JPWO2007105800A1 - Surface treatment liquid for copper material, surface treatment method for copper material, copper material with surface treatment film, and laminated member - Google Patents

Abstract

Provided are a surface treatment solution for copper material, a surface treatment method, and a surface treatment film formed on the surface of the copper material. For copper materials characterized by containing a copper oxide etchant, a compound containing at least one metal element selected from the group consisting of Ti, Zr, Hf and Si, and a fluorine-containing compound as a source of HF Surface treatment solution, surface treatment method characterized by immersing copper and copper alloy material in the solution, and selected from the group consisting of Ti, Zr, Hf and Si formed on copper and copper alloy thereby A surface treatment film characterized by containing at least one kind of metal element, Cu, O, and F, and a copper material having the surface treatment film and a resin layer are bonded via the surface treatment film A laminated member.

Description

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

Various metal materials are used for industrial products, and in addition to corrosion resistance and adhesion, various surface treatments are often applied to provide functionality such as heat resistance, hydrophilicity, and slidability. .
Copper materials such as copper and copper alloys are often required to have functionality on the surface, but metal ions such as iron, zinc, aluminum, etc. are coupled with metal ion reduction reactions. As surface treatment methods known at present, most of them are coating type treatments using inhibitors such as silane coupling agents and benzotriazole, and surface roughening by oxidation treatment or etching is performed. Apart from this, there are few useful chemical conversion reactive surface treatments.

  One of the features of the copper material is high electrical conductivity and heat dissipation characteristics. As one example, it has recently been widely applied to electronic and electrical parts such as printed wiring boards, lead frames, and LSIs. There are many joint portions between the copper material and the resin in the member, and these require the adhesion between the metal and the resin in a heated state. Specifically, thermosetting resins such as epoxy resins and polyimide resins used for superior thermal stability, chemical stability, insulation properties, etc., or thermoplastic resins with a high molding temperature, these resins are used as metals. When forming on a raw material, it is necessary to expose the entire part to a high temperature of 150 to 300 ° C. Furthermore, when mounting active parts such as semiconductor elements and passive parts such as LCR, soldering is used. However, since lead solder cannot be used due to recent environmental problems, the solder reflow temperature is becoming higher and higher. .

In such a situation, if the adhesion between the copper material and the resin is inferior, the moisture adsorbed on the surface of the copper material and the moisture absorbed in the resin adhesion interface in the manufacturing process, especially when the temperature becomes high Expands and promotes peeling at the interface between the copper material and the resin. Also, the copper material swells up and damages the internal corrosion resistance, and in some cases, the wiring pattern is destroyed by cracking the resin. Can result.
In addition, a brittle oxide 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 or Si single crystal, resulting in deterioration of electrical characteristics. These measures are also required when using copper materials for wiring materials such as inviting.

In general, in order to improve the adhesion between a metal material and a resin, a technique of mechanically roughening the surface of a metal substrate by blasting or the like to form a so-called anchor has been used for a long time.
However, such machining generally tends to be low in productivity and high cost, and the fine particles generated during the processing often impair the precision of electronic and electrical components.
Therefore, recently, some chemical surface treatment is often performed on the surface of the metal material for the purpose of improving the adhesion due to the anchor effect and chemical affinity with the resin.

For example, as surface treatment for improving adhesion, Patent Documents 1 and 2 describe a method for improving adhesion by performing chromate treatment on the surface of a metal material.
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.

However, these methods all use a hexavalent chromium compound that is harmful to the surface treatment solution, and it is considered that hexavalent chromium is contained on the surface of the formed metal substrate. It is not preferable.
In addition, based on the ELV command effective in October 2000 and the RoHS command effective in February 2003, specifications are particularly limited in electronic and electrical equipment, automobile parts, and the like.
Therefore, research and development of surface treatment of metal materials for the purpose of improving adhesion with a resin without using a hexavalent chromium compound has been conducted, and the same applies to copper materials.

