TWI424087B - Submerged treatment of metallic materials and bottom treatment of metallic materials - Google Patents

Description

Underlayer treatment agent for metal materials and underlayer treatment method for metal materials

The present invention relates to an underlayer treatment agent for a metal material for forming an underlayer treatment film on a surface of a metal material, a primer treatment method for a metal material using the same, a metal material with a primer film, and a laminate member.

A wide variety of metal materials are used in industrial products, and in addition to corrosion resistance and adhesion, various surface treatments for imparting heat resistance, slidability, and the like are often applied.

In general, in order to improve the adhesion between a metal material and a resin, a method of mechanically roughening a surface by a blast or the like to form a so-called anchor has been conventionally used.

However, such machining generally results in poor productivity and high cost, and the precision of the electrical and electronic parts is often impaired by the particles generated during processing.

Therefore, recently, in order to enhance the adhesion by the anchor effect and the chemical affinity with the resin, some chemical surface treatments are often performed on the surface of the metal material.

For example, in the surface treatment for improving the adhesion, Patent Documents 1 and 2 disclose a method for improving the adhesion by applying a chromic acid treatment to the surface of the metal material.

Further, Patent Document 3 describes a method of forming a special chromium compound layer having a plurality of minute scale-like projections on the surface by an electrolytic method.

However, in these methods, the surface treatment liquid uses a harmful hexavalent chromium compound, and the film formed on the surface of the metal substrate also contains hexavalent chromium, which is environmentally unsatisfactory.

In addition, the ELV Directive, which came into effect in October 2000, and the RoHS Directive, which came into effect in February 2003, are particularly restricted for use in electrical and electronic equipment and automotive parts.

Therefore, the research and development of the surface treatment of the metal material for the purpose of improving the adhesion to the resin without using the hexavalent chromium compound is being carried out.

On the other hand, among the metal materials, one of the characteristics of the copper material such as copper or copper alloy is known to have high conductivity and heat dissipation characteristics. The copper material is widely used for electronic and electrical parts such as printed wiring boards, lead frames, and LSIs.

Among the components used in electronic and electrical parts, there are many joints of copper material and resin. These are required to have adhesion between the copper material and the resin in a state of being heated. Specifically, when a thermosetting resin such as an epoxy resin or a polyimide resin which is excellent for thermal stability, chemical stability, insulating properties, or the like, or a thermoplastic resin having a high molding temperature is used, When these resins are formed on a copper material, the entire part must be exposed to a high temperature of 150 to 350 °C. Further, when an active component such as a semiconductor element or a passive component such as an LCR is used, soldering is used, but since the lead solder cannot be used due to environmental problems today, the solder reflow temperature is increasing.

Under such conditions, if the adhesion between the copper material and the resin is poor, especially at high temperatures, the moisture adsorbed on the surface of the copper material or the moisture absorbed at the interface of the resin in the manufacturing step may swell, thereby promoting the copper material and The peeling of the interface of the resin causes the copper material to swell or the like to impair the internal corrosion resistance, and as a result, the wiring pattern is broken due to cracking of the resin.

Further, at the interface between the copper material and the resin during heating, a weak oxide film is formed, which is deteriorated due to aggregation failure, and is easily diffused into the polyimide film or the Si single crystal to cause deterioration of electrical characteristics. When a copper material is used as the wiring material, such countermeasures are also sought.

Even in the case of the "blackening treatment" of copper oxide which is known as a chemical surface treatment of a copper material which does not use a hexavalent chromium compound, the initial adhesion is not maintained during heating, and the initial adhesion is good. However, it has been pointed out that there is a problem that the joint strength with time is lowered due to poor durability. Moreover, in the case of blackening treatment, it is easily dissolved in hydrochloric acid or the like. Therefore, it has also been pointed out that the plating step of the through-hole connection at the time of manufacture of the printed wiring board causes the copper oxide around the hole to be dissolved and eroded by the acid in the plating bath, resulting in a problem such as a so-called pink ring. The problem.

In addition, in recent years, the density of printed wiring boards and the speed of signals have been increased, and the thickness and narrowness of copper wiring have been continuously advanced.

Therefore, in the chemical surface treatment, regarding the surface roughening technique, the formation of fine patterns has its limits, and the components used in the high frequency bands above gigahertz (giga Hz) are due to the skin effect (skin). The effect is increased, so if the surface is roughened, the transmission loss will increase. Therefore, development of a surface treatment which improves the bonding with the resin by chemical affinity without roughening the surface is urgently desired. .

However, at the present time, a chemical surface treatment without surface roughening is known, and a coating type treatment using a decane coupling agent is known, but the current state of the art cannot provide a practical strength.

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

If the problems of the prior art are summarized, firstly, in the conventional etching method or chemical processing method, a large amount of the metal material surface cleaning step necessary at the time of the processing step or after the etching or the chemical treatment may cause a large amount of unusable The waste liquid, so the environmental load is large, from the viewpoint of environmental protection is not good. Further, as the number of steps such as the washing step increases, the manufacturing steps become complicated, resulting in a decrease in productivity. In particular, in the chemical treatment method, since a certain reaction time is required, the step itself takes time, which further leads to a decrease in productivity. Furthermore, since the device has to be enlarged, it is not cost-effective.

Further, as described above, the surface of the metal material after the surface treatment is roughened, and the transmission loss when the high-frequency current flows during the production of the circuit is increased, or as described in Patent Document 4, it is difficult to form a minute circuit. Further, when it is used for a printed wiring board or the like, if the surface of the metal substrate becomes rough, in order to alleviate the roughness, it is necessary to increase the thickness of the prepreg to be laminated, which is uneconomical.

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

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

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

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

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an underlayer treatment agent for a metal material, an underlayer treatment method using a metal material excellent in productivity and environmentally friendly, and an underlayer obtained by the underlayer treatment method. The metal material and the laminate member of the film are treated, and the underlayer treatment agent for the metal material can bond the metal material to the resin such as the prepreg (especially at a high temperature) without roughening the surface of the metal material. It is good, and it does not use a substance which causes environmental pollution, such as hexavalent chromium, and the environmental load is small, and it is low cost.

The present inventors have found through enthusiasm research that the use of an underlayer treatment agent for a metal material containing a compound having a benzene nucleus and a predetermined functional group and/or a thiourea derivative and a predetermined elastomer is obtained. The present invention can be completed by providing excellent adhesion between a metal material and a resin (particularly, adhesion at a high temperature).

That is, the present invention provides the following (1) to (12).

(1) A primer for a metal material, comprising a compound (A) and at least one elastomer (B) selected from the group consisting of having one or more benzene nucleuses, and being selected from a hydroxyl group and a carboxyl group. And a group consisting of an amine group and a compound (A-1) and a thiourea derivative (A-2) directly bonded to two or more functional groups constituting a carbon atom of the benzene nucleus At least one.

(2) The primer for a metal material according to (1), which further contains at least one oxidizing agent (C).

(3) The primer for a metal material according to (2), wherein the oxidizing agent (C) is selected from the group consisting of a nitric acid compound, a sulfuric acid compound, a hydrohalic acid compound, and a VA having an oxidation number of 4 or 5. At least one of a group element compound, a group VIA element compound having an oxidation number of 6, a copper (II) compound, an iron (III) compound, and an organic peroxide.

(4) The underlayer treatment agent for a metal material according to the above formula (1), wherein the compound (A-1) is a cyclic organic compound represented by the following formula (1) or (2), and the cyclic group a polycondensate of an organic compound or a copolymer of the cyclic organic compound and another polymerizable compound;

(In the 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 group selected from a group consisting of a hydroxyl group, a carboxyl group and an amine group. Functional group;

In the 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 ³ represent a group selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group. Functional group).

(5) The primer for treating a metal material according to the above aspect, wherein the thiourea derivative (A-2) is a compound represented by the following formula (3);

(In the formula (3), Z ¹ and Z ² each independently represent an alkyl group, an aryl group, an alkoxycarbonyl group, an amine group, an alkylamino group, an allylamino group, an ethylamino group, a hydroxyethyl group. Amino, N-benzylideneamino, cyclohexylamino, phenylamino, tolylamino, naphthylamino group, phenylazo, guanylamino group, A nicotinic base, a thiol group, a benzoinyl group, an amine thiomethionyl group, or an amine thioformamide group).

(6) The primer for a metal material according to the above aspect, wherein the thiourea derivative (A-2) is a compound represented by the following formula (4);

(In the formula (4), 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).

(7) A metal material with a primer film, which is obtained by treating a metal material with a primer for a metal material according to any one of (1) to (6), a metal derived from the metal material The atom is concentrated on the surface layer of the metal material side of the underlayer film, and a part of the metal atom exists in a metallic state.

(8) A metal material to which a primer film is applied, which is obtained by treating a metal material with a primer for treating a metal material according to any one of (2) to (6), and a metal derived from the metal material The atom is concentrated on a surface layer of the metal material side of the underlayer film, a part of the metal atom is present in a metal state, and further, at least one metal atom selected from the group consisting of vanadium, niobium, tantalum, molybdenum, and tungsten The surface layer on the side of the metal material of the underlying film is concentrated.

(9) A method for treating an underlayer of a metal material, which has:

The coating step of applying the metal material described in (1) to the surface of the metal material, and the drying step of forming the underlying film without drying with water after the coating step.

(10) The method for treating a metal material according to (9), wherein before the coating step, the surface of the metal material is applied by Ni and/or Co by electrolysis or electroless method. The metal plating is constituted and the step of washing with water is performed.

(11) A metal material to which a base film is attached, which is obtained by treating a metal material by a method of treating a metal material as described in (9) or (10).

(12) A laminate comprising the metal material having the underlayer film described in (11) and the resin layer provided on the underlayer film.

According to the present invention, there is provided an underlayer treatment for a metal material, an underlayer treatment method for a metal material excellent in productivity and environmentally friendly using the underlayer treatment agent for the metal material, and an underlayer treatment obtained by the underlayer treatment method The metal material and the laminated member of the film, the underlayer treatment agent for the metal material can be used to make the adhesion between the metal material and the resin such as the prepreg (especially the adhesion at high temperature) without roughening the surface of the metal material. It is good, and it does not use substances such as hexavalent chromium, which causes environmental pollution, and the environmental load is small and low in cost.

Hereinafter, the underlayer treatment agent for a metal material of the present invention, the underlayer treatment method of the metal material using the underlayer treatment agent for the metal material, the metal material with the underlayer treatment film obtained by the underlayer treatment method, and the laminate member will be described in detail.

The underlayer treatment agent for metal materials of the present invention (hereinafter, simply referred to as "the underlayer treatment agent of the present invention") contains the compound (A) and at least one elastomer (B) selected from a compound (A-1) having one or more benzene nuclei and two or more functional groups directly bonded to a carbon atom constituting the benzene nucleus and a group selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group, and sulfur At least one of the group consisting of the urea derivative (A-2).

The object of the surface treatment of the underlying treatment agent of the present invention is a metal material.

The metal material is not particularly limited, and specific examples thereof include pure copper and copper alloy (hereinafter, collectively referred to as "copper material"), pure aluminum, and aluminum alloy (hereinafter, these are collectively referred to as " Aluminum material"), ordinary steel, alloy steel (hereinafter, collectively referred to as "iron material"), pure nickel, nickel alloy (hereinafter, these are also collectively referred to as "nickel materials").

Further, the shape, structure, and the like of the metal material are not particularly limited, and may be, for example, a shape such as a plate shape, a foil shape, or a rod shape.

