especially at high temperatures, and to cause environmental pollution such as hexavalent chromium without harmonizing the surface of the metal material. Since the environmental load is low, the low-cost base material treatment agent for metal materials, the base material treatment agent for the metal material is excellent, and the environment is advantageous in terms of the environment. An attachment metal material and a laminated member can be provided.

1 is a schematic cross-sectional view showing a laminated member of the present invention.
2 is a distribution diagram of peak intensity derived from the C1s level.
3 is a distribution diagram of peak intensity derived from the Cu 2 p level.
4 is a narrow spectrum of the CuLMM region in each sputtering depth on the peeling interface epoxy resin side.
5 is a distribution diagram of peak intensity derived from the V2p level.

EMBODIMENT OF THE INVENTION Hereinafter, the base material processing agent for metal materials of this invention, the base material processing method of the metal material using this base material processing agent, the metal material with a base material coating film obtained by this base material processing method, and a laminated member are demonstrated in detail.

The base treatment agent for a metal material of the present invention (hereinafter also referred to simply as the "base treatment agent of the present invention") is selected from the group consisting of one or more benzene cores, hydroxyl groups, carboxyl groups and amino groups, and constitutes the benzene cores. At least one compound (A) selected from the group consisting of a compound (A-1) having two or more functional groups directly bonded to an atom, and a thiourea derivative (A-2), and at least one elastomer (B) A ground treatment agent for metal materials to contain.

The object of the surface treatment by the base treatment agent of this invention is a metal material.

The metal material is not particularly limited, and specific examples thereof include pure copper and copper alloy (hereinafter also referred to as "copper materials"), pure aluminum and aluminum alloys (hereinafter also referred to as "aluminum materials" collectively). Steels, alloy steels (hereinafter, also referred to as "iron materials" collectively), pure nickel, and nickel alloys (hereinafter, collectively referred to as "nickel materials").

In addition, the shape, structure, etc. of a metal material are not specifically limited, For example, shapes, such as plate shape, thin shape, and rod shape, may be sufficient.

In addition, the metal material may be coated on a substrate of another metal material, ceramic material, or organic material by, for example, plating or vapor deposition.

It is preferable that a copper alloy contains 50 mass% or more of copper, For example, brass etc. are mentioned. As alloy components other than copper in a copper alloy, Zn, P, Al, Fe, Ni, etc. are mentioned, for example.

Moreover, it is preferable that aluminum alloy contains 50 mass% or more of aluminum, For example, Al-Mg type alloy etc. are mentioned. As alloy components other than aluminum in an aluminum alloy, Si, Fe, Cu, Mn, Cr, Zn, Ti, etc. are mentioned, for example.

Moreover, it is preferable that alloy steel contains 50 mass% or more of iron, and stainless steel etc. are mentioned, for example. As alloy components other than iron in alloy steel, C, Si, Mn, P, S, Ni, Cr, Mo etc. are mentioned, for example.

Moreover, it is preferable that nickel alloy contains 50 mass% or more of nickel, for example, Ni-P alloy etc. are mentioned. As alloy components other than nickel in a nickel alloy, Al, C, Co, Cr, Cu, Fe, Zn, Mn, Mo, P etc. are mentioned, for example.

Among the above metal materials, the base treatment agent of the present invention can be preferably used for copper materials and the like, and particularly preferably for pure copper. Usually, when copper is used as a metal material, surface technology, Vol. 57, pp. 356 (2006), there is a problem that the adhesiveness under high temperature (hereinafter also referred to as high temperature adhesiveness) of the film laminated thereon is insufficient, but excellent high temperature is achieved by using the substrate treatment agent of the present invention. Adhesion can be provided.

Next, at least one benzene nucleus contained in the base treatment agent of the present invention, a compound selected from the group consisting of hydroxyl groups, carboxyl groups and amino groups, and having two or more functional groups directly bonded to the carbon atoms constituting the benzene nucleus ( A-1), and a compound (A) and an elastomer (B) selected from the group consisting of thiourea derivatives (A-2), and an oxidizing agent (C), zirconium compound and / or titanium which may be contained as desired. One or more (D) of a compound, one or more (E) of a phosphate and / or a phosphate ester compound, water-dispersible silica sol, etc. are described in detail.

<Compound (A)>

Compound (A) used in the present invention is selected from the group consisting of at least one benzene nucleus and a hydroxyl group, a carboxyl group and an amino group, and has a compound (A) having two or more functional groups directly bonded to the carbon atoms constituting the benzene nucleus. -1) and thiourea derivatives (A-2).

Hereinafter, the compound (A-1) and the thiourea derivative (A-2) will be described in detail.

<Compound (A-1)>

Compound (A-1) is a compound selected from the group consisting of at least one benzene nucleus, a hydroxyl group, a carboxyl group and an amino group, and having at least two functional groups directly bonded to the carbon atoms constituting the benzene nucleus.

Here, a benzene nucleus means aromatic carbon 6-membered ring, and also includes the individual 6-membered ring which comprises condensed rings, such as naphthalene.

As compound (A-1), Preferably, the cyclic organic compound represented by following formula (1) or 2, the polycondensate of this cyclic organic compound, the copolymer of this cyclic organic compound and another polymeric compound, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

[Formula 1]

[Formula 2]

In said Formula (1), X <^1> -X <^6> respectively independently represents a hydrogen atom or a functional group, and two or more of X <^1> -X <^6> represent the functional group chosen from the group which consists of a hydroxyl group, a carboxy group, and an amino group.

In the above formula (2), Y ¹ to Y ⁸ each independently represent a hydrogen atom or a functional group, and two or more of Y ¹ to Y ⁸ each represent a functional group selected from the group consisting of a hydroxyl group, a carboxy group and an amino group.

Specific examples of the cyclic organic compound represented by Formula 1 include hexahydroxybenzene, pyrogallol, 1,2,4-trihydroxybenzene, phloroglucinol, catechol, resorcinol, hydroquinone and 5- Methylpyrogallol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 3-methylcatechol, 4-methylcatechol, methylhydroquinone, 2,6-dimethylhydroquinone, 5 -Methoxyresorcinol, 3-methoxycatechol, methoxyhydroquinone, 2,5-dihydroxy-1,4-benzoquinone, molar asset, pyrogallol-4-carboxylic acid, 2-hydroxybenzoic acid, 3-hydroxy benzoic acid, 4-hydroxy benzoic acid, 2,3-dihydroxy benzoic acid, 2,4-dihydroxy benzoic acid, 2,5-dihydroxy benzoic acid, 2,6-dihydroxy benzoic acid, 3, 4-dihydroxy benzoic acid, 3,5-dihydroxy benzoic acid, 2,4,6-trihydroxy benzoic acid, 2,6-dihydroxy-4-methyl benzoic acid, 4-hydroxy-3,5-dimethyl Benzoic acid, 1,4-dihydrate Ci-2-naphthoic acid, methyl methyl formol, methyl 2,4-dihydroxy benzoate, methyl 2,6-dihydroxy benzoate, methyl 3,4-dihydroxy benzoate, 3,5-dihydroxy benzoic acid Methyl, 3,4-dihydroxybenzoate, 2-aminophenol, amidol, 3-aminophenol, 4-aminophenol, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4- Phenylenediamine, 2-amino-p-cresol, 3-amino-o-cresol, 4-amino-m-cresol, 4-amino-o-cresol, 5-amino-o-cresol, 6-amino-m- Cresol, 2-amino-m-cresol, 2-amino-4-methylphenol hydrochloride, o-phenylenediamine hydrochloride, 1,3-phenylenediamine hydrochloride, 1,4-phenylenediamine hydrochloride, 4,6-dia Minoresorcinol dihydrochloride, 4,6-diaminoresorcinol, 2-nitroresorcinol, 4-nitrocatechol, melitric acid, benzenepentacarboxylic acid, pyromellitic acid, trimellitic acid, hemimelic acid , Trimesic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedica Acids, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4-methylphthalic acid, 5-methylisophthalic acid, 2,5-dimethylterephthalic acid, 4-hydroxyphthalic acid, 5-hydric Hydroxyisophthalic acid, 4-nitrophthalic acid, 5-nitroisophthalic acid, 5-aminoisophthalic acid, 4-aminosalicylic acid, 4-amino-3-hydroxybenzoic acid, etc. may be used, and these may be used individually by 1 type, You may use 2 or more types together.

Among them, pyrogallol, molar acid, fluoroglucinol, catechol, resorcinol, hydroquinone, 2,4-dihydroxy benzoic acid, 2,6-dihydroxy benzoic acid, 3,4-dihydroxy benzoic acid, 3 , 5-dihydroxybenzoic acid and amidol are preferable because of their high solubility in water which can be used as a preferable solvent as described later.

Specifically as a cyclic organic compound represented by the said Formula (2), For example, 1, 3- dihydroxy naphthalene, 1, 4- dihydroxy naphthalene, 1, 5- dihydroxy naphthalene, 1, 6-, Dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 3-amino-2-naphthol, 5-amino-1-naphthol, 5- Amino-2-naphthol, 6-amino-1-naphthol, 8-amino-2-naphthol, 1-amino-2-naphthol hydrochloride, 2-amino-1-naphthol hydrochloride and the like. You may use and may use 2 or more types together.

As a polycondensate of the cyclic organic compound represented by the said Formula (1) or (2), the polycondensate of the various cyclic organic compounds illustrated above is mentioned, for example, Digalic acid etc. are mentioned specifically ,.

Moreover, as a cocondensate of the cyclic organic compound represented by the said Formula (1) or (2) with another organic compound (for example, glucose etc.), Specifically, For example, hydrolyzable tannins, such as tannic acid; Condensed tannins such as gamma tannin, theaflavin and thearubizin; Etc. can be mentioned.

Of these, digal acid and tannic acid are preferable because of their high solubility in water.

<Thiourea derivative (A-2)>

The thiourea derivative (A-2) is not particularly limited, and conventionally known compounds dissolved or dispersed in various solvents can be used.

As a specific example of a thiourea derivative (A-2), for example, 1-acetyl-2-thiourea, 1-allyl-2-thiourea, 1-allyl-3- (2-hydroxyethyl) -2- Thiourea, 1-adamantylthiourea, N-benzoylthiourea, N, N'-diisopropylthiourea, N, N'-dicyclohexylthiourea, 1,3-diethyl-2-thiourea , 1,3-di (o-tolyl) thiourea, 1,3-di (p-tolyl) thiourea, 1,3-dimethylthiourea, 1,1-diphenyl-2-thiourea, 2,5 Dithiobiurea, N-methylthiourea, 1- (1-naphthyl) -2-thiourea, 1-ethyl-3-guanidinothiourea hydrochloride, guanylthiourea, ethylenethiourea, 1-phenyl 2-thiourea, 1,3-diphenyl-2-thiourea, p-tolylthiourea, o-tolylthiourea, trimethylthiourea, 1,3-di-n-butylthiourea, 1-phenyl- 3-guanylthiourea, tetramethylthiourea, thiourea dioxide, diphenylthiocarbazide, 4,4-dimethyl-3-thiosemiccarbazide, 4-methylthiosemicarbazide, 1-phenyl- 3-thiosemica Levazide, 4-phenyl-3-thiosemicarbazide, thiosemicarbazide, 1,4-diphenyl-3-thiosemicarbazide, thioacetamide, thiobenzamide, thiopropionamide, tee Isonicotinamide, thionicotinamide, acetone thio semicarbazone, dithione, rubeanic acid, ethyl thioxamate, diphenylthiocarbazide, and the like, and these may be used alone, or You may use 2 or more types together.