As a chemical conversion surface treatment of a copper material that does not use a hexavalent chromium compound, a copper oxide (CuO) treatment called “black dyeing” is known. However, this copper oxide treatment has good adhesion at the initial stage of adhesion, but has poor durability, so that the bonding strength decreases with time, and the initial adhesion cannot be maintained during heating.
In addition, when used as a wiring material for printed wiring boards, higher density of printed wiring boards and higher speed of signals are demanded, and copper wiring is becoming thinner and narrower. Along with this, the copper surface roughening technology that has been widely used to provide adhesion between the insulating layer and the copper wiring so far roughens the surface because the transmission loss increases due to the skin effect. There is a need for a surface treatment that can be bonded to an insulating layer only with chemical affinity.

Japanese Patent Laid-Open No. 9-209167 JP-A-9-172125 JP 2000-183235 A

  The present invention provides a copper material surface that is excellent in adhesiveness with a resin, particularly at high temperatures, and does not roughen the surface without using substances that cause environmental pollution such as hexavalent chromium. It aims at providing a processing liquid, the surface treatment method using the same, a copper material, and a laminated member.

  As a result of intensive studies to achieve the above object, the present inventors have found that a specific copper oxide etchant, a compound containing at least one metal element selected from the group consisting of Ti, Zr, Hf and Si, and HF By using a surface treatment solution for copper materials containing a fluorine-containing compound as a supply source of copper at a specific ratio, the adhesion between the copper material and the resin, particularly at high temperatures, should be excellent. The present invention was completed.

That is, the present invention provides the following (1) to (12).
(1) The following component (A), component (B), and component (C):
(A) HClO ₄ , HClO ₃ , HClO ₂ , HBrO ₄ , HBrO ₃ , HBrO ₂ , HBrO, HNO ₃ , HNO ₂ , H ₂ S ₂ O ₆ , H ₂ O ₂ , HMNO ₄ , HVO ₃ , H ₂ WO ₄ and oxygen acid selected from the group consisting of H ₂ MoO _4, and salts, ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy esters, the group consisting of peroxydicarbonate And an organic peroxide selected from the group consisting of at least one copper oxide etching agent selected from the group consisting of salts thereof (B) containing at least one metal element selected from the group consisting of Ti, Zr, Hf and Si Compound (C) Fluorine-containing compound as source of HF, and total molar concentration A of metal elements of Ti, Zr, Hf and Si in compound of component (B) and fluorine-containing compound of component (C) In Copper material for surface treatment solution, characterized in that the fluorine atom is the ratio of the molar concentration B of when converted to HF K = A / B is a composition in the range of 0.03 ≦ K ≦ 0.18.
(2) Furthermore, component (D):
The surface treatment liquid for copper material according to (1), which contains 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) The amino group-containing organic compound (E) is vinylamine, polyvinylamine, allylamine, diallylamine, polyallylamine, polyamine polyamide, amine-modified phenol resin, amine-modified polyvinyl phenol, amine-modified urethane resin, benzotriazole, triazine thiol and The surface treatment liquid for copper material according to (3), which is at least one selected from the group consisting of these derivatives.
(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) A copper material with a surface-treated film, comprising at least one metal element selected from the group consisting of Ti, Zr, Hf and Si, Cu, O, and F.
(7) The copper material with a surface treatment film according to (6), further containing 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), further containing carbon C.
(9) At least one metal element selected from the group consisting of Ti, Zr, Hf and Si contained in the surface treatment film and Cu, and further Ag, Al, Fe, Mn, Mg, Ni, Co, Cr, The surface treatment film according to any one of (6) to (8), wherein at least one selected from the group consisting of Ta and Zn is present in the state of a hydrous oxide, a fluoride, or an intermediate product thereof With copper material.
(10) The copper material with a surface treatment 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) It has a gradient structure in which the content of at least one metal element selected from the group consisting of Ti, Zr, Hf, and Si decreases and the Cu content increases as it goes to the film-material interface side. The copper material with a surface treatment film according to any one of (7) 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 surface treatment liquid for copper material according to the present invention is excellent in adhesiveness to a resin, particularly at high temperatures, with almost no roughening of the surface, and does not use a substance that causes environmental pollution.

It is an example of the graph of the XPS analysis of the surface treatment film | membrane of a gradient structure. It is an example of the graph of the XPS analysis of the surface treatment film of uniform structure. It is typical sectional drawing which shows the laminated member of this invention.