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

The copper alloy preferably contains 50% by mass or more of copper, and examples thereof include brass. Examples of the alloy component other than copper in the copper alloy include Zn, P, Al, Fe, Ni, and the like.

Further, the aluminum alloy preferably contains 50% by mass or more of aluminum, and examples thereof include an Al-Mg-based alloy. Examples of the alloy component other than aluminum in the aluminum alloy include Si, Fe, Cu, Mn, Cr, Zn, Ti, and the like.

Further, the alloy steel preferably contains 50% by mass or more of iron, and examples thereof include stainless steel. Examples of the alloy component other than iron in the alloy steel include C, Si, Mn, P, S, Ni, Cr, Mo, and the like.

Further, the nickel alloy preferably contains 50% by mass or more of nickel, and examples thereof include a Ni-P alloy. Examples of the alloy component other than nickel in the nickel alloy include Al, C, Co, Cr, Cu, Fe, Zn, Mn, Mo, and P.

Among the above metal materials, the undercoating agent of the present invention can be applied to a copper material or the like, and is particularly applicable to pure copper. In general, when copper is used as the metal material, as described in Surface Technology Vol. 57, pp. 356 (2006), the film laminated thereon has a lack of adhesion at a high temperature (hereinafter, also referred to as high temperature adhesion). The problem is that, if the underlying treatment agent of the present invention is used, excellent high-temperature adhesion can be imparted.

Next, the bottom treatment agent of the present invention is selected to be selected from the group consisting of a group having one or more benzene nucleuses and a group selected from a hydroxyl group, a carboxyl group, and an amine group, and directly bonded to a carbon atom constituting the benzene nucleus. Compound (A) and elastomer (B) in a group consisting of a compound having at least one functional group (A-1) and a thiourea derivative (A-2), and an oxidizing agent (C) which may optionally be contained And at least one (D) of a zirconium compound and/or a titanium compound, at least one of a phosphoric acid and/or a phosphate compound, and a water-dispersible cerium oxide sol.

<compound (A)>

The compound (A) used in the present invention is selected from two or more carbon atoms having one or more benzene nuclei and a group selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group and directly bonded to the carbon atom constituting the benzene nucleus. A group consisting of a functional group (A-1) and a thiourea derivative (A-2).

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

<Compound (A-1)>

The compound (A-1) is one or more functional groups having one or more benzene nucleuses and a group selected from the group consisting of a hydroxyl group, a carboxyl group, and an amine group and directly bonded to a carbon atom constituting the benzene nucleus.

Here, the benzene nucleus refers to a carbon six-membered ring having an aromaticity, and also includes six-membered rings constituting a condensed ring such as naphthalene.

The compound (A-1) is preferably a cyclic organic compound represented by the following formula (1) or (2), a polycondensate of the cyclic organic compound, or a cyclic organic compound and another polymerizable compound. Copolymers, etc. These may be used alone or in combination of two or more.

In the above 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 group selected from a group consisting of a hydroxyl group, a carboxyl group and an amine group. Functional group.

Further, 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 represent a group selected from a hydroxyl group, a carboxyl group and an amine group. a functional group in the group.

Specific examples of the cyclic organic compound represented by the above formula (1) include hexahydrobenzene, gallic phenol, 1,2,4-trihydroxybenzene, phloroglucinol, catechol, and resorcinol. , hydroquinone, 5-methyl gallophenol, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 3-methylcatechol, 4-methylcatechol , methylhydroquinone, 2,6-dimethylhydroquinone, 5-methoxy resorcinol, 3-methoxycatechol, methoxyhydroquinone, 2,5-dihydroxy-1, 4-benzoquinone, gallic acid, gallicol-4-carboxylic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-di Hydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid , 2,6-dihydroxy-4-toluic acid, 4-hydroxy-3,5-xylenecarboxylic acid, 1,4-dihydroxy-2-naphthoic acid, methyl gallate, 2,4-dihydroxy Methyl benzoate, methyl 2,6-dihydroxybenzoate, methyl 3,4-dihydroxybenzoate, methyl 3,5-dihydroxybenzoate, ethyl 3,4-dihydroxybenzoate, 2 -Amine phenol, 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-hydrochloride Phenylenediamine, 1,4-phenylenediamine hydrochloride, 4,6-diaminoresorcinol dihydrochloride, 4,6-diaminoresorcinol, 2-nitroresorcinol, 4-nitrocatechol, meliic acid, phenylpentacarboxylic acid, pyrogalic acid, trimeric acid, hemi-milicate, symmetrical trimellitic acid, phthalic acid, isophthalic acid, terephthalic acid , 1,4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4-methyl phthalic acid, 5-methylisophthalic acid, 2,5-di Methyl terephthalic acid, 4-hydroxyphthalic acid, 5-hydroxyisophthalic acid, 4-nitrophthalic acid, 5-nitroisophthalic acid, 5-aminoisophthalic acid, 4- Aminosalicylic acid, 4-amino-3-hydroxybenzoic acid, etc. may be used alone or in combination of two or more.

Among these, gallic phenol, gallic acid, phloroglucinol, catechol, resorcinol, hydroquinone, 2,4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3, 4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, and succinic acid are preferred because they can be used as a preferred solvent because of their high solubility in water.

Specific examples of the cyclic organic compound represented by the above formula (2) include 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, and 1,6-dihydroxyl group. Naphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 3-amino-2-naphthol, 5-amino-1-naphthol, 5-amino group -2-naphthol, 6-amino-1-naphthol, 8-amino-2-naphthol, 1-amino-2-naphthol hydrochloride, 2-amino-1-naphthol hydrochloride For the salt or the like, these may be used alone or in combination of two or more.

The polycondensate of the cyclic organic compound represented by the above formula (1) or (2) may, for example, be a polycondensate of various cyclic organic compounds exemplified above, and specifically, for example, a ruthenium gallic acid (for example) Digallic acid) and so on.

In addition, a copolycondensate of a cyclic organic compound represented by the above formula (1) or (2) and another compound (for example, glucose), for example, hydrolyzable tannin such as tannic acid; Condensed tannins such as persimmon tannin, theaflavins, and thearubigin.

Among these, a gallium acid, a tannic acid or the like is preferred because of its high solubility in water.

<thiourea derivative (A-2)>

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

Specific examples of the thiourea derivative (A-2) include, for example, 1-ethenyl-2-thiourea, 1-allyl-2-thiourea, and 1-allyl-3-(2-hydroxyl). Ethyl)-2-thiourea, 1-adamantanethiourea, N-benzhydrylthiourea, N,N'-diisopropylthiourea, N,N'-dicyclohexylthiourea, 1,3 -diethyl-2-thiourea, 1,3-bis(o-tolyl)thiourea, 1,3-bis(p-tolyl)thiourea, 1,3-dimethylthiourea, 1,1- Diphenyl-2-thiourea, 2,5-dithiobiurea, N-methylthiourea, 1-(1-naphthyl)-2-thiourea, 1-ethyl-3-anthracene Thiourea hydrochloride, guanyl thiourea, ethylene thiourea, 1-phenyl-2-thiourea, 1,3-diphenyl-2-thiourea, p-tolyl thiourea, neighbor Tolylthiourea, trimethylthiourea, 1,3-di-n-butyl thiourea, 1-phenyl-3-methyl thiourea, tetramethyl thiourea, thiourea dioxide, diphenyl thiocarbazone , 4,4-dimethyl-3-thiosuccinium (thiosemicarbazide), 4-methylthiocarbazone, 1-phenyl-3-thiosemicarbazone, 4-phenyl-3-sulfanium card Bismuth, sulphur semicarbazone, 1,4-diphenyl-3-thiosemicarbazide, thioacetamide, thiobenzamide, thiopropionamide, thioisonicotinamide, sulfur fumes Amidoxime, acetone thiosemicarbazone, dithizone, lysine, ethyl thioglycolate, diphenyl thiocarbazone, etc., which may be used alone or in combination More than one species.

One of the preferred embodiments of the above-mentioned thiourea derivative (A-2) is, for example, a compound represented by the following formula (3). When this compound is used, the adhesion of the metal material to the underlying treatment film described later can be further enhanced.

(In the formula (3), Z ¹ and Z ² each independently represent an alkyl group, an aryl group, an alkoxycarbonyl group, an amine group, an alkylamino group, an allylamino group, an ethylamino group, a hydroxyethyl group. Amine, N-benzamide, cyclohexylamino, phenylamino, tolylamine, naphthylamino, phenylazo, formamylamine, nicotinic base, sulfhydryl, benzene Sulfhydryl, amine thiomethionyl, or amine thioformamide).

In the formula (3), Z ¹ and Z ² each independently represent an alkyl group (preferably having a carbon number of 1 to 3, specifically, for example, a methyl group or an ethyl group) or an aryl group (preferably The carbon number is 6 to 10. Specifically, for example, a phenyl group or a naphthyl group, an alkoxycarbonyl group, an amine group, an alkylamino group, an allylamino group, an ethenyl group, a hydroxyethylamino group, N-benzamide, cyclohexylamino, phenylamino, tolylamine, naphthylamino, phenylazo, carbenylamino, nicotinic, fluorenyl, benzoinyl, Amine thiomethionine or amine thioformamide

Among them, an alkylamino group, an allylamino group or a hydroxyethylamino group is preferred.

One of preferred embodiments of the compound represented by the formula (3) is, for example, a compound represented by the following formula (4). When this compound is used, the adhesion between the metal material and the underlying treatment film described later can be further improved.

(In the formula (4), 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).

In the 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. The alkyl group is not particularly limited, and preferably has 1 to 3 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, etc. are mentioned, for example.

The alkenyl group is not particularly limited, and preferably has 2 to 3 carbon atoms. Specifically, a vinyl group, an allyl group, etc. are mentioned, for example.

The hydroxyalkyl group is not particularly limited, and preferably has 1 to 3 carbon atoms. Specific examples thereof include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

In the compound represented by the formula (4), R ¹ and R ³ are each a hydrogen atom, and R ² and R ⁴ each independently represent a hydrogen atom, an alkyl group, a hydroxyalkyl group or an alkenyl group.

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

Among the undertreatment agents of the present invention, by containing such a compound (A-1) and/or (A-2), the adhesion between the metal material and the resin can be achieved without roughening the surface of the metal material. (especially the adhesion at high temperatures) is good.

Further, by using the oxidizing agent (C) described later in combination, the adhesion between the metal material and the resin (especially the adhesion at a high temperature) can be further improved.

Further, in the undertreatment agent of the present invention, the content of the compound (A) is preferably from 0.01 to 20% by mass, more preferably from 0.02 to 10% by mass, based on the total amount of the underlayer treatment agent. When the content of the above compound (A) is in this range, the adhesion between the metal material and the resin (especially the adhesion at a high temperature) can be further improved.

<elastomer (B)>

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

Specific examples of the elastomer (B) include natural rubber, isopropylene rubber, butadiene rubber, styrene butadiene rubber, chloropropene rubber, acrylonitrile butadiene rubber, and acrylonitrile butadiene benzene. Diene rubber such as ethylene rubber; butyl rubber, ethylene propylene rubber, urethane rubber, fluorenone rubber, chlorosulfonated rubber, chlorinated polyethylene, acrylic rubber, epichlorohydrin rubber, fluororubber, etc. In the state of being dispersed in various solvents, these may be used alone or in combination of two or more.

