JP2005350708A - Composition for etching - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an etching composition for completely removing such a metallic content as to deposit on a part other than a wiring pattern and cause the lowering of insulation reliability, without eroding the surface of the wiring pattern formed of a layer of a conductor such as copper. <P>SOLUTION: The composition for etching, which selectively removes a metal except copper and a copper alloy, is an aqueous solution including (1) hydrochloric acid of 10 to 300 g/l in terms of HCl, (2) nitric acid of 1 to 100 g/l in terms of HNO<SB>3</SB>, (3) phosphoric acid of 1 to 100 g/l in terms of H<SB>3</SB>PO<SB>4</SB>, (4) at least one compound selected from the group consisting of nitrous acid and a salt thereof, in an amount of 0.001 to 10 g/l in terms of NO<SB>2</SB>, and (5) a surfactant of 0.01 to 50 g/l. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an etching treatment composition, an etching treatment method, and an article subjected to an etching treatment.

  A semi-additive method is known as a method for manufacturing a printed wiring board. In this method, after a catalytic metal is adsorbed on an insulating substrate, an electroless plating film is formed, then a plating resist is formed, and then a circuit portion is formed by an electrolytic copper plating method. It is a method including a step of peeling and removing the electroless plating film formed first by etching. According to this method, a high-density wiring board can be manufactured. However, when the electroless plating film formed first is removed by etching, the catalyst substance may not be completely removed and may remain partially. As the catalytic material, a metal colloid mainly composed of Pd having high activity is usually used. If this remains, an unnecessary plating film is formed between the wirings in the subsequent electroless plating process (Ni-Au plating or the like). This causes generation of a circuit failure in the printed wiring board and a decrease in insulation reliability.

  In recent years, with the miniaturization and portability of electronic devices, the use of flexible printed boards, TAB tapes, COF tapes, and the like based on polyimide films that are lightweight and have a high degree of design freedom is increasing.

  As a printed wiring board based on a polyimide film, a non-adhesive type copper-clad laminate in which a copper film as a conductor layer and a polyimide base material are laminated without using an adhesive has attracted attention. As one of the methods, a metalizing method is known. In this method, a conductor film called a “plating seed layer” is formed on a polyimide base material by a dry method such as sputtering, and then a copper film having a predetermined film thickness is formed by a plating method. Thereafter, ferric chloride is formed. In this method, a wiring pattern is formed by etching with a solution or the like. However, even in this method, removal of the plating seed layer by etching may be incomplete, and the metal component of the plating seed layer remains on the surface of the substrate other than the wiring pattern made of copper, which induces migration and causes printing. This is a cause of lowering the insulation reliability of the wiring board.

  As countermeasures against these problems, a substance that causes a decrease in insulation reliability is removed from the surface of the resin substrate using a method of washing with a cyanide solution or an aqueous solution containing permanganate and alkali hydroxide as main components. The way is done. However, these methods cannot be applied to a part of the polyimide film that is weak in an alkaline atmosphere because the treatment liquid is alkaline, which causes the selection range of the substrate to be narrowed. Furthermore, due to the strong toxicity of cyanide compounds, it may not be possible to meet recent environmental regulations.

Examples of acidic type processing solutions include cerium (IV) salt solutions; compositions containing nitric acid, sulfuric acid, oxidizing agents and chlorine ions (see, for example, Patent Document 1); nitric acid, chlorine ions, nitrogen-containing heterocyclic compounds, many A composition containing a monohydric alcohol, a nonionic surfactant, a cationic surfactant, an iron ion and a urea derivative (see, for example, Patent Document 2); hydrogen peroxide, inorganic acid, quaternary ammonium salt and aliphatic alcohol An etching solution containing, for example, see Patent Document 3 is known. However, even when these various processing solutions are used, it is difficult to completely remove metal components that remain on the surface of the substrate other than the wiring pattern of the printed wiring board and cause a decrease in insulation reliability. .
JP 2001-140084 JP 2001-339142 A JP 2003-342756 A

  The present invention has been made in view of the above-described prior art, and its main purpose is insulation reliability that adheres to portions other than the wiring pattern without eroding the surface of the wiring pattern by a conductor layer such as copper. It is an object of the present invention to provide a novel etching treatment composition capable of completely removing a metal component that causes a decrease in the temperature.

  The present inventor has intensively studied to achieve the above-described object. As a result, according to the acidic aqueous solution containing hydrochloric acid, nitric acid, phosphoric acid, nitrous acid compound and surfactant, the substrate other than the wiring pattern hardly erodes the surface of the wiring pattern made of copper or copper alloy. It has been found that a metal component that causes a reduction in insulation reliability remaining on the surface can be completely removed, and a substrate weak in an alkaline atmosphere can be applied as a substrate material. Moreover, it has been found that this aqueous solution is excellent in stability and can maintain excellent performance for a long period of time, and the present invention has been completed here.

