JP2007016263A - Detergent composition for copper or copper alloy - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition, in the cleaning of a structure containing the material containing copper or a copper alloy in copper foil, copper alloy foil or the like, which has high water wettability after cleaning and also having durability to copper ion contamination and repeated use. <P>SOLUTION: The detergent composition for copper or a copper alloy comprises alkanolamine, an alkali agent other than alkanolamine, a nonionic surfactant and water, and in which the weight ratio of the alkanolamine to the whole alkali agent lies in a specified range. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a cleaning composition for copper or copper alloy.

  Conventionally, a surface cleaning agent composed of copper and / or a copper alloy is intended to remove processing oil such as rolling oil and cutting oil adhering to the surface, and corrosion and discoloration of the surface after cleaning. In order to suppress this, a rust inhibitor such as benzotriazole was added.

  In Patent Document 1, an antirust agent is added to an alkaline cleaning solution to try to achieve both cleanability and prevention of discoloration of the surface. Further, Patent Document 2 shows that since the alkaline detergent containing NaOH etches the surface made of copper, the wettability after washing is high. Patent Document 3 discloses an alkanolamine-based cleaning agent.

JP 2001-262384 A Japanese Patent Laid-Open No. 10-324900 JP 7-34090 A

  In recent years, flexible wiring boards and lead frames made of copper and their alloys have become indispensable parts for electronic devices, but cleaning in these manufacturing processes has factors that are not found in conventional cleaning agents. It is necessary to consider. For example, for rolled copper foil used in flexible wiring boards, after cold rolling to a predetermined thickness, washing and plating treatment or chromate treatment is performed, but with a detergent added with a rust preventive agent as described above It has been pointed out that rust preventives remain on the surface and cause plating defects.

  In addition, since the production of these copper foils is all managed by rolls, the tact time required for cleaning and plating is as short as several seconds. Therefore, since the cleaning is repeated with a relatively strong physical force such as spray cleaning, durability of the cleaning liquid (for example, the cleaning power can be maintained even after repeated cleaning) is also required.

  That is, as a state before the plating treatment of such rolled copper foil, a surface with high water wettability from which oil such as rolling oil used at the time of processing is removed is required, and a cleaning agent with high repeated cleaning properties is required. It is done.

  In response to this requirement, a conventional cleaning agent, for example, the cleaning agent disclosed in Patent Document 1, has a rust preventive agent remaining on the surface made of copper or a copper alloy and is not suitable for plating properties, and is disclosed in Patent Document 2. In the cleaning agent, copper oxide is formed in the cleaning solution due to Cu ions and NaOH mixed during etching, so that the cleaning property is repeatedly lowered. The cleaning agent disclosed in Patent Document 3 uses air such as spray cleaning. In the case of the entraining cleaning method, there is a problem that the pH immediately decreases due to absorption of carbon dioxide gas and the repetitive cleaning properties are low.

  The subject of the present invention is a structure comprising a material containing copper or a copper alloy, in particular, high wettability after washing in washing of copper foil or copper alloy foil, and for copper ion contamination and repeated use. On the other hand, a highly durable cleaning composition is provided.

  The present invention comprises (A) an alkanolamine, (B) an alkali agent other than alkanolamine, (C) a nonionic surfactant, and water, and comprises (A) / [(A) + (B)] weight. It is related with the cleaning composition for copper or copper alloys whose ratio is 0.15-0.98.

  The present invention also includes (A) a composition containing alkanolamine (A), (B) a composition containing an alkaline agent other than alkanolamine (B), and (C) a composition containing a nonionic surfactant. (C) or (A) an alkanolamine (hereinafter referred to as component (A)), (B) an alkali agent other than alkanolamine (hereinafter referred to as component (B)), and (C) Among the nonionic surfactants (hereinafter referred to as the component (C)), the composition (i) that includes any two and does not include the remaining one, and the remaining one that does not include the composition (i) The present invention relates to a kit for obtaining a cleaning composition for copper or copper alloy according to the present invention, comprising a combination with a composition (ii) containing.

  Moreover, this invention is comprised including the material containing copper or a copper alloy including the process of wash | cleaning the surface which consists of copper or a copper alloy using the cleaning composition for copper or a copper alloy of the said invention. The present invention relates to a method for manufacturing a structure.

  According to the present invention, a structure containing copper or a copper alloy, particularly a copper foil surface or a copper alloy foil surface, has high water wettability after washing, and is durable against copper ion contamination and repeated use. A high detergent composition is provided.

