WO2007105800A1

WO2007105800A1 - Surface treatment liquid for copper material, method of surface treatment for copper material, copper material with surface treatment coating, and laminate member

Info

Publication number: WO2007105800A1
Application number: PCT/JP2007/055255
Authority: WO
Inventors: Masaya Miyazaki; Hiroki Hayashi; Kuniyoshi Murakami
Original assignee: Nihon Parkerizing Co., Ltd.
Priority date: 2006-03-15
Filing date: 2007-03-15
Publication date: 2007-09-20
Also published as: CN101400826B; KR20080100821A; JPWO2007105800A1; CN101400826A; KR101067993B1; JP5111362B2

Abstract

A surface treatment liquid for copper material; a method of surface treatment therefor; and a surface treatment coating formed on the surface of copper material thereby. There is provided a surface treatment liquid for copper material, characterized by containing a copper oxidation etchant, a compound containing at least one metal element selected from the group consisting of Ti, Zr, Hf and Si and, as an HF supply source, a fluorinated compound. Further, there is provided a method of surface treatment characterized in that a copper or copper alloy material is immersed in the surface treatment liquid. Still further, there is provided a surface treatment coating, disposed on copper or copper alloy by the method, characterized by containing not only at least one metal element selected from the group consisting of Ti, Zr, Hf and Si but also Cu, O and F. Still further, there is provided a laminate member characterized in that the copper material with surface treatment coating and a resin layer are joined together via the surface treatment coating.

Description

Specification

Surface treatment solution for copper material, surface treatment method for copper material, copper material with surface treatment film, and laminated member

Technical field

TECHNICAL FIELD [0001] The present invention relates to a surface treatment solution for copper material for forming a film on the surface of a copper material, a surface treatment method for a copper material using the same, a copper material with a surface treatment film, and a laminated member

[0002] Various metal materials are used for industrial products, and various surface treatments are applied to impart functionality such as heat resistance, hydrophilicity, and slidability in addition to corrosion resistance and adhesion. There are many things.

Copper materials such as copper and copper alloys are often required to have functionality on the surface, but the dissolution of metals coupled with the reduction reaction of hydrogen ions, such as iron, zinc, and aluminum. The surface treatment methods known at present are mostly coating-type treatments using inhibitors such as silane coupling agents and benzotriazoles. Except for surface roughness due to treatment and etching, there are few useful chemical reactive surface treatments.

[0003] One of the features of copper materials is high electrical conductivity and heat dissipation. As one example, these materials have recently been widely applied to electronic and electrical components such as printed wiring boards, lead frames, and LSIs. There are many joints between the copper material and the resin in the member, and these require the adhesion between the metal and the resin in a state where heat is applied. Specifically, epoxy resins used for their excellent thermal stability, chemical stability, insulation properties, etc., thermosetting resins such as polyimide resins, or high molding temperatures, and thermoplastic resins When molding these resins on a metal material, it is necessary to expose the entire part to a high temperature of 150 to 300 ° C. In addition, when mounting active components such as semiconductor elements and passive components such as LCR, the power used for soldering. Since lead solder can no longer be used in recent environmental issues, the solder reflow temperature is becoming higher and higher. . [0004] In such a situation, if the adhesiveness between the copper material and the resin is inferior, the water adsorbed on the surface of the copper material, especially at a high temperature, and the resin interface in the manufacturing process. The absorbed moisture expands and promotes peeling at the interface between the copper material and the resin. Also, the copper material swells, etc., thereby impairing the internal corrosion resistance and possibly cracking the resin. The wiring pattern can be destroyed, which can cause t ヽぅ results.

In addition, a brittle acid film is formed at the interface between the copper material and the resin during heating, causing adhesion degradation due to cohesive failure, and easily diffusing into the polyimide resin and Si single crystal. These measures are also required when copper materials are used for wiring materials, such as deterioration of air characteristics.

[0005] Generally, in order to improve the adhesion between a metal material and a resin, a method of roughening the surface of a metal base material mechanically by blasting or the like to form a V or a loose anchor has been used for a long time. It has been.

However, such machining generally tends to be low in productivity and high cost, and the fine particles generated during processing often impair the precision of electronic and electrical components. Therefore, recently, the surface of a metal material is often subjected to some kind of chemical surface treatment for the purpose of improving the adhesion due to the anchor effect and chemical affinity with the resin.

[0006] For example, as surface treatments for improving adhesion, Patent Documents 1 and 2 describe methods aimed at improving adhesion by subjecting the surface of a metal material to chromate treatment. Yes.

Patent Document 3 describes a method of forming a special chromium compound layer having a large number of fine scaly projections on the surface using an electrolytic method.

[0007] However, all of these methods use a hexavalent chromium compound that is harmful to the surface treatment liquid, and the surface of the formed metal substrate contains hexavalent chromium. This is considered environmentally undesirable.

In addition, based on the ELV Directive that came into effect in October 2000 and the RoHS Directive that came into effect in February 2003, the specifications are particularly restricted for electronic and electrical equipment and automotive parts. Therefore, it aims to improve the adhesion with rosin without using a hexavalent chromium compound. Research and development of surface treatment of metal materials is being conducted, and the same is true for copper materials.

