Surface-treated titanium copper foil, titanium copper-clad laminate, and printed wiring board

Abstract

Provided is surface-treated titanium copper foil and a titanium copper-clad laminate with which it is possible to form a circuit pattern that excels in adhesion to a resin base material. Surface-treated titanium copper foil 1 has: titanium copper foil 2; and a surface-treated layer 3 formed on at least one surface of the titanium copper foil 2. The surface-treated layer 3 contains Cr and Zn.

Description

Surface-treated titanium copper foil, titanium copper clad laminate and printed wiring board

[0001] The present disclosure relates to a surface-treated titanium copper foil, a titanium copper-clad laminate, and a printed wiring board.

[0002] In recent years, with the increasing need for miniaturization and higher performance of electronic devices, there has been a demand for finer pitches (miniaturization) of circuit patterns (also referred to as "conductor patterns") on printed wiring boards mounted on electronic devices. Various methods are known for manufacturing printed wiring boards, such as subtractive methods and semi-additive methods. Among them, the subtractive method involves bonding an insulating substrate to copper foil to form a copper-clad laminate, applying and exposing a resist to the copper foil surface to form a predetermined resist pattern, and then removing the portions where the resist pattern is not formed (unnecessary portions) by etching, thereby forming the circuit pattern.

[0003] In response to the demand for finer pitches, for example, Patent Document 1 describes that a surface-treated copper foil capable of forming finer pitches in circuit patterns can be obtained by roughening the surface of a copper foil with copper-cobalt-nickel alloy plating, then forming a cobalt-nickel alloy plating layer, and then further forming a zinc-nickel alloy plating layer.

[0004] Patent No. 2849059

[0005] Copper foil is commonly used as a raw material in the manufacture of printed wiring boards. Titanium-copper foil, a copper alloy material with high strength and bendability, has been attracting attention as a new raw material. The inventors used a surface-treated titanium-copper foil with an organic anticorrosion treatment layer, such as benzotriazole, on the titanium-copper foil. They then bonded a polyimide (PI) resin substrate as an insulating substrate to the surface of the organic anticorrosion treatment layer to produce a titanium-copper clad laminate, and measured its adhesion strength. However, the adhesion strength was insufficient. While roughening the surface of the titanium-copper foil is considered a method for improving adhesion strength, it is difficult to form a roughened layer on the surface of titanium-copper foil using current technology.

[0006] The present invention has been made to solve the above-mentioned problems, and aims to provide a surface-treated titanium copper foil and a titanium copper clad laminate that are capable of forming a circuit pattern with excellent adhesion to a resin substrate. Another aim of the present invention is to provide a printed wiring board having a circuit pattern with excellent adhesion to a resin substrate.

[0007] As a result of intensive research conducted by the present inventors to solve the above problems, it was discovered that by forming a surface treatment layer containing Cr and Zn on one surface of a titanium copper foil, adhesion to a resin substrate is improved, and this led to the embodiment of the present invention.

[0008] That is, an embodiment of the present invention relates to a surface-treated titanium copper foil having a titanium copper foil and a surface treatment layer formed on at least one surface of the titanium copper foil, the surface treatment layer containing Cr and Zn. Another embodiment of the present invention relates to a titanium copper clad laminate comprising the surface-treated titanium copper foil and a resin substrate formed on the surface of the surface treatment layer of the surface-treated titanium copper foil. Still another embodiment of the present invention relates to a printed wiring board comprising the titanium copper clad laminate.

[0009] According to an embodiment of the present invention, it is possible to provide a surface-treated titanium copper foil and a titanium copper clad laminate that are capable of forming a circuit pattern that has excellent adhesion to a resin substrate, and also to provide a printed wiring board having a circuit pattern that has excellent adhesion to a resin substrate.

[0010] 1 is a cross-sectional view of a titanium copper clad laminate using a surface-treated titanium copper foil according to embodiment 1 of the present invention. FIG. 2 is a cross-sectional view for explaining a method for manufacturing a printed wiring board according to embodiment 2 of the present invention.