  As the alkanolamine which is the component (A) of the present invention, any water-soluble alkanolamine can be used. Specifically, monoethanolamine, diethanolamine, triethanolamine, N-ethylethanolamine, Nn-butylethanolamine, Nn-butyldiethanolamine, Nt-butylethanolamine, Nt-butyldiethanolamine, N, N -Dimethylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N- (β-aminoethyl) ethanolamine, N-methylethanolamine, N-methyldiethanolamine , N- (β-aminoethyl) isopropanolamine, N, N-diethylisopropanolamine are mentioned, and from the viewpoint of obtaining repetitive detergency against copper ion contamination, preferably monoethanolamine, diethanolamine, N-ethylethanolamine, Nn-Butylethanolamine, Nt- Tyrethanolamine, N- (β-aminoethyl) ethanolamine, N-methylethanolamine, N- (β-aminoethyl) isopropanolamine, N, N-diethylisopropanolamine, more preferably diethanolamine, N-ethyl Ethanolamine, N- (β-aminoethyl) ethanolamine, and N-methylethanolamine are preferable, and N- (β-aminoethyl) ethanolamine and N-methylethanolamine are more preferable.

  As the alkaline agent other than the alkanolamine, which is the component (B) of the present invention, any water-soluble alkaline agent can be used. Specific examples include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, sodium orthosilicate, sodium metasilicate, sodium sesquisilicate, No. 1 sodium silicate, No. 2 sodium silicate, No. 3 sodium silicate, etc. Examples thereof include phosphates such as salts, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, and the like. Two or more water-soluble alkaline agents may be used in combination. Among these alkali agents, sodium hydroxide, potassium hydroxide, sodium orthosilicate, and sodium metasilicate are preferable, sodium hydroxide and potassium hydroxide are more preferable, and sodium hydroxide is still more preferable.

  In the cleaning composition of the present invention, the weight ratio (A) / [(A) + (B)] of the component (A) and the sum of the components (A) and (B) is repeatedly cleaned by spraying. In addition, from the viewpoint of preventing detergency from being deteriorated against copper ion contamination, it is 0.15 to 0.98, preferably 0.30 to 0.95, more preferably 0.40 to 0.93, Especially preferably, it is 0.50-0.90.

  As a nonionic surfactant which is (C) component of this invention, a contact angle is 70 degrees or less, Furthermore, a 60 degrees or less thing is preferable. The contact angle referred to here is a contact angle of a 0.5% by weight aqueous solution of a nonionic surfactant to be measured with respect to a copper surface having a contact angle with water of 90 ° or more. It was measured with the same equipment as the example.

  As the component (C), polyoxyalkylene alkyl ether is suitable, and any polyoxyalkylene alkyl ether can be used, but from the viewpoint of detergency, linear or branched having 8 to 20 carbon atoms is preferable. A chain alkyl group or alkenyl group, more preferably a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, more preferably a linear or branched alkyl group or alkenyl group having 8 to 16 carbon atoms, More preferably, it has a linear or branched alkyl group having 8 to 16 carbon atoms.

  Among the nonionic surfactants of the component (C), specific examples of the raw material alcohol before adding ethylene oxide or propylene oxide used when obtaining a polyoxyalkylene alkyl ether include decyl alcohol, lauryl alcohol, Linear alcohol such as myristyl alcohol (trade name “Calcoal 1095”, “Calcoal 2098”, “Calcoal 4098”, etc.) manufactured by Kao Corporation), mixed alcohol mixed in the range of 6 to 24 carbon atoms (Kao Co., Ltd.) ), Trade name "Calcoal 2474", etc.), branched alcohols synthesized using the oxo method or Ziegler method (made by Kyowa Hakko Co., Ltd., trade names "Oxocol 900", " "Oxocol 1213", "Decanol" and "Tridecanol", manufactured by Mitsubishi Chemical Corporation, trade names "Dobanol 23", "Dobanol 25" And “Diadol 115H”, manufactured by Shell Chemical Co., Ltd., trade names “Neodoll 23”, “Neodoll 25”, “Neodoll 1”, “Lineaball 911”, and the like).

Moreover, as a method of adding alkylene oxide to these alcohols, a known alkoxylation method may be used. The catalyst used for the alkoxylation may be either an acid catalyst or a base catalyst, and MgO—ZnO, MgO—SnO, MgO—TiO ₂ , MgO— described in JP-A-7-227540 may be used. It can be synthesized using a catalyst that gives a narrow alkylene oxide addition distribution (such as SbO) or a catalyst that gives a narrow alkylene oxide addition distribution, such as a similar Mg-based catalyst described in JP-A-1-164437. . These catalysts are preferably neutralized after completion of the reaction or removed by adsorption treatment in terms of product stability. The neutralizing agent for the alkali catalyst is preferably a low molecular weight organic acid such as acetic acid, glycolic acid, lactic acid or levulinic acid.