As one of the preferable embodiment of the said thiourea derivative (A-2), the compound represented by following formula (3) is mentioned. Use of this compound improves the adhesion between the metal material and the underlying treatment film described later.

(3)

In Formula 3, Z ¹ and Z ² each independently represent an alkyl group, an aryl group, an alkoxycarbonyl group, an amino group, an alkylamino group, an allylamino group, an acetylamino group, a hydroxyethylamino group, an N-benzoylamino group, a cyclohexylamino group, a phenylamino group, Tolylamino group, naphthylamino group, phenylazo group, guanylamino group, nicotine group, hydrazino group, phenylhydrazino group, thiocarbamoyl group, or thiocarbamoylamino group.)

In the general formula (3), Z ¹ and Z ² each independently represent an alkyl group (preferably having 1 to 3 carbon atoms; specifically, a methyl group, an ethyl group, etc.), and an aryl group (preferably having 6 to 10 carbon atoms). Specifically, a phenyl group, a naphthyl group, etc. are mentioned.), An alkoxycarbonyl group, an amino group, an alkylamino group, an allylamino group, an acetylamino group, a hydroxyethylamino group, an N-benzoylamino group, a cyclohexylamino group, a phenylamino group, a tolylamino group , Naphthylamino group, phenylazo group, guanylamino group, nicotine group, hydrazino group, phenylhydrazino group, thiocarbamoyl group, or thiocarbamoylamino group.

Especially, alkylamino group, allylamino group, and hydroxyethylamino group are preferable.

As one of the preferable embodiment of the compound represented by General formula (3), the compound represented by following General formula (4) is mentioned. When this compound is used, the adhesion between the metal material and the underlying treatment film described later is further excellent.

[Formula 4]

(In formula, R <^1> , R <^2> , R <^3> and R <^4> show a hydrogen atom, an alkyl group, an alkenyl group, or a hydroxyalkyl group each independently.)

In formula (X), R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or a hydroxyalkyl group. It does not specifically limit as an alkyl group, C1-C3 is preferable. Specifically, a methyl group, an ethyl group, a propyl group, etc. are mentioned.

It does not specifically limit as an alkenyl group, C2-C3 is preferable. Specifically, a vinyl group, an allyl group, etc. are mentioned.

It does not specifically limit as a hydroxyalkyl group, C1-C3 is preferable. Specifically, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, etc. are mentioned.

As the compound represented by the formula (4), it is preferable that R ¹ and R ³ are hydrogen atoms, and R ² and R ⁴ are each independently a hydrogen atom, an alkyl group, a hydroxyalkyl group, or an alkenyl group.

Among these thiourea derivatives (A-2), thiourea, N-methylthiourea, 1-allyl-2-thiourea and the like are preferable because of their high solubility in water which can be used as a preferable solvent as described later. .

In the base treatment agent of the present invention, by containing such a compound (A-1) and / or (A-2), the adhesion between the metal material and the resin, particularly under high temperature, without satisfactory surface of the metal material can do.

Moreover, by using together the oxidizing agent (C) mentioned later, the adhesiveness of a metal material and resin, especially adhesiveness under high temperature becomes favorable.

Moreover, in the base treatment agent of this invention, it is preferable that it is 0.01-20 mass% with respect to the base treatment agent whole quantity, and, as for content of the said compound (A), it is more preferable that it is 0.02-10 mass%. When content of the said compound (A) exists in this range, the adhesiveness of a metal material and resin, especially adhesiveness under high temperature will become more favorable.

<Elastomer (B)>

The elastomer (B) is not particularly limited, and conventionally known elastomers dissolved or dispersed in various solvents can be used.

Specific examples of the elastomer (B) include diene rubbers such as natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, chloroprene rubber, acrylonitrile butadiene rubber and acrylonitrile butadiene styrene rubber; Butyl rubber, ethylene propylene rubber, urethane rubber, silicone rubber, chlorosulfonated rubber, chlorinated polyethylene, acrylic rubber, epichlorohydrin rubber, fluorine rubber, and the like are dissolved or dispersed in various solvents. You may use individually by species and may use 2 or more types together.

Furthermore, these rubbers may be modified with functional groups such as hydroxyalkyl groups such as amino groups, hydroxyl groups and methylol groups, carboxyl groups, sulfone groups, phosphone groups, epoxy groups, isocyanate groups and carbodiimide groups.

Here, as a solvent, Specifically, For example, Water; Alkanes such as hexane and pentane; Aromatic systems such as benzene and toluene; Alcohols such as ethanol, 1-butanol and ethyl cellosolve; Ethers such as tetrahydrofuran and dioxane; Esters such as ethyl acetate and butoxyethyl acetate; Amides such as dimethylformamide and N-methylpyrrolidone; Sulfone solvents such as dimethyl sulfoxide; Phosphate amides such as hexamethyl phosphate triamide; Etc. can be used preferably.

Among the elastomers (B), the glass transition temperature (Tg) of the elastomer (B) is preferably -100 to 300 ° C.

In addition, the specific gravity of the elastomer (B) is preferably 0.8 to 2.0 among the elastomers (B).

Among these rubbers, acrylonitrile butadiene styrene rubber, acrylonitrile butadiene rubber, isoprene rubber, styrene butadiene rubber, chloroprene rubber, urethane rubber, and acrylic rubber are preferable because of their high affinity with the resin to be bonded.

In the base treatment agent of the present invention, the method of dissolving or dispersing the elastomer (B) in various solvents is not particularly limited, and can be performed by a conventionally known method such as emulsification by adding a surfactant. .

Although it does not specifically limit as an elastomer concentration in the elastomer dispersion solution (also called an emulsion) which disperse | distributed the elastomer (B) in various solvents, 1-80 mass% is preferable from a viewpoint of the ease of handling of a processing agent, and 10-60 mass% is more preferable. Do.

Although the pH of the said dispersion solution is not specifically limited, Specifically, pH 2-11 are preferable from a viewpoint of the ease of handling of a processing agent, or the adhesiveness to the metal material of the base film mentioned later, More preferably, pH is more preferable. 4-10.

Although it does not restrict | limit especially as a viscosity of the said dispersion solution, 0-3000 cP is preferable at the point of the handleability of a processing agent.

Although the particle diameter of the elastomer (B) in the said dispersion solution is not specifically limited, 0.01-10 micrometers is preferable and 0.1-2 micrometers is more preferable.

The surfactant used in the preparation of the dispersion solution is not particularly limited, and anionic surfactants, cationic surfactants, nonionic surfactants, and the like can be used.

In the base treatment agent of the present invention, by containing such an elastomer (B), the stress generated when the laminated member of the present invention described later is exposed or deformed under a high temperature environment can be alleviated.

Moreover, in the base treatment agent of this invention, it is preferable that it is 0.5-80 mass% with respect to the base treatment agent whole quantity, and, as for content of the said elastomer (B), it is more preferable that it is 1-50 mass%. When the content of the elastomer (B) is within this range, flexibility is provided to the underlying film, so that stress generated when exposed or deformed in a high temperature environment can be alleviated.

<Oxidizer (C)>

The oxidant (C) is not particularly limited, and a conventionally known oxidant can be used.

In the base treatment agent of the present invention, the oxidizing agent (C) is a nitric acid compound, a sulfuric acid compound, a halogen acid compound, a Group IV element compound having an oxidation number of 4 or 5, a Group VIA element compound having an oxidation number of 6, copper (II) And at least one member selected from the group consisting of a compound, an iron (III) compound and an organic peroxide are preferable for the reason of having sufficient oxidizing power to oxidize various metal materials including a copper material.

Among these, it is preferable that the said oxidizing agent (C) is a nitric acid type compound and / or a sulfuric acid type compound.

Here, specifically, as a nitric acid type compound, For example, nitric acid, nitrous acid, peroxo nitric acid, peroxo nitrous acid, nitric acid, trioxonitric acid, tetraoxo dinitric acid, these salts (sodium salt, potassium salt, lithium) Salts, ammonium salts, etc. The same.), Etc. may be used, and these may be used individually by 1 type, and may use 2 or more types together.

Moreover, as a sulfuric acid type compound, a peroxo monosulfuric acid, a peroxodisulfate, a thiosulfate, a dithiic acid, a sulfurous acid, a disulfuric acid, a thiosulfuric acid, adithiic acid, a sulfoxylic acid, a polythionic acid, these are specifically, Salts, etc. may be used, and these may be used individually by 1 type, and may use 2 or more types together.

Next, it is preferable that the said oxidizing agent (C) is a halogen acid type compound.

Here, as the halogen acid compound, specifically, for example, perchloric acid, chloric acid, hypochlorous acid, hypochlorous acid, perbromic acid, bromic acid, abromic acid, hypobromic acid, periodic acid, iodic acid, hypoiodic acid These salts etc. can be mentioned, These may be used individually by 1 type, and may use 2 or more types together.

Next, it is preferable that the said oxidizing agent (C) is a group VA element compound whose oxidation number is 4 or 5.

Here, as the Group VA element compound having an oxidation number of 4, specifically, for example, vanadium oxyacetylacetonate (IV), nioboxy acetylacetonate (IV), tantaloxy acetylacetonate (IV), and salts thereof These may be mentioned, These may be used individually by 1 type, and may use 2 or more types together. Of these, vanadium oxyacetylacetonate (IV) is preferable because of its high solubility in water.

Specific examples of the Group VA element compound having an oxidation number of 5 include oxygen acids such as metavanadium acid (V), metaniobonic acid (V), and metatantalic acid (V); Isopolyacid of enzymatic acid; Salts of enzyme acids; Two or more heteropoly acids selected from metavanadium acid (V), metaniobonic acid (V), and metatantalic acid (V); Salts of heteropolyacids; These may be mentioned, These may be used individually by 1 type, and may use 2 or more types together. Among them, ammonium metavanadate (V) is preferable because of its high solubility in water.

Next, it is preferable that the oxidizing agent (C) is a group VIA element having 6 oxidation numbers.