The treatment liquid of the present invention comprises the following components (A), (B), and (C);
(A) HClO ₄ , HClO ₃ , HClO ₂ , HBrO ₄ , HBrO ₃ , HBrO ₂ , HBrO, HNO ₃ , HNO ₂ , H ₂ S ₂ O ₆ , H ₂ O ₂ , HMNO ₄ , HVO ₃ , H ₂ WO ₄ and oxygen acid selected from the group consisting of H ₂ MoO _4, and salts, ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy esters, the group consisting of peroxydicarbonate At least one copper oxide etchant selected from the group consisting of organic peroxides selected from:
(B) a compound containing at least one metal element selected from the group consisting of Ti, Zr, Hf and Si, and (C) a fluorine-containing compound as a source of HF, and a compound of component (B) K = A / which is the ratio of the total molar concentration A of the metal elements of Ti, Zr, Hf and Si in it to the molar concentration B when all fluorine atoms in the fluorine-containing compound of component (C) are converted to HF B is a surface treatment liquid for copper material, wherein B has a composition in a range of 0.03 ≦ K ≦ 0.18.
Moreover, the surface treatment liquid of the present invention further comprises component (D):
(D) One of the preferred embodiments is to contain 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. .
Further, the surface treatment liquid of the present invention further comprises an organic compound (E) containing an amino group: (E) vinylamine, polyvinylamine, allylamine, diallylamine, polyallylamine, polyamine polyamide, amine-modified phenol resin, amine-modified polyvinyl phenol resin It is one of the preferable embodiments to contain 10 to 50000 ppm of a compound containing at least one selected from the group consisting of amine-modified urethane resin, benzotriazole, triazine thiol and derivatives thereof.

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.
What contains 50 mass% or more of copper is preferable for a copper alloy, For example, the brass containing 30-40 mass% of Zn is mentioned. 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. Examples of the shape include a plate shape, a foil shape, and a rod shape.

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) is HClO ₄ , HClO ₃ , HClO ₂ , HBrO ₄ , HBrO ₃ , HBrO ₂ , HBrO, HNO ₃ , HNO ₂ , H ₂ S ₂ O ₆ , H ₂ O ₂ , HMNO ₄ , HVO ₃ , oxygen acid selected from the group consisting of H ₂ WO ₄ and H ₂ MoO _4, and salts, ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy esters, peroxydicarbonates An organic peroxide selected from the group consisting of: and at least one copper oxide etching agent selected from the group consisting of salts thereof.
More specifically, diisobutyryl peroxide, cumyl peroxyneodecanoate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3 , 3-Tetramethylbutyl peroxyodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, t-butyl Peroxyneodecanoate, t-butylperoxyneoheptanoate, t-hexylperoxypivalate, t-butylperoxypivalate, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl Peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di Succinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethyhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, Di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxy-2-ethylhexanoate, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t- Butylperoxy) cyclohexane, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t-butyl-peroxymaleic acid, -butyl- -Oxy-3,5,5-trimethylhexanoate, t-butyl peroxylauric acid, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 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) valerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2 , 5-Di- (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumin hydroperoxide Examples include xylene, t-butyl hydroperoxide, and 2,3-dimethyl-2,3-diphenylbutane.
Ingredient (A) acts as an oxidizing agent that promotes the oxidative dissolution of copper, and this involves an increase in pH.
The concentration of the component (A) in the surface treatment solution is preferably 10 ppm to 100,000 ppm. More preferably, the concentration range is 50 ppm to 50000 ppm. When the concentration is 10 ppm or less, there are cases where the copper oxide etching power is insufficient and the amount of film formation is not sufficient. If it is 50000 ppm or more, the cost becomes high, which may be disadvantageous economically.