  In the polyoxyalkylene alkyl ether, examples of the alkylene oxide include ethylene oxide and propylene oxide, and the average added mole number of ethylene oxide is preferably from the viewpoint of maintaining the permeability to oil and improving the detergency. It is 1-20, More preferably, it is 3-16, More preferably, it is 4-12, Most preferably, it is 4-10, The average addition mole number of propylene oxide improves a washability, and foaming property From a viewpoint of suppressing, Preferably it is 0-10, More preferably, it is 0-8, More preferably, it is 0-5, Most preferably, it is 0-4. The addition form of ethylene oxide and propylene oxide may be either random addition or block addition, but block addition is more preferable.

From the viewpoint of enhancing detergency, the component (C) is a nonionic surfactant selected from nonionic surfactants represented by the following formula (I) and nonionic surfactants represented by the following formula (II): A surfactant is particularly preferred.
R ₁ -O- (EO) _x1- (PO) _y1- (EO) _x2 -H (I)
R ₂ -O- (EO) _x3 − (PO) _y2 −H (II)
[Wherein R ₁ and R ₂ represent a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group. x1, x2, and x3 are numbers indicating the average added mole number of ethylene oxide, and x1, x2, and x3 are numbers of 1 or more, and x1 + x2 is 4 to 20. y1 and y2 are numbers indicating the average added mole number of propylene oxide, and 0 <y1 <x1 + x2 and y2 are 0 to 8. ]

In the general formulas (I) and (II), R ₁ and R ₂ are each a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, preferably 8 to 8 carbon atoms from the viewpoint of detergency. 20 linear or branched alkyl group or alkenyl group, more preferably a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, and particularly preferably a linear chain having 8 to 16 carbon atoms. Or it is a branched alkyl group or an alkenyl group, More preferably, it is a C8-C16 linear or branched alkyl group.

  Among the (C) component of the present invention, in the nonionic surfactant represented by the general formula (I), x1 and x2 indicating the average number of moles of ethylene oxide added are each 1 or more, and x1 The sum of x2 is a number of 4 or more. The sum of x1 and x2 is preferably 4 or more from the viewpoint of good compatibility between the nonionic surfactant represented by the general formula (I) and water. Moreover, even if the sum of x1 and x2 exceeds 20, the washing performance does not change, but since problems such as wastewater treatment and foaming can be suppressed, the sum of x1 and x2 is a number of 20 or less, preferably 6 to 15 Is the number of

  In addition, the average addition mole number y1 of propylene oxide of the nonionic surfactant represented by the general formula (I) is larger than 0 and smaller than the sum of x1 and x2 which is the average addition mole number of ethylene oxide. The number is preferably 0.5 to 6, more preferably 1 to 5. It is preferable that y1 is smaller than the sum of x1 and x2 from the viewpoint of good detergency and biodegradability.

  In addition, in the nonionic surfactant represented by the general formula (II) among the components (C) of the present invention, x3 indicating the average added mole number of ethylene oxide is a number of 1 or more and penetrates into oil. From the viewpoints of maintaining the properties and improving the cleaning properties, it is preferably 1 to 20, more preferably 3 to 16, further preferably 4 to 12, and particularly preferably 4 to 10.

  In the nonionic surfactant represented by the general formula (II) of the present invention, y2 indicating the average added mole number of propylene oxide is a number of 0 or more, from the viewpoint of achieving both detergency and foam suppression. 0-8, preferably 0-6.

  As other component (C), polyoxyethylene alkylphenyl ethers, polyoxypropylene alkylphenyl ethers, sucrose fatty acid esters, fatty acid alkanolamides, fatty acid glycerin monoesters, amine oxides, alkylglycosides, etc. An ionic surfactant is mentioned.

  Total weight ratio of the nonionic surfactant (C1) represented by the general formula (I) and the nonionic surfactant (C2) represented by the general formula (II) to the total component (C) [ [(C1) + (C2)] / total (C) component] is preferably 0.1 to 1.0, more preferably 0.5 to 1.0. Here, the total (C) component is the total of (C1), (C2) and other nonionic surfactants.