That is, the present invention provides the following etching composition, etching method, and etched article.
1. (1) hydrochloric acid as HCl amount of 10 to 300 g / l, (2) nitric acid as HNO ₃ amount of 1 to 100 g / l, (3) phosphoric acid as H ₃ PO ₄ amount of 1 to 100 g / l, (4) Copper and at least one selected from the group consisting of nitrous acid and salts thereof in an aqueous solution containing 0.001 to 10 g / l as NO ₂ amount, and (5) 0.01 to 50 g / l of surfactant, An etching treatment composition capable of selectively removing metals other than copper alloys.
2. Item 2. The etching composition according to Item 1, wherein the surfactant contains 100 parts by weight of a nonionic surfactant and 0.1 to 50 parts by weight of an anionic surfactant.
3. The composition for etching treatment according to Item 1 or 2, further comprising 0.01 to 10 g / l of a copper or copper alloy corrosion inhibitor.
4). Furthermore, the composition for an etching process in any one of said claim | item 1-3 containing 0.1-20 g / l of oxidizing agents.
5. Item 5. An etching treatment method comprising contacting the composition for etching treatment according to any one of Items 1 to 4 with an object to be treated containing a copper or copper alloy portion and another metal portion.
6). Item 6. The method according to Item 5, wherein the object to be processed is a printed wiring board having a conductor circuit made of copper or a copper alloy and a remaining portion of the catalyst metal.
7). Item 6. The method according to Item 5, wherein the object to be processed is a printed wiring board having a conductor circuit made of copper or a copper alloy and a remaining portion of the plating seed layer.
8). Articles etched by the method of item 5 above.

The etching treatment composition of the present invention comprises (1) hydrochloric acid, (2) nitric acid, (3) phosphoric acid, (4) at least one selected from the group consisting of nitrous acid and salts thereof, and (5) a surfactant. Is an aqueous solution containing as an essential component.

  By using such an etching composition, it is possible to selectively remove other metal components by etching without substantially eroding copper and copper alloys. Further, since the composition is an acidic aqueous solution, the substrate is hardly eroded even when a printed wiring board or the like whose base material is a material weak in an alkaline atmosphere is used. For this purpose, the composition for etching treatment of the present invention can use articles of a wide range of materials as objects to be treated.

  The amount of hydrochloric acid in the etching composition of the present invention is about 10 to 300 g / l, preferably about 50 to 250 g / l as the amount of HCl. If the hydrochloric acid concentration is too low, the removal property of the etching object may be reduced and a part of the etching object may remain. On the other hand, if the concentration of hydrochloric acid is too high, there is no significant adverse effect, but it is economically disadvantageous.

The amount of nitric acid is about 1 to 100 g / l, preferably about 5 to 50 g / l as the amount of HNO ₃ . When the concentration of nitric acid is too low, the removability of the object to be etched may be reduced and a part of the object to be etched may remain. On the other hand, when the nitric acid concentration is too high, copper and copper alloys are easily eroded, which is not preferable.

The amount of phosphoric acid is about 1 to 100 g / l, preferably about 5 to 50 g / l as the amount of H ₃ PO ₄ . When the phosphoric acid concentration is too low, the removability of the etching target may be reduced, and a part of the etching target may remain. On the other hand, when the phosphoric acid concentration is too high, copper and copper alloys are easily eroded, which is not preferable.

  In the etching treatment composition of the present invention, the hydrochloric acid, nitric acid and phosphoric acid described above can be used at industrially distributed concentrations, and appropriately diluted and mixed depending on the blending amount. Can be used.

  The etching composition of the present invention further needs to contain at least one component selected from the group consisting of nitrous acid and salts thereof (hereinafter referred to as “nitrite compound”). The nitrite may be a water-soluble salt, and examples thereof include alkali metal salts such as lithium nitrite, potassium nitrite, and sodium nitrite; ammonium nitrite; calcium nitrite. These nitrous acid compounds can be used singly or in combination of two or more.

The amount of the nitrous acid compound is about 0.001 to 10 g / l, preferably about 0.01 to 1 g / l as the amount of NO ₂ . When the concentration of the nitrous acid compound is too low, the removability of the etching target may be reduced and a part of the etching target may remain. On the other hand, when the phosphoric acid concentration is too high, copper and copper alloys are easily eroded, which is not preferable.