Component (B) is a compound containing at least one metal element selected from the group consisting of Ti, Zr, Hf and Si.
For example, TiCl ₃ , TiCl ₄ , Ti ₂ (SO ₄ ) ₃ , Ti (SO ₄ ) ₂ , Ti (NO ₃ ) ₄ , H ₂ TiF ₆ , H ₂ TiF ₆ salt (for example, K ₂ TiF ₆ ), TiO, Ti ₂ O ₃ , TiO ₂ , TiF ₄ , ZrCl ₄ , Zr (SO ₄ ) ₂ , Zr (NO ₃ ) ₄ , H ₂ ZrF ₆ , H ₂ ZrF ₆ salt (for example, K ₂ ZrF ₆ ), ZrO ₂ , ZrF ₄ , HfCl ₄ , Hf (SO ₄ ) ₂ , H ₂ HfF ₆ , H ₂ HfF ₆ salt (for example, K ₂ HfF ₆ ), HfO ₂ , HfF ₄ , H ₂ SiF ₆ , H ₂ SiF ₆ salts (for example, K ₂ SiF ₆ ), Al ₂ O ₃ (SiO ₂ ) ₃ , and SiO ₂ . Two or more of these may be used in combination.
The concentration of the 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. When the concentration is 5 ppm or less, the content of the component (B) in the surface treatment film may be insufficient in performance. If it is 10000 ppm or more, the cost becomes high, which may be disadvantageous economically.

Component (C) is a fluorine-containing compound that can supply HF.
For example, HF, H ₂ TiF ₆ , TiF ₄ , H ₂ ZrF ₆ , ZrF ₄ , H ₂ HfF ₆ , HfF ₄ , HBF ₄ , NaHF ₂ , KHF ₂ , NH ₄ HF ₂ , NaF, KF, NH ₄ F Can be mentioned. Two or more of these may be used in combination.

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 ³⁺ , Ta, and Zn. Examples thereof include hydrated oxides, chlorides, fluorides, sulfates, nitrates, and carbonates of the above elements.
The concentration of the 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. When the concentration is 5 ppm or less, the effect of adding the component (D) cannot be expected. If it is 10000 ppm or more, the cost becomes high, which may be disadvantageous economically.

When the processing liquid of this invention contains a component (E), the corrosion resistance of the surface treatment film obtained 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 a copper material is used for the wiring material described above, various problems such as formation of a brittle copper oxide film in a high temperature environment and diffusion into a polyimide resin or Si single crystal are less likely to occur.
According to the study of the present inventor, it is known that when the treatment liquid of the present invention contains the component (E), the obtained surface treatment film contains C (carbon) and N (nitrogen). Therefore, it is considered that the film structure is made denser by incorporating the organic compound containing the amino group of the component (E) into the film.

Component (E) is selected from the group consisting of vinylamine, polyvinylamine, allylamine, diallylamine, polyallylamine, polyamine polyamide, amine-modified phenolic resin, amine-modified polyvinylphenol, amine-modified urethane resin, benzotriazole, triazinethiol and derivatives thereof. At least one organic compound selected.
Here, the derivative is selected from the group consisting of, for example, vinylamine, polyvinylamine, allylamine, diallylamine, polyallylamine, polyamine polyamide, amine-modified phenol resin, amine-modified polyvinyl phenol, amine-modified urethane resin, benzotriazole, and triazine thiol. The compound which contains at least 1 in a molecule | numerator, the compound derived from this compound, and also the salt of these compounds are mentioned.
The addition amount of the organic compound (E) is preferably 10 to 50000 ppm from the viewpoint of the obtained film performance.

The mechanism of surface treatment film generation is as follows.
In the aqueous solution containing a sufficient amount of HF, the metal element in the compound of component (B) is MF ₆ ²⁻ (wherein M represents Ti, Zr, Hf or Si; the same shall apply hereinafter). Exists.
Here, a chemical equilibrium represented by the following formula (1) is established between MF ₆ and F ⁻ .

MF ₆ ²⁻ + 2OH ⁻ ＭＯ MO ₂ + 2H ⁺ + 6F ⁻ (1)

  When a copper material is immersed in the treatment liquid of the present invention, it is coupled with a reduction reaction of the copper oxide etchant of the component (A) (the following formula (2)), and a Cu dissolution reaction (the following formula (3) ) Occurs.