  In the cleaning composition for copper or copper alloy of the present invention, a chelating agent can be blended for the purpose of improving cleaning properties. The chelating agents used in the present invention are alkali metal salts or lower amine salts of aldonic acids such as glyceric acid, tetronic acid, pentonic acid, hexonic acid, heptonic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, tetraethylene. Alkali metal salts or lower amine salts of aminocarboxylic acids such as tetramine hexaacetic acid, alkali metal salts or lower amine salts of oxycarboxylic acids such as citric acid and malic acid, aminotrimethylenephosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetra Examples include alkali metal salts or lower amine salts of phosphonic acids such as methylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Among these chelating agents, gluconic acid, glucoheptonic acid, ethylenediaminetetraacetic acid, citric acid, malic acid, and hydroxyethylidene diphosphonic acid alkali metal salts or lower amine salts are preferable, and sodium gluconate and glucoheptone are particularly preferable. Sodium acetate, sodium ethylenediaminetetraacetate, sodium citrate, sodium hydroxyethylidene diphosphonate.

The detergent composition for copper or copper alloy of the present invention is generally used in this kind of detergent composition for the purpose of improving the washability, and is an anionic surfactant or amphoteric surfactant. Etc. can be blended in consideration of COD and cost increase.

  The content of the component (A) in the cleaning composition of the present invention is 0.01 to 50% by weight, the content of the component (B) is 0.01 to 10% by weight, and the content of the component (C) is 0.05 to 30% by weight. Is preferred.

  In addition, when the cleaning composition of the present invention is used as it is without being diluted, the content of the component (A) is preferably 0.01 to 30 in the composition from the viewpoint of preventing deterioration of cleaning properties due to copper ion contamination. % By weight, more preferably 0.1-30% by weight, still more preferably 0.2-15% by weight, still more preferably 0.3-10% by weight, and particularly preferably 0.5-8% by weight. In this case, the content of the component (B) is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight in the composition from the viewpoint of preventing repeated degradability due to spraying. Preferably it is 0.05 to 1 weight%, Most preferably, it is 0.1 to 0.7 weight%. In this case, the content of the component (C) is preferably 0.05 to 20% by weight, more preferably 0.1 to 15% by weight in the composition from the viewpoint of maintaining the detergency in a short time. More preferably, it is 0.2 to 10% by weight, and particularly preferably 0.3 to 5% by weight.

  Moreover, the cleaning composition for copper or copper alloy of the present invention satisfies the above (A) / [(A) + (B)] weight ratio, and then (A) component, (B) component, and (C ) Component weight ratio is (A) / (B) / (C) = 0.1-10 / 0.02-1.0 / 0.1-5, more preferably 0.1-5.0 / 0. It is preferable that it is 05-0.5 / 0.1-3.0.

  Moreover, the cleaning composition for copper or copper alloy of the present invention is commercially available as a concentrated product, and can be diluted with a water-soluble medium such as water during cleaning. At that time, a solubilizer for suppressing the separation of the cleaning agent can be used as necessary.

Examples of the solubilizer include a carboxylic acid represented by the general formula (a) or a salt thereof (hereinafter referred to as a solubilizer (a)), a carboxylic acid represented by the general formula (b) or a salt thereof (hereinafter referred to as a solubilizer). (B)) and a carboxylic acid represented by the general formula (c) or a salt thereof (hereinafter referred to as a solubilizer (c)).
^{_{-X- R 1a (CH 2) m}} COOM 1 (a)
R ^2b COOM ² (b)
R ^3c COOM ³ (c)
[Wherein, R ^1a represents a saturated or unsaturated linear or branched aliphatic hydrocarbon group having 4 to 22 carbon atoms or an aromatic hydrocarbon group having 5 to 18 carbon atoms, and X represents a group> NH, > N (CH ₂ ) _n COOM ¹ or> CHCOOM ¹ R ^2b represents a saturated or unsaturated linear aliphatic hydrocarbon group having 3 to 22 carbon atoms or an aromatic hydrocarbon group having 5 to 18 carbon atoms. R ^3c represents a saturated or unsaturated branched aliphatic hydrocarbon group having 4 to 22 carbon atoms. M ¹ , M ² and M ³ each represent a hydrogen atom, or a salt of an alkali metal, an aliphatic amine having 1 to 4 carbon atoms or ammonia, and m and n each represent an integer of 1 to 3. ]

As the solubilizer (a), R ^1a is an alkyl group or alkenyl group having 5 to 17 carbon atoms, or a phenyl group, X is> NH or> N (CH ₂ ) _n COOM ¹ , m and n are each 1 to 1 What is an integer of 3 is preferable. Specifically, the following is exemplified.