[0008] A copper oxide (CuO) treatment called "black dyeing" is known as a chemical conversion surface treatment of a copper material that does not use a hexavalent chromium compound. However, this copper oxide treatment has good adhesion at the initial stage of adhesion, but it is inferior in durability, so the bonding strength decreases with time, and the initial adhesion can be maintained during heating. There are two problems.

In addition, when used as a wiring material for printed wiring boards, higher density of printed wiring boards and higher speed of signals are required, and copper wiring is becoming thinner and narrower. Along with this, the copper surface roughening technology, which has been widely used to provide adhesion between the insulating layer and the copper wiring, has the effect of increasing the skin effect and transmission loss, thus roughening the surface. There is a need for a surface treatment that can be bonded to the insulating layer with only chemical affinity.

Patent Document 1: Japanese Patent Application Laid-Open No. 9209167

Patent Document 2: JP-A-9-172125

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

Disclosure of the invention

Problems to be solved by the invention

[0010] The present invention is excellent in adhesiveness with a resin, especially at high temperatures, and does not use substances that cause environmental contamination such as hexavalent chromium, and can almost roughen the surface. An object of the present invention is to provide a surface treatment solution for copper material, a surface treatment method using the same, a copper material and a laminated member.

Means for solving the problem

[0011] As a result of intensive studies to achieve the above object, the inventors of the present invention include a specific copper oxide etching agent, at least one metal element selected from the group force of Ti, Zr, Hf, and S. By using a surface treatment solution for copper materials containing a specific proportion of a compound and a fluorine-containing compound as a supply source of HF, excellent adhesion between the copper material and the resin, particularly at high temperatures The present invention has been completed.

That is, the present invention provides the following (1) to (12). (1) Next component (A), component (B), and component (C):

(A) HCIO, HCIO, HCIO, HBrO, HBrO, HBrO, HBrO, ΗΝΟ, ΗΝΟ, Η S Ο

4 3 2 4 3 2 3 2 2 2 6

Oxyacids selected from the group consisting of, Η Ο, ΗΜηΟ, HVO, Η WO and Η ΜοΟ,

2 2 4 3 2 4 2 4

And organic peroxides selected from the group consisting of salt, ketone peroxide, peroxyketal, hydride peroxide, dialkyl peroxide, disilver oxide, peroxyester, peroxydicarbonate, and At least one copper acid etchant selected for its salt power

(B) Group force consisting of Ti, Zr, Hf and S Compound containing at least one metal element selected

(C) Fluorine-containing compound as a source of HF

The total molar concentration A of the metal elements of Ti, Zr, Hf and Si in the compound of component (B) and the total fluorine atoms in the fluorine-containing compound of component (C) are converted to HF. A surface treatment solution for copper materials, characterized in that K = AZB, which is the ratio to the molar concentration B at that time, is in the range of 0.03≤K≤0.18.

(2) In addition, component (D):

The surface treatment liquid for copper material according to (1), comprising a compound containing at least one element selected from the group consisting of Ag, Al, Cu, Fe, Mn, Mg, Ni, Co, Cr, Ta, and Zn .

(3) The surface treatment liquid for copper material according to (1) or (2), further containing 10 to 50,000 ppm of an organic compound (E) containing an amino group.

(4) An amino group-containing organic compound (E) is bullamine, polybulamine, allylamin, diarylamine, polyallylamine, polyamine polyamide, ammine-modified phenolic resin, amamine-modified polybutanol, ammine-modified urethane resin, benzotriazole, The surface treatment solution for copper material according to (3), which is at least one selected from triazine thiol and a derivative force thereof.

(5) A surface treatment method for a copper material, wherein the copper material is brought into contact with the surface treatment liquid according to any one of (1) to (4).

(6) Group material consisting of Ti, Zr, Hf and Si A copper material with a surface treatment film characterized by containing at least one metal element selected from the group consisting of Cu, 0 and F. (7) The copper material with a surface treatment film according to (6), further comprising at least one selected from the group consisting of Ag, Al, Cu, Fe, Mn, Mg, Ni, Co, Cr, Ta and Zn.

(8) The copper material with a surface treatment film according to (6) or (7), which further contains carbon C.

(9) Group force including Ti, Zr, Hf and Si forces contained in the surface treatment film At least one kind of metal element and Cu selected, and Ag, Al, Fe, Mn, Mg, Ni, Co, Cr Or (6) to (8), wherein at least one selected from the group forces consisting of Ti, Ta and Zn is present in the state of a hydrous oxide, a fluoride, or an intermediate product thereof Copper material with a surface treatment coating.

(10) The copper material with a surface-treated film according to any one of (6) to (9), wherein the Cu content is 0.3 to 60 atm% at a depth of 5 nm from the surface of the copper material.

(11) Coating As the material goes to the interface side, the group force of Ti, Zr, Hf, and S is selected. It has a graded structure in which the content of at least one metal element decreases and the content of Cu increases (7 The copper material with a surface treatment film according to any one of) to (10).

(12) A laminated member having a resin layer on the copper material with a surface treatment film according to any one of claims 6 to 11.

The invention's effect

[0013] The surface treatment liquid for copper material according to the present invention has excellent adhesion to a resin, particularly at high temperatures, with almost no rough surface, and a substance that causes environmental pollution. Not used.