Ox + ne ⁻ → Red + mOH ⁻ (2)
^{Cu → Cu 2+ + 2e - (} 3)

Due to the increase in pH accompanying the reduction reaction of the above formula (2), the equilibrium of the above formula (1) advances to the right, and fluoride ions coordinated to the metal element M are sequentially replaced by hydroxide ions (formula (4 )), And finally the metal M hydroxide. Thereafter, the hydroxide of metal M is dehydrated and condensed to become a partial oxide (formula (5)). The metal element M is deposited on the surface of the copper material in at least one state selected from the group consisting of MF _(6-x) (OH) _x , M (OH) ₄ , MO ₂ , or hydrates thereof. Conceivable.
^{_{MF 6 2- + 4OH - → MF}} (6-x) (OH) x + xF - + (4-x) OH - → M (OH) 4 + 6F - (4)
M (OH) ₄ + M (OH) ₄ → 2MO ₂ + 4H ₂ O (5)

Further, if the treatment solution of the present invention contains the component (D) is a compound of component (D) is free of F ^- proceeds from forming a complex, the equilibrium is more right above formula (1), Generation of the surface treatment film is promoted, and the film is formed in a shorter time. Further, as another effect of containing the component (D), the component (D) itself is co-deposited together with the metal element M, thereby further improving the adhesion to the resin. Component (D) is present in the form of a hydrated oxide, a fluoride, or an intermediate product thereof, like the metal element M.

Simultaneously with the deposition of MO ₂ described above, the copper ions (Cu ²⁺ ) eluted by the above formula (3) are deposited in the state of hydrous oxide, fluoride, or an intermediate product thereof, and these also form a surface treatment film. Constitute.

  As described above, in the coated copper material obtained by the present invention, at least one metal element selected from the group consisting of Ti, Zr, Hf and Si and Cu, and further Ag, Al, Fe, Mn, Mg, At least one selected from the group consisting of Ni, Co, Cr (III), Ta, and Zn is at least one state selected from the group consisting of a hydrous oxide, a fluoride, or an intermediate product thereof. A treatment film is formed.

The molar concentration of the treatment liquid of the present invention when 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 converted to HF. The ratio K to B (= A / B) satisfies 0.03 ≦ K ≦ 0.18.
When K is too large, a sufficient amount of film can be deposited to obtain adhesion, but the stability of the treatment liquid is significantly impaired, which causes trouble in continuous operation. On the other hand, if K 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 to obtain adhesion in a short time.

As described above, the treatment liquid of the present invention deposits a surface treatment film on the surface of a copper material by an equilibrium reaction between H ₂ MF ₆ and HF.
Here, the molar concentration of the compound containing at least one metal element selected from the group consisting of Ti, Zr, Hf and Si of the component (B) (when two or more compounds are used, the total molar concentration) However, it is preferable that it is 0.05-100 mmol / L in conversion of the said metal element.
Within the above range, the molar concentration of the metal element as the film component becomes sufficiently large, and a sufficient amount of film can be formed to obtain various performances such as adhesion, which is economically disadvantageous. Never become.

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 surface treatment film described above. For this reason, sludge does not occur in the treatment liquid of the present invention.
In addition, in order to solubilize the component of the eluted copper material, the process liquid of this invention may contain the chelating agent which can chelate the acid other than HF and the metal ion eluted from a copper material. it can. For example, it is effective when the amount of the copper material to be processed is very large relative to the amount of the 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, citric acid, succinic acid, gluconic acid, and phthalic acid.
Examples of chelating agents include EDTA and thiourea.

  Although the pH of the treatment liquid of the present invention is not particularly limited, it is preferably pH 2 to 6 and more preferably pH 3 to 5 in terms of stability of the treatment liquid and ease of film formation.

The processing method of this invention comprises the surface treatment process which makes a copper material contact the processing liquid of this invention mentioned above.
By bringing the copper material into contact with the treatment liquid of the present invention, a surface treatment film containing a metal element oxide of component (B) and a 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).
Moreover, the presence or absence of stirring 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 are not particularly limited.
Moreover, in the processing method of this invention, it is possible to form a surface treatment film | membrane also by carrying out the electrolytic treatment by using a copper material as a cathode in the processing liquid of this 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, and more preferably 20 to 60 ° C. Since the use of useless energy can be suppressed as the treatment temperature is 60 ° C. or lower, it is preferable from an economical viewpoint.
The processing time can be set as appropriate.