Here, as the VIA group compound having an oxidation number of 6, specifically, for example, invanado molybdate H _15-X [PV _12-x Mo _x O ₄₀ ] .nH ₂ O (6 <x <12, n <30), molybdenum oxide, molybdate H ₂ MoO ₄ , ammonium molybdate, ammonium paramolybdate, sodium molybdate, potassium molybdate, calcium molybdate, molybdenylacetylacetonate, molybdate phosphoric acid compound (e.g. Examples include ammonium molybdate phosphate (NH ₄ ) ₃ [PO ₄ Mo ₁₂ O ₃₆ ] .3H ₂ O, sodium molybdate phosphate Na ₃ [PO ₄ .12MoO ₃ ] .nH ₂ O and the like); Metatungstate H ₆ [H ₂ W ₁₂ O ₄₀ ], ammonium metatungstate (NH ₄ ) ₆ [H ₂ W ₁₂ O ₄₀ ], sodium metatungstate, paratungstate H ₁₀ [W ₁₂ O ₄₆ H ₁₀ ] para tungstate, ammonium para tungstate, sodium tungstophosphoric acid compound (e. g., 12-tungstophosphoric acid n hydrate _{H 3 (PW 12 O 40)} · nH 2 O, a tungstate ammonium n hydrate 2 (nH _{4) 3} PO ₄ .24WO ₃ .nH ₂ O and the like); These may be mentioned, These may be used individually by 1 type, and may use 2 or more types together.

Next, the oxidizing agent (C) is preferably a copper (II) compound and / or an iron (III) compound.

Here, specifically, as a copper (II) compound, For example, copper (II) formate, copper (II) acetate, copper propionate (II), copper gil acetate (II), copper gluconate (II), tartaric acid, for example Copper salts of organic acids such as copper (II); Copper chloride (II), copper bromide (II), copper hydroxide (II), copper acetate (II), copper nitrate (II), copper sulfate (II), copper carbonate (II), copper oxide (II); These may be mentioned, These may be used individually by 1 type, and may use 2 or more types together.

As the iron (III) compound, specifically, for example, iron (III) chloride, iron bromide (III), iron iodide (III), iron sulfate (III), iron (III) nitrate, iron acetate (III) And the like, and these may be used alone, or two or more thereof may be used in combination.

Next, it is preferable that the said oxidizing agent (C) is an organic peroxide.

Here, as an organic peroxide, hydrogen peroxide, a ketone peroxide, a peroxy ketal, a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, a peroxy ester, a peroxy dicarbonate etc. are mentioned specifically, These may be used individually by 1 type and may use 2 or more types together.

As described above, in the base treatment agent of the present invention, by containing such an oxidizing agent (C), the adhesion between the metal material and the resin, particularly under high temperature, can be made better without compromising the surface of the metal material.

The reason why the adhesion between the metal material and the resin is further improved is not clear in detail, but the anchoring effect due to the oxidizing agent (C) oxidizing the metal material and being very minutely etched, and the dissolved metal ion It is thought that high adhesiveness is expressed by the affinity improvement effect with the metal material by inserting in the surface of the metal material surface of this film.

Among the above-described oxidizing agents (C), from the viewpoint of better adhesion, a Group VA element compound having an oxidation number of 5 and a Group VIA element compound having an oxidation number of 6 are preferable, and more preferably ammonium vanadate, ammonium molybdate, Ammonium metatungstate.

Moreover, in the base treatment agent of this invention, it is preferable that content of the said oxidizing agent (C) which can be contained as desired is 0.01-20 mass% with respect to the base treatment agent whole quantity, and it is more preferable that it is 0.02-10 mass%. desirable. When content of the said oxidizing agent (C) exists in this range, since it has appropriate oxidizing power, the adhesiveness of a metal material and resin, especially adhesiveness under high temperature can be made more favorable.

<Zirconium Compound, Titanium Compound (D)>

The ground treatment agent of the present invention preferably contains a zirconium compound and / or a titanium compound (D) for the reason that the adhesion between the metal material and the resin can be made better without roughening the surface of the metal material. The zirconium compound and / or titanium compound (D) is not particularly limited, and conventionally known compounds can be used. Here, as zirconium compound and / or titanium compound (D), specifically, Zr or Ti carbonate, oxide, nitrate, sulfate, phosphate, fluoride, fluoroacid (salt), organic acid salt, organic complex compound, etc. can be used. have. More specifically, basic zirconium carbonate, zirconium oxycarbonate, zirconium ammonium carbonate, zirconyl ammonium carbonate (NH ₄ ) ₂ [Zr (CO ₃ ) ₂ (OH) ₂ ], zirconium oxide (IV) (zirconia), titanium oxide (IV) (titania), zirconium nitrate, zirconyl nitrate ZrO (NO ₃ ) ₂ , titanium nitrate, zirconium sulfate (IV), zirconyl sulfate, titanium (III), titanium sulfate (IV), titanium sulfate TiOSO ₄ , Zirconium oxyphosphate, zirconium pyrophosphate, zirconium dihydrogen phosphate, zirconium fluoride, titanium fluoride (III), titanium fluoride (IV), hexafluorozirconium acid (H ₂ ZrF ₆ ), hexafluorozirconium acid Ammonium [(NH ₄ ) ₂ ZrF ₆ ]], hexafluorotitanic acid (H ₂ TiF ₆ ), ammonium hexafluoro titanate [(NH ₄ ) ₂ TiF ₆ ]], zirconyl acetate, titanium laurate, zirconium acetylaceto Nate Zr (OC (= CH ₂ ) CH ₂ COCH ₃ )) ₄ , diisopropoxytitaniumbisacetylacetone (C ₅ H ₇ O ₂ ) ₂ Ti [OCH (CH ₃ ) ₂ ] ₂ , Titanium acetylacetonate Ti (OC (= CH ₂ ) CH ₂ COCH ₃ )) ₃ and the like. These may be anhydrides or hydrates. These compounds may be used alone or in combination of two or more thereof.

In addition, in the base treatment agent of the present invention, the content of the zirconium compound and / or titanium compound which may be contained as desired is preferably 0.01 to 20 mass%, and 0.02 to 10 mass%, based on the total amount of the base treatment agent. It is more preferable. When content of the said zirconium compound and / or titanium compound exists in this range, the adhesiveness of a metal material and resin can be made more favorable.

<Phosphates, Phosphate Ester Compounds (E)>

The ground treatment agent of the present invention preferably contains phosphoric acid and / or phosphate ester compound (E) for the reason that the adhesion between the metal material and the resin can be made better without roughening the surface of the metal material. . The said phosphoric acid and / or phosphate ester compound (E) is not specifically limited, A conventionally well-known compound can be used.

Here, phosphoric acid is phosphoric acid (= orthophosphoric acid), metaphosphoric acid, condensed phosphoric acid containing polyphosphoric acid, and its salt (ammonium salt, sodium salt, calcium salt, magnesium salt, etc.), More specifically, metaphosphate is, Trimethic acid, tetramethic acid, hexamethic acid, and the like, and polyphosphoric acid is a chain-shaped phosphoric acid condensate and includes pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, and the like.

Specific examples of the phosphate ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, monomethyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, monobutyl phosphate and dibutyl phosphate.

These compounds may be used alone or in combination of two or more thereof.

Moreover, in the base treatment agent of this invention, it is preferable that content of the said phosphate and / or phosphate ester compound (E) which can be contained as desired is 0.01-20 mass% with respect to the base treatment agent whole quantity, and is 0.02 It is more preferable that it is -10 mass%. When content of the said phosphoric acid and / or phosphate ester compound (E) exists in this range, since it has appropriate oxidation power, the adhesiveness of a metal material and resin can be made more favorable.

The base treatment agent of this invention can contain a water dispersible silica sol, an alumina sol, and a zirconia sol.

Examples of the water-dispersible silica sol include liquid silica synthesized from the liquid phase and gas phase silica synthesized from the gas phase, and both of them can be used in the base treatment agent of the present invention.

Specifically as liquid silica, For example, Snowtex C, Snowtex O, Snowtex N, Snowtex S, Snowtex UP, Snowtex PS-M, Snowtex PS-L, Snowtex 20, Snowtex 30, Snowtex 40 (all are the Nissan Chemical Industries, Ltd. product) etc. can be mentioned, These may be used individually by 1 type, and may use 2 or more types together.

As the vapor phase silica, specifically, for example, aerosil 50, aerosil 130, aerosil 200, aerosil 300, aerosil 380, aerosil TT600, aerosil MOX80, aerosil MOX170 (both Japan Aerosol Etc.), These may be used individually by 1 type, and may use 2 or more types together.

Examples of alumina sol include alumina sol 100, alumina sol 200, alumina sol 520 (all manufactured by Nissan Chemical Industries, Ltd.), and the like, and these may be used alone. You may use 2 or more types together.

 As zirconia sol, specifically, for example, nano use ZR-40BL, nano use ZR-30BS, nano use ZR-30BH, nano use ZR-30AL, nano use ZR-30AH (both Nissan Chemical Co., Ltd.) ), ZSL-10A, ZSL-10T, and ZSL-20N (all are manufactured by Cheil Hee Soon Co., Ltd.), etc. may be used individually by 1 type, and may use 2 or more types together.

In the base treatment agent of the present invention, the content of the water-dispersible silica sol added as desired is preferably 30% by mass or less, preferably 0.01 to 10% by mass, and 0.05 to 10% by mass, based on the total amount of the substrate treatment agent. It is more preferable that it is%.

The base treatment agent of the present invention may contain a silane coupling agent.

Specific examples of the silane coupling agent include N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane and N-β ( Aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl- γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl Triethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, N- β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrie Oxysilane, γ-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane , γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, vinyltriacetoxysilane, γ Chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropylmethyldiethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane , γ-anilinopropylmethyldimethoxysilane, γ- Nilinopropyltriethoxysilane, γ-anilinopropylmethyldiethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, octadecyldimethyl [3- (tri Methoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methyldimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (triethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- ( Methyldiethoxysilyl) propyl] ammonium chloride, gamma-chloropropylmethyldimethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, and the like. You may use independently and may use 2 or more types together.

In the base treatment agent of the present invention, the content of the silane coupling agent to be added as desired is preferably 30% by mass or less, preferably 0.01 to 10% by mass, and 0.05 to 10% by mass, based on the total amount of the substrate treatment agent. It is more preferable that is.

The base treatment agent of the present invention may contain one or more selected from the group consisting of triazole, benzotriazole, tetrazole, imidazole, thiazole, pyrazole, isoxazole, indazole and triazine thiol. .

