KR102323027B1 - Method for manufacturing soldered circuit board, method for manufacturing circuit board having electronic component mounted thereon, and cleaning agent composition for flux - Google Patents

Abstract

A circuit board with solidified solder capable of suppressing discoloration of the electrode that has not solidified the solder after the step of solidifying the solder on the other part of the electrode without solidifying the solder on the part of the electrode on the circuit board.
A manufacturing method of a circuit board comprising the following steps (1) to (4).
(1) The process of processing the metal conductive part of the circuit board which has an electrode which forms a circuit in the 1st area|region and 2nd area|region of a support base material with the metal treatment agent A.
(2) A step of solidifying the solder by using the flux B and the solder for the electrodes in the first region of the circuit board obtained in the step (1).
(3) The process of washing|cleaning the flux residue of the circuit board obtained in the process (2) using the cleaning agent C containing the imidazole compound represented by glycol ether and an alkanolamine, and the following general formula (I).
(4) A step of solidifying the solder on the electrode in the second region of the circuit board following the step (3).

Description

TECHNICAL FIELD [0002] A method for manufacturing a circuit board in which solder is solidified, a method for manufacturing a circuit board on which electronic components are mounted, and a cleaning composition for fluxes TECHNICAL FIELD [0002] }

The present invention relates to a method for manufacturing a circuit board in which solder is solidified, a method for manufacturing a circuit board on which electronic components are mounted, and a cleaning composition for a flux.

Metals, such as copper and a copper alloy, are used for the electrode which forms the circuit of electronic board|substrates, such as a semiconductor package, in order to reduce manufacturing cost.

On the other hand, as a mounting method of a printed wiring board, the surface mounting which improved the mounting density is employ|adopted widely. An example of such a surface mounting method is double-sided surface mounting. In double-sided surface mounting, in order to solidify solder on both surfaces of a printed wiring board, the process of heating a printed wiring board 2 times or more, and the process of washing|cleaning a printed wiring board 2 times or more are required. Moreover, also in the same surface of a printed wiring board, among the metal conductive parts formed in plurality, some metal conductive parts may be brazed, and the remaining metal conductive parts may be brazed after washing|cleaning of a flux residue. In this way, even if it is the same printed wiring board, not all the metal conductive parts are soldered simultaneously, but the soldering process may be carried out over a plurality of times. The metal surface, such as copper, copper alloy, etc. of the electrode which comprises the circuit part of a printed wiring board is heated, formation of an oxide film is accelerated|stimulated and causes discoloration, and the solderability of the surface of the conductive part may not be maintained well.

For this problem, there is a method of treating the surface of the electrode with a water-soluble pre-flux (Organic Solderability Preservative: OSP treatment). For example, Japanese Patent Application Laid-Open No. 2007-308776 discloses a metal treatment agent containing an imidazole compound and a gluconic acid compound as a surface treatment agent (metal treatment agent) for a metal that improves the wettability of the solder to the surface of the conductive part. .

In addition, water-soluble fluxes that can be washed with water-based detergents have been developed with respect to conventional rosin-based fluxes. For example, Japanese Patent Application Laid-Open No. 2000-42786 discloses a water-soluble flux for reflow soldering using a molded solder containing as a main component an ester of an organic acid and a polyhydric alcohol.

Japanese Patent Application Laid-Open No. 2009-298940 discloses a flux detergent containing glycol ether, alkanolamine, and alkylbenzenesulfonic acid.