Further, the rubber may be a hydroxyalkyl group such as an amine group, a hydroxyl group or a hydroxymethyl group, a carboxyl group, a sulfone group, a phosphonic group, an epoxy group, an isocyanate group or a carbon two. The functional group of the quinone imine group or the like is denatured.

Here, as the solvent, specifically, for example, water; an alkyl group such as hexane or pentane; an aromatic system such as benzene or toluene; an alcohol such as ethanol, 1-butanol or acesulfame; tetrahydrofuran; Ethers such as dioxane; esters such as ethyl acetate and butoxyethyl acetate; guanamines such as dimethylformamide and N-methylpyrrolidone; anthraquinone solvents such as dimethyl hydrazine; hexamethyl phosphate Ammonium phosphate such as triamine.

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

Further, among the above elastomers (B), the specific gravity of the elastomer (B) is preferably from 0.8 to 2.0.

Among these rubbers, acrylonitrile butadiene styrene rubber, acrylonitrile butadiene rubber, isopropylene rubber, styrene butadiene rubber, and the like are preferred because of their high affinity with the resin to be subsequently used. Chlorophene rubber, urethane rubber, acrylic rubber.

The method for dissolving or dispersing the above-mentioned elastomer (B) in various solvents is not particularly limited. For example, it can be carried out by a conventional method such as emulsification by adding a surfactant.

The concentration of the elastomer in which the elastomer (B) is dispersed in the elastomer dispersion solution (also referred to as latex) of various solvents is not particularly limited, and is preferably from 1 to 80 by weight from the viewpoint of ease of handling of the treatment agent. % is more preferably 10 to 60% by mass.

The pH of the dispersion solution is not particularly limited, and is particularly preferably pH 2 to 11, more preferably pH 4, from the viewpoints of ease of handling of the treatment agent and adhesion to a metal material of the underlayer film to be described later. ~10.

The viscosity of the dispersion solution is not particularly limited, and is preferably from 0 to 3000 cP from the viewpoint of ease of handling of the treatment agent.

The particle diameter of the elastomer (B) in the dispersion solution is not particularly limited, but is preferably 0.01 to 10 μm, more preferably 0.1 to 2 μm.

The surfactant used in the production of the dispersion solution is not particularly limited, and an anionic surfactant, a cationic surfactant, a nonionic surfactant, or the like can be used.

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

Further, in the undertreatment agent of the present invention, the content of the elastomer (B) is preferably from 0.5 to 80% by mass, more preferably from 1 to 50% by mass, based on the total amount of the underlayer treatment agent. When the content of the elastomer (B) is in this range, flexibility can be imparted to the underlayer film, and the stress generated when exposed to a high temperature environment or during deformation can be alleviated.

<Oxidant (C)>

The oxidizing agent (C) is not particularly limited, and conventionally known oxidizing agents can be used.

In the undertreatment agent of the present invention, the oxidizing agent (C) is preferably selected from the group consisting of a nitric acid compound, a sulfuric acid compound, and a hydrohalic acid because it has sufficient oxidizing power to oxidize various metal materials containing a copper material. At least one of a group consisting of a VA group 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 an organic peroxide. .

Among these, the oxidizing agent (C) is preferably a nitric acid compound and/or a sulfuric acid compound.

Here, the nitric acid compound may specifically be, for example, nitric acid, nitrous acid, peroxy nitric acid, peroxynitrite, nitrogen hydroxy acid, trioxane dinitrate, tetraoxane dinitrate, or the like (referred to as a sodium salt). The potassium salt, the lithium salt, the ammonium salt, etc. are the same as the following.) These may be used alone or in combination of two or more.

Further, the sulfuric acid compound may specifically be, for example, persulfuric acid, peroxodisulfuric acid, thiosulfuric acid, disulfuronic acid, sulfurous acid, disulfurous acid, thiosulfuric acid, disulfuric acid, The sulfic acid, the polysulfuric acid, the salt, and the like may be used alone or in combination of two or more.

Next, the oxidizing agent (C) is preferably a hydrohalic acid compound.

Here, examples of the hydrohalic acid-based compound include perchloric acid, chloric acid, chlorous acid, hypochlorous acid, perbromic acid, bromic acid, bromic acid, hypobromous acid, and periodic acid. The iodic acid, the iodic acid, the salt, etc. may be used alone or in combination of two or more.

Next, the oxidizing agent (C) is preferably a VA group element compound having an oxidation number of 4 or 5.

Here, the VA group element compound having an oxidation number of 4 may specifically be, for example, vanadyl (IV) oxoacetate, ruthenium oxyhydroxide (IV), oxime acetonide (IV), or the like. For the salt or the like, these may be used alone or in combination of two or more. Among these, acetoacetone vanadium (IV) is preferred because of its high solubility in water.

Further, the VA group element compound having an oxidation number of 5, specifically, an oxo acid such as metavanadic acid (V), metafluoric acid (V) or metafluoric acid (V); a salt of an enzyme acid; a heterogeneous polymeric acid selected from the group consisting of metavanadic acid (V), bismuthic acid (V) and metafluoric acid (V); a salt of an isotropic polymeric acid, etc., which may be used alone. It is also possible to use two or more types together. Among these, ammonium metavanadate (V) is preferred because of its high solubility in water.

Next, the oxidizing agent (C) is preferably a compound of a group VIA having an oxidation number of 6.

Here, the compound of the group VIA having an oxidation number of 6, specifically, for example, phosphovanaddomolybdic acid 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, molybdenyl acetylacetonate, phosphorus molybdenum Acid compound (for example, ammonium phosphomolybdate (NH ₄ ) ₃ [PO ₄ Mo ₁₂ O ₃₀ ] ‧3H ₂ O, sodium molybdate Na ₃ [PO ₄ ‧12MoO ₃ ]‧nH ₂ O, etc.; H ₆ [H ₂ W ₁₂ O ₄₀ ], ammonium metatungstate (NH ₄ ) ₆ [H ₂ W ₁₂ O ₄₀ ], sodium metatungstate, paratungstic acid H ₁₀ [W ₁₂ O ₄₆ H ₁₀ ], ammonium paratungstate, Sodium paratungstate, phosphotungstic acid compound (for example, 12 phosphotungstic acid n-hydrate H ₃ (PW ₁₂ O ₄₀ ) ‧nH ₂ O, ammonium phosphotungstate n-hydrate 2 (NH ₄ ) ₃ PO ₄ ‧24WO ₃ ‧nH ₂ O, etc.) These may be used alone or in combination of two or more.

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

Here, as the copper (II) compound, specifically, for example, copper (II) acrylate, copper (II) acetate, copper (II) propionate, copper (II) valerate, copper (II) gluconate, and tartaric acid are mentioned. Copper salt of organic acid such as copper (II); copper (II) chloride, copper (II) bromide, copper (II) hydroxide, copper (II) acetate, copper (II) nitrate, copper (II) sulfate, Copper (II) carbonate, copper (II) oxide, etc. may be used alone or in combination of two or more.

Further, examples of the iron (III) compound include iron (III) chloride, iron (III) bromide, iron (III) iodide, iron (III) sulfate, iron (III) nitrate, and iron acetate. (III), etc., these may be used alone or in combination of two or more.

Next, the organic oxidizing agent (C) is preferably an organic peroxide.

Here, as the organic peroxide, specifically, for example, hydrogen peroxide, ketone peroxide, aldehyde peroxide, hydrogen peroxide, dialkyl peroxide, mercapto peroxide, peroxyester, Peroxydicarbonate or the like may be used alone or in combination of two or more.

As described above, in the underlying treatment agent of the present invention, by including such an oxidizing agent (C), the adhesion of the metal material to the resin (especially the adhesion at a high temperature) can be performed without roughening the surface of the metal material. For the good.

Although the reason for further improving the adhesion between the metal material and the resin in the above manner is not fully understood, it is presumed that the oxidizing agent (C) oxidizes the metal material, and the quenching effect of the minute etching and the dissolution of the metal ions are entered. The affinity between the surface of the metal material of the film and the metal material is enhanced to exhibit high adhesion.

Among the above-mentioned oxidizing agents (C), a VA group element compound having an oxidation number of 5 and a VIA group element compound having an oxidation number of 6 are preferable from the viewpoint of further excellent adhesion, and more preferably ammonium vanadate or ammonium molybdate. , ammonium metatungstate.

Further, the amount of the oxidizing agent (C) to be contained in the underlying treatment agent of the present invention is preferably 0.01 to 20% by mass, and more preferably 0.02 to 10% by mass based on the total amount of the underlying treatment agent. When the content of the oxidizing agent (C) is in this range, the adhesion between the metal material and the resin (especially the adhesion at a high temperature) can be further improved because of the moderate oxidizing power.

<Zirconium compound, titanium compound (D)>

The underlayer treatment agent of the present invention preferably further contains a zirconium compound and/or a titanium compound (D) from the viewpoint of further improving the adhesion between the metal material and the resin without roughening the surface of the metal material. The zirconium compound and/or the titanium compound (D) are not particularly limited, and conventionally known compounds can be used.

Here, the zirconium compound and/or the titanium compound (D) may specifically be, for example, a carbonate of Zr or Ti, an oxide, a nitrate, a sulfate, a phosphate, a fluoride, a hydrofluoric acid, or an organic compound. Acid salts, organic complexes, and the like. More specifically, basic zirconium carbonate, zirconyl carbonate, ammonium zirconium carbonate, ammonium zirconium carbonate (NH ₄ ) ₂ [Zr(CO ₃ ) ₂ (OH) ₂ ], zirconium oxide (IV) (zirconia), titanium oxide (IV)(titania), zirconium nitrate, zirconium nitrate ZrO(NO ₃ ) ₂ , titanium nitrate, zirconium sulfate (IV), zirconium sulfate, titanium (III) sulfate, titanium (IV) sulfate, titanium TiOSO ₄ , phosphoric acid Zirconium, zirconium pyrophosphate, zirconium dihydrogen phosphate, zirconium fluoride, titanium (III) fluoride, titanium (IV) fluoride, hexafluorozirconic acid (H ₂ ZrF ₆ ), ammonium hexafluorozirconate [(NH ₄ ) ₂ ZrF ₆ ]], hexafluorotitanate (H ₂ TiF ₆ ), ammonium hexafluorotitanate [(NH ₄ ) ₂ TiF ₆ ]], zirconium acetate, titanium laurate, zirconium acetonate Zr (OC (=CH) ₂ ) CH ₂ COCH ₃ )) ₄ , Diisopropoxy acetoacetone titanium (C ₅ H ₇ O ₂ ) ₂ Ti[OCH(CH ₃ ) ₂ ] ₂ , acetonitrile acetone Ti (OC (=CH) ₂ ) CH ₂ COCH ₃ )) ₃ and the like. These may be anhydrate or a hydrate. These compounds may be used singly or in combination of two or more.

Further, the content of the zirconium compound and/or the titanium compound which may be contained in the undertreatment agent of the present invention is preferably 0.01 to 20% by mass, more preferably 0.02 to 10% by mass based on the total amount of the underlying treatment agent. . When the content of the zirconium compound and/or the titanium compound is within this range, the adhesion between the metal material and the resin can be further improved.

<phosphoric acid, phosphate compound (E)>

The underlayer treatment agent of the present invention preferably further contains a phosphoric acid and/or phosphate compound (E) from the viewpoint of further improving the adhesion between the metal material and the resin without roughening the surface of the metal material. The phosphoric acid and/or phosphate compound (E) is not particularly limited, and conventionally known compounds can be used.