  Furthermore, it is necessary to mix | blend surfactant with the etching processing composition of this invention. By compounding a surfactant, the permeability of the treatment liquid into the gaps in the fine wiring pattern is improved, and the metal component that causes a reduction in the insulation reliability remaining on the substrate surface other than the wiring pattern is removed. Is greatly improved. Moreover, there is also an effect of suppressing excessive erosion of the wiring pattern surface made of copper or a copper alloy.

  As the surfactant, any surfactant can be used as long as it is soluble in the treatment liquid, and any of a nonionic surfactant, an anionic surfactant, a cationic surfactant and an amphoteric surfactant may be used. . Also, two or more surfactants can be mixed and used.

  As the nonionic surfactant, for example, an ether type, an ether ester type, an ester type, a nitrogen-containing type, or the like can be used. In particular, HLB having excellent solubility and dispersibility: 10 or more and a number average molecular weight of about 1000 to 10,000 are preferable.

  As the anionic surfactant, for example, anionic surfactants such as a carboxylate salt type, a sulfonate salt type, a sulfate ester salt type, and a phosphate ester salt type can be used.

  As the cationic surfactant, for example, an aliphatic amine salt type, a quaternary ammonium salt type, an aromatic quaternary ammonium salt type, a heterocyclic quaternary ammonium type, or the like can be used.

  Examples of amphoteric surfactants that can be used include amphoteric surfactants such as carboxybetaine type, sulfobetaine type, aminocarboxylate type, and imidazoline derivative type.

  Of these surfactants, nonionic surfactants having excellent solubility and low foaming properties are preferred. Furthermore, since the permeability is improved by blending an anionic surfactant, a particularly excellent effect can be obtained when a nonionic surfactant and an anionic surfactant are used in combination. When a nonionic surfactant and an anionic surfactant are used in combination, the usage ratio of both is about 0.1 to 50 parts by weight of the anionic surfactant with respect to 100 parts by weight of the nonionic surfactant. It is preferable to make it about 0.5 to 20 parts by weight.

  Suitable nonionic surfactants include polyethylene glycol, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl naphthyl ether, polyoxyethylene polyoxypropylene glycerin ether. And polyoxyethylene polyoxypropylene polyamine, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine and the like.

  Suitable anionic surfactants include polyoxyethylene alkyl ether carboxylic acid alkali metal salts (Na, K, the same shall apply hereinafter), alkylbenzene sulfonic acid alkali metal salts, alkyl naphthalene sulfonic acid alkali metal salts, and dialkyl sulfosuccinates. Alkali metal salts of acid esters, alkali metal salts of alkylsulfosuccinic acids, alkali metal salts of polyoxyethylene alkylsulfosuccinic acids, alkali metal salts or amine salts of alkyl alcohol sulfates, alkali metal salts of polyoxyethylene alkyl ether sulfates, poly Alkali metal salt of oxyethylene alkylphenyl ether sulfate, alkali metal salt of polyoxyethylene alkyl ether phosphate, alkali metal salt of polyoxyethylene phenyl ether phosphate, polyoxy Alkali metal salts of Chi alkylphenyl ether phosphoric acid, and the like alkali metal salts of alkyl phosphoric acids can be exemplified.

  The blending amount of the surfactant is about 0.01 to 50 g / l, preferably about 0.1 to 20 g / l. If the surfactant concentration is too low, the permeability of the processing solution may be reduced, and a part of the etching target may remain, and the surface of the wiring pattern made of copper or copper alloy is more easily eroded. . On the other hand, when the surfactant concentration is too high, the foaming property becomes strong, and it is necessary to strengthen the washing conditions.

  You may add to the etching process composition of this invention alkali metal salts, such as sodium salt of each acid component of hydrochloric acid, nitric acid, and phosphoric acid, potassium salt, ammonium salt, etc. About content of these salts, it can be set as about 0.1-100 g / l as a total amount of the salt of hydrochloric acid, nitric acid, and phosphoric acid, for example.

  If necessary, the etching treatment composition of the present invention may further contain a copper or copper alloy corrosion inhibitor. A corrosion inhibitor for copper or copper alloy is widely used as a component that inhibits corrosion of a substrate, that is, an inhibitor, for example, when peeling a plating film formed on a substrate made of copper or copper alloy. Usually, it is known as a component having an effect of suppressing dissolution and roughening by adsorbing on the surface of copper or copper alloy. By adding a copper or copper alloy corrosion inhibitor to the etching treatment composition of the present invention, the effect of inhibiting the corrosion of the wiring circuit is further improved when a printed wiring board or the like is to be treated. In this invention, if it is a thing soluble in the etching processing composition of this invention among well-known corrosion inhibitors, it can be used without limitation. Specific examples of copper or copper alloy corrosion inhibitors include benzotriazole, derivatives thereof; mercaptobenzothiazole, derivatives thereof; alkyl imidazole derivatives; organic acids, esters thereof, amides; amine compounds; phosphonic acids, derivatives thereof; And nitrogen-containing compounds such as thiourea derivatives; sulfur-containing compounds; and phosphorus-containing compounds. The compounding quantity of these corrosion inhibitors can be normally about 0.01-10 g / l.