  The coated copper material of the present invention is a coated copper material having a surface treatment film containing at least one metal element selected from the group consisting of Ti, Zr, Hf, and Si, copper, oxygen, and fluorine on the surface. It is.

Further, the surface treatment film preferably further contains at least one selected from the group consisting of Ag, Al, Cu, Fe, Mn, Mg, Ni, Co, Cr (III), Ta and Zn. Thereby, adhesiveness with resin improves.
At least one metal element selected from the group consisting of Ti, Zr, Hf and Si contained in the surface treatment film and Cu, and further Ag, Al, Fe, Mn, Mg, Ni, Co, Cr (III), It is preferable that at least one selected from the group consisting of Ta and Zn exists in the state of a hydrous oxide, a fluoride, or an intermediate product thereof.
The surface treatment film preferably further contains carbon. As a result, the coating structure becomes denser, and the discoloration resistance when the coated copper material is exposed to a high temperature is improved. Also, when the copper material is used for the wiring material described above, Various problems such as formation of a brittle copper oxide film and diffusion into a polyimide resin or Si single crystal are less likely to occur.

In the copper material with a film of the present invention, the surface treatment film is composed of the composition of the treatment liquid of the present invention (for example, the type of the metal element of the component (B), the type of the copper oxide etchant of the component (A), and various components. The film structure can be made desired by appropriately selecting the concentration). Specifically, the copper content of the surface treatment film and its distribution in the depth direction can be varied.
1 and 2 show the depth of at least one metal element (M), copper (Cu), and oxygen (O) selected from the group consisting of Ti, Zr, Hf and Si in the surface treatment film. FIG. 1 is a result of a lateral XPS analysis. FIG. 1 is an example of a surface treatment film having an inclined structure and FIG. 2 is a uniform structure. In FIG. 1 and FIG. 2, “M”, “Cu”, and “O” indicate atomic contents of at least one metal element selected from the group consisting of Ti, Zr, Hf, and Si, copper, and oxygen, respectively. .
In the graded surface treatment film shown in FIG. 1, the metal element (M) content generally decreases and the copper (Cu) content increases from the film surface toward the interface with the copper material. ing.
In the uniform surface treatment film shown in FIG. 2, the metal element (M) content is high near the film surface (Etch Time: 0 to about 40 seconds), the copper (Cu) content is low, and , They are almost constant in the depth direction.

  In the coated copper material of the present invention, it is one of preferred embodiments 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 using a copper material as a wiring material, there are problems such as formation of a brittle copper oxide film in a high temperature environment, diffusion into a polyimide resin or Si single crystal, etc. Since it becomes easy to occur, it may be inferior to adhesiveness with resin, etc.

  Further, as shown in FIG. 1, the content of at least one metal element selected from the group consisting of Ti, Zr, Hf and Si decreases from the surface of the surface treatment film toward the interface with the copper material. And it is one of the preferable aspects that the content rate of copper increases. 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. Also, the thickness of the surface treatment film is on the order of submicrons, and the copper material with the film of the present invention is much more resistant than the conventional roughening treatment in order to uniformly etch the copper material surface during the surface treatment. A smooth surface can be obtained. One of the preferred embodiments is that the center line average roughness Ra of the surface of the coated copper material is 0.50 or less.

Since the coated copper material of the present invention is excellent in the adhesion between the surface-treated film and the resin, particularly the adhesion at high temperatures, it is suitably used for various applications. For example, it is suitably used for the laminated member of the present invention described later.
Moreover, since the copper material with a film | membrane of this invention is excellent also in corrosion resistance, it is used suitably for various uses.

The laminated member of this invention is a laminated member which has the copper material with a film | membrane of this invention mentioned above, and the resin layer provided on the said surface treatment film | membrane.
FIG. 3 is a schematic cross-sectional view showing the laminated member of the present invention. The laminated member 10 shown in FIG. 3 has a copper material 2 and at least one metal element selected from the group consisting of Ti, Zr, Hf and Si, copper, oxygen, fluorine, and further Ag, Al, Fe. , Mn, Mg, Ni, Co, Cr (III), Ta and Zn, and a surface-treated film 4 containing carbon and a surface-treated film 4 containing carbon. And a resin layer 8 provided on the surface treatment film 4.