Brief Description of Drawings

FIG. 1 is an example of a graph of XPS analysis of a surface treatment film having a gradient structure.

FIG. 2 is an example of an XPS analysis graph of a surface treatment film having a uniform structure.

FIG. 3 is a schematic cross-sectional view showing a laminated member of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0015] The treatment liquid of the present invention comprises the following component (A), component (B), and component (C);

(A) HC10, HC10, HC10, HBrO, HBrO, HBrO, HBrO, HNO, HNO, H S O

4 3 2 4 3 2 3 2 2 2 6

Oxyacids selected from the group consisting of, HO, HMnO, HVO, HWO and HMoO, And organic peroxides selected from the group consisting of salt, ketone peroxide, peroxyketal, hydride peroxide, dialkyl peroxide, disilver oxide, peroxyester, peroxydicarbonate, and At least one copper acid etchant selected for its salt strength, group power,

(B) a group force consisting of Ti, Zr, Hf and S, a compound containing at least one metal element selected, and

(C) Fluorine-containing compound as a source of HF

The total molar concentration A of the metal elements of Ti, Zr, Hf and Si in the compound of component (B) and the total fluorine atoms in the fluorine-containing compound of component (C) are converted to HF. The surface treatment solution for copper material is characterized in that K = AZB, which is the ratio to the molar concentration B at that time, is in the range of 0.03≤K≤0.18.

The surface treatment liquid of the present invention further comprises component (D):

(D) a compound containing at least one element selected from the group consisting of Ag, Al, Cu, Fe, Mn, Mg, Ni, Co, Cr, Ta and Zn

It is one of the preferable embodiments to contain.

The surface treatment liquid of the present invention further comprises an organic compound containing an amino group (E): (E) berylamine, polyvinylamine, allylamamine, diarylamine, polyallylamine, polyamine polyamide, ammine-modified phenolic resin, ammine-modified Polyburfenol resin, amine-modified urethane resin, benzotriazole, triazine thiol, and their group power that also has a derivative power One of the preferred embodiments containing 10 to 50,000 ppm of a compound containing at least one selected from them One.

The object of the surface treatment with the treatment liquid of the present invention is a copper material. The copper material is not particularly limited, and examples thereof include pure copper and copper alloy.

An example of pure copper is oxygen-free copper.

The copper alloy is preferably one containing 50 mass% or more of copper, for example, brass containing 30 to 40 mass% Zn. Examples of alloy components other than copper in the copper alloy include Zn, P, Al, Fe, and Ni.

The copper material is not particularly limited in shape, structure and the like. Shape is, for example, plate, foil, rod Is mentioned.

The surface treatment liquid for copper and copper alloy material of the present invention contains component (A), component (B), and component (C), more preferably component (D), more preferably component (E).

Component (A) consists of HCIO, HCIO, HCIO, HBrO, HBrO, HBrO, HBrO, HNO, HNO

4 3 2 4 3 2 3

, H S O, H 2 O 3, HMnO 2, HVO 2, H 2 WO and H MoO

2 2 2 6 2 2 4 3 2 4 2 4

Organic peroxides selected from the group consisting of acids and their salts, ketone peroxides, peroxyketals, hydrated peroxides, dialkyl peroxides, disilver oxides, peroxyesters, and nonoxydicarbonates. It is at least one copper acid etchant that is chosen for its porcelain and its salt strength.

More specifically, diisoptylyl peroxide, Tamil peroxyneodecanoate

, Di-n-propinoleveroxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3,3-tetramethylbutylperoxydecanoate , Di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexyloxyneodecanoate, t-butylperoxy Neodecanoate, t-butylperoxyneoheptanoate, t-hexyloxyxivalate, t-butylperoxybivalate, di (3,5,5-trimethylhexanoyl) peroxide , Dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethyl) To (Xanoylperoxy) Xan, t-hexyloxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butyl peroxide- 2-ethylhexanoate, 1,1-di (t-butylcarboxy) -2-methylcyclohexane, 1,1-di (t-hexyloxy) -3,3,5-trimethylcyclohexane, 1, 1-di (t-hexyloxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane , T-Hexylperoxyisopropyl monocarbonate, t-Butinoleoxypersimaleic acid, -Butyl-peroxy-3,5,5-trimethylhexanoate, t-Butylperoxyla Ururic acid, t-butyl peroxyisopropyl monocarbonate, t-butyl per Oxy-2-ethylhexyl monocarbonate, t-hexyloxybenzoate, 2,5-di-methyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate 2,2-di_ (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl 4,4-di- (t-butylperoxy) vallate, di (2-butylperio Xyisopropyl) benzene, dicumyl peroxide, di-t-hexylsilver oxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne-3, diisopropylbenzene hydride baroxide, Examples are 1,1,3,3-tetramethylbutylhydride peroxide, cuminhydride peroxide, t-butylhydride peroxide, and 2,3-dimethyl-2,3-diphenylbutane.

Ingredient (A) acts as an oxidant that promotes copper acid dissolution, with a rise in pH. The concentration of component (A) in the surface treatment solution is preferably 10 ppm to 100,000 ppm. More preferably 50ρρπ! The concentration range is ~ 50000ppm. If the concentration is 10 ppm or less, there may be cases where the copper oxide etching force is insufficient and the film formation is not sufficient. Above 50000ppm, the cost is high and may be economically disadvantageous.