[0011] Preferred embodiments of the present invention will be described in detail below, but the present invention should not be construed as being limited thereto, and various modifications and improvements can be made based on the knowledge of those skilled in the art without departing from the gist of the present invention. The multiple components disclosed in each embodiment can be appropriately combined to form various inventions. For example, some components may be deleted from all the components shown in each embodiment, or components from different embodiments may be appropriately combined.

[0012] (Embodiment 1) Figure 1 is a cross-sectional view of a titanium copper clad laminate using a surface-treated titanium copper foil according to embodiment 1 of the present invention. As shown in Figure 1, the surface-treated titanium copper foil 1 comprises a titanium copper foil 2 and a surface treatment layer 3 formed on one surface of the titanium copper foil 2. The titanium copper clad laminate 10 comprises the surface-treated titanium copper foil 1 and a resin substrate 11 bonded to the surface of the surface treatment layer 3 of the surface-treated titanium copper foil 1. The surface treatment layer 3 may be formed on both surfaces of the titanium copper foil 2.

[0013] Although not particularly limited, the titanium copper foil 2 typically contains 1.5 to 5.0 mass % Ti, with the remainder being Cu and inevitable impurities. In this specification, "unavoidable impurities" refers to components that are difficult to remove, such as H and O. The inevitable impurities are inevitably mixed in during the process of producing the titanium copper foil, such as the stage of melting the raw materials.

[0014] If the Ti concentration of the titanium copper foil 2 is within the above range, the hardness of the titanium copper foil 2 can be controlled within a desired range, thereby improving the adhesion between the surface-treated titanium copper foil 1 and the resin substrate 11. From the viewpoint of further improving the adhesion, the Ti concentration is preferably 2.9 to 4.3 mass %.

[0015] The titanium copper foil 2 may further contain at least one element selected from the group consisting of Ag, B, Co, Fe, Mg, Mn, Mo, Ni, P, Si, Cr, and Zr (hereinafter referred to as "third element") in a total amount of 1.0 mass% or less. By controlling the total concentration of the third element within this range, deterioration of workability can be prevented.

[0016] The thickness of the titanium copper foil 2 is not particularly limited, but from the viewpoint of further improving adhesion, it can be preferably 5 to 150 μm, more preferably 30 to 100 μm, and even more preferably 35 to 50 μm.

[0017] The surface treatment layer 3 contains Cr and Zn. Although the detailed reason is not clear, it has been experimentally confirmed that the inclusion of Cr and Zn in the surface treatment layer 3 improves adhesion to the resin substrate 11 (for example, the adhesion is improved by strengthening the interfacial interaction between the titanium copper foil 2 and the polyimide resin substrate).

[0018] The surface treatment layer 3 may further contain Ni. By containing Ni, adhesion can be stably improved. The deposition amounts of Cr, Zn, and Zi in the surface treatment layer 3 are not particularly limited, but are preferably in the following ranges.

[0019] The Cr deposition amount in the surface treatment layer 3 is preferably 0 μg / dm 2 Super 100μg / dm 2 or less, more preferably 10 to 100 μg / dm 2 , more preferably 25 to 51 μg / dm 2 By controlling the amount of Cr deposited in the surface treatment layer 3 within the above range, it is possible to improve the rust prevention properties in addition to the adhesion.

[0020] The amount of Zn attached in the surface treatment layer 3 is preferably 0 μg / dm 2 Super 700μg / dm 2 or less, more preferably 10 to 500 μg / dm 2 , more preferably 20 to 237 μg / dm 2 By controlling the amount of Zn deposited in the surface treatment layer 3 within the above range, it is possible to improve the heat resistance as well as the adhesion.