The material of the resin layer is not particularly limited. For example, thermoplastic resin such as AS resin, ABS resin, fluororesin, polyamide, polyethylene, polyethylene terephthalate, polyvinylidene chloride, polycarbonate, polystyrene, polysulfone, polypropylene, liquid crystal polymer; epoxy Examples thereof include thermosetting resins such as resins, phenol resins, polyimides, polyurethanes, bismaleimide / triazine resins, modified polyphenylene ethers, and cyanate esters. These resins may be modified with a functional group.
Among these, epoxy resins and polyimide resins are both excellent in heat-resistant adhesiveness, and thus are useful for use in electronic parts such as printed wiring boards, lead frames, and LSI packages.
The resin layer can contain fibers such as glass fibers and aramid fibers. By containing the fibers, the resin layer is reinforced.

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 heat-pressed onto a surface treatment film is generally performed. In the case of a polyimide resin layer, for example, (1) a coating method in which a polyimide layer is formed by applying a polyamic acid, which is a polyimide precursor, to a surface treatment film of a copper material with a film, and then drying and curing (2) A laminating method in which a polyimide film coated with a thermoplastic polyimide layer is laminated on a surface-treated film of a copper material with a film so that the surface-treated film and the thermoplastic polyimide layer are in contact with each other, followed by thermocompression bonding. Can be mentioned.

  Since the laminated member of the present invention is excellent in adhesiveness between a copper material and a resin, particularly adhesiveness at high temperature, it is suitably used for various applications.

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

1. Production of Copper Material with Film Using the surface treatment liquid shown in Table 1, the surface treatment conditions of Examples 1 to 10 and Comparative Examples 1 to 3 shown in Table 2 for the materials to be treated shown in Table 2 Then, the treatment process shown below was performed to obtain a copper material with a film. 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 μm

[Processing process]
As processing steps, the following steps (1) to (8) were performed in order.
(1) Degreasing (60 ° C., 10 minutes, immersion method, using 5 mass% aqueous solution prepared using Fine Cleaner 4360 (registered trademark) manufactured by Nihon Parkerizing Co., Ltd.)
(2) Washing with water (normal temperature, 30 seconds, spray method)
(3) Pickling (using a 10% aqueous solution prepared using room temperature, 30 seconds, immersion method, commercially available sulfuric acid)
(4) Washing with water (normal 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)

About the copper material with a film | membrane obtained above, various evaluation was performed as follows. The results are shown in Table 2. In Tables 1 and 2, “-” indicates no measurement. Further, the coating amount and component E indicate the measured carbon amount.
(1) Coating Amount Using a fluorescent X-ray analyzer, at least one metal element (component B) selected from the group consisting of Ti, Zr, Hf and Si in the coating and Ag, Al, Fe, Mn, Mg, The amount of at least one metal element (component C) selected from the group consisting of Ni, Co, Cr (III), Ta and Zn was measured. Moreover, the carbon content (component D) in the film was measured by total carbon component thermogravimetric analysis.

(2) Film structure analysis and Cu content of film Using XPS analyzer, distribution in thickness direction of at least one metal element, Cu and O selected from the group consisting of Ti, Zr, Hf and Si in the film Was measured to analyze whether the film structure was an inclined structure or a uniform structure, and the Cu content in the outermost layer (region from the surface to 5 nm) was measured.
In addition, the centerline average roughness Ra of the copper material with a film | membrane of Examples 1-10 was 0.50 or less.