[0018] The component) is a compound containing at least one metal element selected from the group force of Ti, Zr, Hf and S.

For example, TiCl, TiCl, Ti (SO), Ti (SO), Ti (NO), HTiF, HTiF salts (

3 4 2 4 3 4 2 3 4 2 6 2 6 For example, K TiF), TiO, Ti O, TiO, TiF, ZrCl, Zr (SO), Zr (NO), H ZrF

2 6 2 3 2 4 4 4 2 3 4 2 6

, H ZrF salts (eg, K ZrF), ZrO, ZrF, HfCl, Hf (SO), H HfF, H Hf

2 6 2 6 2 4 4 4 2 2 6 2

F salt (eg, K HfF), HfO, HfF, H SiF, H SiF salt (eg, K SiF),

6 2 6 2 4 2 6 2 6 2 6

Examples include Al 2 O 3 (SiO 2) 2 and SiO 2. Two or more of these may be used in combination.

2 3 2 3 2

The concentration of component (B) in the surface treatment solution is preferably 5 ppm to 10,000 ppm. More preferably, the concentration range is 5 ppm to 5000 ppm. If the concentration is 5 ppm or less, the content of component (B) in the surface treatment film may be insufficient in terms of performance. Above lOOOOppm, the cost is high and may be economically disadvantageous.

[0019] Component (C) is a fluorine-containing compound capable of supplying HF.

For example, HF, H TiF, TiF, H ZrF, ZrF, H HfF, HfF, HBF, NaHF, K

2 6 4 2 6 4 2 6 4 4 2

HF, NH HF, NaF, KF, NH F. These may be used in combination of two or more [0020] Component (D) is a compound containing at least one element selected from the group consisting of Ag, Al, Cu, Fe, Mn, Mg, Ni, Co, Cr, Ta and Zn. For example, hydrated oxides, chlorides, fluorides, sulfates, nitrates and carbonates of the above elements can be mentioned.

The concentration of component (D) in the surface treatment solution is preferably 5 ppm to 10,000 ppm. More preferably, the concentration range is 5 ppm to 5000 ppm. If the concentration is 5 ppm or less, the effect of adding component (D) cannot be expected. lOOOOppm and higher costs may be disadvantageous economically

[0021] When the treatment liquid of the present invention contains the component (E), the corrosion resistance of the obtained surface treatment film becomes more excellent. Specifically, for example, the discoloration resistance when the coated copper material is exposed to high temperatures becomes more excellent. In addition, when copper materials are used for the above-mentioned wiring materials, various problems such as formation of brittle copper oxide film under high temperature environment, diffusion to polyimide resin and Si single crystal are less likely to occur. .

According to the study of the present inventor, when the treatment liquid of the present invention contains the component (E), the surface treatment film to be obtained contains C (carbon) and N (nitrogen). Therefore, it is considered that the film structure becomes denser by incorporating an organic compound containing the amino group of component (E) into the film!

[0022] Component (E) is composed of buluamine, polyburuamine, arlylamin, diarylamin, polyallylamine, polyamine polyamide, amamine-modified phenolic resin, ammine-modified polybutanol, ammine-modified urethane resin, benzotriazole, triazine thiol and These derivative forces are the group forces that are chosen at least one organic compound.

Derivatives here include, for example, buramine, polybulamine, arrylamine, diarylamine, polyallylamine, polyamine polyamide, amamine-modified phenol resin, amine-modified polybutanol, amine-modified urethane resin, benzotriazole, and triazine glycol. Group powers Compounds containing at least one selected from the group, compounds derived from this compound, and salts of these compounds.

The addition amount of the organic compound (E) is preferably 10 to 50,000 ppm from the viewpoint of the obtained film performance. [0023] The mechanism for generating the surface treatment film is as follows.

The metal element in the compound of component (B) exists as MF ² "(wherein M represents Ti, Zr, Hf or Si. The same shall apply hereinafter) in an aqueous solution containing a sufficient amount of HF. To do.

6

Here, a chemical equilibrium represented by the following formula (1) is established between MF and F-.

6

[0024] MF ² "+ 20H" MO + 2H ++ 6F— (1)

6 2

[0025] When a copper material is immersed in the treatment liquid of the present invention, it is coupled with a reduction reaction of the copper oxidation etchant of component (A) (the following formula (2)) to form a Cu dissolution reaction (the following formula (3) Power is generated.

[0026] Ox + ne— → Red + mOH— (2)

Cu → Cu ²⁺ + 2e "(3)

[0027] Due to the increase in pH associated with the reduction reaction of the above formula (2), the equilibrium of the above formula (1) advances to the right, and the fluoride ion coordinated to the metal element M becomes the hydroxide ion. It is replaced in sequence (formula (4)) and finally becomes a hydroxide of metal M. Thereafter, the metal M hydroxide undergoes dehydration condensation and partially becomes an oxide (formula (5)). The metal element M is MF (OH), M (OH), MO, or

It is considered that (6-x) x 4 2 or its hydrate strength is a group force that is deposited on the surface of the copper material in at least one selected state.