[0021] The amount of Ni attached in the surface treatment layer 3 is preferably 0 μg / dm 2 Super 200μg / dm 2 or less, more preferably 1 to 180 μg / dm 2 , more preferably 3 to 103 μg / dm 2In this way, by controlling the Ni deposition amount in the surface treatment layer 3 within the above range, it is possible to improve the rust prevention property in addition to the adhesion property.

[0022] The arithmetic mean roughness Sa of the surface of the surface treatment layer 3 opposite to the surface on the titanium copper foil 2 side is not particularly limited, but is preferably 0.020 to 0.100 μm, more preferably 0.041 to 0.087 μm. Thus, even if the arithmetic mean roughness Sa of the surface of the surface treatment layer 3 opposite to the surface on the titanium copper foil 2 side of the surface treatment layer 3 of the surface treatment layer 1 is relatively small, the surface treatment titanium copper foil 1 can ensure adhesion between the surface treatment layer 3 and the resin substrate 11. This differs significantly from conventional techniques that increase the surface roughness of the surface treatment layer 3 and improve adhesion between the surface treatment layer 3 and the resin substrate 11 through an anchor effect. Herein, "Sa" refers to the surface roughness Sa measured in accordance with ISO 25178-2:2012.

[0023] The surface treatment layer 3 can be formed of, for example, a heat-resistant treatment layer and / or a chromate treatment layer.

[0024] The heat-resistant layer is not particularly limited and can be formed from materials known in the art. Since the heat-resistant layer may also function as a rust-preventing layer, a single layer having both the functions of a heat-resistant layer and a rust-preventing layer may be formed. The heat-resistant layer and / or the rust-preventing layer may be a layer containing one or more elements (which may be in any form, such as metal, alloy, oxide, nitride, or sulfide) selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. An example of the heat-resistant layer and / or the rust-preventing layer is a layer containing a nickel-zinc alloy. The heat-resistant layer and the rust-preventing layer can be formed by electroplating. The conditions are not particularly limited, but typical conditions for the heat-resistant layer (Ni-Zn layer) are as follows: Plating solution composition: 1 to 30 g / L Ni, 1 to 30 g / L Zn Plating solution pH: 2 to 5 Plating solution temperature: 30 to 50°C Electroplating conditions: current density 0.1 to 10 A / dm2 , time 0.1 to 5 seconds Number of electroplating treatments: 1 or more

[0025] The chromate-treated layer is not particularly limited and can be formed from materials known in the art. Here, in this specification, the term "chromate-treated layer" refers to a layer formed from a solution containing chromic anhydride, chromic acid, dichromate, chromate salt, or dichromate salt. The chromate-treated layer can be a layer containing elements such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium (which may be in any form, such as metal, alloy, oxide, nitride, or sulfide). Examples of chromate-treated layers include chromate-treated layers treated with an aqueous solution of chromic anhydride or potassium dichromate, and chromate-treated layers treated with a treatment solution containing chromic anhydride or potassium dichromate and zinc.

[0026] The chromate treatment layer can be formed by electrolytic chromate treatment or immersion chromate treatment. The conditions for these chromate treatments are not particularly limited, but typical conditions for the chromate treatment layer are as follows: Chromate solution composition: 1 to 10 g / L K2Cr2O7, 0.01 to 10 g / L Zn Chromate solution pH: 2 to 5 Chromate solution temperature: 30 to 55°C Electrolysis conditions: current density 0.1 to 10 A / dm 2 , time 0.1 to 5 seconds (if immersed without applying electricity, immersion time: 0.1 to 5 seconds) Number of chromate treatments: 1 or more

[0027] In addition to the heat-resistant layer and the chromate-treated layer, the surface treatment layer 3 may also include a known layer such as a silane coupling treatment layer, provided that the effects of the present invention are not impaired. The silane coupling treatment layer is not particularly limited and can be formed from materials known in the art. Herein, the term "silane coupling treatment layer" refers to a layer formed from a silane coupling agent. The silane coupling agent is not particularly limited and can be any known agent in the art. Examples of silane coupling agents include amino-based silane coupling agents, epoxy-based silane coupling agents, mercapto-based silane coupling agents, methacryloxy-based silane coupling agents, vinyl-based silane coupling agents, imidazole-based silane coupling agents, and triazine-based silane coupling agents. Among these, amino-based silane coupling agents and epoxy-based silane coupling agents are preferred. The above-mentioned silane coupling agents can be used alone or in combination of two or more.