(3) Heat-resistant adhesive property A thermoplastic polyimide resin sheet having a thickness of about 50 μm and a glass cloth base epoxy resin sheet are laminated on a film of a copper material with a film, and a copper foil having a thickness of 35 μm is disposed thereon at 250 ° C. The glass cloth base epoxy resin sheet was press-bonded under the conditions of 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 50 mm square, the laminated member was left in a heated and humid environment of 85 ° C. and 85% RH for 24 hours and then floated in a 300 ° C. molten solder bath. The time during which blistering occurred was measured, and heat-resistant adhesion was evaluated according to the following evaluation criteria.
* Heat-resistant adhesion 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

As a supply source of component (A) Cu oxidizing etchant, component (B) compound containing at least one metal element selected from the group consisting of Ti, Zr, Hf and Si, component (C) HF The total molar concentration A of the metal elements of Ti, Zr, Hf and Si in the component (B) compound and the total fluorine atoms in the component (C) fluorine-containing compound are converted to HF. Examples 1, 2, and 4 using a surface treatment liquid having a composition in which K = A / B, which is a ratio with respect to the molar concentration B, is 0.03 ≦ K ≦ 0.18, In Example 4, the film structure obtained by the surface treatment had an inclined structure, and the heat resistant adhesiveness was higher. Further, the component (D) uses a surface treatment liquid 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. In Examples 3, 5, 6, and 7, the heat-resistant adhesion was further excellent. Furthermore, Examples 8-10 using the surface treatment liquid containing the organic compound containing component (E) amino group had higher heat-resistant adhesion.
On the other hand, in Comparative Examples 1 and 2 in which a specific copper oxide etchant was not used, and in Comparative Example 3 in which K was too small, a surface treatment film was not formed, and the heat resistant adhesiveness was poor.

Claims (12)

Next component (A), component (B), and component (C)
(A) HClO ₄ , HClO ₃ , HClO ₂ , HBrO ₄ , HBrO ₃ , HBrO ₂ , HBrO, HNO ₃ , HNO ₂ , H ₂ S ₂ O ₆ , H ₂ O ₂ , HMNO ₄ , HVO ₃ , H ₂ WO ₄ and oxygen acid selected from the group consisting of H ₂ MoO _4, and salts, ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy esters, the group consisting of peroxydicarbonate At least one copper oxide etchant selected from the group consisting of organic peroxides selected from the group consisting of salts thereof, and salts thereof (B) at least one metal element selected from the group consisting of Ti, Zr, Hf and Si 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 atom in the fluorine-containing compound of component (C) converted to HF A surface treatment solution for copper material in which K = A / B, which is a ratio to the concentration B, is in the range of 0.03 ≦ K ≦ 0.18. In addition, component (D);
(D) The copper material according to claim 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. Surface treatment liquid.   Furthermore, the surface treatment liquid for copper materials of Claim 1 or 2 which contains the organic compound (E) containing an amino group 10 to 50000 ppm.   The organic compound (E) containing an amino group is vinylamine, polyvinylamine, allylamine, diallylamine, polyallylamine, polyamine polyamide, amine-modified phenol resin, amine-modified polyvinyl phenol resin, amine-modified urethane resin, benzotriazole, triazine thiol and The surface treatment liquid for copper material according to claim 3, which is at least one selected from the group consisting of these derivatives.   A surface treatment method for a copper material, wherein the copper material is brought into contact with the surface treatment liquid according to claim 1.   A copper material with a surface-treated film, characterized by containing at least one metal element selected from the group consisting of Ti, Zr, Hf, and Si, Cu, O, and F.   The copper material with a surface-treated film according to claim 6, further comprising at least one selected from the group consisting of Ag, Al, Cu, Fe, Mn, Mg, Ni, Co, Cr, Ta, and Zn.   Furthermore, the copper material with a surface treatment film of Claim 6 or 7 containing carbon C.   At least one element selected from the group consisting of Ti, Zr, Hf, Si, Cu, Ag, Al, Fe, Mn, Mg, Ni, Co, Cr, Ta and Zn contained in the surface treatment film, The copper material with a surface treatment film according to any one of claims 6 to 8, which is present in a state of a hydrous oxide, a fluoride, or an intermediate product thereof.   The copper material with a surface-treated film according to any one of claims 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%.   8. A gradient structure in which the content of at least one metal element selected from the group consisting of Ti, Zr, Hf, and Si decreases and the content of Cu increases as it goes to the film-copper material interface side. The copper material with a surface treatment film according to any one of 10.   A laminated member, wherein a resin layer is provided on the surface-treated coating-coated copper material according to claim 6.

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