  The solubilizer (b) is a linear saturated fatty acid or linear unsaturated fatty acid having 4 to 23 carbon atoms, a carboxylic acid having 6 to 19 carbon atoms having an aromatic group, or a salt thereof. Examples of linear saturated fatty acids include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, butyric acid, valeric acid and the like. Examples of linear unsaturated fatty acids include caproleic acid, oleic acid, 9-undecylenic acid, elaidic acid, 10-undecylenic acid, 2-laurolenic acid, pasenic acid, lindelic acid, succinic acid, 5-lauroleic acid, 11-laurolein Acid, 2-palmitoleic acid, 7-palmitoleic acid, cis-9-palmitoleic acid, zomarinic acid, trans-9-palmitoleic acid, tuzuic acid, 5-myristoleic acid, myristoleic acid, petrothelinic acid, petroceniridine acid Etc. As the carboxylic acid having an aromatic group, phenylacetic acid, β-phenylpropionic acid, γ-phenylacetic acid, δ-phenylvaleric acid, τ-phenylcaproic acid, ζ-phenylenatonic acid, η-phenylcaprylic acid, θ- Examples include phenyl pelargonic acid, ι-phenyl capric acid, naphthenic acid and toluic acid.

  Among these, a linear saturated fatty acid having 4 to 18 carbon atoms or a linear unsaturated fatty acid or a salt thereof is preferable, and a linear saturated fatty acid having 4 to 12 carbon atoms is particularly preferable.

  The solubilizer (c) is a branched chain saturated fatty acid or branched chain unsaturated fatty acid having 5 to 23 carbon atoms or a salt thereof. Examples of branched chain saturated fatty acids include 2-ethylhexanoic acid, isopalmitic acid, isostearic acid, neoheptanoic acid, 2-butyl-5-methylpentanoic acid, 2-isobutyl-5-methylpentanoic acid, 4,6-dimethyloctane Acid, 4,7-dimethyloctanoic acid, 2,3-dimethyloctanoic acid, 2,3-dimethylnonanoic acid, 4,8-dimethylnonanoic acid, 2-butyl-5-methylhexanoic acid, 2-methylundecanoic acid, 10-methylundecanoic acid, 4,4-dimethyldecanoic acid, 2-ethyl-3-methylnonanoic acid, 2,2-dimethyl-4-ethyloctanoic acid, 2-methyldocosanoic acid, 3-methyldocosanoic acid, (+)-3D -Methyldocosanoic acid, 2-propyl-3-methylnonanoic acid, 12-methyltridecanoic acid, 2,2-dimethyldodecanoic acid, 2,3-di- Chirudodekan acid, 4,10-dimethyl dodecanoic acid, and 2-butyl-3-methylnonanoic acid. Examples of branched chain unsaturated fatty acids include trans-2-methyl-2-pentenoic acid, trans-4-methyl-3-pentenoic acid, cis-2-methyl-2-hexenoic acid, trans-2-methyl-2- Hexenoic acid, 2-methylene-hexanoic acid, 3,4-dimethyl-3-pentenoic acid, trans-2-methyl-2-heptenoic acid, 3-methyl-2-nonenoic acid, 3-methyl-3-nonenoic acid, 5-methyl-2-undecenoic acid, 2,4-dimethyl-2-decenoic acid, 5,9-dimethyl-2-decenoic acid, 2-methyl-2-dodecenoic acid, (−)-5-methyl-2- Examples include tridecenoic acid, L (+)-2,4-dimethyl-2-dodecenoic acid, L (+)-2,5-dimethyl-2-tridecenoic acid, and the like.

  In these, a C5-C18 branched saturated fatty acid or branched unsaturated fatty acid, or those salts are preferable, and a C5-C12 branched saturated fatty acid is especially preferable.

In the general formulas (a) to (c), as specific examples of the compounds that form the salts represented by M ¹ , M ² , and M ³ , examples of the alkali metal include potassium, sodium and the like having 1 to 4 carbon atoms. Examples of the amine include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, diethylenetriamine and the like. M ¹ , M ² , and M ³ are preferably a hydrogen atom or an alkali metal salt.