  Furthermore, an oxidizing agent can be mix | blended with the etching processing composition of this invention as needed. By blending the oxidizing agent, it is possible to improve the effect of removing the etching object that is firmly adsorbed. The oxidizing agent that can be blended is not limited as long as it is soluble in the treatment liquid. For example, peroxides such as hydrogen peroxide and sodium peroxide; nitrobenzenesulfonic acid and its alkali metal salt (Na salt) And aromatic salts such as nitrobenzoic acid and alkali metal salts thereof (Na salt, K salt, etc.). The compounding quantity of these oxidizing agents can be about 0.1-20 g / l.

  The etching treatment composition of the present invention is an aqueous solution containing the above-described components at a predetermined ratio. In the composition of the present invention, each component may be dissolved separately, or a mixture obtained by mixing each component in advance may be added. Further, it may be prepared as a concentrated solution containing all components and diluted at the time of use.

  An etching method using the etching treatment composition of the present invention is not particularly limited, and the etching treatment composition may be brought into contact with an object to be processed. Specific examples of the method include a method of immersing an object to be processed in an etching treatment composition liquid, a method of spraying an etching treatment composition liquid on the surface of the object to be processed (spray method), and the like. In particular, according to the method of immersing in the etching processing solution, uniform and smooth processing can be easily performed.

  About the temperature of a process liquid, it is preferable to set it as about 10-60 degreeC, and it is more preferable to set it as about 20-40 degreeC. When the liquid temperature of the treatment liquid is too low, the reactivity of the treatment liquid is lowered, and the removability of the etching object is lowered. Further, when the liquid temperature is too high, the wiring pattern is excessively dissolved, and the electrical characteristics and reliability required for the wiring circuit are lowered. Furthermore, it is not economically preferable because the thermal loss during the processing operation increases.

  About processing time, it can be made into the wide range of about 1 to 300 seconds, processing time should be shortened when the liquid temperature of processing liquid is high, and processing time should be lengthened when the liquid temperature is low. For example, in order to perform a good etching process, the processing time may be about 10 to 120 seconds in the temperature range of 20 to 40 ° C. of the processing solution.

  A typical object to be treated by the etching composition of the present invention is an article in which copper or a copper alloy and other metals are present simultaneously. By performing an etching process on the object to be processed using the composition for etching process of the present invention, the copper and copper alloy portions are hardly eroded, and only the other metal components are selective. It can be etched away well. The copper alloy is not particularly limited as long as it is an alloy containing copper as a main component, that is, an alloy containing about 50% by weight or more of copper. For example, when processing an article containing copper-phosphorus, copper-zinc, etc., which are known as copper alloys having excellent electrical characteristics, rolling workability, etc., these copper alloys are hardly eroded and others This metal component can be removed by etching with high selectivity.

  Typical examples of the metal to be etched away include Pd, Sn, Ag, Mo, Ta, Ti, V, W, In, Cr, Fe, Ni, Co, and alloys containing these.

  Specific examples of the object to be treated of the present invention include articles having a conductor circuit made of copper or a copper alloy, such as a printed wiring board, a flexible printed board, a TAB tape, and a COF tape. Among these, for example, in a printed wiring board in which a conductor circuit is formed by a semi-additive method, a plating catalyst such as Pd may remain in a portion other than the circuit in an etching process when forming the conductor circuit. For such a printed wiring board, the residual catalyst is almost completely removed by performing an etching process using the etching process composition of the present invention, with almost no erosion of the conductor circuit portion made of copper or copper alloy. can do. As a result, an unnecessary plating film is not generated between the wirings in the subsequent electroless plating process or the like, and a highly reliable printed wiring board in which a short circuit or the like hardly occurs can be obtained.

  Moreover, about the board | substrate obtained by the metalizing method, when forming a wiring pattern by an etching, the removal of a plating seed layer may be incomplete. By performing an etching process on such a substrate using the etching process composition of the present invention, the plating seed layer made of Ni, Cr, an alloy thereof, or the like is hardly eroded. The residue can be removed almost completely, and a printed circuit board with high insulation reliability can be obtained.