Specific examples of such a compound include 1,2,3-triazole, 1,2,4-triazole, tolyltriazole and 5-methyltriazole;

1,2,3-benzotriazole, 1-hydroxybenzotriazole, 1-aminobenzotriazole, 1- (hydroxymethyl) benzotriazole, carboxybenzotriazole;

Tetrazole, 5-aminotetrazole, 1-methyltetrazole, 2-methyltetrazole, 1-phenyltetrazole, 5-phenyltetrazole;

Imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-phenylimidazole, 1-benzylimidazole, 1-vinylimidazole, 1-hydroxyethyl Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole, 2-butylimidazole, 2-undecylimidazole, 2- Heptadecylimidazole, 2-phenylimidazole, 2-benzylimidazole, 4-methylimidazole, 4-phenylimidazole, 4-benzylimidazole, 1,2-dimethylimidazole, 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-vinyl-2-methylimidazole, 2,4-dimethylimidazole, 2 -Ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-butyl-4-hydroxymethylimidazole, 2-butyl-4-formylimidazole, 2,4- Diphenylimidazole, 4,5-dimethylimidazole, 4,5-diphenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2 , 5-trimethylimidazole, 1,4,5-trimethylimidazole, 1-methyl-4,5-di Phenylimidazole, 2-methyl-4,5-diphenylimidazole, 2,4,5-trimethylimidazole, 2,4,5-triphenylimidazole, 1-cyanoethyl-2- Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolebenzimimi Dozol; Thiazole; Pyrazoles; Isoxazole; Indazole;

1,3,5-triazine-2,4,6-tritriol, 1,3,5-triazine-2,4,8-tritriol, 2-methylamino-1,3,5-triazine- 4,6-dithiol, 2-anilino-1,3,5-triazine-4,6-dithiol, 2-dimethylamino-1,3,5-triazine-4,6-dithiol, 2 -Di-n-butylamino-1,3,5-triazine-4,6-dithiol, 2-diallylamino-1,3,5-triazine-4,6-dithiol, 2- (3 '-Hydroxyanilino) -1,3,5-triazine-4,6-dithiol, 2-cyclohexylamino-1,3,5-triazine-4,6-dithiol, 2- (3 '-Methylphenylamino) -1,3,5-triazine-4,6-dithiol, 2-benzylamino-1,3,5-triazine-4,6-dithiol, 2- (3'-bro Mophenylamino) -1,3,5-triazine-4,6-dithiol, 2- (3 ', 4'-thiopropylthio) -1,3,5-triazine-4,6-dithiol , 2-methoxy-1,3,5-triazine-4,6-dithiol, 2- (2'-hydroxyethylamino) -1,3,5-triazine-4,6-dithiol; These may be mentioned, These may be used individually by 1 type, and may use 2 or more types together.

In the base treatment agent of the present invention, the content of these compounds to be added as desired is preferably 30% by mass or less, preferably 0.01 to 10% by mass, and preferably 0.05 to 5% by mass, based on the total amount of the substrate treatment agent. More preferred.

In order to improve the adhesiveness of a metal material and resin, the base treating agent of this invention can contain the thing of the state which melt | dissolved or disperse | distributed resin in the solvent from a viewpoint of improving affinity of a metal material and resin.

Specifically, for example, polyolefin resin, epoxy resin, acrylic resin, urethane resin, phenol resin, urea resin, melamine resin, polyamide, polyimide, polyamine, nylon resin, polyphenylene sulfide and the like are dissolved or dissolved in a solvent. The thing of the state disperse | distributed is mentioned.

Moreover, these resin may be modified | denatured by functional groups, such as hydroxyalkyl groups, such as an amino group, a hydroxyl group, and a methylol group, a carboxyl group, a maleic acid group, a sulfone group, a phosphone group, an epoxy group, a carbodiimide group, and an isocyanate group.

In addition, the method of melt | dissolving or disperse | distributing the said resin in a solvent is not specifically limited, For example, it can carry out by a conventionally well-known method, such as adding and emulsifying surfactant.

Here, although various solvents can be used as said solvent, Specifically, For example, Water; Alkanes such as hexane and pentane; Aromatic systems such as benzene and toluene; Alcohols such as ethanol, 1-butanol and ethyl cellosolve; Ethers such as tetrahydrofuran and dioxane; Esters such as ethyl acetate and butoxyethyl acetate; Amides such as dimethylformamide and N-methylpyrrolidone; Sulfone solvents such as dimethyl sulfoxide; Phosphate amides such as hexamethyl phosphate triamide; Etc. can be used preferably.

In the base treatment agent of the present invention, the content of the resin solution, the emulsion, and the suspension to be added as desired is preferably 60% by mass or less, and more preferably 1 to 50% by mass with respect to the total amount of the substrate treatment agent.

The base treatment agent of the present invention may contain various solvents as necessary from the viewpoint of workability when applied to the metal material surface.

Specific examples of such a solvent include water; Alkanes such as hexane and pentane; Aromatic systems such as benzene and toluene; Alcohols such as ethanol, 1-butanol and ethyl cellosolve; Ethers such as tetrahydrofuran and dioxane; Esters such as ethyl acetate and butoxyethyl acetate; Amides such as dimethylformamide and N-methylpyrrolidone; Sulfone solvents such as dimethyl sulfoxide; Phosphate amides such as hexamethyl phosphate triamide; Etc. can be mentioned.

Among them, water is preferable for environmentally and economically advantageous reasons.

The manufacturing method of the ground treatment agent for metal materials of this invention is not specifically limited about the manufacturing method. For example, it can manufacture by mixing a compound (A), the water dispersion of an elastomer (B), and the oxidizing agent (C) which can be used as needed, other additives, and water sufficiently using a stirrer, such as a mixing mixer. .

The base treatment method of the metal material of the present invention (hereinafter referred to simply as the "base treatment method of the present invention") includes a coating step of applying the above-described base treatment agent of the present invention to a metal material surface,

After the said coating process, it is a base material processing method of the metal material which has a drying process which dries without washing with water and forms a base film.

<Application process>

The said application process is a process of apply | coating the base treatment agent of this invention mentioned above to the metal material surface.

In the base treatment method of the present invention, the coating method in the coating step is not particularly limited, and for example, by a method such as spray coat, dip coat, roll coat, curtain coat, spin coat, or a combination thereof. It can be applied.

In the base treatment method of the present invention, the conditions for use of the base treatment agent of the present invention in the coating step are not particularly limited.

For example, it is preferable that it is 10-90 degreeC, and, as for the temperature of the processing agent and metal material at the time of apply | coating a ground treatment agent, it is more preferable that it is 20-60 degreeC. When temperature is 60 degrees C or less, since use of unnecessary energy can be suppressed, it is preferable from an economical viewpoint. In addition, the time to apply a base treatment agent can be set suitably.

<Drying process>

The said drying process is a process of drying without washing with water and forming a base film.

In the ground treatment method of the present invention, the drying temperature is not particularly limited because it depends on the solvent used. For example, when water is used as the solvent, the drying temperature is preferably in the range of 50 to 200 ° C.

Moreover, as a film thickness of the base film obtained, 0.01-50 micrometers is preferable and 0.1-20 micrometers is more preferable.

Plating process

The ground treatment method of the present invention includes a step of performing a metal plating composed of Ni and / or Co on the surface of a metal material and washing with water (plating step) prior to the coating step in an electrolytic or electroless manner. The adhesion between the material and the resin, in particular under high temperature, can be further improved.

Although the adhesion amount of the metal plating which consists of Ni and / or Co is not specifically limited, 1-1,000,000 mg / m <2> is preferable and 10-1,000 mg / m <2> is more preferable. If it exists in the said range, adhesiveness will improve more.

Moreover, you may provide a drying process after water washing as needed. Since drying temperature differs depending on the solvent to be used, it is not specifically limited, For example, when water is used as a solvent, it is preferable that it is the range of 50-200 degreeC.

The metal plating composed of Ni and / or Co can be produced by a known electroplating method or a plating method such as an electroless plating method.

Ni and / or Co plating by the electrolytic method can be performed by using an electroplated material as a cathode, and energizing after filling a plating liquid between an anode and a cathode. Ni and / or Co metals are used on the anode side, but an insoluble anode may be used in some cases.

The Ni plating bath is generally used having a composition composed of nickel sulfate, nickel chloride and boric acid called a watt bath. In addition, cobalt sulfate (including hydrate) may be added to the Ni plating bath to obtain Ni-Co alloy plating.

Ni and / or Co plating by an electroless method can be performed by immersing a to-be-plated material in the process liquid containing Ni and / or Co salt, a complexing agent, and a reducing agent as a main component for predetermined time.

Ni plating is generally a hypophosphite bath using hypophosphite as a reducing agent.

In the case where the metal material is a copper material, there is a problem that it is difficult to directly deposit on the copper in the hypophosphite bath. Therefore, the hypophosphite described in Japanese Patent Application Laid-Open No. 2000-256866, which can be directly plated on copper, or a method of two-stage treatment in which a catalyst is applied by a palladium lean aqueous solution prior to electroless Ni plating. In addition, a method of using an aqueous chemical agent containing dimethylamine borane as a second reducing agent and gluconic acid as a complexing agent, or further, the nickel compound and / or described in JP-A-6-101054 It is also possible to use a method using an aqueous chemical agent containing a cobalt compound and thioureas.

As for the method of using the above-mentioned nickel compound and / or cobalt compound and an aqueous plating solution containing thioureas, the nickel compound used includes nickel acetate, nickel ammonium sulfate, nickel benzoate, nickel bromide, nickel carbonate, chloride Nickel, nickel citrate, nickel hydroxide, nickel iodide, nickel nitrate, nickel oxalate, nickel oxide, nickel stearate, nickel sulfamate, nickel sulfate and the like can be exemplified.

As the cobalt compound, cobalt acetate, ammonium cobalt chloride, cobalt ammonium sulfate, cobalt bromide, cobalt carbonate, cobalt chloride, diammonium cobalt sulfate, cobalt formate, cobalt naphthenate, cobalt sulfate, cobalt oleate, cobalt oxalate, cobalt oxide, Cobalt stearate, cobalt sulfate, etc. can be illustrated.

As for the addition amount of the 1 or more types of compound chosen from a nickel compound and / or a cobalt compound to the plating process liquid, about 0.1-40 mass% is preferable, and about 0.5-20 mass% is more preferable.

In addition to at least one compound selected from nickel compounds and cobalt compounds, it is necessary to blend thioureas. Thereby, the precipitation potential of a copper-based material can be lowered and substitution with nickel or cobalt can be made possible.

Examples of thioureas include thiourea, dimethylthiourea, trimethylthiourea, allylthiourea, acetylthiourea, ethylenethiourea, and phenylthiourea, and one or more of these may be used. As for the addition amount to a plating process liquid, about 0.1-20 mass% is preferable, and about 0.5-10 mass% is more preferable.