  In the case of a concentrated composition, in addition to the one-component stability viewpoint of the composition, in the (A) component, from the viewpoint of preventing detergency due to copper ion contamination when diluted, in the (B) component, From the viewpoint of preventing repeated degradability due to spray when diluted, the component (C) preferably has the following content from the viewpoint of maintaining detergency in a short time when diluted. That is, the upper limit of the content of the component (A) is preferably 50% by weight or less, more preferably 40% by weight or less, further 20% by weight or less, particularly preferably 15% by weight or less in the composition, and the lower limit is 0.01% in the composition. % By weight or more, further 0.1% by weight or more, more preferably 0.2% by weight or more, and particularly preferably 0.3% by weight or more. The upper limit of the content of component (B) is 10% by weight or less in the composition, 7% by weight or less, particularly 5% by weight or less is preferable, and the lower limit is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and particularly preferably 0.1% by weight or more in the composition. The upper limit of the amount is preferably 30% by weight or less, more preferably 25% by weight or less, further 20% by weight or less, particularly preferably 10% by weight or less in the composition, and the lower limit is 0.05% by weight or more in the composition, further 0.9%. % By weight or more, particularly 1.5% by weight or more is preferred. Moreover, when using the said solubilizer, content in a composition is 0.1-20 weight%, Furthermore, 1-15 weight% is preferable. The concentrated detergent having such a composition is preferably used at a dilution ratio of 3 to 30 times, and more preferably 5 to 20 times.

  Further, the cleaning composition of the present invention includes an antifoaming agent that suppresses foam generated in the cleaning process, such as silicon-based, higher alcohol-based, higher fatty acids and salts thereof, pluronic-type copolymer, tetranic-type copolymer, Polyethylene glycol, polypropylene glycol and the like can also be blended.

The cleaning composition of the present invention comprises:
(1): a kit comprising a composition (A) containing (A), a composition (B) containing component (B), and a composition (C) containing component (C),
(2): The composition (i) that includes any two of the components (A), (B), and (C) and does not include the remaining one, and the remaining that does not include the composition (i) Can be obtained from a kit comprising a combination with a composition (ii) comprising one of preferable.

  The cleaning composition of the present invention is a structure comprising a material containing copper or a copper alloy (hereinafter sometimes simply referred to as a structure), and in particular, copper parts such as copper foil, copper strips and lead frames. This is effective for cleaning the rolled copper foil, and is particularly effective for continuous cleaning of rolled copper foil or the like, which is a short time cleaning with a cleaning time tact of several seconds to 10 seconds. Moreover, it is effective for immersion cleaning, spray cleaning, and ultrasonic cleaning, and has high repetitive cleaning properties particularly for spray cleaning. The process of washing | cleaning the surface which consists of copper or a copper alloy using the cleaning composition for copper or copper alloys of this invention can be integrated in the manufacturing method of the said structure. In particular, in a copper foil manufacturing process used for flexible wiring or the like, the surface made of copper or copper alloy is hydrophilized by etching using the cleaning composition for copper or copper alloy of the present invention before plating treatment such as heat treatment. Is particularly preferable for obtaining good plating properties.

  Since the detergent composition of the present invention is excellent in cleanability at low temperatures, it is preferably used for washing at 0 to 50 ° C., more preferably 10 to 50 ° C.

  Moreover, when using for continuous washing | cleaning etc. with comparatively short washing | cleaning time, such as a rolled copper foil, it is also possible to obtain high detergency by wash | cleaning 2-3 times with a cleaning composition depending on the amount of adhesion oil.

  Moreover, the processing oil adhering to the surface which consists of copper or a copper alloy after rolling is removed beforehand with a solvent type cleaning agent or a semi-aqueous type cleaning agent, and it wash | cleans with the cleaning composition for copper or copper alloy of this invention after that. Therefore, it can be efficiently removed in a short time.

  The pH of the cleaning composition of the present invention is preferably 12.0 to 14.0, more preferably 13.0 to 13.8 at 25 ° C. In addition, when the cleaning composition of the present invention is diluted with water or the like, it is preferably used as a cleaning solution having a pH of 10.5 to 13.5, more preferably 11.0 to 13.5. It is preferable to adjust the contents of the components (A) and (B) so as to be in this range.

  The reason why the cleaning composition of the present invention provides high wettability after cleaning and high durability against copper ion contamination and repeated use in cleaning a surface made of copper or a copper alloy is as follows. It is assumed that That is, the cleaning composition of the present invention increases the wettability by etching the surface made of copper or copper alloy with a short time cleaning with the alkali component, thereby increasing the plating property in the subsequent process. In general, since an oil film such as rolling oil or a solvent cleaning agent remains on the surface made of copper or a copper alloy before cleaning, it is not sufficiently etched only with an alkali component. However, the nonionic surfactant contained in the cleaning composition of the present invention increases the wettability of the alkali component and the surface composed of copper or a copper alloy in which the oil film remains in a short time. High cleanability can be obtained by etching a surface made of a copper alloy.