Here, the phosphoric acid is phosphoric acid (=orthophosphoric acid), metaphosphoric acid, condensed phosphoric acid containing polyphosphoric acid, and salts thereof (ammonium salt, sodium salt, calcium salt, magnesium salt, etc.), more specifically, metaphosphoric acid The invention comprises a phosphoric acid condensate of a polyphosphoric acid chain, such as a phosphoric acid, a tetraphosphoric acid or a hexametaphosphoric acid, and comprises pyrophosphoric acid, a tripolyphosphoric acid, a tetrapolyphosphoric acid or 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 phosphoric acid. Dibutyl ester and the like.

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

Further, the content of the phosphoric acid and/or the phosphate compound (E) which may be contained in the undertreatment agent of the present invention is preferably 0.01 to 20% by mass, more preferably 0.01 to 20% by mass based on the total amount of the underlying treatment agent. 0.02 to 10% by mass. When the content of the phosphoric acid and/or the phosphate compound (E) is within this range, since the oxidizing power is moderate, the adhesion between the metal material and the resin can be further improved.

The undertreatment agent of the present invention may contain a water-dispersible cerium oxide sol, an alumina sol, or a zirconia sol.

The water-dispersible cerium oxide sol may be a liquid phase cerium oxide synthesized from a liquid phase or a gas phase cerium oxide synthesized from a gas phase, and any of the underlying treating agents of the present invention may be used.

The liquid phase cerium oxide, 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 manufactured by Nissan Chemical Industries Co., Ltd.), etc., etc. They may be used alone or in combination of two or more.

Further, the gas phase ruthenium oxide, specifically, Aerosil 50, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil TT 600, Aerosil MOX 80, Aerosil MOX 170 (all manufactured by Japan Aerosil Co., Ltd.), etc., may be used singly or in combination of two. the above.

In addition, as the alumina sol, for example, an alumina sol 100, an alumina sol 200, and an alumina sol 520 (all manufactured by Nissan Chemical Industries Co., Ltd.) may be used, and these may be used alone or in combination. Two or more.

Further, as the zirconia sol, specifically, for example, Nanonus ZR-40BL, Nano Nis ZR-30BS, Nano Nis ZR-30BH, Nano Nis ZR-30AL, Nano Nis ZR -30AH (both manufactured by Nissan Chemical Industry Co., Ltd.), ZSL-10A, ZSL-10T, and ZSL-20N (all of which are manufactured by First Rare Elements Co., Ltd.), etc., which can be used alone. Two or more types can be used in combination.

The content of the water-dispersible cerium oxide sol to be added to the primer of the present invention is preferably 30% by mass or less, preferably 0.01% to 10% by mass, more preferably, based on the total amount of the underlying treatment agent. It is 0.05 to 10% by mass.

The underlayer treating agent of the present invention may contain a decane coupling agent.

The above decane coupling agent may, for example, be, for example, N-β(aminoethyl)γ-aminopropyltrimethoxyoxane or N-β(aminoethyl)γ-aminopropylmethylmethyl Oxane, N-β (aminoethyl) γ-aminopropyl triethoxy decane, N-β (aminoethyl) γ-aminopropyl methyl diethoxy decane, γ-aminopropyl Triethoxy oxane, γ-aminopropyltrimethoxy decane, N-phenyl-γ-aminopropyltrimethoxy decane, N-phenyl-γ-aminopropyltriethoxy decane, γ-A Propenyloxypropyltrimethoxydecane, γ-methacryloxypropylmethyldimethoxydecane, γ-methylpropoxypropyltriethoxysilane, γ-methylpropoxypropylpropyl Diethoxy oxane, N-β-(N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxy decane, N-β-(N-vinylbenzylaminoethyl) γ- Aminopropylmethyldimethoxydecane, N-β-(N-vinylbenzylaminoethyl)γ-aminopropyltriethoxyoxane, N-β-(N-vinylbenzylamine Benzyl) γ-aminopropylmethylmethyldiethoxy decane, γ-glycidoxypropyltrimethoxy decane, γ-glycidoxypropylmethyldimethoxy decane, - glycidoxypropyl triethoxy decane, γ-glycidoxypropylmethyldiethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, γ- Mercaptopropyltrimethoxy decane, γ-mercaptopropylmethyldimethoxydecane, γ-mercaptopropyltriethoxy decane, γ-mercaptopropylmethyldiethoxy decane, methyltrimethoxy decane, dimethyl Dimethoxy decane, methyl triethoxy decane, dimethyl diethoxy decane, vinyl triethoxy decane, γ-chloropropyl trimethoxy decane, γ-chloropropyl methyl dimethoxy decane, γ -Chloropropyltriethoxy decane, γ-chloropropylmethyldiethoxy decane, hexamethyldioxane, γ-anilinopropyltrimethoxy decane, γ-anilinopropylmethyldimethoxy Decane, γ-anilinopropyl triethoxy decane, γ-anilinopropyl methyldiethoxy decane, vinyl trimethoxy decane, vinyl methyl dimethoxy decane, vinyl triethoxy decane, vinyl Methyldiethoxy decane, octadecyldimethyl[3-(trimethoxydecyl)propyl]ammonium chloride, octadecyldimethyl[3-(methyldimethoxydecyl)propane Ammonium chloride, octadecyl dimethyl [3- (triethoxydecyl)propyl]ammonium chloride, octadecyldimethyl[3-(methyldiethoxydecyl)propyl]ammonium chloride, γ-chloropropylmethyl dimethyl Oxy decane, γ-mercaptopropyl dimethyl dimethyl decane, methyl trichloro decane, dimethyl dichloro decane, trimethyl chloro decane, etc. may be used alone or in combination of two or more.

The content of the above-mentioned decane coupling agent to be added to the primer of the present invention is preferably 30% by mass or less, more preferably 0.01 to 10% by mass, even more preferably 0.05%, based on the total amount of the underlying treatment agent. 10% by mass.

The undertreatment agent of the present invention may contain at least one selected from the group consisting of triazole, benzotriazole, tetrazole, imidazole, thiazole, pyrazole, isoxazole, oxazole 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;

4-, 5-aminotetrazole, 1-methyltetrazole, 2-methyltetrazole, 1-phenyltetrazole, 5-phenyltetrazole;

Imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-phenylimidazole, 1-benzylimidazole, 1-vinylimidazole, 1-hydroxyethylimidazole, 2-methylimidazole , 2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole, 2-butylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-benzyl Imidazole, 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-carbamimidazole, 2,4-diphenylimidazole, 4,5-dimethylimidazole, 4,5-diphenyl Imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2,5-trimethylimidazole, 1,4,5-trimethylimidazole, 1-methyl -4,5-diphenylimidazole, 2-methyl-4,5-diphenylimidazole, 2,4,5-trimethylimidazole, 2,4,5-triphenylimidazole, 1-cyano Ethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano Ethyl-2-phenylimidazole, benzimidazole, thiazole, pyrazole, isoxazole, indazole;

1,3,5-triazine-2,4,6-trithiol, 1,3,5-triazine-2,4,8-trithiol, 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 group -1,3,5-triazine-4,6-dithiol, 2-(3'-bromophenylamino)-1,3,5-triazine-4,6-dithiol, 2- (3',4'-thiophenylthio)-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, etc. These may be used alone or in combination of two or more.

The amount of the compound to be added to the primer of the present invention is preferably 30% by mass or less, more preferably 0.01 to 10% by mass, still more preferably 0.05 to 5, based on the total amount of the underlying treatment agent. quality%.

In order to improve the adhesion between the metal material and the resin, the underlayer treatment agent of the present invention may contain a state in which a resin is dissolved or dispersed in a solvent from the viewpoint of improving the affinity between the metal material and the resin.

Specifically, for example, a polyolefin resin, an epoxy resin, an acrylate resin, a urethane resin, a phenol resin, a urea resin, a melamine resin, a polyamide, or a polyphthalamide may be dissolved or dispersed in a solvent. State of amine, polyamine, nylon resin, polyphenylene sulfide, etc.

Further, the resins may be a hydroxyalkyl group such as an amine group, a hydroxyl group or a methylol group, a carboxyl group, a maleic acid group, a decyl group, a phosphonic acid group, an epoxy group, a carbodiimide group or an isocyanate group. Such functional groups are transgendered.

Further, the method of dissolving or dispersing the above resin in a solvent is not particularly limited, and for example, it can be carried out by a conventionally known method of emulsification by adding a surfactant.

Here, as the solvent, various solvents can be used. Specifically, for example, water; alkane such as hexane or pentane; an aromatic system such as benzene or toluene; ethanol, 1-butanol, and acesulfame An alcohol system; an ether system such as tetrahydrofuran or dioxane; an ester system such as ethyl acetate or butoxyethyl acetate; a guanamine system such as dimethylformamide or N-methylpyrrolidone; and an anthraquinone solvent such as dimethyl hydrazine; A guanamine phosphate such as hexamethylphosphoric acid triamide.

The content of the resin solution, the latex, and the suspension to be added to the primer of the present invention is preferably 60% by mass or less, and more preferably 1 to 50% by mass based on the total amount of the underlying treatment agent.

The underlayer treatment agent of the present invention contains various solvents as needed from the viewpoint of workability when applied to the surface of a metal material.

Specific examples of such a solvent include water; an alkyl group such as hexane or pentane; an aromatic system such as benzene or toluene; an alcohol such as ethanol, 1-butanol or acesulfame; tetrahydrofuran or dioxane; and the like. Ether system; esters such as ethyl acetate and butoxyethyl acetate; guanamines such as dimethylformamide and N-methylpyrrolidone; anthraquinone solvents such as dimethyl hydrazine; trimethylamine hexamethylphosphate; Ammonium phosphate and the like.

Among these, water is preferred from an environmentally and economically advantageous point of view.

The method for producing the underlayer treatment agent for a metal material of the present invention is not particularly limited in its production method. For example, the compound (A), the aqueous dispersion of the elastomer (B), the oxidizing agent (C) which can be used as needed, other additives, and water can be produced by thoroughly mixing them using a mixer such as a mixer.

The underlayer treatment method of the metal material of the present invention (hereinafter, simply referred to as "the underlayer treatment method of the present invention") has a coating step of applying the underlayer treatment agent of the present invention to the surface of the metal material, and After the coating step, it is directly dried without washing with water to form a drying step of the underlayer film.

<Coating step>

This coating step is a step of applying the above-mentioned underlayer treating agent of the present invention to the surface of a metal material.

In the underlayer treatment method of the present invention, the coating method in the coating step is not particularly limited, and may be, for example, a spray coating method, a dip coating method, a roll coating method, a curtain coating method, or a spin coating method. Coating by a coating method or a combination of the above.

Further, in the underlayer treatment method of the present invention, the conditions of use of the undertreatment agent of the present invention in the coating step are not particularly limited.

For example, the temperature of the treating agent and the metal material when the undercoating agent is applied is preferably from 10 to 90 ° C, more preferably from 20 to 60 ° C. When the temperature is 60 ° C or lower, the use of excess energy can be suppressed, which is preferable from the viewpoint of economy.

Further, the time for applying the undercoating agent can be appropriately set.

<drying step>

This drying step is a step of directly drying without washing with water to form an underlayer film.

In the underlayer treatment method of the present invention, the drying temperature varies depending on the solvent to be used, and is not particularly limited. For example, when water is used as the solvent, it is preferably 50 to 200 °C.

Further, the film thickness of the obtained underlayer film is preferably from 0.01 to 50 μm, more preferably from 0.1 to 20 μm.