In addition to at least one compound or thioureas selected from nickel compounds and / or cobalt compounds, a chelating agent may be further added as necessary. Specifically, ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic acid disodium salt (EDTA.2Na), hydroxyethylethylenediamine triacetic acid (HEDTA), diethylenetriamine octanoic acid (DPTA), triethylenetetramine hexaacetic acid ( TTHA), ethylenediaminetetrapropionic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, such as nitrilomic acetic acid (NTA), iminodiacetic acid (IDA), iminodipropionic acid (IDP), aminotrimethylene Phosphonic acid, aminotrimethylenephosphonic acid sodium salt, methylamine, ethylamine, propylamine, dimethylamine, trimethylamine, dimethylethylamine, benzylamine, 2-naphthylamine, isobutylamine, isoamylamine, methylenediamine , Ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, cinnamilamine, p-methoxycinnamilamine, ammonia, hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid trisodium salt, citric acid, tartaric acid, malic acid, malonic acid Glycine, alanine, N-methylglycine, glycosamine, dimethylglycine, hydantophosphoric acid, aminogilic acid, β-alanine, etc., valine, norvaline, leucine, norleucine, isoleucine, serine, cysteine, asparagine, aspartic acid , Glutamic acid, ornithine, lysine, arginine, glutamine, diaminopropionic acid, citrulline, hydroxy-L-lysine, diaminobutyric acid, aminoadipic acid, cannaline, kynurenine, diaminopimeric acid, homocysteine , Histidine, methionine and the like, aspartyl-histidine, alanyl-alanine, alanyl-β-alanine, β-alanyl-β-alanine, glycyl-lysine, alanyl-ornithine, lysyl-lysine, ornithyl -Ornithine, glycyl-ornithine, β-alanyl-lysyl-lysine, orni Imidazoline, 2,4,5-triphenyl-2-imidazoline, 2,2'-bis (2-imidazoline), pyridine, such as yl-lysyl-lysine, glycyl-ornithyl-ornithine , Morpholine, bipyridyl, pyrazole, triazine and the like.

It is preferable to make about 0.1-50 mass% in the plating process liquid, and, as for the compounding quantity of a chelating agent, about 0.5-10 mass% is more preferable.

Although the pH of a plating process liquid is not specifically limited, pH 1-8 are preferable. When performing pH adjustment, if necessary, it is by using an alkaline compound such as HCl, an acid such as H ₂ SO ₄ or NaOH, NH _3.

In addition, it is also possible to add surfactants such as nonionic, cationic, anionic and amphoteric into the plating solution, thereby lowering the surface tension of the catalyst liquid and improving the catalytic activity on the surface of the copper-based material. It can be made uniform.

In addition, as a pH buffer, hydrochloric acid-potassium chloride, potassium hydrogen phthalate-hydrochloric acid, potassium hydrogen phthalate-sodium hydroxide, potassium dihydrogen phosphate-sodium hydroxide, boric acid-sodium hydroxide, sodium bicarbonate-sodium hydroxide, disodium hydrogen phosphate-sodium hydroxide, It is also possible to add sodium hydroxide-potassium chloride, tris (hydroxymethyl) aminomethane-hydrochloric acid, sodium acetate-acetic acid and the like. Surfactant and pH buffer can be used individually or in mixture suitably as needed.

In the treatment method using the plating treatment liquid, the object to be treated is immersed in a catalyst liquid at a liquid temperature of about 10 to 90 ° C, preferably about 25 to 70 ° C for about 10 seconds to about 20 minutes, and the plating solution is stirred as necessary. By rocking the plated object, the plated film can be formed uniformly on the surface of the plated object.

The metal material with a base film of this invention is a metal material obtained by surface treatment using the base treatment agent of this invention mentioned above, It is preferable that it is a metal material obtained by processing by the base treatment method of this invention mentioned above.

The undercoat on the metal material obtained by the undertreatment method of the present invention is near the surface on the metal material side of the undercoat (preferably within 2 μm, more preferably within 1 μm from the surface on the metal material side of the undercoat). It is preferable to contain a metal atom derived from the treated metal material. More specifically, it is preferable that metal atoms derived from the metal material are concentrated in the surface layer on the metal material side of the base film, and a part of the metal atoms are present in the metal state. For example, when copper foil is used as a metal material, copper atoms are concentrated in the surface layer on the metal material side of the underlying film, and a part thereof is present in the metal state. The same applies to the case where other metal materials (for example, aluminum and nickel) are used.

In addition, when the base treating agent contains, as the oxidizing agent (C), a group IV compound having an oxidation number of 4 or 5 and / or a group VIA element having an oxidation number of 6, the surface near the surface of the metal material side of the base coating ( In the same range), at least one metal atom selected from the group consisting of vanadium, niobium, tantalum, molybdenum, and tungsten is present in concentration. That is, in the vicinity of the surface of the base material on the metal material side, metal elements such as vanadium and metal atoms derived from the metal material are concentrated.

Although the mechanism by which such a film structure is obtained is not clear, at the time of the ground treatment, the metal ions eluted from the metal material by the oxidizing agent (C) are reduced by the reducing action of the compound (A) in the vicinity of the metal material, and again. The possibility of being in a metal state and inserted into the base film can be considered. As a result, in the vicinity of the metal material of the undercoat, a coexistence area between the undercoat and the metal material is formed, which may be considered to be a cause of the development of adhesion between the undercoat and the metal material of the present invention.

In the metal material treated with the substrate treatment agent for metal materials of the present invention, unlike the prior art, roughening of the surface of the metal material is suppressed.

In particular, in printed wiring boards, when used in applications in which high-frequency waveforms are used as signals, surface roughness of Ra is preferably 0.35 µm or less in terms of the skin effect, as disclosed in Japanese Patent Application Laid-Open No. 7-314603. Preferably, copper foil of 0.2 µm or less is used.

According to the treatment using the substrate treatment agent for metal materials of the present invention, the adhesion with the resin can be improved while suppressing the change of the metal surface roughness, specifically, the metal surface roughness after the treatment with respect to the metal surface roughness Ra ₀ before the treatment. The change (ΔRa) of (Ra ₁ ) may be 0.5 μm or less, preferably 0.3 μm or less.

In the roughening method by etching conventionally used, even when the surface of a metal material is harmonized and copper foil whose surface roughness is 0.2 micrometer or less is used, the surface average roughness Ra exceeds 1 micrometer normally, The same effect is not obtained.

As the measuring method of ΔRa, the metal material with base film of the present invention and the metal material before treatment were embedded in the resin, cross-sectional SEM observation was performed at a magnification of 10,000 times, and Ra ₁ and Ra ₀ were calculated from the metal surface roughness profiles, respectively. ΔRa (= Ra ₁ -Ra ₀ ) was calculated therefrom.

In addition, average surface roughness Ra (arithmetic mean surface roughness Ra) is a value represented by the abbreviation of Ra by JIS B 0601, and shows the average value of the absolute value deviation from the average line of surface roughness values.

The base film formed on the metal material by the above-described method is excellent in flatness. Specifically, the surface average roughness Ra of the undercoat is preferably 0.5 μm or less, and more preferably 0.3 μm or less. Regarding the lower limit, the smaller the smaller, the better, and 0 is preferable. If the surface average roughness of the underlying film is within the above range, a resin layer such as a prepreg laminated on the underlying film at the time of manufacturing a printed wiring board can be made thin and economical.

The laminated member of this invention is a laminated member which has the above-mentioned metal film with base material of this invention, and the resin layer provided on the base film.

1 is a schematic cross-sectional view showing a laminated member of the present invention. The laminated member 1 shown in FIG. 1 is provided on the metal material 2, the base film 3 formed on the metal material 2 using the base treatment agent of this invention, and the base film 3 It has the resin layer 4.

The material of the resin layer is not particularly limited, and for example, acrylic resin, polyolefin resin, polyester resin, polyvinylidene chloride, polycarbonate, polysulfone, polyphenylene sulfide, liquid crystal polymer, epoxy resin, phenol resin, urea Resins, melamine resins, polyimides, polyurethanes, bismaleimide-triazine resins, polyphenylene ethers, cyanate esters, aramid fibers, fluorine resins, aromatic polyether ketone resins, nylon resins, and the like. You may use individually by species and may use 2 or more types together. These resins may be modified by a functional group.

In addition, the resin layer may contain fillers, such as glass fiber, calcium carbonate, aramid fiber, and graphite, etc. from a viewpoint of strengthening improvement.

Prepreg is mentioned as one of the preferable aspects of the material of a resin layer. The prepreg means that the thermosetting resin is impregnated into a sheet-like fibrous base to be in a semi-cured state.

Examples of the material of the sheet-like fiber base include fibers of inorganic materials such as E glass, D glass, S glass and Q glass, fibers of organic materials such as aramid, polyimide, polyester and polytetrafluoroethylene, and mixtures thereof. Can be mentioned. These fibrous bases have the shape of, for example, woven fabrics, nonwovens, rovings, chopped strand mats, and surfacing mats, but the materials and shapes are intended for use and performance of the target moldings. According to the necessity, it is possible to combine single or two or more kinds of materials and shapes as necessary.

Although it does not specifically limit as a thermosetting resin, An epoxy resin, a phenol resin, a polyester resin, a polyimide resin, a bismaleimide triazine resin, a cyanate resin, or these modified substances are mentioned preferably.

The laminated member of the present invention can be obtained by bonding a resin layer to the metal material with a base film of the present invention described above through a base film.

The method of joining is not specifically limited, Specifically, when a resin layer is an epoxy resin, (1) After apply | coating uncured liquid epoxy resin to the base film of the metal material with a base film, The coating method which forms a resin layer by drying and hardening, (2) The laminated method which heat-presses after laminating an epoxy resin film so that a base film and an epoxy resin film may contact the base film of the metal material with a base film, ( 3) Injection molding adhesion method etc. which form an epoxy resin layer by inject | pouring out the epoxy resin melt | dissolved in a metal mold | die are set for a metal material with a base film in contact with a base film, and the like.

In the laminated member of the present invention, the adhesive strength between the metal material and the resin layer bonded through the base film is excellent. In particular, it has the characteristic that the adhesiveness under high temperature is excellent. In addition, since the formed undercoat has excellent acid resistance, problems such as pink rings generated during the production of a printed wiring board are suppressed. In addition, the undercoat also has excellent moisture resistance, and exhibits excellent adhesive strength in a high humidity environment.

As described above, the substrate treatment agent for metal materials of the present invention improves the adhesiveness between the metal material and the resin such as prepreg, especially at high temperatures, without roughening the surface of the metal material. Moreover, in the processing method using this base treatment agent, generation | occurrence | production of waste liquid etc. is suppressed compared with the prior art, and environmental load is small. Moreover, since this base treatment agent can be applied suitably to a coating method, since the number of process steps can be reduced and processing time can be shortened compared with the past, productivity improves dramatically.

Example

An Example is shown to the following and this invention is concretely demonstrated to it. However, the present invention is not limited to these.

1. Fabrication of metal material with base film

As shown in the examples and comparative examples described later, the following treatment steps were performed on the material to be treated using various base treatment agents to obtain a metal material with a base film.

[Treatment Material]

The symbol and description of a to-be-processed material are shown below.