MF ² — + 40H— → MF (OH) + xF— + (4- x) OH— → M (OH) + 6F— (4)

6 (6-x) x 4

M (OH) + M (OH) → 2MO + 4H O (5)

4 4 2 2

[0028] Further, when the treatment liquid of the present invention contains the component (D), the compound of the component (D) forms a complex with free F-, so that the equilibrium of the above formula (1) is more on the right side. The generation of the surface treatment film is promoted and the film is formed in a shorter time. In addition, as another effect of containing component (D), component (D) itself prays together with metal element M, thereby further improving the adhesion to the resin. Component (D) is present in the form of a hydrous oxide, a fluoride, or an intermediate product thereof, like the metal element M.

[0029] Simultaneously with the MO precipitation described above, the copper ions (Cu ²⁺ ) eluted by the above formula (3)

2

It precipitates in the state of fluoride, fluoride, or an intermediate product thereof, and these also constitute a surface treatment film.

[0030] As described above, in the coated copper material obtained by the present invention, at least one metal element selected from the group force consisting of Ti, Zr, Hf and Si and Cu, and further Ag, Al , Fe , Mn, Mg, Ni, Co, Cr (lll), Ta and Zn, at least one selected from the group consisting of hydrous oxide, fluoride, or its intermediate product is selected at least The surface treatment film is formed in one kind of state.

[0031] In the treatment liquid of the present invention, the total molar concentration A of the metal elements in the compound of the component (B) and the amount of fluorine atoms in the fluorine-containing compound of the component (C) are HF. When converted, the ratio K (= A / B) to molarity B satisfies 0.03≤K≤0.18.

If the wrinkles are too large, a sufficient amount of film can be deposited to obtain adhesion, but the stability of the treatment liquid is significantly impaired, resulting in problems in continuous operation. On the other hand, if the wrinkle is too small, it is difficult for the balance of the above formula (1) to move to the right, so that it is not possible to form a sufficient amount of film in a short time to obtain adhesion.

[0032] As described above, the treatment liquid of the present invention has a surface of a copper material by an equilibrium reaction between HMF and HF.

2 6

A surface treatment film is deposited on the surface.

Here, the component concentration of Ti, Zr, Hf, and S is the molar concentration of the compound containing at least one metal element selected (the total molar concentration when two or more compounds are used) ) In terms of the metal element is preferably 0.05 to LOOmmolZL.

Within the above range, the molar concentration of the metal element as the film component is sufficiently large, and a sufficient amount of film can be formed to obtain various performances such as adhesion, and economically. There is no disadvantage.

[0033] HF supplied by the component (C) plays a role of holding the component of the copper material eluted by the etching reaction as a fluorine complex in the treatment liquid, in addition to the role of forming the above-described surface treatment film. . For this reason, sludge does not occur in the treatment liquid of the present invention.

The treatment liquid of the present invention contains a chelating agent capable of chelating an acid other than HF and a metal ion that elutes the copper material force in order to dissolve the components of the eluted copper material. be able to. For example, it is effective when the amount of copper material to be processed is very large relative to the amount of processing liquid.

Examples of acids other than HF include inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid, oxalic acid, tartaric acid, succinic acid, succinic acid, darconic acid, and phthalic acid.

Examples of chelating agents include EDTA and thiourea. [0034] Although the pH of the treatment liquid of the present invention is not particularly limited, it is preferably pH 2 to 6 in terms of the stability of the treatment liquid and the ease of film formation. Is more preferable.

[0035] The treatment method of the present invention includes a surface treatment step of bringing a copper material into contact with the above-described treatment liquid of the present invention.

By bringing the copper material into contact with the treatment liquid of the present invention, a surface treatment film containing the metal element oxide of component (B) and the copper oxide is formed on the surface thereof.

The method for bringing the copper material into contact with the treatment liquid of the present invention is not particularly limited, and examples thereof include spray treatment, immersion treatment, and pouring treatment. Two or more of these can be used in combination (for example, combined use of dipping treatment and spray treatment).

Further, there is no particular limitation on the presence / absence of force balance in the treatment liquid tank in the immersion treatment, the spray pressure in the spray treatment, the type of the spray nozzle, and the like.

In the treatment method of the present invention, it is also possible to form a surface treatment film by electrolytic treatment using the copper material as a cathode in the treatment liquid of the present invention.

In the treatment method of the present invention, the use conditions of the treatment liquid of the present invention are not particularly limited.

The treatment temperature is preferably 10 to 90 ° C, more preferably 20 to 60 ° C. When the processing temperature is 60 ° C or less, use of useless energy can be suppressed, so that economical viewpoint power is also preferable.

The processing time can be set as appropriate.

[0037] The coated copper material of the present invention is a surface-treated film containing at least one metal element selected from the group consisting of Ti, Zr, Hf and Si, copper, oxygen, and fluorine. Is a copper material with a coating.

[0038] Further, the surface treatment film further contains at least one selected from the group force consisting of Ag, Al, Cu, Fe, Mn, Mg, Ni, Co, Cr (lll), Ta and Zn. preferable. As a result, the adhesion to the resin is improved.

The group force of Ti, Zr, Hf and S contained in the surface treatment film is selected from at least one metal element and Cu, as well as Ag, Al, Fe, Mn, Mg, Ni, Co, Cr (lll), At least one kind of force selected from the group forces consisting of Ta and Zn Hydrous oxide, fluoride, or U, which preferably exists in the state of intermediate products.