[0028] The silane coupling agent can be produced by a known method, but a commercially available product may also be used. Examples of commercially available products that can be used as the silane coupling agent include the KBM series and KBE series manufactured by Shin-Etsu Chemical Co., Ltd. A commercially available silane coupling agent may be used alone, but from the viewpoint of the adhesiveness (peel strength) between the surface treatment layer 3 and the resin substrate 11, it is preferable to use a mixture of two or more silane coupling agents. Among them, preferred mixtures of silane coupling agents are a mixture of KBM603 (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane) and KBM503 (3-methacryloxypropyltrimethoxysilane), a mixture of KBM602 (N-2-(aminoethyl)-3-aminopropyldimethoxysilane) and KBM503 (3-methacryloxypropyltrimethoxysilane), a mixture of KBM603 (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane) and KBE503 (3-methacryloxypropyltriethoxysilane), a mixture of KBM602 (N-2-(aminoethyl)-3-aminopropyldimethoxysilane) and KBE503 (3-methacryloxypropyltriethoxysilane), Examples of suitable silane coupling agents include a mixture of KBE903 (3-aminopropyltrimethoxysilane) and KBE503 (3-methacryloxypropyltrimethoxysilane), a mixture of KBM903 (3-aminotriethoxysilane) and KBM503 (3-methacryloxypropyltrimethoxysilane), a mixture of KBE903 (3-aminotriethoxysilane) and KBE503 (3-methacryloxypropyltrimethoxysilane), a mixture of KBE903 (3-aminotriethoxysilane) and KBE503 (3-methacryloxypropyltriethoxysilane), and a mixture of KBM903 (3-aminopropyltrimethoxysilane) and KBE503 (3-methacryloxypropyltriethoxysilane). When a mixture of two or more silane coupling agents is used, the mixing ratio is not particularly limited and may be adjusted appropriately depending on the type of silane coupling agent used.

[0029] The titanium-copper-clad laminate 10 can be produced by adhering a resin substrate 11 to the surface of the surface-treated layer 3 of the surface-treated titanium-copper foil 1. The resin substrate 11 is not particularly limited, and any substrate known in the art can be used. Examples of the resin substrate 11 include substrates formed from a paper substrate with a phenolic resin, a paper substrate with an epoxy resin, a synthetic fiber cloth substrate with an epoxy resin, a glass cloth / paper composite substrate with an epoxy resin, a glass cloth / glass nonwoven fabric composite substrate with an epoxy resin, a glass cloth substrate with an epoxy resin, a polyester film, a polyimide film, a liquid crystal polymer, a fluororesin, etc.

[0030] The method for bonding the surface-treated titanium copper foil 1 and the resin substrate 11 is not particularly limited and can be performed according to a method known in the art. For example, the surface-treated titanium copper foil 1 and the resin substrate 11 may be laminated and then thermocompression bonded.

[0031] (Embodiment 2) A printed wiring board according to Embodiment 2 of the present invention comprises a circuit pattern formed by etching the surface-treated titanium copper foil 1 of the titanium copper clad laminate of Embodiment 1. The method for producing this printed wiring board is not particularly limited, and known methods such as the subtractive method and the semi-additive method can be used, although the subtractive method is preferably used.