  In addition to the purpose of removing components (seed layer) that cause a decrease in insulation reliability remaining on the substrate surface other than the wiring pattern formed on the silicon wafer that is the material of the semiconductor component, such semiconductor components When the seed layer is formed, the composition for etching treatment of the present invention can also be used effectively for the purpose of peeling off and removing the seed layer film adhering to the inside of the vapor deposition apparatus as a manufacturing apparatus.

According to the composition for etching treatment of the present invention, the following remarkable effects are exhibited.
(1) Various metal components that cause a decrease in insulation reliability remaining on the substrate surface other than the wiring pattern made of copper or copper alloy can be almost completely removed.
(2) The surface of the wiring pattern made of copper or a copper alloy is eroded very little.
(3) The etching solution has good stability and can maintain excellent performance for a long time.
(4) It is possible to apply a base material that is weak in an alkaline atmosphere as a substrate material, and the selection range of the base material becomes very wide.

Hereinafter, the present invention will be described in more detail with reference to examples.
(Preparation of test piece)
Test piece 1
A 2.5 cm × 5.0 cm copper-clad substrate (FR-4, copper film thickness: 35 μm) is subjected to 0.5 cm × 5.0 cm striped masking and exposed using a ferric chloride solution. The test piece 1 was produced by dissolving and removing the copper foil. FIG. 1 is a schematic view of the surface state of the obtained test piece 1, and two resin exposed portions having a size of 0.5 cm × 5 cm are formed on the substrate.

Test piece 2
A seed layer mainly composed of Ni—Cr was formed on a 2.5 cm × 5.0 cm quartz glass plate by a sputtering method, and a copper plating film having a thickness of 10 μm was formed by an electroplating method. Thereafter, striped masking of 0.5 cm × 5.0 cm was applied, and the exposed copper film was dissolved and removed using a sodium persulfate solution to prepare a test piece 2. FIG. 2 is a schematic view of the surface state of the obtained test piece 2, and two exposed portions of the seed layer having a size of 0.5 cm × 5 cm are formed on the substrate.

Example 1
About the test piece 1, the Pd catalyst was provided and the electroless copper plating was performed by the process process 1 shown in following Table 1, and the electroless copper plating film | membrane formed in the resin part of the test piece 1 was removed after that. It is visually confirmed that there is no residue of the electroless copper plating film on the resin exposed portion of the test piece 1 after the treatment, and then immersed in the following etching solution to leave the catalyst metal remaining on the resin exposed portion. Was removed by etching.

（エッチング液組成）
３５％塩酸 ２４０ｇ／ｌ
６２％硝酸 ３０ｇ／ｌ
８９％リン酸 ５０ｇ／ｌ
亜硝酸ナトリウム ０．５ｇ／ｌ
非イオン界面活性剤（ポリエチレングリコール） １０ｇ／ｌ
（製品名：ＰＥＧ４０００、三洋化成工業（株））
（処理条件）
液温 ４０℃
浸漬時間 ３０秒

次いで、下記表２に示す処理工程２により無電解ニッケルめっきを行った。

(Etching solution composition)
35% hydrochloric acid 240g / l
62% nitric acid 30g / l
89% phosphoric acid 50g / l
Sodium nitrite 0.5g / l
Nonionic surfactant (polyethylene glycol) 10g / l
(Product name: PEG4000, Sanyo Chemical Industries, Ltd.)
(Processing conditions)
Liquid temperature 40 ℃
Immersion time 30 seconds

Next, electroless nickel plating was performed by the treatment step 2 shown in Table 2 below.

乾燥後の試験片１について、銅皮膜部及び樹脂露出部の外観と残留物除去性を下記の方法で評価した。また、エッチング液の安定性についても下記の方法で評価した。結果を下記表３に示す。
（外観）
試験片に対する無電解ニッケルめっきの析出状態を目視によって評価した。

About the test piece 1 after drying, the following method evaluated the external appearance and residue removability of the copper membrane | film | coat part and the resin exposure part. The stability of the etching solution was also evaluated by the following method. The results are shown in Table 3 below.
(appearance)
The state of deposition of electroless nickel plating on the test piece was visually evaluated.

The state in which the electroless nickel plating was uniformly deposited on the copper and no precipitation was observed in the resin material portion was judged as good as a comprehensive evaluation.
(Confirmation of residue removal)
Pd was measured by X-ray photoelectron spectroscopy (XPS) on the surface of the resin material portion of the test piece etched by the above method (dried without performing the processing step 2). A resin material where no detection of Pd was observed was considered good.
(Stability test)
The etching solution was put in a container, sealed, and left in a 40 ° C. water bath for 30 days. The etching solution was used in the same manner as described above, and the appearance and residue removability of the test piece after electroless nickel plating were evaluated by the above evaluation method.