The surface treatment film preferably further contains carbon. As a result, the coating structure becomes denser and the coating-coated copper material has better discoloration resistance when exposed to high temperatures. Various problems such as the formation of brittle copper oxide film below, diffusion into polyimide resin and Si single crystal are less likely to occur.

[0039] For the coated copper material of the present invention, the surface-treated film comprises the composition of the treatment liquid of the present invention (for example, the type of the metal element of component (B), the copper acid of component (A)). The film structure can be made desired by appropriately selecting the type of etching agent and the concentration of each component. Specifically, the copper content and the distribution in the depth direction of the surface treatment film can be various.

Fig. 1 and Fig. 2 show the depth of at least one metal element (M), copper (Cu), and oxygen (O) selected from the group strength of Ti, Zr, Hf and S in the surface treatment film. Fig. 1 shows an example of a surface treatment film with a tilted structure and Fig. 2 shows a uniform surface structure. In FIG. 1 and FIG. 2, “M”, “Cu” and “0” represent the atomic contents of at least one metal element selected from the group consisting of Ti, Zr, Hf and Si, copper and oxygen, respectively. Show. In the surface-treated film having the inclined structure shown in FIG. 1, the content of the metal element (M) generally decreases as the force from the film surface to the interface with the copper material decreases, and the copper (Cu) The content of is increasing.

In the surface-treated film with a uniform structure shown in Fig. 2, the content of copper (Cu) with a high metal element (M) content is low near the film surface (Etch Time: 0 to about 40 seconds). And they are almost constant in the depth direction.

[0040] In the coated copper material of the present invention, one preferred embodiment is that the copper content in the region from the surface of the copper material to 5 nm is 0.3 to 60 atm%. If the copper content is too high, as described above, when copper material is used as the wiring material, formation of a brittle copper acid film in a high temperature environment, polyimide resin or Si single crystal Since problems such as diffusion are likely to occur, the adhesiveness to the resin may be poor.

[0041] Further, as shown in FIG. 1, from the surface of the surface treatment film toward the interface with the copper material, One preferred embodiment is that the content of at least one metal element selected from the group force of Ti, Zr, Hf and S is decreased and the content of copper is increased. The surface-treated film having such a structure can prevent problems such as copper diffusion in a high-temperature environment described above while having excellent adhesion with a copper material. Moreover, the thickness of the surface treatment film is on the order of submicrons, and the copper material with a film of the present invention is compared with the conventional roughening treatment in order to uniformly etch the copper material surface during the surface treatment. A very smooth surface can be obtained. One of the preferred embodiments is that the center line average roughness Ra of the coated copper material surface is 0.50 or less.

[0042] The coated copper material of the present invention is excellent in adhesiveness between the surface-treated film and the resin, particularly adhesiveness at high temperature, and thus is suitably used for various applications. For example, it is suitably used for a laminated member of the present invention described later.

Moreover, since the coated copper material of the present invention is excellent in corrosion resistance, it is suitably used for various applications.

[0043] The laminated member of the present invention is a laminated member having the above-described coated copper material of the present invention and a resin layer provided on the surface treatment film.

FIG. 3 is a schematic cross-sectional view showing the laminated member of the present invention. The laminated material 10 shown in Fig. 3 is made of copper material 2 and at least one metal element whose surface is selected from the group forces of Ti, Zr, H, and Si, copper, oxygen, fluorine, Ag, Al, Coated copper of the present invention having a surface treatment film 4 containing at least one selected from the group force consisting of Fe, Mn, Mg, Ni, Co, Cr (III), Ta and Zn, and further carbon. It has a material 6 and a resin layer 8 provided on the surface treatment film 4.

[0044] The material of the resin layer is not particularly limited. For example, AS resin, ABS resin, fluorine resin, polyamide, polyethylene, polyethylene terephthalate, polysalt vinylidene, polycarbonate, polystyrene, polysulfone. Thermoplastic resins such as epoxy resin, polypropylene resin, epoxy resin, epoxy resin, polyimide resin, polyimide, polyurethane, bismaleimide 'triazine resin, modified polyphenylene ether, cyanate ester, etc. It is done. These rosins may be modified by functional groups.

Among them, epoxy resin and polyimide resin are both excellent in heat-resistant adhesion, Useful for electronic components such as printed wiring boards, lead frames, and LSI packages. Moreover, the resin layer can contain fibers such as glass fibers and aramid fibers. By containing the fiber, the resin layer is reinforced.

[0045] The laminated member of the present invention can be obtained by bonding a resin layer to the above-described coated copper material of the present invention via the surface treatment film.

The bonding method is not particularly limited. Specifically, when the resin layer is an epoxy resin layer, a laminating method in which an epoxy resin film is thermocompression bonded onto the surface treatment film is generally performed. In the case where the resin layer is a polyimide resin layer, for example, (1) a polyamic acid which is a polyimide precursor is applied to a surface treatment film of a copper material with a film, and then dried and cured. (2) A polyimide film coated with a thermoplastic polyimide layer on a surface-treated film of a copper material with a coating so that the surface-treated film and the thermoplastic polyimide layer are in contact with each other. A laminating method in which heat lamination is performed after laminating can be mentioned.