<plating step>

The underlayer treatment method of the present invention comprises a step of plating (electrolyzing or chemically applying a metal plating consisting of Ni and/or Co on the surface of the metal material and performing water washing) before the coating step ), the adhesion between the metal material and the resin (especially the adhesion at high temperatures) can be made better.

In metal composed of Ni and / or Co plating deposition amount of plating is not particularly limited, but is preferably 1 ~ 1000000mg / m ^2, more preferably 10 ~ 1000mg / m ^2. As long as it is within the range, the continuation is improved.

Further, after washing with water, a drying step may be provided as needed. The drying temperature varies depending on the solvent to be used, and is not particularly limited. For example, when water is used as the solvent, it is preferably 50 to 200 °C.

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

Ni and/or Co plating by electrolysis can be carried out by using a material to be plated as a cathode and filling the plating solution between the anode and the cathode. Ni and/or Co metal is used on the anode side, and an insoluble anode can also be used.

In the Ni plating bath, a Watts bath made of nickel sulfate, nickel chloride or boric acid is generally used. Further, cobalt sulfate (hydrated) may be added to the Ni plating bath to be plated as a Ni-Co alloy.

The Ni and/or Co plating which is chemically performed can be carried out by immersing the material to be plated in a treatment liquid containing Ni and/or a Co salt, a crosslinking agent, and a reducing agent as a main component for a predetermined period of time.

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

When the metal material is a copper material, in the hypophosphorous acid bath, there is a problem that it is difficult to directly precipitate on copper. Therefore, it is also possible to use a method of two-stage treatment of a catalyst-imparting treatment by a palladium thin aqueous solution before performing electroless Ni plating, or as a direct plating on copper, in addition to containing a Japanese special open 2000. In addition to the hypophosphite described in the publication No. 256866, the method further includes a method of using a dimethylamine borane as a second reducing agent, a gluconic acid aqueous reagent as a crosslinking agent, or a method of using Japanese Patent Publication No. 6-100054 A method of containing a nickel compound and/or a cobalt compound and a thiourea aqueous agent, and the like.

The nickel compound used in the above-described method using an aqueous plating solution containing a nickel compound and/or a cobalt compound and a thiourea may, for example, be nickel acetate, nickel ammonium sulfate, nickel benzoate, nickel bromide or nickel carbonate. , nickel chloride, nickel citrate, nickel hydroxide, nickel iodide, nickel nitrate, nickel oxalate, nickel oxide, nickel stearate, nickel sulfamate, nickel sulfate, and the like.

Further, examples of the cobalt compound include cobalt acetate, cobalt ammonium chloride, cobalt ammonium sulfate, cobalt bromide, cobalt carbonate, cobalt chloride, cobalt diammonium sulfate, cobalt formate, cobalt naphthalate, cobalt nitrate, cobalt oleate, and the like. Cobalt oxalate, cobalt oxide, cobalt stearate, cobalt sulfate, and the like.

The amount of the plating treatment liquid to be at least one compound selected from the group consisting of a nickel compound and/or a cobalt compound is preferably from about 0.1 to 40% by mass, more preferably from about 0.5 to 20% by mass.

In addition to at least one compound selected from the group consisting of a nickel compound and a cobalt compound, it is necessary to compound a thiourea. Thereby, the precipitation potential of the copper-based raw material can be lowered, and it can be replaced with nickel or cobalt.

Examples of the thiourea include thiourea, dimethyl thiourea, trimethyl thiourea, allyl thiourea, acetyl thiourea, vinyl thiourea, phenyl thiourea, etc., which can be used. At least one. The amount of the plating solution added is preferably about 0.1 to 20% by mass, more preferably about 0.5 to 10% by mass.

Further, in addition to at least one compound selected from the group consisting of a nickel compound and/or a cobalt compound, and a thiourea, a chelating agent may be further blended as needed, and specifically, for example, ethylenediaminetetraacetic acid (EDTA) or ethylenediamine may be exemplified. Disodium tetraacetate (EDTA‧2Na), hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), triethylenetetramine hexaacetic acid (TTHA), ethylenediaminetetrapropionic acid, Ethylenediamine tetramethylene phosphonic acid, diethylenetriamine penta methylene phosphonic acid, etc., nitrogen triacetic acid (NTA), imine diacetic acid (IDA), imine dipropionic acid (IDP), amine triamethylene Phosphonic acid, aminotrimethylene phosphonic acid pentasodium salt, methylamine, ethylamine, propylamine, dimethylamine, trimethylamine, dimethylethylamine, benzylamine, 2-naphthylamine, isobutylamine, isoprene Amine, Methylenediamine, Ethylenediamine, Tetraethylenediamine, Pentamethylenediamine, Hexamethylenediamine, Diethylenetriamine, Tetraethylenepentamine, Pentaethyleneamine, Liujinyi Heptamine, cinnamamine, p-methoxycinnamamine, ammonia, hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid trisodium salt, citric acid, tartaric acid , malic acid, malonic acid, etc., glycine, alanine , N-methylglycine, indole acetic acid, dimethylglycine, hydantoic acid, valeric acid, β-alanine, valine, ortho-amine, leucine, white Aminic acid, isoleucine, serine, cysteine, aspartic acid, aspartic acid, glutamic acid, ornithine, lysine, arginine, glutamine, diamine Propionate, citrulline, hydroxy-L-isoamine, diaminobutyric acid, amino adipic acid, concanavalin, kynurenic acid, diaminopimelic acid, cysteine, Histamine, methionine, etc., aspartame-histamine, alanine-alanine, propylamine-β-alanine, β-alaninyl-β-alanine, glycine -Amino acid, alanine-ornithine, amidino-isoamine, aminyl-ornithine, glycidyl-ornithine, beta-alanamine-isoamine Amino acid, aminoxime-aminoxime-lysine, glycyl-guanamine-ornyl-ornithine, imidazoline, 2,4,5-triphenyl-2- Imidazoline, 2,2'-bis(2-imidazoline), pyridine, morpholine, dipyridyl, pyrazole, triazine, and the like.

The amount of the chelating agent is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 10% by mass, based on the plating treatment liquid.

The pH of the plating treatment liquid is not particularly limited, but is preferably pH 1 to 8. When pH adjustment is performed, an acid such as HCl or H ₂ SO ₄ or an alkali compound such as NaOH or NH ₃ may be used as needed.

Further, in the plating treatment liquid, a surfactant such as nonionic, cationic, anionic or amphoteric may be added, whereby the surface tension of the catalyst liquid can be lowered, and the catalytic activity of the surface of the copper-based raw material can be reduced. Uniform.

Further, hydrochloric acid-potassium chloride, potassium hydrogen phthalate-hydrochloric acid, potassium hydrogen phthalate-sodium hydroxide, potassium dihydrogen phosphate-sodium hydroxide, boric acid-sodium hydroxide, sodium hydrogencarbonate-hydrogen peroxide may be added. Sodium, sodium dihydrogen phosphate-sodium hydroxide, sodium hydroxide-potassium chloride, tris(hydroxymethyl)aminomethane-hydrochloric acid, sodium acetate-acetic acid or the like is used as a pH buffering agent. The surfactant and pH buffer may be used alone or in combination as needed.

By using the treatment method of the plating treatment liquid, the material to be treated may be immersed in a catalyst liquid having a liquid temperature of about 10 to 90 ° C (preferably about 25 to 70 ° C) for about 10 seconds to 20 minutes, and optionally stirred. The plating solution is shaken and the plating solution is shaken, whereby the plating film can be uniformly formed on the surface of the object to be plated.

The metal material to which the underlayer film of the present invention is attached is a metal material obtained by surface treatment using the above-described underlayer treatment agent of the present invention, and preferably the metal material obtained by the above-described underlayer treatment method of the present invention.

The underlayer film on the metal material obtained by the underlayer treatment method of the present invention is preferably in the vicinity of the surface of the metal material side of the underlayer film (preferably, within 2 μm from the surface of the metal material side of the underlayer film, more preferably Within 1 μm), containing metal atoms from the treated metal material. More specifically, it is preferable that the metal atom from the metal material is concentrated on the surface layer of the metal material side of the underlayer film, and one part of the metal atom exists in a metal state. For example, if a copper foil is used as the metal material, the copper atoms are concentrated on the surface layer on the side of the metal material of the underlayer film, and a part thereof is present in a metallic state. The same is true when other metal materials (for example, aluminum, nickel) are used.

Further, when the underlayer treatment agent contains a compound of a group VA having an oxidation number of 4 or 5 as an oxidizing agent (C), and/or a compound of a group VIA having an oxidation number of 6, it is selected from the group consisting of vanadium, niobium, tantalum, and molybdenum. At least one metal atom of the group consisting of tungsten and tungsten is concentrated in the vicinity of the surface of the metal material side of the underlayer film (the same range as described above). That is, a metal element such as vanadium or the like and a metal atom derived from the metal material are concentrated near the surface of the metal material side of the underlayer film.

Although the mechanism for obtaining such a film structure has not been clarified, it is presumed that there is a possibility that a metal ion which is eluted from a metal material by an oxidizing agent (C) or the like in the vicinity of the metal material due to the compound ( The reduction of A) is reduced and becomes a metallic state again and enters the underlying film. As a result, a coexistence region between the underlayer film and the metal material is formed in the vicinity of the metal material of the underlayer film, and it is presumed to be one of the causes for exhibiting the adhesion between the underlying film-metal material of the present invention.

The metal material treated with the underlying treatment agent for the metal material of the present invention can suppress the roughening of the surface of the metal material unlike the prior art.

In particular, in the case of using a high-frequency waveform as a signal, as described in Japanese Laid-Open Patent Publication No. Hei 7-314603, it is preferable to use surface roughness (in terms of Ra). It is a copper foil of 0.35 μm or less (more preferably 0.2 μm or less).

By using the treatment with the underlying treatment agent for the metal material of the present invention, the change in the surface roughness of the metal can be suppressed and the adhesion to the resin can be improved. Specifically, the surface roughness (Ra ₁ ) of the treated metal can be improved. The change ΔRa with respect to the surface roughness (Ra ₀ ) of the metal before the treatment is 0.5 μm or less, preferably 0.3 μm or less.

Since the method of etching roughening has been used in the past, even when a copper foil having a surface roughness (in terms of Ra) of 0.2 μm or less is used, the surface average roughness Ra is usually more than 1 μm. The effect as the present invention cannot be obtained.

In the method of measuring ΔRa, the metal material with the underlying film of the present invention and the metal material before the treatment are embedded in the resin, and the cross-sectional SEM observation is performed at a magnification of 10,000 times, and Ra _{1 is} calculated from the roughness map of the metal surface, respectively. And R _a0 , thereby calculating ΔRa (=Ra ₁ -Ra ₀ ).

Further, the average surface roughness Ra (arithmetic average surface roughness Ra) is a value represented by abbreviated value of Ra according to JIS B 0601, and is an average value indicating the deviation of the absolute value of the average curve from the value of the surface roughness.

The underlayer formed on the metal material by the above method is excellent in flatness by the metal mold. Specifically, the average surface roughness Ra of the underlayer film is preferably 0.5 μm or less, more preferably 0.3 μm or less. Regarding the lower limit, the smaller the better, the better is 0. When the average surface roughness of the underlying film is within the above range, it is economically advantageous to reduce the thickness of the resin layer such as the prepreg laminated on the underlying film when the printed wiring board is produced.

The laminated member of the present invention has the above-described metal material with a primer film of the present invention and a resin layer provided on the underlayer film.