Copper foil: Electrolytic copper foil (purity 99.8 mass% or more), thickness 18 micrometers, Ra 0.3 micrometer

Aluminum foil (purity 99% by mass or more), thickness 18 μm

Aluminum foil (purity 99% by mass or more), thickness 50 μm

Nickel foil (purity 99% by mass or more), thickness 20 μm

304 stainless steel foil, 20 μm thick

Stainless steel 430 foil, 20 μm thick

[Processing process]

As the treatment step, the following steps (1) to (7) were performed in order.

(1) 5 mass% aqueous solution prepared using degreasing (60 degreeC, 10 minutes, an immersion method, the fine cleaner 4360 (trademark) by Nippon Parker Co., Ltd. was used.) Moreover, when the to-be-processed material is aluminum foil, Nippon Parkarizing A 3 mass% aqueous solution prepared using Fine Cleaner 315 (registered trademark) was manufactured.)

(2) washing with water (room temperature, 30 seconds, immersion method)

(3) Pickling (at room temperature, 30 seconds, dipping, using a 10% aqueous solution prepared using commercial sulfuric acid)

(4) washing with water (room temperature, 30 seconds, immersion method)

(5) moisture removal

(6) Surface treatment (as described later)

(7) Heat drying (predetermined temperature, five minutes, hot air oven)

[Surface treatment]

(Example 1)

Aqueous solution containing 0.2 mass% of a molten form monohydrate as a compound (A), 30 mass% of acrylonitrile butadiene styrene rubber as an elastomer (B), and 0.5 mass% of ammonium metavanadate (V) as an oxidizing agent (C) are adjusted. Then, the ground treatment agent (Ia) was obtained.

As the elastomer (B), an aqueous dispersion of acrylonitrile butadiene styrene rubber having a carboxyl group and a methylol group (solid content concentration: 47%, pH: 8, viscosity: 45 cP, Tg: 18 ° C, specific gravity: 1.01, anionic) Surfactant) was used to adjust the content of the elastomer (B) in the aqueous solution.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base treatment agent (I-a) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 2.5 micrometers.

(Example 2)

0.2 mass% of fluoroglucinol (anhydrous) as a compound (A), 30 mass% of acrylonitrile butadiene styrene rubbers as an elastomer (B), and 0.5 mass% of ammonium metavanadate (V) as an oxidizing agent (C) The aqueous solution to adjust was adjusted and the base treatment agent (Ib) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heat-drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-b) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 2.5 micrometers.

(Example 3)

An aqueous solution containing 0.2% by mass of catechol as compound (A), 30% by mass of acrylonitrile butadiene styrene rubber as elastomer (B), and 0.5% by mass of ammonium metavanadate (V) as oxidizing agent (C) And the ground treatment agent (Ic) were obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-c) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 2.5 micrometers.

(Example 4)

An aqueous solution containing 0.2% by mass of amidol as compound (A), 30% by mass of acrylonitrile butadiene styrene rubber as elastomer (B), and 0.5% by mass of ammonium metavanadate (V) as the oxidizing agent (C) And base treatment agent (Id) were obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-d) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 2.5 micrometers.

(Example 5)

The aqueous solution containing 0.1 mass% of tannic acid as a compound (A), 15 mass% of acrylonitrile butadiene styrene rubber as an elastomer (B), and 0.25 mass% of ammonium metavanadate (V) as an oxidizing agent (C) is adjusted, A ground treatment agent (Ie) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-e) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 0.5 micrometer.

(Example 6)

The aqueous solution containing 1 mass% of tannic acid as a compound (A), 30 mass% of acrylonitrile butadiene styrene rubber as an elastomer (B), and 0.5 mass% of ammonium metavanadate (V) as an oxidizing agent (C) is adjusted, A ground treatment agent (If) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heat-drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-f) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 1.0 micrometer.

(Example 7)

0.05 mass% of 2,4-dihydroxy benzoic acid as a compound (A), 30 mass% of acrylonitrile butadiene styrene rubber as an elastomer (B), and 0.5 mass% of ammonium metavanadate (V) as an oxidizing agent (C) The aqueous solution to contain was adjusted and the base treatment agent (Ig) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-g) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 1.0 micrometer.

(Example 8)

0.3 mass% of 3,4-dihydroxy benzoic acid as compound (A), 30 mass% of acrylonitrile butadiene styrene rubber as elastomer (B), and 0.5 mass% of ammonium metavanadate (V) as an oxidizing agent (C) The aqueous solution to contain was adjusted and the base treatment agent (Ih) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base treatment agent (I-h) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 1.0 micrometer.

(Example 9)

0.5 mass% of 3,5-dihydroxy benzoic acid as a compound (A), 30 mass% of acrylonitrile butadiene styrene rubber as an elastomer (B), and 0.5 mass% of ammonium metavanadate (V) as an oxidizing agent (C) The aqueous solution to contain was adjusted and the base treatment agent (Ii) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heat-drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-i) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 1.0 micrometer.

(Example 10)

Without using an oxidizing agent (C), the aqueous solution containing 1 mass% of tannic acid as a compound (A), and 15 mass% of acrylonitrile butadiene styrene rubber as an elastomer (B) was adjusted, and the base treatment agent (I-j) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base treatment agent (I-j) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 0.5 micrometer.

(Example 11)

After heating and drying (temperature: 100 DEG C), the surface treatment agent (I-a) (temperature 25 DEG C) was applied to the surface of an aluminum foil having a thickness of 18 mu m by bar coating so that the film thickness became 2.5 mu m.

(Example 12)

Aqueous solution containing 0.4 mass% of a molybdenum monohydrate as a compound (A), 30 mass% of acrylonitrile butadiene styrene rubber as an elastomer (B), and 0.5 mass% of ammonium metavanadate (V) as an oxidizing agent (C) are adjusted. Then, the ground treatment agent (Ik) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-k) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 13)

An aqueous solution containing 0.4% by mass of the molybdenum monohydrate as the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber as the elastomer (B), and 0.5% by mass of the ammonium ammonium hexamolybdate tetrahydrate as the oxidizing agent (C) And the base treatment agent (Il) were obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-1) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 14)

An aqueous solution containing 0.4% by mass of the molar compound monohydrate as the compound (A), 30% by mass of acrylonitrile butadiene styrene rubber as the elastomer (B), and 0.4% by mass of ammonium metatungstate as the oxidizing agent (C) was adjusted. Treatment agent (Im) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heat-drying (temperature: 150 degreeC), the surface treatment which apply | coats the base material (I-m) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 15)

An aqueous treatment solution containing 0.2% by mass of the molybdenum monohydrate as the compound (A), 30% by mass of the acrylic rubber as the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) as the oxidizing agent (C) was adjusted. (In) was obtained. As the elastomer (B), an aqueous dispersion of an acrylic rubber having a carboxyl group (solid content concentration: 48%, pH: 5, viscosity: 120 cP, Tg: 0 ° C, specific gravity: 1.07, surface tension: 42 dyne / cm, anion System surfactant) was used to adjust the content of the elastomer (B) in the aqueous solution.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base treatment agent (I-n) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 16)

An aqueous treatment solution containing 0.2% by mass of the molybdenum monohydrate as the compound (A), 30% by mass of the acrylic rubber as the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) as the oxidizing agent (C) was adjusted. (Io) was obtained. As the elastomer (B), an aqueous dispersion of an acrylic rubber having a carboxyl group (solid content concentration: 52%, pH: 6.1, viscosity: 55 cP, Tg: -15 ° C, specific gravity: 1.07, surface tension: 36.5 dyne / cm, Anionic surfactant-containing) was used to adjust the content of the elastomer (B) in the aqueous solution.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-o) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 17)

An aqueous treatment solution containing 0.2% by mass of the molybdenum monohydrate as the compound (A), 30% by mass of the acrylic rubber as the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) as the oxidizing agent (C) was adjusted. (Ip) was obtained. As the elastomer (B), an aqueous dispersion of an acrylic rubber having a carboxyl group (solid content concentration: 50.5%, pH: 4.5, viscosity: 40 cP, Tg:-15 ° C, specific gravity: 1.06, surface tension: 38 dyne / cm, Anionic surfactant-containing) was used to adjust the content of the elastomer (B) in the aqueous solution.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-p) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 18)

An aqueous treatment solution containing 0.2% by mass of the molybdenum monohydrate as the compound (A), 30% by mass of the acrylic rubber as the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) as the oxidizing agent (C) was adjusted. (Iq) was obtained. As the elastomer (B), an aqueous dispersion of acrylic rubber having a carboxyl group (solid content concentration: 50%, pH: 3.5, viscosity: 200 cP, Tg: -25 ° C, specific gravity: 1.06, anionic surfactant and nonionic system) Surfactant) was used to adjust the content of the elastomer (B) in the aqueous solution.

After heat-drying (temperature: 150 degreeC), the surface treatment which apply | coats the base material (I-q) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 19)

An aqueous solution containing 0.4% by mass of the monohydrate monohydrate as the compound (A), 30% by mass of the acrylic rubber as the elastomer (B), and 0.2% by mass of ammonium metatungstate as the oxidizing agent (C) was adjusted. Got. As the elastomer (B), an aqueous dispersion of an acrylic rubber having a carboxyl group (solid content concentration: 48.5%, pH: 8, viscosity: 70 cP, particle size: 0.24 µm, Tg: -29 ° C, specific gravity: 1.04, surface tension: 42 dyne / cm and containing an anionic surfactant) to adjust the content of the elastomer (B) in the aqueous solution.

After heating and drying (temperature: 150 degreeC), the surface treatment which apply | coats the base material (I-r) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 10.0 micrometers.

(Example 20)

An aqueous solution containing 0.2% by mass of the molar compound monohydrate as the compound (A), 30% by mass of nitrile butadiene rubber as the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) as the oxidizing agent (C) was adjusted. Treatment agent (Is) was obtained. As the elastomer (B), an aqueous dispersion of a nitrile butadiene rubber having a methylol group (solid content concentration: 47%, pH: 6.6, viscosity: 65 cP, particle size: 0.06 to 0.25 μm, Tg: -30 ° C, specific gravity: 0.99 , Containing anionic surfactant), to adjust the content of the elastomer (B) in the aqueous solution.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-s) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 21)

An aqueous solution containing 0.2% by mass of the molar compound monohydrate as the compound (A), 30% by mass of styrene-butadiene rubber as the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) as the oxidizing agent (C) was adjusted. Treatment agent (It) was obtained. As the elastomer (B), an aqueous dispersion of styrene-butadiene rubber having a methylol group (solid content concentration: 40%, pH: 9.1, viscosity: 50 cP, Tg: 10 ° C, specific gravity: 1.01, surface tension: 70 dyne / cm ) Was used to adjust the content of the elastomer (B) in the aqueous solution.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-t) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 22)

0.2% by mass of the monohydrate monohydrate as the compound (A), 30% by mass of acrylonitrile butadiene styrene rubber as the elastomer (B), 0.5% by mass of ammonium metavanadate (V) as the oxidizing agent (C), and 0.5% by mass of phosphoric acid The aqueous solution to contain was adjusted and the base treatment agent (Iu) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heat-drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-u) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 23)

0.2% by mass of a monohydrate monohydrate as the compound (A), 30% by mass of acrylonitrile butadiene styrene rubber as the elastomer (B), 0.5% by mass of ammonium metavanadate (V) as the oxidizing agent (C), and 1.0% by mass of ammonium zirconium carbonate An aqueous solution containing% was adjusted to obtain a ground treatment agent (Iv). In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 150 degreeC), the surface treatment which apply | coats the base treatment agent (I-v) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 24)

After heating and drying (temperature: 100 DEG C), the surface treatment agent (I-k) (temperature 25 DEG C) was applied on the surface of aluminum foil having a thickness of 50 mu m by bar coating so that the film thickness was 6.0 mu m.