[0032] FIG. 2 is a cross-sectional view illustrating a method for manufacturing a printed wiring board according to a second embodiment of the present invention. In FIG. 2, a resist is first applied to the surface of the surface-treated titanium copper foil 1 of the titanium copper clad laminate 10, followed by exposure and development to form a predetermined resist pattern 30 (step (a)). Next, the surface-treated titanium copper foil 1 in the areas where the resist pattern 30 is not formed (unnecessary areas) is removed by etching (step (b)). Finally, the resist pattern 30 on the surface-treated titanium copper foil 1 is removed (step (c)). The conditions for this subtractive process are not particularly limited and can be based on conditions known in the art (Embodiment 2). The printed wiring board according to the second embodiment of the present invention has a circuit pattern formed by etching the surface-treated titanium copper foil 1 of the titanium copper clad laminate 10 according to the first embodiment. The method for manufacturing this printed wiring board is not particularly limited, and known methods such as subtractive and semi-additive processes can be used, but the subtractive process is preferred.

[0033] Hereinafter, the embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples in any way.

[0034] Example 1 A 35 μm thick titanium copper foil (C1990-GSH foil, manufactured by JX Nippon Mining & Metals Corporation) was prepared. The titanium copper foil had a composition of Cu-3.1 mass% Ti. The "C1990-GSH foil" was manufactured by rolling or the like. Next, after degreasing and pickling, a heat-resistant treatment layer and a chromate treatment layer were sequentially formed as surface treatment layers, thereby obtaining the surface-treated titanium copper foil of Example 1. The conditions for forming the heat-resistant treatment layer and the chromate treatment layer were as follows: Heat-resistant treatment layer <Conditions for forming Ni-Zn layer> Plating solution composition: 23.5 g / L Ni, 4.5 g / L Zn Plating solution pH: 3.6 Plating solution temperature: 40°C Immersion time (immersion without current flow): 1.17 seconds Number of immersion treatments: 1 Chromate treatment layer <Conditions for forming chromate treatment layer> Chromate solution composition: 3 g / L K2Cr2O7, 0.33 g / L Zn Chromate solution pH: 3.65 Chromate solution temperature: 55°C Electrolysis conditions: current density 0.53 A / dm2 , time 1.17 seconds Number of chromate treatments: 2 times

[0035] Example 2 A 50 μm thick titanium copper foil (C1990-GSH foil manufactured by JX Nippon Mining & Metals Corporation) was prepared, degreased, and pickled. After that, a heat-resistant treatment layer (Ni—Zn layer) and a chromate treatment layer were sequentially formed as surface treatment layers, thereby obtaining the surface-treated titanium copper foil of Example 2. The conditions for forming each treatment layer were as follows: Heat-resistant treatment layer <Conditions for forming the Ni—Zn layer> Plating solution composition: 23.5 g / L Ni, 4.5 g / L Zn Plating solution pH: 3.6 Plating solution temperature: 40° C. Electroplating conditions: current density 0.73 A / dm 2 , time 1.17 seconds Number of electroplating treatments: 1 time Chromate treatment layer <Conditions for forming chromate treatment layer> Chromate solution composition: 3 g / L K2Cr2O7, 0.33 g / L Zn Chromate solution pH: 3.65 Chromate solution temperature: 55°C Immersion time (immersion without current flow): 0.73 seconds Number of chromate treatments: 1 time

[0036] Example 3 A surface-treated titanium copper foil of Example 3 was obtained under the same conditions as Example 2, except that the electroplating conditions for the Ni-Zn layer were changed as follows: Heat-resistant layer <Conditions for forming the Ni-Zn layer> Electroplating conditions: current density 1.22 A / dm 2 , time 1.17 seconds

[0037] Example 4 A surface-treated titanium copper foil of Example 4 was obtained under the same conditions as Example 2, except that the electroplating conditions for the Ni-Zn layer were changed as follows: Heat-resistant layer <Conditions for forming the Ni-Zn layer> Electroplating conditions: current density 1.71 A / dm 2 , time 1.17 seconds

[0038] Example 5 A surface-treated titanium copper foil of Example 5 was obtained under the same conditions as in Example 4, except that a titanium copper foil having a thickness of 35 μm (C1990-GSH foil, manufactured by JX Nippon Mining & Metals Corporation) was used.