Fig. 1 is a schematic cross-sectional view showing a laminated member of the present invention. The laminated member 1 shown in Fig. 1 has a metal material 2, an underlayer film 3 formed on the metal material 2 using the underlayer treating agent of the present invention, and a resin layer 4 provided on the underlying film 3.

The material of the resin layer is not particularly limited, and examples thereof include acrylic resin, polyolefin resin, polyester resin, polydivinylidene chloride, polycarbonate, polyfluorene, polyphenylene sulfide, liquid crystal polymer, and epoxy resin. Phenol resin, urea resin, melamine resin, polyimine, polyurethane resin, bismaleimide ‧ triazine resin, polyphenylene ether, cyanate ester, guanamine fiber, fluorine fiber, aromatic The polyether ketone resin, the nylon resin, etc. may be used alone or in combination of two or more. These resins can also be denatured by functional groups.

Further, the resin layer may be a filler such as glass fiber, calcium carbonate, guanamine fiber or graphite, as considered from the viewpoint of strengthening and strengthening.

One of the preferred aspects of the material of the resin layer may, for example, be a prepreg. The prepreg refers to a fiber substrate in which a sheet-like fibrous substrate is impregnated with a thermosetting resin, and is in a semi-hardened state.

Examples of the material of the sheet-like fibrous base material include fibers of an inorganic material such as E glass, D glass, S glass, and Q glass, and organic substances such as decylamine, polyimine, polyester, and polytetrafluoroethylene. Fiber, and mixtures of these. The fiber base material has a shape, a material, and a shape such as a woven fabric, a non-woven fabric, a roving, a chopped strand mat, and a surfacing mat, depending on the use and performance of the intended molded product. Alternatively, two or more materials and shapes may be used alone or in combination.

The thermosetting resin is not particularly limited, and preferably, for example, an epoxy resin, a phenol resin, a polyester resin, a polyimide resin, a bismaleimide triazine resin, a cyanate resin, or the like Denatures, etc.

The laminate member of the present invention can be obtained by bonding the metal layer with the underlayer film of the present invention to the resin layer through the underlayer film.

The bonding method is not particularly limited. Specifically, in the case where the resin layer is an epoxy resin, for example, (1) a primer film of a metal material to which a primer film is attached, and an unhardened liquid ring is applied. After the oxygen resin, it is dried and hardened to form a coating method of the resin layer; (2) an epoxy resin film is laminated on the underlying film of the metal material to which the underlying film is attached, and the underlying film is brought into contact with the epoxy resin. Then, a lamination method of hot pressing is performed; (3) a metal material with an underlying film is mounted on the metal mold, and the molten epoxy is injected into the metal mold in contact with the underlying film, thereby forming an epoxy resin. The injection molding of the layer is followed by a method or the like.

In the laminated member of the present invention, the metal material and the resin layer which is passed through the underlying film are excellent in adhesion strength. In particular, it has characteristics of excellent adhesion properties at high temperatures. Further, since the formed underlayer film is excellent in acid resistance, it is possible to suppress problems such as a pink ring generated during the production of the printed wiring board. Further, the underlying film is also excellent in moisture resistance and exhibits excellent bonding strength in a high humidity environment.

As described above, the primer for a metal material according to the present invention can improve the adhesion (especially the adhesion at a high temperature) of the metal material to the resin such as the prepreg without roughening the surface of the metal material. Moreover, the treatment method using the underlying treatment agent can suppress the generation of waste liquid or the like as compared with the prior art, and the environmental load is small. Further, since the undercoating agent can be applied to the coating method, the number of processing steps can be reduced as compared with the prior art, and the processing time can be shortened, so that productivity can be greatly improved.

[Examples]

The examples are disclosed below to specifically illustrate the invention. However, the invention is not limited to the embodiments.

Production of metal materials with underlying film

As shown in the examples and comparative examples described later, the following treatment steps were applied to the material to be treated using various underlayer treatment agents to obtain a metal material to which the underlayer film was attached.

[treated material]

The abbreviations and details of the materials to be processed are shown below.

‧ Copper foil: Electrolytic copper foil (purity of 99.8 mass% or more), thickness of 18 μm, Ra 0.3 μm

‧ Aluminum foil (purity of 99% by mass or more) and thickness of 18 μm

‧ Aluminum foil (purity of 99% by mass or more) and thickness of 50 μm

‧ Nickel foil (purity of 99% by mass or more) and thickness of 20 μm

‧SUS304 foil, thickness 20μm

‧SUS430 foil, thickness 20μm

[Processing steps]

The processing steps are carried out in the following steps (1) to (7).

(1) Degreasing (60 ° C, 10 minutes, dipping method, using a 5 mass % aqueous solution prepared by a fine cleaner 4360 (registered trademark) manufactured by Paccarat Co., Ltd., Japan. When the material is aluminum foil, a 3 mass% aqueous solution prepared by a fine filter 315 (registered trademark) manufactured by Paccarat Co., Ltd., Japan is used.)

(2) Washing (normal temperature, 30 seconds, dipping method)

(3) Pickling (normal temperature, 30 seconds, dipping method, using a 10% aqueous solution prepared by using commercially available sulfuric acid)

(4) Washing (normal temperature, 30 seconds, dipping method)

(5) remove moisture

(6) Surface treatment (described later)

(7) Heat drying (established temperature, 5 minutes, hot air oven)

[surface treatment]

(Example 1)

0.2% by mass of gallic acid monohydrate containing compound (A), 30% by mass of acrylonitrile butadiene styrene rubber of elastomer (B), and ammonium metavanadate (V) of oxidizing agent (C) An aqueous solution of a mass % to prepare a primer (Ia). Further, the elastomer (B) is 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, containing an anionic surfactant), adjusted to the content of the elastomer (B) in the above aqueous solution.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-a) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 2.5 μm.

(Example 2)

The amount of the acrylonitrile butadiene styrene rubber containing 0.2% by mass of the benzenetriol (anhydrous) in the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and the ammonium metavanadate (V) of the oxidizing agent (C) are adjusted. An aqueous solution of a mass % to prepare an underlayer treating agent (Ib). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-b) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 2.5 μm.

(Example 3)

An aqueous solution containing 0.2% by mass of catechol of the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) of the oxidizing agent (C) The underlying treatment agent (Ic) is obtained. Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-c) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 2.5 μm.

(Example 4)

Adjusting an aqueous solution containing 0.2% by mass of the amino acid of the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) of the oxidizing agent (C) The bottom treatment agent (Id) was prepared. Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-d) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 2.5 μm.

(Example 5)

An aqueous solution containing 0.1% by mass of the tannic acid of the compound (A), 15% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and 0.25 mass% of the ammonium metavanadate (V) of the oxidizing agent (C) The bottom treatment agent (Ie) was prepared. Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted. After heating and drying (temperature: 100 ° C), the surface treatment agent (I-e) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 0.5 μm.

(Example 6)

An aqueous solution containing 1% by mass of tannic acid of the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) of the oxidizing agent (C) The underlayer treatment agent (If) was obtained. Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-f) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 1.0 μm.

(Example 7)

Adjusting 0.05% by mass of 2,4-dihydroxybenzoic acid containing the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and ammonium metavanadate (V) with the oxidizing agent (C) A 0.5% by mass aqueous solution was used to prepare a primer (Ig). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-g) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 1.0 μm.

(Example 8)

Adjusting 0.3% by mass of 3,4-dihydroxybenzoic acid containing the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and ammonium metavanadate (V) with the oxidizing agent (C) A 0.5% by mass aqueous solution was used to prepare a primer (Ih). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-h) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 1.0 μm.

(Example 9)

Adjusting 0.5% by mass of 3,5-dihydroxybenzoic acid containing the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and ammonium metavanadate (V) with the oxidizing agent (C) A 0.5% by mass aqueous solution was used to prepare an underlayer treating agent (Ii). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-i) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 1.0 μm.

(Embodiment 10)

An aqueous solution containing at least 1% by mass of the tannic acid of the compound (A) and 15% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B) was adjusted without using the oxidizing agent (C) to obtain a primer (I-j). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-j) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 0.5 μm.

(Example 11)

After heating and drying (temperature: 100 ° C), the surface treatment agent (Ia) (temperature: 25 ° C) was applied to the surface of the aluminum foil having a thickness of 18 μm by a bar coating method so as to have a film thickness of 2.5 μm. .

(Embodiment 12)

Adjusting 0.4% by mass of the gallic acid monohydrate containing the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and ammonium metavanadate (V) 0.5 with the oxidizing agent (C) An aqueous solution of mass% to prepare an underlayer treating agent (Ik). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-k) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm.

(Example 13)

Adjusting 0.4% by mass of the gallic acid monohydrate containing the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and hexammonium heptamolybdate tetrahydrate with the oxidizing agent (C) A 0.5% by mass aqueous solution was used to prepare a primer (I-1). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heat drying (temperature: 100 ° C), the surface treatment agent (I-1) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness was 6.0 μm. .

(Example 14)

0.4% by mass of the gallic acid monohydrate containing the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and 0.4% by mass of the ammonium metatungstate of the oxidizing agent (C). An aqueous solution was used to prepare an underlayer treating agent (Im). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 150 ° C), the surface treatment agent (I-m) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm.

(Example 15)

Adjusting an aqueous solution containing 0.2% by mass of the gallic acid monohydrate of the compound (A), 30% by mass of the acrylic rubber of the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) of the oxidizing agent (C). A bottom treatment agent (In) is obtained. Further, the elastomer (B) is 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). And containing an anionic surfactant) adjusted to the content of the elastomer (B) in the above aqueous solution.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-n) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm.

(Embodiment 16)

Adjusting an aqueous solution containing 0.2% by mass of the gallic acid monohydrate of the compound (A), 30% by mass of the acrylic rubber of the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) of the oxidizing agent (C). The bottom treatment agent (Io) is obtained. Further, the elastomer (B) was 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 dynes). /cm, containing an anionic surfactant), adjusted to the content of the elastomer (B) in the above aqueous solution.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-o) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm.

(Example 17)

Adjusting an aqueous solution containing 0.2% by mass of the gallic acid monohydrate of the compound (A), 30% by mass of the acrylic rubber of the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) of the oxidizing agent (C). The bottom treatment agent (Ip) is obtained. Further, the elastomer (B) is 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 dynes/ Cm, containing an anionic surfactant), adjusted to the content of the elastomer (B) in the above aqueous solution.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-p) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm.

(Embodiment 18)

Adjusting an aqueous solution containing 0.2% by mass of the gallic acid monohydrate of the compound (A), 30% by mass of the acrylic rubber of the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) of the oxidizing agent (C). The bottom treatment agent (Iq) is obtained. Further, the elastomer (B) is an aqueous dispersion of an acrylic rubber having a carboxyl group (solid content concentration: 50%, pH: 3.5, viscosity: 200 cP, Tg: -25 ° C, specific gravity: 1.06, and anionic interfacial activity) The agent and the nonionic surfactant are adjusted to the content of the elastomer (B) in the aqueous solution.

After heating and drying (temperature: 150 ° C), the surface treatment agent (I-q) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm.

(Embodiment 19)

An aqueous solution containing 0.4% by mass of the gallic acid monohydrate of the compound (A), 30% by mass of the acrylic rubber of the elastomer (B), and 0.2% by mass of ammonium metatungstate of the oxidizing agent (C) was adjusted to obtain an underlayer treatment. Agent (Ir). Further, the elastomer (B) is an aqueous dispersion of an acrylic rubber having a carboxyl group (solid content concentration: 48.5%, pH: 8, viscosity: 70 cP, particle diameter: 0.24 μm, Tg: -29 ° C, specific gravity: 1.04). Surface tension: 42 dyne/cm, containing an anionic surfactant), adjusted to the content of the elastomer (B) in the above aqueous solution.