(Example 25)

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base treatment agent (I-a) (temperature 25 degreeC) on the nickel foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 26)

In the above-described treatment step, after the pickling and washing step, the electroless nickel plating bath (containing 5% by mass of nickel sulfate hexahydrate and 5% by mass of thiourea) was adjusted to pH = 3 with sulfuric acid without removing water. Copper foil was immersed for 5 minutes at 30 degreeC of processing temperature in the aqueous solution), and the copper foil which has a nickel plating layer was produced.

Then, after washing with water and removing water, the surface treatment is performed by applying a base coating agent (Ik) (temperature 25 ° C.) on the surface of the nickel plated layer with a bar coating so that the film thickness after heating and drying (temperature: 100 ° C.) is 6.0 μm. It was done.

(Example 27)

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (I-k) (temperature 25 degreeC) on SUS304 foil surface was performed by bar coating so that a film thickness might be 6.0 micrometer.

(Example 28)

After heating and drying (temperature: 100 DEG C), the surface treatment was performed by applying a base coating agent (I-k) (temperature 25 DEG C) on the surface of SUS430 foil so as to have a film thickness of 6.0 mu m.

(Example 29)

An aqueous solution containing 0.5% by mass of thiourea as compound (A), 30% by mass of acrylonitrile butadiene styrene rubber as elastomer (B), and 0.5% by mass of ammonium metavanadate (V) as oxidizing agent (C) And the ground treatment agent (II-a) were obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 150 degreeC), the surface treatment which apply | coats the base material (II-a) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 30)

An aqueous solution containing 0.5% by mass of thiourea as the compound (A), 30% by mass of acrylonitrile butadiene styrene rubber as the elastomer (B), and 1% by mass of hexamolemonium hexaammonium tetrahydrate as the oxidizing agent (C) were adjusted. Base treatment agent (II-b) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heat-drying (temperature: 150 degreeC), the surface treatment which apply | coats the base treatment agent (II-b) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 31)

The aqueous solution containing 0.5 mass% of thiourea as a compound (A), 30 mass% of acrylonitrile butadiene styrene rubber as an elastomer (B), and 0.4 mass% of ammonium metatungstate as an oxidizing agent (C) was adjusted, (II-c) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heat-drying (temperature: 150 degreeC), the surface treatment which apply | coats the base treatment agent (II-c) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 32)

An aqueous solution containing 0.1% by mass of thiourea as the compound (A), 30% by mass of acrylic rubber as the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) as the oxidizing agent (C) was adjusted. II-d). In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 19. FIG.

After heating and drying (temperature: 150 degreeC), the surface treatment which apply | coats the base treatment agent (II-d) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 33)

Aqueous solution containing 0.5 mass% of N-methylthiourea as a compound (A), 30 mass% of acrylonitrile butadiene styrene rubber as an elastomer (B), and 0.5 mass% of ammonium metavanadate (V) as an oxidizing agent (C) Was adjusted to obtain a ground treatment agent (II-e). In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 150 degreeC), the surface treatment which apply | coats the base material (II-e) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 34)

0.5 mass% of 1-allyl-2-thiourea as the compound (A), 30 mass% of acrylonitrile butadiene styrene rubber as the elastomer (B), and 0.5 mass% of ammonium metavanadate (V) as the oxidizing agent (C) The aqueous solution to contain was adjusted and the base treatment agent (II-f) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heat-drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (II-f) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 35)

0.5 mass% of 1-allyl-3- (2-hydroxyethyl) thiourea as compound (A), 30 mass% of acrylonitrile butadiene styrene rubber as elastomer (B), and ammonium metavanadate as oxidizing agent (C) (V) The aqueous solution containing 0.5 mass% was adjusted, and the base treatment agent (II-g) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 150 degreeC), the surface treatment which apply | coats the base material (II-g) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Example 36)

An aqueous solution containing 0.5% by mass of thiourea as compound (A), 30% by mass of acrylic rubber as elastomer (B), and 0.5% by mass of ammonium ammonium hexamolybdate tetrahydrate as oxidizing agent (C) was adjusted to provide a ground treatment agent (II). -h). In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 19. FIG.

In the above-described treatment step, after the pickling and washing step, the electroless nickel plating bath (containing 5% by mass of nickel sulfate hexahydrate and 5% by mass of thiourea) was adjusted to pH = 3 with sulfuric acid without removing water. Copper foil was immersed for 5 minutes at 30 degreeC of processing temperature in the aqueous solution), and the copper foil which has a nickel plating layer was produced.

After that, after washing with water and removing water, the surface coating agent (II-h) (temperature: 25 ° C) is coated on the surface of the nickel plated layer by bar coating so that the film thickness is 6.0 µm after heating and drying (temperature: 150 ° C). The treatment was performed.

(Example 37)

An aqueous solution containing 0.5% by mass of thiourea as compound (A), 30% by mass of acrylic rubber as elastomer (B), and 0.5% by mass of ammonium ammonium hexamolybdate tetrahydrate as oxidizing agent (C) was adjusted to provide a ground treatment agent (II). -i) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 19. FIG.

After heat-drying (temperature: 150 degreeC), the surface treatment which apply | coats the base material (II-i) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Comparative Example 1)

Without using compound (A), the aqueous solution containing 15 mass% of acrylonitrile butadiene styrene rubber as an elastomer (B) and 0.25 mass% of ammonium metavanadate (V) as an oxidizing agent (C) was adjusted, and the base treatment agent (III-a) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (III-a) (temperature 25 degreeC) on copper foil surface was performed by bar coating so that a film thickness might be set to 1.0 micrometer.

(Comparative Example 2)

Without using a compound (A) and an oxidizing agent (C), the aqueous solution containing 30 mass% of acrylonitrile butadiene styrene rubbers as an elastomer (B) was adjusted, and the base treating agent (III-b) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (III-b) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 2.5 micrometers.

(Comparative Example 3)

Without using an elastomer (B), an aqueous solution containing 0.2% by mass of the monohydrate monohydrate as the compound (A) and 0.5% by mass of ammonium metavanadate (V) as the oxidizing agent (C) was adjusted to provide a base treatment agent (III- c) was obtained.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base treatment agent (III-c) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 0.1 micrometer.

(Comparative Example 4)

Without using compound (A), the aqueous solution containing 30 mass% of acrylonitrile butadiene styrene rubber as an elastomer (B) and 0.5 mass% of ammonium metavanadate (V) as an oxidizing agent (C) was adjusted, and the base treatment agent (III-d) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base treatment agent (III-d) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Comparative Example 5)

Without using a compound (A) and an oxidizing agent (C), the aqueous solution containing 30 mass% of acrylonitrile butadiene styrene rubbers as an elastomer (B) was adjusted, and the base treating agent (III-e) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 1.

After heating and drying (temperature: 100 degreeC), the surface treatment which apply | coats the base material (III-e) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Comparative Example 6)

Without using an elastomer (B), an aqueous solution containing 0.5% by mass of thiourea as compound (A) and 0.5% by mass of ammonium menavanadate (V) as oxidizing agent (C) was adjusted to provide a ground treatment agent (III-f). )

After heating and drying (temperature: 150 degreeC), the surface treatment which apply | coats the base material (III-f) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 0.1 micrometer.

(Comparative Example 7)

Without using a compound (A) and an oxidizing agent (C), the aqueous solution containing 30 mass% of acrylic rubbers as an elastomer (B) was adjusted, and the ground treatment agent (III-g) was obtained. In addition, as elastomer (B), content was adjusted using the same water dispersion as Example 19. FIG.

After heat-drying (temperature: 150 degreeC), the surface treatment which apply | coats the base material (III-g) (temperature 25 degreeC) on the copper foil surface was performed by bar coating so that a film thickness might be set to 6.0 micrometers.

(Comparative Example 8)

(4) Copper foil is processed in blackening treatment bath (an aqueous solution containing 30 g / L sodium chlorite, 10 g / L trisodium phosphate 12-hydrate, and 15 g / L sodium hydroxide) in the said processing process, after performing to water washing. It was immersed for 3 minutes at the temperature of 90 degreeC. Then, the blackening process sample was produced by heat-drying at 100 degreeC for 5 minutes in the hot air oven after washing with water.

2. Evaluation of Metallic Materials with Undercoat

Various evaluation was performed as follows about the metal material with a base film obtained in Examples 1-37 and Comparative Examples 1-8.

(1) Evaluation of arithmetic mean surface roughness of metal material surface and arithmetic mean surface roughness of following film

The sample which filled the obtained base material with a base film to the epoxy resin was produced, and the cross section of the sample was observed using the scanning electron microscope (magnification: 10000 times), and the arithmetic mean of the surface of the metal material of the base material with a base film was observed. the surface roughness (R _a) was confirmed that the estimate of a bar, which is also the sample R is _a smooth surface of less than 0.50 ㎛.

In Example 12, the arithmetic mean surface roughness Ra of the metal material surface of the metal material with base film was 0.3 μm, and the change (ΔRa) of the metal material surface roughness before and after the treatment was 0.0 μm, Arithmetic mean surface roughness (Ra) was also very flat at 0.1 mu m.

In addition, in Example 31, the arithmetic mean surface roughness Ra of the metal material surface of the metal material with a base film was 0.3 micrometer, and the change (△ Ra) of the metal material surface roughness before and after a process was 0.0 micrometer, Arithmetic mean surface roughness (Ra) was also very flat at 0.1 mu m.

(2) adhesive

A glass cloth based epoxy resin sheet (manufactured by Hitachi Chemical Co., Ltd., product name: GEA-679N) having a thickness of about 100 μm is pasted to the obtained metal film with a base film, and the heating temperature is 180 ° C., the pressure is 45 kgf / cm 2, and the heating is performed. It press-bonded on the conditions of time 1 hour, and obtained the laminated member of metal material-epoxy resin.