  In addition, strong base alkaline agents such as NaOH included in the present invention, with respect to copper ion contamination, may cause copper hydroxide to remain on the surface made of copper or a copper alloy due to a decrease in detergency due to precipitation of copper hydroxide alone. Although stain stains due to copper oxide or the like are generated, precipitation of copper hydroxide is suppressed by using an alkanolamine that forms a water-soluble copper amine complex, thereby suppressing the occurrence of stain stains. Further, the weak base alkanolamine included in the present invention is neutralized immediately by itself with respect to carbon dioxide gas absorbed by spray cleaning. In combination with the alkaline agent, carbon dioxide gas preferentially reacts with a strong base alkaline agent, so that alkanolamine is not consumed.

  Therefore, it has durability with respect to the accumulation of copper ion contamination that occurs when it is repeatedly used by combining the alkali agent and alkanolamine included in the present invention, and pH reduction due to carbon dioxide absorption.

The cleaning composition of Table 4 was prepared using the following compounding ingredients, and the following tests were performed. The compositions in Table 4 had a pH of 10.0 to 12.5 at 25 ° C., and were used as they were without being diluted.
<Compounding ingredients>
(A-1): N- (β-aminoethyl) ethanolamine (Nippon Emulsifier Co., Ltd. Amino Alcohol EA)
(A-2): N-methylethanolamine (Nippon Emulsifier Co., Ltd. Amino Alcohol MMA)
(A-3): N-ethylethanolamine (Nippon Emulsifier Co., Ltd. Amino Alcohol MEM)
(B-1): Sodium hydroxide (C-1): Polyoxyethylene (5 mol) Polyoxypropylene (1.5 mol) Polyoxyethylene (5 mol) Alkyl (C _12-14 ) ether (general formula ( I), R ₁ = alkyl group having 12 to 14 carbon atoms, x1 = 5, y1 = 1.5, x2 = 5, Kao Corporation Emulgen LS-110)
(C-2): polyoxyethylene (8 mol) polyoxypropylene (4 mol) alkyl (C ₁₀ ) ether (in general formula (II), R ₂ = C10 alkyl group, x3 = 8, y2 = 4)
(C-3): polyoxyethylene (5 mol) polyoxypropylene (2 mol) polyoxyethylene (5 mol) alkyl (sec-C _12-14 ) ether (in formula (I), R ₁ = carbon number 12-14 secondary alkyl groups, x1 = 5, y1 = 2, x2 = 5)
(D-1): Lauric acid (Lunac L-98, Kao Corporation)
(D-2): Coconut amine acetate (Kao Co., Ltd. Acetamine 24)

<Copper foil cleaning test>
(1) Preparation of cleaning sample A copper foil cold-rolled with mineral oil was cut into 12 cm x 7 cm, and affixed to an acrylic plate was used as cleaning sample 1. Sample 1 for washing was pre-washed, that is, spray-washed with a semi-aqueous detergent (dipropylene glycol monomethyl ether 23% by weight, dipropylene glycol monopropyl ether 15% by weight, remaining water), and after spray rinsing washing, 60 ° C. The sample dried for was used as a cleaning sample 2. The conditions for this pre-cleaning are as shown in Table 1.

(2) Preparation of pseudo-deteriorating cleaning liquids 1 to 3 (2-1) Pseudo-deteriorating cleaning liquid 1
In order to reproduce the state of repeated use by the spray test, the pseudo-deteriorated cleaning liquid 1 was obtained by circulating the cleaning composition (new liquid) in Table 4 for 2 hours at 10 L / min while entraining air.

(2-2) Preparation of simulated deterioration cleaning liquid 2 In order to confirm the influence of copper ion contamination, copper sulfate pentahydrate was added so that the concentration of copper ions in the cleaning composition (new liquid) in Table 4 was 300 ppm. Was added as a pseudo-deterioration cleaning liquid 2.

(2-3) Preparation of Pseudo-Deteriorated Cleaning Solution 3 Pseudo-deterioration cleaning solution 3 was prepared by adding copper sulfate pentahydrate to pseudo-deterioration solution 1 so that the copper ion concentration was 300 ppm.