[0039] Example 6 A surface-treated titanium copper foil of Example 6 was obtained under the same conditions as Example 2, except that the electroplating conditions for the Ni-Zn layer, the electrolysis conditions for the chromate treatment layer, and the number of chromate treatments were changed as follows: Heat-resistant treatment layer <Conditions for forming the Ni-Zn layer> Electroplating conditions: current density 1.71 A / dm 2 , time 1.17 seconds Chromate treatment layer <Conditions for forming chromate treatment layer> Electrolysis conditions: current density 2.65 A / dm 2 , time 1.17 seconds Number of chromate treatments: 2 times

[0040] Comparative Example 1 The same titanium copper foil as in Example 1 (titanium copper foil not subjected to surface treatment) was used.

[0041] The surface-treated titanium copper foils obtained in the above examples and the titanium copper foils of the comparative examples were subjected to the following property evaluations.

[0042] <Surface roughness Sa> Measurements and analyses were carried out in accordance with ISO 25178-2:2012 under the conditions shown in Table 1. Measurements were carried out at 10 randomly selected locations on the surface of the surface treatment layer of the surface-treated titanium copper foil of the Example and on the surface of the titanium copper foil of the Comparative Example. The average value of the surface roughness Sa at these measurement locations is shown in Table 2. The temperature during measurement was 23 to 25°C.

[0043]

[0044] <Peel Strength> Peel strength was measured in accordance with JIS C5016:1994. A polyamic acid solution, a polyimide precursor, was applied to the surface of the surface-treated layer of the surface-treated titanium copper foil of the Example or the surface of the titanium copper foil of the Comparative Example. The resulting solution was then heated in air at 100°C for 20 minutes to dry, and then heated at 300°C for 30 minutes in a nitrogen atmosphere to produce a copper-clad laminate. A 0.4 mm wide circuit was then formed in the MD direction (parallel to the rolling direction of the rolled titanium copper foil). The circuit was formed according to a conventional method. The strength (MD 90° peel strength) when the circuit (surface-treated titanium copper foil) was peeled at 90° to the surface of the resin substrate, i.e., vertically upward relative to the surface of the resin substrate, was measured. Measurements were performed twice, and the average values ​​are shown in Table 2.

[0045] <Heat Resistance> The surface-treated titanium copper foils of Examples and Comparative Examples were left to stand in an oven at 200°C in an air atmosphere for 30 minutes, and then the surface of the surface-treated titanium copper foil or titanium copper foil was visually observed. In Table 2, foils in which discoloration was observed were rated as not having heat resistance, and foils in which no discoloration was observed were rated as having heat resistance.

[0046] <Amount of each element in the surface treatment layer> The Zn and Ni deposition amounts in the surface treatment layer of the surface-treated titanium copper foil of the Examples were measured by dissolving the surface treatment layer of the surface-treated titanium copper foil in an aqueous nitric acid solution prepared by mixing nitric acid and water at a volume ratio of 1:2, and then measuring the resulting solution by ICP analysis. An inductively coupled plasma optical emission spectrometer (Hitachi High-Tech Science Corporation, SPS3520UV) was used for the measurement. The Cr deposition amount in the surface treatment layer of the surface-treated titanium copper foil was measured by boiling and dissolving the surface treatment layer of the surface-treated titanium copper foil in an aqueous hydrochloric acid solution prepared by mixing hydrochloric acid and water at a volume ratio of 1:4, and then quantitatively analyzing the resulting solution by atomic absorption spectrometry. An atomic absorption spectrophotometer (Agilent, 200 Series AA) was used for the measurement. The deposition amounts of Zn, Ni, and Cr were measured per unit area (dm ) of the respective surface-treated titanium copper foils. 2 The weights are expressed as the masses (μg) of Zn, Ni and Cr deposited per 1000g of Zn, Ni and Cr.