<Primary adhesiveness>

This laminated member was cut | disconnected to 1 cm width, and the peeling strength was measured by carrying out the 90 degree peeling test which pulled the part of the copper material unbonded partially in the vertical direction in the state which fixed the glass cloth base epoxy resin sheet.

<Heat resistant secondary adhesiveness>

The laminated member was cut to a width of 1 cm, heated in an oven at 275 ° C. for 1 minute, and then subjected to a 90-degree peel test similar to that of the primary adhesiveness to measure peel strength.

<Evaluation Criteria>

Peeling strength of 0.4 kgf / cm or less was evaluated as inferior to adhesiveness. The obtained results are shown in Table 1 below.

As is clear from Table 1, the base material-coated copper material (Examples 1 to 36) obtained by the base treatment method of the present invention using the base treatment agent of the present invention is laminated with an epoxy resin, and the laminated member of the present invention. In this case, it was confirmed that excellent adhesion between the metal material and the epoxy resin, particularly excellent adhesion under high temperature.

On the other hand, in Comparative Examples 1-7, both the primary adhesiveness and the heat-resistant secondary adhesiveness were inferior. Moreover, although the primary adhesiveness was favorable in the comparative example 8 which performed blackening process, it was confirmed that heat-resistant secondary adhesiveness was inferior.

<Long term heat resistance secondary adhesive test>

Copper material-epoxy resin by the same method as described in said (2) using Example 19, 24-28, 31, 32, 36 and 37 mentioned above and the base material with a base film obtained by the comparative example 5 The laminated member of was obtained.

The laminated member was cut to 1 cm in width, heated in an oven at 180 ° C. for 48 hours, and in a state in which the glass cloth base epoxy resin sheet was fixed, and 90 ° pulling the portion of the copper material which was not bonded to each other in the vertical direction. A peel test was conducted to determine the peel strength. The obtained results are shown in Table 2 below.

As is clear from Table 2, when the base material copper coating material of the present invention obtained by the base treatment method of the present invention using the base treatment agent of the present invention is laminated with an epoxy resin to form the lamination member of the present invention, It was confirmed to exhibit excellent long-term heat resistance between the material and the epoxy resin.

In contrast, Comparative Example 5 did not show any adhesiveness.

Moisture resistance secondary adhesion test

Using the above-described Examples 15 to 19, 23, 24, 26, 29, and 32 and the base film-bearing metal material obtained in Comparative Examples 5, 7, and 8, copper was prepared in the same manner as described in (2) above. A laminated member of the material-epoxy resin was obtained.

The laminated member was cut into a width of 1 cm, heated in an oven at 121 ° C., 2 atm, and 100% relative humidity for 1 hour, and then fixed with a glass cloth-based epoxy resin sheet. Peeling strength was measured by performing a 90 degree peel test which pulls a part to a vertical direction. The results obtained are shown in Table 3 below.

As is clear from Table 3, when the base coating secondary metal material of the present invention obtained by the base treatment method of the present invention using the base treatment agent of the present invention is laminated with an epoxy resin to form the laminate member of the present invention, high humidity Under the same conditions, it was confirmed that excellent adhesion between the metal material and the epoxy resin was exhibited.

In contrast, in Comparative Examples 5 and 7, the adhesion was inferior. Moreover, also about the comparative example 8 which performed blackening process, it was confirmed that moisture resistance secondary adhesiveness is inferior.

Acid resistance secondary adhesion test

Using the above-mentioned Examples 12, 19 and 37 and the base material with base film obtained in Comparative Example 8, a lamination member of a copper material-epoxy resin was obtained by the same method as described in (2) above.

The laminated member was cut into a width of 1 cm, immersed in a 25 M 1 M hydrochloric acid solution for 15 minutes, and then partially pulled a portion of the non-bonded copper material in the vertical direction while the glass cloth base epoxy resin sheet was fixed. A 90 degree peel test was done and peel strength was measured. The obtained results are shown in Table 4 below.

It was confirmed that the metal film with a base film obtained in Examples 12, 19, and 37 exhibited good adhesion even after treatment with an acidic solution. In Comparative Example 8 subjected to the blackening treatment, it was confirmed that the peel strength was inferior to 0.0 kgf / cm. By this characteristic, when the metal material with base film of this invention is used, the problem, such as a pink ring which arises at the time of manufacture of a printed wiring board, is suppressed.

(3) Peeling interface analysis

Using the copper base material with base film obtained in Example 1, after the primary adhesive evaluation of said (2), XPS depth direction analysis was performed on the peeling surface of a copper material side and an epoxy resin side on the conditions shown below. It was. The results are shown in FIGS. 2 to 5.

<XPS depth direction analysis>

· Device used; Shimazu Corporation ESCA850

X-ray here; Mg-Kα

Measuring area; About 50 mm2

Measuring area; C1s, Cu2p, CuLMM, V2p

Sputtering depth; 240 nm (80 nm / min sputtering rate in terms of SiO ₂ )

Sputtering time; 3 minutes (XPS analysis at 0, 1, 8.5, 16, 23.5, 31, 38.5, 76, 180 sec)

2 is a distribution diagram of peak intensity derived from the C1s level. The sputtering time of 0 sec corresponds to the peeling interface, and the plot on the negative side of the sputtering time on the horizontal axis is on the epoxy resin side, and on the plus side on the copper material side. From Fig. 2, on the copper material side of the peeling interface, no carbon was detected except in the vicinity of the pole surface, and it was confirmed that the peeling mode was the interface peeling between the copper material and the undercoat.

3 is a distribution diagram of peak intensity derived from the Cu 2 p level. 3, copper was detected on the peeling interface epoxy resin side (detection range; sputtering time 0-180 sec, peak maximum point 8.5-38.5 sec). Since the exact sputtering speed of the underlying film is not known, it is impossible to estimate the exact range of the copper enrichment region in the underlying film, but it is assumed that the order is about several hundred nm. In addition, from the narrow spectrum of the CuLMM area | region in each sputtering depth on the peeling interface epoxy resin side of FIG. It was confirmed that it contained copper in the surface layer (region of several hundred nm from the surface of a base film) of the copper material surface side of a base film, and also that the copper exists in the metal state and monovalent state. Confirmed.

5 is a distribution diagram of peak intensity derived from the V2p level. In the copper side peeling interface, the peak derived from the V2p level was detected in the surface vicinity (the area | region of 0-8.5 sec of sputtering time). Since the exact sputtering rate is not known, it is impossible to estimate the exact range of the concentrated region of the vanadium element, but it is estimated to be an order of several tens of nm. It was confirmed that there was a concentrated layer of vanadium element in the surface layer (region of several tens nm from the surface of the underlying film) of the copper material surface side of the underlying film.

The base treatment agent of the present invention is not only bonded to a copper material and a resin in a printed wiring board described in the background art but also applied to various metal materials by a coating method, a laminate bonding method, an injection molding bonding method, or the like. It is also useful as a base treatment agent at the time of formation.

1 laminated member
2 metal materials
3 Lower film
4 resin layers

Claims (12)

Compound (A-1) selected from the group consisting of at least one benzene nucleus, a hydroxyl group, a carboxyl group and an amino group, and having at least two functional groups directly bonded to the carbon atoms constituting the benzene nucleus, and a thiourea derivative (A- A ground treatment agent for metal materials containing at least one compound (A) selected from the group consisting of 2) and at least one elastomer (B). The method of claim 1,
In addition, the base material for metal materials containing at least one oxidizing agent (C). The method of claim 2,
The oxidizing agent (C) is a nitric acid compound, a sulfuric acid compound, a halogen acid compound, a Group IV element compound having an oxidation number of 4 or 5, a Group VIA element compound having an oxidation number of 6, a copper (II) compound, an iron (III) compound And at least one base material treating agent for metal materials selected from the group consisting of organic peroxides. 4. The method according to any one of claims 1 to 3,
A base material treating agent for metal materials, wherein the compound (A-1) is a cyclic organic compound represented by the following formula (1) or (2), a polycondensate of the cyclic organic compound, or a copolymer of the cyclic organic compound and another polymerizable compound.
[Formula 1]

(2)

In Formula 1, X ¹ to X ⁶ each independently represent a hydrogen atom or a functional group, and two or more of X ¹ to X ⁶ represent a functional group selected from the group consisting of a hydroxyl group, a carboxy group and an amino group.
In formula (2), Y ¹ to Y ⁸ each independently represent a hydrogen atom or a functional group, and two or more of Y ¹ to Y ⁸ each represent a functional group selected from the group consisting of a hydroxyl group, a carboxy group and an amino group.) The method according to any one of claims 1 to 4,
The base agent for a metal material, wherein the thiourea derivative (A-2) is a compound represented by the following general formula (3).
(3)

In Formula 3, Z ¹ and Z ² each independently represent an alkyl group, an aryl group, an alkoxycarbonyl group, an amino group, an alkylamino group, an allylamino group, an acetylamino group, a hydroxyethylamino group, an N-benzoylamino group, a cyclohexylamino group, a phenylamino group, Tolylamino group, naphthylamino group, phenylazo group, guanylamino group, nicotine group, hydrazino group, phenylhydrazino group, thiocarbamoyl group, or thiocarbamoylamino group.) The method according to any one of claims 1 to 5,
The base agent for a metal material, wherein the thiourea derivative (A-2) is a compound represented by the following general formula (4).
[Chemical Formula 4]

(In formula, R <^1> , R <^2> , R <^3> and R <^4> show a hydrogen atom, an alkyl group, an alkenyl group, or a hydroxyalkyl group each independently.) A metal material with an undercoat obtained by treating a metal material using the undertreatment agent for metal materials according to any one of claims 1 to 6, wherein metal atoms derived from the metal material are formed on the surface layer on the metal material side of the undercoat. A metal material with an undercoat, which is concentrated and a part of said metal atom exists in a metal state. A metal material with an undercoat obtained by treating a metal material using the undertreatment agent for metal materials according to any one of claims 2 to 6, wherein metal atoms derived from the metal material are formed on the surface layer on the metal material side of the undercoat. Concentrated and some of the metal atoms are present in the metal state,
The base film-coated metal material, wherein at least one metal atom selected from the group consisting of vanadium, niobium, tantalum, molybdenum, and tungsten is concentrated on the surface layer on the metal material side of the base film. An application step of applying the base treatment agent for a metal material according to any one of claims 1 to 6 to the surface of the metal material;
After the coating step, drying without washing with water to form a base film
The method of treating the base material of the metal material having a. 10. The method of claim 9,
A method for treating a base material of a metal material, comprising a step of performing a metal plating composed of Ni and / or Co on the surface of the metal material and washing with water before the coating step, in an electrolytic or electroless manner. A metal material with an undercoat obtained by treating the metal material by the method for treating the metal material of claim 9 or 10. The laminated member which has the metal material with a base film of Claim 7, 8 or 11, and the resin layer provided on the base film.

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