(3) Cleaning test (3-1) Cleaning test 1
The cleaning sample 2 was spray-washed with a detergent composition (new solution, pseudo-deteriorated cleaning solution 1, 2 or 3) stirred at 40 ° C., spray rinsed, and dried at 60 ° C. did. The cleaning conditions of this cleaning test 1 are as shown in Table 2.

(3-2) Cleaning test 2
The cleaning sample 1 was spray-washed with a detergent composition (new liquid, pseudo-deteriorated cleaning liquid 1, 2 or 3) stirred at 40 ° C., spray-rinsed, and dried at 60 ° C. did. The cleaning conditions of this cleaning test 2 are as shown in Table 3.

(4) Evaluation (4-1) Detergency About the detergency evaluation sample obtained in the cleaning test 1 or 2, the contact angle of 10 points was measured using a contact angle measuring device (FACE Kyowa Interface Chemistry). The average value was calculated. If the average contact angle was less than 60 °, it was evaluated as acceptable, and if it was 60 ° or more, it was evaluated as unacceptable.

(4-2) Precipitation of copper hydroxide Moreover, the presence or absence of copper hydroxide precipitation after adding copper sulfate pentahydrate to 300 ml of the detergent composition shown in Table 4 so that the copper ion concentration becomes 300 ppm was visually observed. Observed.

  As is clear from Table 4, the cleaning compositions of Examples 1 to 7 containing the component (A), the component (B) and the component (C) have improved repeatability and copper ion contamination cleanability. On the other hand, in Comparative Example 1 containing no component (A), the cleaning performance of the pseudo-deterioration cleaning liquid 1 is high and the repeated cleaning performance is relatively good, but the cleaning performance by the pseudo-deterioration cleaning liquid 2 is reduced, and the cleaning performance is reduced by copper ion contamination. descend. As shown in the table, it is presumed that copper hydroxide is precipitated due to the presence of copper ion contamination, and that the formation consumes NaOH and lowers the etching ability. Further, Comparative Example 2 not containing the component (B) has low cleaning performance with the pseudo-deteriorating cleaning liquids 1 and 3, so that carbon dioxide in the air is absorbed by circulation involving air, and the cleaning performance decreases due to a decrease in pH. I understand that Moreover, since the comparative example 3 which does not contain (C) component does not have surfactant, since a washing | cleaning liquid cannot wet and spread on the copper foil surface in a short time, in any case of new liquid and pseudo-deterioration cleaning liquids 1-3 Also, the detergency decreased. In addition, instead of the nonionic surfactant of component (C), an anionic surfactant was used in Comparative Example 4, and a cationic surfactant was used in Comparative Example 5, but in each case, component (C) was used. It did not show the high detergency as in the case.

Claims (5)

  (A) Alkanolamine, (B) Alkaline agent other than alkanolamine, (C) Nonionic surfactant, and water, (A) / [(A) + (B)] weight ratio is 0. A cleaning composition for copper or a copper alloy, which is 15 to 0.98.   The cleaning composition for copper or copper alloy according to claim 1, comprising 0.01 to 50% by weight of (A), 0.01 to 10% by weight of (B), and 0.05 to 30% by weight of (C). object. (C) is a nonionic surfactant selected from a nonionic surfactant represented by the following formula (I) and a nonionic surfactant represented by the following formula (II): Or the cleaning composition for copper or copper alloys of 2.
R ₁ -O- (EO) _x1- (PO) _y1- (EO) _x2 -H (I)
R ₂ -O- (EO) _x3 − (PO) _y2 −H (II)
[Wherein R ₁ and R ₂ represent a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group. x1, x2, and x3 are numbers indicating the average added mole number of ethylene oxide, and x1, x2, and x3 are numbers of 1 or more, and x1 + x2 is 4 to 20. y1 and y2 are numbers indicating the average added mole number of propylene oxide, and 0 <y1 <x1 + x2 and y2 are 0 to 8. ]   (A) a composition (B) containing an alkanolamine, (B) a composition (B) containing an alkaline agent other than an alkanolamine, and (C) a composition (C) containing a nonionic surfactant. Or (A) an alkanolamine, (B) an alkali agent other than alkanolamine, and (C) a nonionic surfactant, and a composition that does not contain the remaining one The cleaning for copper or copper alloy according to any one of claims 1 to 3, comprising a combination of (i) and a composition (ii) comprising the remaining one not comprising the composition (i). A kit for obtaining an agent composition.   A material containing copper or a copper alloy, comprising a step of cleaning a surface made of copper or a copper alloy using the cleaning composition for copper or a copper alloy according to any one of claims 1 to 3. A method of manufacturing a structured structure.