Example 2
Except that the following etching solution was used and the etching conditions were as follows, the appearance of the test piece, the residue removability, and the stability of the etching solution were evaluated in the same manner as in Example 1. The results are shown in Table 3 below.
(Etching solution composition)
35% hydrochloric acid 470 g / l
62% nitric acid 70g / l
89% phosphoric acid 35g / l
Sodium nitrite 0.5g / l
Nonionic surfactant (polyoxyalkylene glycerin ether) 1 g / l
(Product name: New Pole GEP2800, Sanyo Chemical Industries, Ltd.
Nonionic surfactant (N-polyoxyalkylene polyamine) 1 g / l
(Product name: Pepol D303, Toho Chemical Industry Co., Ltd.)
(Processing conditions)
Liquid temperature 30 ℃
Immersion time 30 seconds Example 3
Except that the following etching solution was used and the etching conditions were as follows, the appearance of the test piece, the residue removability, and the stability of the etching solution were evaluated in the same manner as in Example 1. The results are shown in Table 3 below.
(Etching solution composition)
35% hydrochloric acid 600g / l
62% nitric acid 40g / l
89% phosphoric acid 35g / l
Sodium nitrite 0.5g / l
Nonionic surfactant (polyoxyalkylene glycerin ether) 1 g / l
(Product name: New Pole GEP2800, Sanyo Chemical Industries, Ltd.)
Nonionic surfactant (N-polyoxyalkylene polyamine) 1 g / l
(Product name: Pepol D303, Toho Chemical Industry Co., Ltd.)
Anionic surfactant (alkyl sodium sulfosuccinate) 0.1 g / l
(Product name: Aerol CT-1 (Toho Chemical Industry Co., Ltd.)
(Processing conditions)
Liquid temperature 40 ℃
Immersion time 10 seconds Comparative Example 1
In the same manner as in Example 1, the treatment process 1 removed the electroless copper plating film formed on the resin. After visually confirming that there was no residue of the electroless copper plating film on the exposed resin portion after removing the copper plating film, electroless nickel plating was performed in the treatment step 2 without performing the etching process.

  The appearance of the copper film part and the resin exposed part of the test piece 1 treated in this step was evaluated in the same manner as in Example 1. Further, Pd was measured by X-ray photoelectron spectroscopy (XPS) on the surface of the resin material portion of the test piece 1 that had been subjected to the removal treatment of the electroless copper plating film formed on the resin in the treatment step 1. The results are shown in Table 3 below.

以上の結果から明らかなように、本発明のエッチング処理用組成物を用いることにより、無電解銅めっき皮膜の除去処理後に樹脂露出部分に残存する触媒金属を完全に除去できることが判る。また、本発明のエッチング処理用組成物を用いる場合に、銅皮膜をほとんど浸食することなく触媒金属のみを除去できるため、その後無電解ニッケルめっきを行った場合に、銅皮膜上に良好なめっき皮膜を形成できた。更に、本発明のエッチング処理組成物は、安定性が良好であり、長期間保存した場合にも、良好な性能を維持できた。

As is apparent from the above results, it can be seen that by using the etching composition of the present invention, the catalyst metal remaining on the resin exposed portion after the removal treatment of the electroless copper plating film can be completely removed. In addition, when the composition for etching treatment of the present invention is used, since only the catalytic metal can be removed without almost eroding the copper film, a good plating film is formed on the copper film when electroless nickel plating is performed thereafter. Could be formed. Furthermore, the etching treatment composition of the present invention has good stability and was able to maintain good performance even when stored for a long time.

Example 4
About the test piece 2, the etching process was immersed in the following etching liquid, and the seed layer which has Ni-Cr alloy as a main component was removed.
(Etching solution composition)
35% hydrochloric acid 350g / l
62% nitric acid 80g / l
89% phosphoric acid 50g / l
Sodium nitrite 0.5g / l
Nonionic surfactant (N-polyoxyalkylene polyamine) 1 g / l
(Product name: Pepol D303, Toho Chemical Industry Co., Ltd.)
(Processing conditions)
Liquid temperature 50 ℃
Immersion time 30 seconds

About the test piece 2 after water washing and drying, the external appearance and residue removal property of the copper film part and the seed layer exposure part were evaluated by the following method. The stability of the etching solution was also evaluated by the following method. The results are shown in Table 4 below.
(appearance)
The state of the treated specimen was visually evaluated.