[0046] The laminated member of the present invention is excellent in adhesiveness between a copper material and a resin, particularly adhesiveness at high temperature, and thus is suitably used for various applications.

Example

[0047] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these.

[0048] 1. Fabrication of coated copper material

Using the surface treatment liquid shown in Table 1, the materials shown in Table 2 are treated as shown below under the surface treatment conditions of Examples 1 to 10 and Comparative Examples 1 to 3 shown in Table 2. The treatment process was performed to obtain a coated copper material. The pH of the surface treatment liquid was adjusted with ammonia water and nitric acid, and the immersion time of the material to be treated in the surface treatment liquid was uniformly 10 minutes at any level. The center line average roughness Ra of the surface of the obtained coated copper material was 0.50 or less, and a smooth surface was obtained.

[Material to be treated]

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

Copper plate: Oxygen-free copper plate (C 1020P, JIS—H—3100) 'Brass plate: Brass plate (C 2600P, JIS-H-3100)

• Copper foil: electrolytic copper foil (purity 99.8% by mass or more), thickness 50 m

[0049] [Processing step]

As processing steps, the following steps (1) to (8) were performed in order.

(1) Degreasing (60 ° C, 10 minutes, immersion method, using a 5% by weight aqueous solution prepared with Fine Cleaner 4360 (registered trademark) manufactured by Nihon Parkerizing Co., Ltd.)

(2) Washing with water (normal temperature, 30 seconds, spray method)

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

(4) Washing with water (room temperature, 30 seconds, spray method)

(5) Surface treatment (as described later)

(6) Washing with water (normal temperature, 30 seconds, spray method)

(7) Pure water washing (normal temperature, 30 seconds, spray method)

(8) Heat drying (80 ° C, 5 minutes, hot air oven)

[0050] The film-coated copper material obtained above was subjected to various evaluations as follows. The results are shown in Table 2. In Tables 1 and 2, “1” indicates no measurement. Also, the amount of coating and component E indicate the measured carbon content.

(1) Amount of coating

Using a fluorescent X-ray analyzer, at least one metal element (component B) selected from the group force consisting of Ti, Zr, Hf and Si in the film, and Ag, Al, Fe, Mn, Mg, Ni, Co, The amount of at least one metal element (component C) for which the group force consisting of Cr (lll), Ta and Zn was also selected was measured. In addition, the amount of carbon in the coating (component D) was measured by total carbon pyrogravimetric analysis.

[0051] (2) Analysis of film structure and Cu content of film

Using an XPS analyzer, measure the distribution in the thickness direction of at least one metal element, Cu and O selected from the group forces of Ti, Zr, Hf and S in the film, and the film structure is an inclined structure. The Cu content in the outermost layer (region from the surface to 5 nm) was measured.

The center line average roughness Ra of the coated copper materials of Examples 1 to 10 is 0.50 or less. It was.

[0052] (3) Heat resistant adhesiveness

A thermoplastic polyimide resin sheet with a thickness of about 50 / zm and a glass cloth base epoxy resin sheet are laminated on the film of copper material with film, and a copper foil with a thickness of 35 m is placed on it. The glass cloth-based epoxy resin sheet was press-bonded at a heating temperature of 200 ° C and a heating time of 2 hours to obtain a laminated member of copper material-polyimide and copper material-epoxy resin.

In order to accelerate the deterioration by cutting this laminated member into 50mm squares, the laminate was left for 24 hours in a heated and humid environment at 85 ° C and 85% RH and then floated in a 300 ° C molten solder bath. The time for the swelling of the member was measured, and the heat resistant adhesion was evaluated according to the following evaluation criteria. * Heat-resistant adhesive evaluation criteria

1 point → 0 to 100 seconds, 2 points → 100 to 300 seconds, 3 points → 300 to 500 seconds, 4 points → 500 to 1000 seconds,

5 points → 1000 seconds or more

[0053] [Table 1]

Table 1

Surface treatment solution composition

Component A Component B Component c Component!) Component E Level Chemical Species Concentration (ppm) Chemical Species Concentration (miiiol / L) Chemical Species K Chemical Species Concentration (PPBl) Chemical Species Concentration (ppm) PH

AH ₂ 0 ₂ 1000 H ₂ TiF ₆ Ti I HF 0.08----3.5 40

BH ₂ 0 ₂ 1000 H ₂ TiF ₆ Ti 1 HF 0.08 AI (N0 ₃ ) ₃ 300-1 3.5 40

C NaNO _z 500 ¾TiF ₆ Ti 1 HF 0.08----3.5 40

D HA 500 H ₂ ZrF ₆ Zr z HF 0.1 TaCl ₅ 500--4 50 t-Futyl hydroparoxy

E side 1000 H Ti: 1 NH4F 0.17 g (N0 ₃ ) ₂ 1000--4 40

F Di-1-butyl peroxide 700 H ₂ TiF ₆ Ti: 4 HF 0.1 ZnO 500--3.5 50

G NaC10 ₃ 500 rP ₆ Zr: 10 NaF 0.15--Polyallylamine 1000 4.5 40

HH ₂ 0 ₂ 1000 H ₂ TiF ₆ Ti 5 HF 0.05 Mg (N0 ₃ ) _z 500 Benzotriazo JlJ 100 3.5 40