[0047]

[0048] As shown in Table 2, the surface-treated titanium copper foils of Examples 1 to 6, on which a surface treatment layer was formed, had higher peel strength than the titanium copper foil of Comparative Example 1, on which no surface treatment layer was formed. Furthermore, as is clear from a comparison of Examples 4 to 6 with Examples 1 to 3, the Zn deposition amount in the surface treatment layer was 237 μg / dm 2 The surface-treated titanium copper foil thus obtained had high heat resistance.

[0049] As can be seen from the above results, the present invention provides a surface-treated titanium copper foil and a titanium copper clad laminate that are capable of forming a circuit pattern with excellent adhesion to a resin substrate. Furthermore, the present invention also provides a printed wiring board having a circuit pattern with excellent adhesion to a resin substrate.

[0050] Therefore, the present invention can be embodied as follows: <1> A surface-treated titanium copper foil comprising a titanium copper foil and a surface treatment layer formed on at least one surface of the titanium copper foil, the surface treatment layer containing Cr and Zn. <2> The surface-treated titanium copper foil according to <1>, wherein the surface treatment layer further contains Ni. <3> The Cr coating amount in the surface treatment layer is 0 μg / dm 2 Super 100μg / dm 2 <4> The surface-treated titanium copper foil according to <1> or <2>, wherein the Cr coating amount in the surface treatment layer is 10 to 100 μg / dm 2 <5> The surface-treated titanium copper foil according to <3>, wherein the Cr coating amount in the surface treatment layer is 25 to 51 μg / dm 2 <6> The surface-treated titanium copper foil according to <4>, wherein the Zn coating amount in the surface treatment layer is 0 μg / dm 2 Super 700μg / dm 2 <7> The surface-treated titanium copper foil according to any one of <1> to <5>, wherein the Zn coating amount in the surface treatment layer is 10 to 500 μg / dm 2 <8> The surface-treated titanium copper foil according to <6>, wherein the Zn coating amount in the surface treatment layer is 20 to 237 μg / dm 2 <9> The surface-treated titanium copper foil according to <7>, wherein the Ni deposition amount in the surface treatment layer is 0 μg / dm 2 Super 200μg / dm 2 <10> The surface-treated titanium copper foil according to any one of <2> to <8>, wherein the Ni deposition amount in the surface treatment layer is 1 to 180 μg / dm 2 <11> The surface-treated titanium copper foil according to <9>, wherein the Ni deposition amount in the surface treatment layer is 3 to 103 μg / dm2 <10> The surface-treated titanium copper foil according to <10>, wherein the titanium copper foil contains 1.5 to 5.0 mass% of Ti, with the remainder consisting of Cu and unavoidable impurities. <12> The surface-treated titanium copper foil according to any one of <1> to <11>, wherein the titanium copper foil contains 1.5 to 5.0 mass% of Ti, with the remainder consisting of Cu and unavoidable impurities. <13> The surface-treated titanium copper foil according to <12>, wherein the titanium copper foil further contains 1.0 mass% or less in total of at least one element selected from the group consisting of Ag, B, Co, Fe, Mg, Mn, Mo, Ni, P, Si, Cr, and Zr. <14> The surface-treated titanium copper foil according to any one of <1> to <13>, wherein the arithmetic mean roughness Sa of the surface of the surface treatment layer opposite to the surface facing the titanium copper foil is 0.020 to 0.100 μm. <15> The surface-treated titanium copper foil according to <14>, wherein the arithmetic mean roughness Sa of the surface of the surface treatment layer opposite to the surface on the titanium copper foil side is 0.041 to 0.087 μm. <16> The surface-treated titanium copper foil according to any one of <1> to <15>, wherein the titanium copper foil has a thickness of 5 to 150 μm. <17> A titanium copper clad laminate comprising the surface-treated titanium copper foil according to any one of <1> to <16>, and a resin substrate formed on the surface of the surface treatment layer of the surface-treated titanium copper foil. <18> A printed wiring board comprising the titanium copper clad laminate according to <17>.