After heating and drying (temperature: 150 ° C), the surface treatment agent (I-r) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 10.0 μm.

(Embodiment 20)

0.2% by mass of gallic acid monohydrate containing the compound (A), 30% by mass of the nitrobutadiene rubber of the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) with the oxidizing agent (C) An aqueous solution to prepare an underlying treatment agent (Is). Further, the elastomer (B) is an aqueous dispersion of a nitrobutadiene rubber having a methylol group (solid content concentration: 47%, pH: 6.6, viscosity: 65 cP, particle diameter: 0.06 to 0.25 μm, Tg). : -30 ° C, specific gravity: 0.99, containing an anionic surfactant), adjusted to the content of the elastomer (B) in the above aqueous solution.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-s) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm.

(Example 21)

0.2% by mass of gallic acid monohydrate containing the compound (A), 30% by mass of the styrene butadiene rubber of the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) of the oxidizing agent (C) An aqueous solution to prepare an underlying treatment agent (It). Further, the elastomer (B) is an aqueous dispersion of a 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), adjusted to the content of the elastomer (B) in the above aqueous solution.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-t) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm.

(Example 22)

0.2% by mass of gallic acid monohydrate containing compound (A), 30% by mass of acrylonitrile butadiene styrene rubber of elastomer (B), and ammonium metavanadate (V) of oxidizing agent (C) An aqueous solution of mass% and 0.5% by mass of phosphoric acid was used to prepare a primer (Iu). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-u) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm.

(Example 23)

0.2% by mass of gallic acid monohydrate containing compound (A), 30% by mass of acrylonitrile butadiene styrene rubber of elastomer (B), and ammonium metavanadate (V) of oxidizing agent (C) An aqueous solution of mass% and ammonium zirconium carbonate 1.0% by mass was used to prepare a primer (Iv). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 150 ° C), the surface treatment agent (I-v) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm.

(Example 24)

After heating and drying (temperature: 100 ° C), the surface treatment agent (Ik) (temperature: 25 ° C) was applied to the surface of the aluminum foil having a thickness of 50 μm by a bar coating method so that the film thickness became 6.0 μm. .

(Embodiment 25)

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-a) (temperature: 25 ° C) was applied to the surface of the nickel foil by a bar coating method so that the film thickness became 6.0 μm.

(Example 26)

In the above-mentioned treatment step, after the pickling and water washing steps, the copper foil is immersed in an electroless nickel bath at a treatment temperature of 30 ° C (containing nickel sulfate 6 hydrate 5 mass %, thiourea 5 mass %) without performing moisture removal. A copper foil having a nickel plating layer was prepared by subjecting it to an aqueous solution adjusted to pH = 3 with sulfuric acid for 5 minutes.

Then, after the water washing and water removal step, the underlayer treatment agent (Ik) (temperature: 25 ° C) was applied by a bar coating method so that the film thickness after heating and drying (temperature: 100 ° C) was 6.0 μm. Surface treatment on the surface of the nickel plating layer.

(Example 27)

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-k) (temperature: 25 ° C) was applied to the surface of the SUS304 foil by a bar coating method so that the film thickness became 6.0 μm.

(Embodiment 28)

After heating and drying (temperature: 100 ° C), the surface treatment agent (I-k) (temperature: 25 ° C) was applied to the surface of the SUS430 foil by a bar coating method so that the film thickness became 6.0 μm.

(Example 29)

Adjusting an aqueous solution containing 0.5% by mass of thiourea of the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) of the oxidizing agent (C). The underlayer treatment agent (II-a) was obtained. Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heat drying (temperature: 150 ° C), the surface treatment agent (II-a) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm. .

(Embodiment 30)

The aqueous solution containing 0.5% by mass of thiourea of the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and 1% by mass of hexammonium heptamolybdate tetrahydrate of the oxidizing agent (C) The bottom treatment agent (II-b) was obtained. Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heat drying (temperature: 150 ° C), the surface treatment agent (II-b) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm. .

(Example 31)

An aqueous solution containing 0.5% by mass of thiourea of the compound (A), 30% by mass of an acrylonitrile butadiene styrene rubber of the elastomer (B), and 0.4% by mass of ammonium metatungstate of the oxidizing agent (C) was adjusted to obtain an underlayer. Treatment agent (II-c). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 150 ° C), the surface treatment agent (II-c) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm. .

(Example 32)

An aqueous solution containing 0.1% by mass of thiourea of the compound (A), 30% by mass of the acrylic rubber of the elastomer (B), and 0.5% by mass of ammonium metavanadate (V) of the oxidizing agent (C) was adjusted to prepare an underlayer treating agent ( II-d). Further, in the elastomer (B), the same aqueous dispersion as in Example 19 was used, and the content was adjusted.

After heating and drying (temperature: 150 ° C), the surface treatment agent (II-d) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm. .

(Example 33)

Adjusting 0.5% by mass of N-methylthiourea containing the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and 0.5 mass of ammonium metavanadate (V) with the oxidizing agent (C) The aqueous solution of % was used to prepare the underlying treatment agent (II-e). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heat drying (temperature: 150 ° C), the surface treatment agent (II-e) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness was 6.0 μm. .

(Example 34)

Adjusting 0.5% by mass of 1-allyl-2-thiourea containing the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and ammonium metavanadate of the oxidizing agent (C) V) 0.5% by mass of an aqueous solution to prepare a primer (II-f). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 100 ° C), the surface treatment agent (II-f) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm. .

(Example 35)

Adjusting 0.5% by mass of 1-allyl-3-(2-hydroxyethyl)thiourea containing the compound (A), 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B), and an oxidizing agent (C) An aqueous solution of ammonium metavanadate (V) of 0.5% by mass to prepare a primer (II-g). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heat drying (temperature: 150 ° C), the surface treatment agent (II-g) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm. .

(Example 36)

An aqueous solution containing 0.5% by mass of thiourea of the compound (A), 30% by mass of the acrylic rubber of the elastomer (B), and 0.5% by mass of hexammonium heptamolybdate tetrahydrate of the oxidizing agent (C) is adjusted to obtain an underlayer treating agent. (II-h). Further, in the elastomer (B), the same aqueous dispersion as in Example 19 was used, and the content was adjusted.

In the above-mentioned treatment step, after the pickling and water washing steps, the copper foil is immersed in an electroless nickel bath at a treatment temperature of 30 ° C (containing nickel sulfate 6 hydrate 5 mass %, thiourea 5 mass %) without performing moisture removal. A copper foil having a nickel plating layer was prepared by subjecting it to an aqueous solution adjusted to pH = 3 with sulfuric acid for 5 minutes.

Then, after the water washing and the water removing step, the undercoating agent (II-h) (temperature 25 ° C) was applied by a bar coating method so that the film thickness after heat drying (temperature: 150 ° C) was 6.0 μm. Surface treatment on the surface of the nickel plating layer.

(Example 37)

An aqueous solution containing 0.5% by mass of thiourea of the compound (A), 30% by mass of the acrylic rubber of the elastomer (B), and 0.5% by mass of hexammonium heptamolybdate tetrahydrate of the oxidizing agent (C) is adjusted to obtain an underlayer treating agent. (II-i). Further, in the elastomer (B), the same aqueous dispersion as in Example 19 was used, and the content was adjusted.

After heat drying (temperature: 150 ° C), the surface treatment agent (II-i) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm. .

(Comparative Example 1)

An aqueous solution containing 15% by mass of the acrylonitrile butadiene styrene rubber containing the elastomer (B) and 0.25% by mass of ammonium metavanadate (V) of the oxidizing agent (C) was prepared without using the compound (A). Agent (III-a). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heat drying (temperature: 100 ° C), the surface treatment agent (III-a) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 1.0 μm. .

(Comparative Example 2)

An aqueous solution containing 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B) was adjusted without using the compound (A) and the oxidizing agent (C) to prepare a primer (III-b). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heat drying (temperature: 100 ° C), the surface treatment agent (III-b) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 2.5 μm. .

(Comparative Example 3)

An aqueous solution containing 0.2% by mass of the gallic acid monohydrate of the compound (A) and 0.5% by mass of ammonium metavanadate (V) of the oxidizing agent (C) was prepared without using the elastomer (B). (III-c).

After heating and drying (temperature: 100 ° C), the surface treatment agent (III-c) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 0.1 μm. .

(Comparative Example 4)

An aqueous solution containing 30% by mass of the acrylonitrile butadiene styrene rubber containing the elastomer (B) and 0.5% by mass of ammonium metavanadate (V) of the oxidizing agent (C) was prepared without using the compound (A). Agent (III-d). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heating and drying (temperature: 100 ° C), the surface treatment agent (III-d) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm. .

(Comparative Example 5)

An aqueous solution containing 30% by mass of the acrylonitrile butadiene styrene rubber of the elastomer (B) was adjusted without using the compound (A) and the oxidizing agent (C) to prepare a primer (III-e). Further, in the elastomer (B), the same aqueous dispersion as in Example 1 was used, and the content was adjusted.

After heat drying (temperature: 100 ° C), the surface treatment agent (III-e) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness was 6.0 μm. .

(Comparative Example 6)

The aqueous solution (III) was prepared by adjusting the aqueous solution containing 0.5% by mass of the thiourea of the compound (A) and 0.5% by mass of ammonium metavanadate (V) of the oxidizing agent (C) without using the elastomer (B). .

After heating and drying (temperature: 150 ° C), the surface treatment agent (III-f) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 0.1 μm. .

(Comparative Example 7)

An aqueous solution containing 30% by mass of the acrylic rubber of the elastomer (B) was adjusted without using the compound (A) and the oxidizing agent (C) to prepare a primer (III-g). Further, in the elastomer (B), the same aqueous dispersion as in Example 19 was used, and the content was adjusted.

After heating and drying (temperature: 150 ° C), the surface treatment agent (III-g) (temperature: 25 ° C) was applied to the surface of the copper foil by a bar coating method so that the film thickness became 6.0 μm. .

(Comparative Example 8)

After being subjected to the above treatment step to (4) water washing, the copper foil is immersed in a blackening treatment bath at a treatment temperature of 90 ° C (containing sodium chlorite 30 g / L, sodium phosphate sodium 12 hydrate 10 g / L, sodium hydroxide) 15 g / L aqueous solution) 3 minutes. Then, it was dried by heating at 100 ° C for 5 minutes in a hot air oven after washing to prepare a blackened sample.

2. Evaluation of metal materials with underlying film

The metal materials with the underlayer coatings obtained in Examples 1 to 37 and Comparative Examples 1 to 8 were subjected to various evaluations as follows.

(1) The arithmetic mean surface roughness of the surface of the metal material and the arithmetic mean surface roughness evaluation of the underlying film

A sample obtained by arranging the obtained metal material with the underlying film into an epoxy resin, and observing the cross section of the sample using a scanning electron microscope (magnification: 10000 times), and estimating the surface of the metal material of the metal material to which the underlying film is attached The average surface roughness Ra was confirmed to be a smooth surface having Ra of 0.50 μm or less.