I--H ₂ TiF ₆ Ti 1 HF 0.08----3.5 40

J Na ₂ S ₂ O _s 1000 R ₂ ZrF ₆ Zr 5 HF 0.08 A1 (N0 ₃ ) ₃ 300--3.5 40

K NaN0 ₂ 500 H ₂ TiF ₆ Ti 1 HF 0.01----3.5 40

From Table 2, component (A) Cu acid etching agent, component (B) Ti Zr Hf and S group Power Compound containing at least one metal element selected, Component (C) Fluorine-containing compound as a source of HF, and Ti, Zr, Hf and Si metal elements in the compound of Component (B) K = AZB is within the range of 0.03≤K≤0.18, which is the ratio between the total molar concentration of A and the molar concentration B of all fluorine atoms in the fluorine-containing compound of component (C) when converted to HF. Examples 1, 2, and 4 using a surface treatment liquid with a certain composition have good heat-resistant adhesion to polyimide and epoxy resins, and in particular, Example 4 shows the film structure obtained by surface treatment. Had an inclined structure and further had high heat-resistant adhesion. Furthermore, component (D) a surface containing a compound containing at least one element selected from the group consisting of Ag, Al, Cu, Fe, Mn, Mg, Ni, Co, Cr ³⁺ , Ta and Zn Examples 3, 5, 6, and 7 using the treatment liquid were further excellent in heat-resistant adhesion. Furthermore, Examples 8 to 10 using the surface treatment liquid containing an organic compound containing component (E) amino group had higher heat-resistant adhesion. In contrast, Comparative Examples 1 and 2, which used a specific copper acid etchant, and Comparative Example 3 where K was too small did not form a surface-treated film, resulting in improved heat resistance. It was inferior.

Claims

The scope of the claims

[1] Next component (A), component (B), and component (C)

(A) HC10, HC10, HC10, HBrO, HBrO, HBrO, HBrO, HNO, HNO, H S O

4 3 2 4 3 2 3 2 2 2 6

Oxyacids selected from the group consisting of H, O, HMnO, HVO, HWO and HMoO,

2 2 4 3 2 4 2 4

And organic peroxides selected from the group consisting of salt, ketone peroxide, peroxyketal, hydride peroxide, dialkyl peroxide, disilver oxide, peroxyester, peroxydicarbonate, and At least one copper acid etchant selected from the group consisting of the salts

(B) a group force consisting of Ti, Zr, Hf and Si forces, a compound containing at least one selected metal element, and

(C) a fluorine-containing compound as a source of HF;

The total molar concentration A of the metal elements of Ti, Zr, Hf and Si in the compound of component (B) and the total fluorine atoms in the fluorine-containing compound of component (C) were converted to HF Surface treatment solution for copper materials with K = AZB in the range of 0.03≤K≤0.18, which is the ratio to the molar concentration B at the time.

[2] In addition, component (D);

The copper material according to claim 1, comprising (D) a compound containing at least one element selected from the group consisting of Ag, Al, Cu, Fe, Mn, Mg, Ni, Co, Cr, Ta, and Zn. Surface treatment liquid.

[3] The surface treatment solution for copper materials according to claim 1 or 2, further comprising 10 to 50,000 ppm of an organic compound (E) containing an amino group.

[4] The amino group-containing organic compound (E) is a bullamine, a polybulamine, a arylamine, a diarylamine, a polyallylamine, a polyamine polyamide, an amine-modified phenol resin, an amine-modified polybutanol resin, an amine-modified urethane resin, 4. The surface treatment solution for a copper material according to claim 3, which is at least one selected from the group force consisting of benzotriazole, triazine thiol and derivatives thereof.

[5] A surface treatment method for a copper material, comprising contacting the copper material with the surface treatment liquid according to any one of claims 1 to 4.

[6] Group force of Ti, Zr, Hf and S, at least one metal element selected, Cu, 0, A copper material with a surface treatment film characterized by containing F and F.

[7] The surface-treated film according to claim 6, further comprising at least one selected from a group force consisting of Ag, Al, Cu, Fe, Mn, Mg, Ni, Co, Cr, Ta, and Zn force Copper material.

[8] The copper material with a surface treatment film according to [6] or [7], further containing carbon C.

[9] Ti, Zr, Hf, Si, Cu, Ag, Al, Fe, Mn, Mg, Ni contained in the surface treatment film

At least one elemental force selected from the group forces consisting of Co, Cr, Ta and Zn

The copper material with a surface treatment film according to any one of claims 6 to 8, wherein the copper material exists in a state of, fluoride, or an intermediate product thereof.

[10] The copper material with a surface-treated film according to any one of [6] to [9], wherein the Cu content at a depth of 5 nm from the surface of the copper material is 0.3 to 60 atm%.

[11] The inclined film structure according to claim 1, wherein the content of at least one metal element selected from the group force Ti, Zr, Hf and S decreases and the content of Cu increases as it goes to the copper material interface side. The copper material with a surface treatment film according to any one of 7 to 10.

[12] A laminated member, wherein a resin layer is provided on the copper material with a surface treatment film according to any one of claims 6 to 11.