[0051] (Potential Contribution to SDGs) According to the above embodiment, it is possible to provide a surface-treated titanium copper foil 1 that can improve adhesion to a resin substrate 11, which may improve product yield in the manufacture of electronic devices and the like. Improving product yield leads to a stable supply of products and reduced loss of metal raw materials, which are limited resources. Therefore, the above embodiment may contribute to Goal 9 "Build resilient infrastructure, promote inclusive and sustainable industrialization and foster innovation" and Goal 12 "Ensure sustainable consumption and production patterns" of the Sustainable Development Goals (SDGs) led by the United Nations.

[0052] REFERENCE SIGNS LIST 1 Surface-treated titanium copper foil 2 Titanium copper foil 3 Surface-treated layer 10 Titanium copper clad laminate 11 Resin substrate 30 Resist pattern

Claims

1. A surface-treated titanium copper foil comprising a titanium copper foil and a surface treatment layer formed on at least one surface of the titanium copper foil, the surface treatment layer containing Cr and Zn.

2. The surface-treated titanium copper foil according to claim 1, wherein the surface treatment layer further contains Ni.

3. The amount of Cr deposited in the surface treatment layer is 0 μg / dm 2 Super 100μg / dm 2 The surface-treated titanium copper foil according to claim 1 or 2, wherein:

4. The amount of Cr deposited in the surface treatment layer is 10 to 100 μg / dm 2 The surface-treated titanium copper foil according to claim 3, wherein 5. The amount of Cr deposited in the surface treatment layer is 25 to 51 μg / dm 2 The surface-treated titanium copper foil according to claim 4, wherein 6. The amount of Zn attached to the surface treatment layer is 0 μg / dm 2 Super 700μg / dm 2 The surface-treated titanium copper foil according to any one of claims 1 to 5, wherein:

7. The amount of Zn attached in the surface treatment layer is 10 to 500 μg / dm 2 The surface-treated titanium copper foil according to claim 6, wherein 8. The amount of Zn deposited in the surface treatment layer is 20 to 237 μg / dm 2 The surface-treated titanium copper foil according to claim 7, wherein 9. The amount of Ni attached in the surface treatment layer is 0 μg / dm 2 Super 200μg / dm 2 The surface-treated titanium copper foil according to any one of claims 2 to 8, wherein:

10. The amount of Ni attached in the surface treatment layer is 1 to 180 μg / dm 2 The surface-treated titanium copper foil according to claim 9, 11. The amount of Ni attached in the surface treatment layer is 3 to 103 μg / dm 2 The surface-treated titanium copper foil according to claim 10, 12. The surface-treated titanium copper foil according to any one of claims 1 to 11, wherein the titanium copper foil contains 1.5 to 5.0 mass% Ti, with the remainder consisting of Cu and unavoidable impurities.

13. The surface-treated titanium copper foil according to claim 12, further containing 1.0 mass% or less in total of at least one element selected from the group consisting of Ag, B, Co, Fe, Mg, Mn, Mo, Ni, P, Si, Cr, and Zr.

14. The surface-treated titanium copper foil according to any one of claims 1 to 13, wherein the arithmetic mean roughness Sa of the surface of the surface treatment layer opposite to the surface on the titanium copper foil side is 0.020 to 0.100 μm.

15. The surface-treated titanium copper foil according to claim 14, wherein the arithmetic mean roughness Sa of the surface of the surface treatment layer opposite to the surface on the titanium copper foil side is 0.041 to 0.087 μm.

16. The surface-treated titanium copper foil according to any one of claims 1 to 15, wherein the thickness of the titanium copper foil is 5 to 150 μm.

17. A titanium-copper clad laminate comprising the surface-treated titanium-copper foil according to any one of claims 1 to 16, and a resin substrate formed on the surface of the surface treatment layer of the surface-treated titanium-copper foil.

18. A printed wiring board comprising the titanium copper clad laminate of claim 17.

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