Further, in the embodiment 12, the arithmetic mean surface roughness Ra of the surface of the metal material to which the metal material of the underlayer film is attached is 0.3 μm, and the change ΔRa of the surface roughness of the metal material before and after the treatment is 0.0 μm, and the arithmetic of the surface of the underlying film The average surface roughness Ra is also 0.1 μm and is very flat.

Further, in the embodiment 31, the arithmetic mean surface roughness Ra of the surface of the metal material to which the metal material of the underlayer film is attached is 0.3 μm, and the change ΔRa of the surface roughness of the metal material before and after the treatment is 0.0 μm, and the arithmetic of the surface of the underlying film The average surface roughness Ra is also 0.1 μm and is very flat.

(2) Adhesiveness

A glass cloth substrate epoxy resin sheet (manufactured by Hitachi Chemical Co., Ltd., trade name: GEA-679N) having a thickness of about 100 μm is attached to the obtained metal material with the underlying film, and the heating temperature is 180 ° C and the pressure is 45 kgf. /cm ² , a heating time of 1 hour was carried out under pressure, and then a metal material-epoxy resin laminated member was obtained.

<1 follow-up>

The laminated member was cut into a width of 1 cm, and a portion of the copper material which was not adhered was stretched in the vertical direction by a 90-degree peeling test in a state where the glass cloth base material epoxy resin sheet was fixed, and the peel strength was measured. .

<heat resistance 2 times adhesion>

The laminated member was cut into a width of 1 cm, and heated at 275 ° C for 1 minute in an oven, and then subjected to a 90-degree peeling test identical to the primary adhesion, and the peel strength was measured.

<Evaluation criteria>

When the peel strength was 0.4 kgf/cm or less, it was evaluated as poor adhesion. The results obtained are shown in Table 1 below.

As is clear from Table 1, the copper material with the underlayer film (Examples 1 to 36) of the present invention obtained by the underlayer treatment method of the present invention, which is obtained by the underlayer treatment method of the present invention, is laminated as an epoxy resin. In the case of the laminated member of the invention, it was confirmed that the metal material and the epoxy resin have excellent adhesion, and particularly excellent adhesion at high temperatures.

On the other hand, in Comparative Examples 1 to 7, the results of the first-order adhesion and the heat-resistant secondary adhesion were both poor. Further, in Comparative Example 8 subjected to the blackening treatment, although the primary adhesion was good, it was confirmed that the heat resistance secondary adhesion was inferior.

<Long-term heat resistance 2 times adhesion test>

Using the metal materials of the underlayer film obtained in the above Examples 19, 24 to 28, 31, 32, 36 and 37 and Comparative Example 5, a copper material was obtained in the same manner as described in the above (2). A laminate of epoxy resin.

The laminated member was cut into a width of 1 cm, heated at 180 ° C for 48 hours in an oven, and then, in a state where the glass cloth base material epoxy resin sheet was fixed, a part of the copper material not followed was vertically oriented. The tensile test was carried out by a 90-degree peel test, and the peel strength was measured. The results obtained are shown in Table 2 below.

As is clear from Table 2, the copper material with the underlayer film of the present invention obtained by the underlayer treatment method of the present invention, which is obtained by the underlayer treatment method of the present invention, when laminated with an epoxy resin as the laminate member of the present invention, It was confirmed that the metal material and the epoxy resin have excellent long-term heat-resistant adhesion.

On the other hand, in Comparative Example 5, there was no adhesion at all.

<moisture resistance 2 times adhesion test>

Using the metal materials of the underlayer film obtained in the above Examples 15 to 19, 23, 24, 26, 29 and 32 and Comparative Examples 5, 7 and 8, in the same manner as described in the above (2) A laminate of copper material-epoxy resin is 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, while the glass cloth substrate epoxy resin sheet was fixed, a part of the laminate was not fixed. The portion of the next copper material was stretched in the vertical direction to perform a 90-degree peeling test, and the peel strength was measured. The results obtained are shown in Table 3 below.

As is clear from Table 3, the copper material with the underlayer film of the present invention obtained by the underlayer treatment method of the present invention, which is obtained by the underlayer treatment method of the present invention, is laminated as an interlayer member of the present invention even when laminated with an epoxy resin. It is also confirmed that the metal material and the epoxy resin have excellent adhesion under high humidity.

On the other hand, in Comparative Examples 5 and 7, the adhesion was inferior. Further, in Comparative Example 8 in which blackening treatment was applied, it was confirmed that the moisture resistance was poor in secondary adhesion.

<acid-resistant 2 times adhesion test>

Using the metal materials of the underlayer film obtained in the above Examples 12, 19, and 37 and Comparative Example 8, a copper material-epoxy resin laminated member was obtained in the same manner as described in the above (2).

The laminated member was cut into a width of 1 cm, and immersed in a 1 M hydrochloric acid aqueous solution at 25 ° C for 15 minutes, and then a part of the copper material which was not adhered was placed in a state where the glass cloth base material epoxy resin sheet was fixed. The 90-degree peel test was performed by stretching in the vertical direction, and the peel strength was measured. The results obtained are shown in Table 4 below.

The metal materials with the underlying film obtained in Examples 12, 19 and 37 were confirmed to have good adhesion even after treatment with an acidic solution. On the other hand, in Comparative Example 8 subjected to the blackening treatment, the peel strength was 0.0 kgf/cm, and it was confirmed that the adhesion was poor. According to this characteristic, when the metal material with the underlying film of the present invention is used, it is possible to suppress problems such as a pink circle which is generated when a printed wiring board is produced.

(3) Stripping interface analysis

Using the copper material with the underlayer film obtained in Example 1, after the evaluation of the adhesion of the above (2), the XPS depth direction was performed on the copper material side and the epoxy resin side peeling surface under the conditions shown below. analysis. The results are shown in Figs. 2 to 5 .

<XPS depth direction analysis>

‧Usage device: ESCA850 manufactured by Shimadzu Corporation

‧Inspire X-ray: Mg‧Kα

‧Measured area: about 50mm ²

‧Measurement area: Cls, Cu2p, CuLMM, V2p

‧ Splash depth: 240mm (spray rate 80nm/min in terms of SiO ₂ )

‧ Splash time 3 minutes (XPS analysis at 0, 1, 8.5, 16, 23.5, 31, 38.5, 76, 180 seconds)

Figure 2 is a plot of the peak intensity from the Cls energy level. The sputtering time of 0 seconds corresponds to the peeling interface, the sputtering time of the horizontal axis, and the graph of the negative side indicates that the epoxy side and the positive side of the graph indicate the copper material side. From Fig. 2, no carbon was detected on the side of the copper material on the peeling interface except for the vicinity of the surface. Therefore, it was confirmed that the peeling mode was the interface between the copper material and the underlying film.

Figure 3 is a plot of the peak intensity from the Cu2p energy level. From Fig. 3, copper was detected on the epoxy side of the peeling interface (detection range: sputtering time 0 to 180 seconds, peak maximum point 8.5 to 38.5 seconds). Since the correct sputtering rate of the underlying film cannot be determined, the correct range of the concentrated region of copper in the underlying film cannot be estimated, but it is estimated to be about several hundred nm. Moreover, the narrow spectrum of the CuLMM region in the respective sputtering depths of the epoxy resin side of the peeling interface of FIG. 4 can be confirmed in the vicinity of 355 eV from the metal state of copper, and 357 eV from the monovalent state of copper. There is a peak in the vicinity, and it is confirmed that the surface layer on the surface side of the copper material of the underlayer film (the region of several hundred nm from the surface of the underlying film) contains copper, and it is confirmed that the copper system exists in a metal state and a monovalent state.

Further, Fig. 5 is a distribution diagram of peak intensities from the V2p energy level. A peak from the V2p energy level is detected near the surface of the copper side peeling interface (the region where the sputtering time is 0 to 8.5 seconds). Since the correct sputtering rate cannot be determined, the correct range of the concentrated region of the vanadium element cannot be estimated, but it is estimated to be about several tens of nm. It was confirmed that the surface layer on the surface side of the copper material of the underlayer film (the region of several tens of nm from the surface of the underlying film) had a concentrated layer of vanadium.

[Industrial availability]

The underlayer treatment agent of the present invention is applicable not only to the copper material and the resin of the printed wiring board described in the prior art, but also to the coating method, the lamination method, and the injection molding method for various metal materials. The underlayer treatment agent when the resin is formed by a method.

1‧‧‧Layered components

2‧‧‧Metal materials

3‧‧‧ bottom film

4‧‧‧ resin layer

Fig. 1 is a schematic cross-sectional view showing a laminated member of the present invention.

Figure 2 is a plot of the peak intensity from the C1s energy level.

Figure 3 is a plot of the peak intensity from the Cu2p energy level.

Figure 4 is a narrow spectrum of the CuLMM region at each sputter depth of the epoxy side of the stripping interface.

Figure 5 is a plot of the peak intensity from the V2p energy level.

Claims (10)

A primer for a metal material, comprising a compound (A) and at least one elastomer (B) selected from the group consisting of having one or more benzene nucleuses and selected from the group consisting of hydroxyl groups, carboxyl groups, and amine groups At least one of a group consisting of a compound (A-1) and a thiourea derivative (A-2) which are directly bonded to a functional group of two or more carbon atoms constituting the carbon atom of the benzene nucleus; The thiourea derivative (A-2) is one selected from the group consisting of thiourea, N-methylthiourea, and 1-allyl-2-thiourea. The underlayer treating agent for a metal material according to claim 1, which further contains at least one oxidizing agent (C). The primer for treating a metal material according to the second aspect of the invention, wherein the oxidizing agent (C) is selected from the group consisting of a nitric acid compound, a sulfuric acid compound, a hydrohalic acid compound, and a VA element having an oxidation number of 4 or 5. At least one of a compound, a group VIA element compound having an oxidation number of 6, a copper (II) compound, an iron (III) compound, and an organic peroxide. The underlayer treatment agent for a metal material according to the first aspect of the invention, wherein the compound (A-1) is a cyclic organic compound represented by the following formula (1) or (2), and the cyclic organic compound. a polycondensate or a copolymer of the cyclic organic compound and another polymerizable compound; (In the 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 group selected from a group consisting of a hydroxyl group, a carboxyl group and an amine group. In the 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 represent a group selected from a hydroxyl group, a carboxyl group and an amine group. a functional group in the group). A metal material with a primer film attached thereto, which is obtained by treating a metal material with a primer for a metal material according to any one of claims 1 to 4, wherein a metal atom derived from the metal material is concentrated The surface layer of the metal material side of the underlayer film, a part of which is present in a metallic state. A metal material with a primer film attached thereto, which is obtained by treating a metal material with a primer for a metal material according to any one of claims 2 to 4, wherein a metal atom derived from the metal material is concentrated. a surface layer of the metal material side of the underlayer film, a part of the metal atom The metal is present in a metal state, and at least one metal atom selected from the group consisting of vanadium, niobium, tantalum, molybdenum, and tungsten is concentrated on the surface of the metal material side of the underlying film. A method for treating a bottom layer of a metal material, comprising the step of applying a primer for treating a metal material according to claim 1 to a surface of a metal material; and after the coating step, directly drying without washing with water A drying step of forming a primer film. The method for processing a metal material according to claim 7, wherein before the coating step, metal plating consisting of Ni and/or Co is applied to the surface of the metal material by electrolysis or chemical reaction. And carry out the steps of washing. A metal material with an underlying film obtained by treating a metal material by an underlying treatment method of a metal material according to claim 7 or 8. A laminated member comprising the metal material with the underlying film attached to the ninth aspect of the patent application and the resin layer provided on the underlying film.