A state in which there was no change in the state of the copper film and no remaining seed layer (glossy metallic film) was observed was judged as good as a comprehensive evaluation.
(Confirmation of residue removal)
The metal component was measured by the X ray photoelectron spectroscopy (XPS) about the surface of the seed layer removal part of the test piece etched by the said method. The case where the metal component (Ni, Cr, etc.) of the seed layer was not detected in the seed layer removal portion was determined to be good.
(Stability test)
The etching solution was put in a container, sealed, and left in a 40 ° C. water bath for 30 days. Using this etching solution, the treatment was performed in the same manner as described above, and the appearance and residue removal property of the treated test piece were evaluated.

Example 5
Using the following etching solution, except that the etching conditions are as follows, the appearance of the copper film part and the seed layer exposed part, the residue removability, and the stability of the etching liquid are the same as in Example 4. evaluated. The results are shown in Table 4 below.
(Etching solution composition)
35% hydrochloric acid 500g / l
62% nitric acid 30g / l
89% phosphoric acid 50g / l
Sodium nitrite 0.5g / l
Nonionic surfactant (polyoxyalkylene glycerin ether) 5 g / l
(Product name: New Pole GEP2800, Sanyo Chemical Industries, Ltd.)
Nonionic surfactant (N-polyoxyalkylene polyamine) 5 g / l
(Product name: Pepol D303, Toho Chemical Industry Co., Ltd.)
(Processing conditions)
Liquid temperature 40 ℃
Immersion time 90 seconds Example 6
Using the following etching solution, except that the etching conditions are as follows, the appearance of the copper film part and the seed layer exposed part, the residue removability, and the stability of the etching liquid are the same as in Example 4. evaluated. The results are shown in Table 4 below.
(Etching solution composition)
35% hydrochloric acid 700g / l
62% nitric acid 50g / l
89% phosphoric acid 50g / l
Sodium nitrite 0.5g / l
Nonionic surfactant (polyoxyalkylene glycerin ether) 1 g / l
(Product name: New Pole GEP2800, Sanyo Chemical Industries, Ltd.)
Nonionic surfactant (N-polyoxyalkylene polyamine) 5 g / l
(Product name: Pepol D303, Toho Chemical Industry Co., Ltd.)
Anionic surfactant (alkyl sodium sulfosuccinate) 0.1 g / l
(Product name: Aerol CT-1 (Toho Chemical Industry Co., Ltd.)
(Processing conditions)
Liquid temperature 30 ℃
Immersion time 120 seconds Example 7
Using the following etching solution, except that the etching conditions are as follows, the appearance of the copper film part and the seed layer exposed part, the residue removability, and the stability of the etching liquid are the same as in Example 4. evaluated. The results are shown in Table 4 below.
(Etching solution composition)
35% hydrochloric acid 600g / l
62% nitric acid 40g / l
89% phosphoric acid 30g / l
Sodium nitrite 0.5g / l
Nonionic surfactant (polyoxyalkylene glycerin ether) 1 g / l
(Product name: New Pole GEP2800, Sanyo Chemical Industries, Ltd.)
Nonionic surfactant (N-polyoxyalkylene polyamine) 5 g / l
(Product name: Pepol D303, Toho Chemical Industry Co., Ltd.)
Anionic surfactant (alkyl sodium sulfosuccinate) 0.1 g / l
(Product name: Aerol CT-1 (Toho Chemical Industry Co., Ltd.)
1,2,3-benzotriazole 1g / l
(Processing conditions)
Liquid temperature 40 ℃
Immersion time 60 seconds Example 8
Using the following etching solution, except that the etching conditions are as follows, the appearance of the copper film part and the seed layer exposed part, the residue removability, and the stability of the etching liquid are the same as in Example 4. evaluated. The results are shown in Table 4 below.
(Etching solution composition)
35% hydrochloric acid 600g / l
62% nitric acid 40g / l
89% phosphoric acid 30g / l
Sodium nitrite 0.5g / l
Nonionic surfactant (polyoxyalkylene glycerin ether) 1 g / l
(Product name: New Pole GEP2800, Sanyo Chemical Industries, Ltd.)
Nonionic surfactant (N-polyoxyalkylene polyamine) 5 g / l
(Product name: Pepol D303, Toho Chemical Industry Co., Ltd.)
Anionic surfactant (alkyl sodium sulfosuccinate) 0.1 g / l
(Product name: Aerol CT-1 (Toho Chemical Industry Co., Ltd.)
35% hydrogen peroxide solution 30g / l
(Processing conditions)
Liquid temperature 40 ℃
Immersion time 60 seconds Example 9
Using the following etching solution, except that the etching conditions are as follows, the appearance of the copper film part and the seed layer exposed part, the residue removability, and the stability of the etching liquid are the same as in Example 4. evaluated. The results are shown in Table 4 below.
(Etching solution composition)
35% hydrochloric acid 600g / l
62% nitric acid 40g / l
89% phosphoric acid 30g / l
Sodium nitrite 0.5g / l
Nonionic surfactant (polyoxyalkylene glycerin ether) 1 g / l
(Product name: New Pole GEP2800, Sanyo Chemical Industries, Ltd.)
Nonionic surfactant (N-polyoxyalkylene polyamine) 5 g / l
(Product name: Pepol D303, Toho Chemical Industry Co., Ltd.)
Anionic surfactant (alkyl sodium sulfosuccinate) 0.1 g / l
(Product name: Aerol CT-1 (Toho Chemical Industry Co., Ltd.)
1,2,3-benzotriazole 1g / l
35% hydrogen peroxide solution 30g / l
(Processing conditions)
Liquid temperature 40 ℃
Immersion time 60 seconds Comparative Example 2
Using the following etching solution, the appearance and residue removability of the copper film part and the seed layer exposed part were evaluated in the same manner as in Example 4 except that the etching conditions were as follows. The results are shown in Table 4 below.
(Etching solution composition)
62% nitric acid 680 g / l
62.5% sulfuric acid 120g / l
35% hydrogen peroxide 10g / l
35% hydrochloric acid 2g / l
2-aminopyridine 2g / l
(Processing conditions)
Liquid temperature 30 ℃
Immersion time 30 seconds Comparative Example 3
Using the following etching solution, the appearance and residue removability of the copper film part and the seed layer exposed part were evaluated in the same manner as in Example 4 except that the etching conditions were as follows. The results are shown in Table 4 below.
(Etching solution composition)
35% hydrochloric acid 350g / l
62% nitric acid 80g / l
89% phosphoric acid 50g / l
(Processing conditions)
Liquid temperature 50 ℃
Immersion time 30 seconds Comparative Example 4
Using the following etching solution, the appearance and residue removability of the copper film part and the seed layer exposed part were evaluated in the same manner as in Example 4 except that the etching conditions were as follows. The results are shown in Table 4 below.
(Etching solution composition)
60% perchloric acid 100g / l
Ceric ammonium nitrate 100g / l
(Processing conditions)
Liquid temperature 30 ℃
Immersion time 60 seconds

以上の結果から明らかなように、本発明のエッチング処理組成物を用いることにより、銅皮膜をほとんど浸食することなく、シード層を完全に除去できることが判る。更に、本発明のエッチング処理組成物は、安定性が良好であり、長期間保存した場合にも、良好な性能を維持できた。

As is clear from the above results, it can be seen that the seed layer can be completely removed by using the etching treatment composition of the present invention without almost eroding the copper film. Furthermore, the etching treatment composition of the present invention has good stability and was able to maintain good performance even when stored for a long time.

Schematic of the surface state of the test piece 1. FIG. Schematic of the surface state of the test piece 2. FIG.

Claims (8)

(1) hydrochloric acid as HCl amount of 10 to 300 g / l, (2) nitric acid as HNO ₃ amount of 1 to 100 g / l, (3) phosphoric acid as H ₃ PO ₄ amount of 1 to 100 g / l, (4) Copper and at least one selected from the group consisting of nitrous acid and salts thereof in an aqueous solution containing 0.001 to 10 g / l as NO ₂ amount, and (5) 0.01 to 50 g / l of surfactant, An etching treatment composition capable of selectively removing metals other than copper alloys. The composition for etching treatment according to claim 1, wherein the surfactant contains 100 parts by weight of a nonionic surfactant and 0.1 to 50 parts by weight of an anionic surfactant. Furthermore, the composition for an etching process of Claim 1 or 2 which contains 0.01-10 g / l of the corrosion inhibitor of copper or a copper alloy. Furthermore, the composition for an etching process in any one of Claims 1-3 which contains 0.1-20 g / l of oxidizing agents. An etching treatment method comprising contacting the composition for etching treatment according to any one of claims 1 to 4 with an object to be treated having a copper or copper alloy portion and another metal portion. The method according to claim 5, wherein the object to be processed is a printed wiring board having a conductor circuit made of copper or a copper alloy and a catalyst metal residue. 6. The method according to claim 5, wherein the object to be processed is a printed wiring board having a conductor circuit made of copper or a copper alloy and a remaining portion of the plating seed layer. An article etched by the method of claim 5.

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