If the electronic components are used for a long period of time without cleaning the flux residues such as soldered electronic components, migration or the like may occur, resulting in a short circuit between the electrodes or poor adhesion in some cases. With the integration and densification of semiconductor devices, many semiconductor chip mounting methods using solder bumps are employed, and further high reliability is demanded. Accordingly, the importance of cleaning the flux residues in the manufacture of semiconductor devices is increasing. For example, in a manufacturing process of a semiconductor package substrate, etc., the electrode surface is previously protected with a metal treatment agent to form a solder bump, and then a flux or solder paste is applied on the electrode, and solder is placed and heated. , and cleaning to remove flux residues is performed. However, when solder bumps are formed on some electrodes on the circuit board and solder bumps are not formed on some electrodes, the metal treatment agent on the electrodes on which the solder bumps are not formed may be removed at the time of cleaning the flux residue. . As a result, there is a problem that the electrode on which the solder bumps are not formed is oxidized and discolored during the solder bump formation process, so that the solder wettability at the time of the solder bump formation deteriorates and connection reliability cannot be secured.

In this indication, "solder is solidified" means soldering an electronic component (solder process) and/or forming a solder bump in one or some embodiment. "Solder does not solidify" means that an electronic component is not soldered and/or a solder bump is not formed in spite of the presence of an electrode in one or more embodiments.

In one or a plurality of embodiments, the present disclosure includes a step of solidifying solder on a part of the electrode without solidifying the solder on a part of the electrode on the circuit board, and after the process, the electrode on which the solder is not solidified Provided are a method for manufacturing a circuit board in which solder is solidified, a method for manufacturing a circuit board on which an electronic component is mounted, and a cleaning composition for flux using a cleaning composition capable of suppressing discoloration.

In one or some embodiment, this invention relates to the manufacturing method of the circuit board with which the solder solidified containing the following process (1)-(4).

(1) Process of treating the electrode of at least 1st area|region of the circuit board which has an electrode which forms a circuit in the 1st area|region and 2nd area|region of a support base material with the metal treatment agent A containing an imidazole compound.

(2) After applying the flux B and arranging the solder to the electrodes in the first region of the circuit board obtained in the step (1), the circuit board is heated to a temperature equal to or higher than the liquidus temperature of the solder to melt the solder, A process of solidifying the solder on the electrode in region 1.

(3) The flux residue of the circuit board obtained in the step (2) contains the component a which is glycol ether, the component b which is an alkanolamine, and 0.005 mass% or more and 4.0 mass% or less of imidazole represented by the following general formula (I). A step of washing using a cleaning agent C containing the component c, which is a compound.

[Formula 1]

(In formula (I), R ₁ , R ₂ and R ₃ each represent at least one selected from a hydrogen atom and a hydrocarbon group having 1 to 22 carbon atoms.)

(4) A step of solidifying the solder on the electrode in the second region of the circuit board following the step (3).

In one or a plurality of other embodiments, the present invention includes a step of mounting at least one electronic component on a circuit board, wherein at least one of the circuit board is a circuit board manufactured by the manufacturing method according to the present disclosure It relates to a method for manufacturing a circuit board on which phosphorus and electronic components are mounted.

In one or a plurality of other embodiments, the present invention is an imidazole compound represented by the general formula (I) in an amount of 0.005 mass % or more and 4.0 mass % or less, with a component a that is a glycol ether, a component b that is an alkanolamine, and It relates to a cleaning composition for fluxes containing component c.

According to the manufacturing method which concerns on this indication, in one or some embodiment, the discoloration in the electrode in which solder is not solidified can be suppressed. When discoloration of an electrode can be suppressed, solderability will become favorable and connection reliability will improve. According to the manufacturing method according to the present disclosure, in one or more embodiments, in addition to suppressing discoloration of the electrode, it is possible to further improve the wettability of the flux on the electrode, thereby further improving the soldering state and connecting reliability. can be further improved.

1 is a diagram schematically illustrating an example of a manufacturing flow of a circuit board;
Fig. 2 is a diagram schematically illustrating an example of a circuit board having a plurality of regions on one main surface used in the embodiment;

The manufacturing process of a semiconductor package board|substrate may include the solder bump formation process several times. In the flow shown in FIG. 1 which is an example which is not limited, about the circuit board provided with the electrode of a 1st area|region on one main surface, and provided with the electrode of a 2nd area|region on the other main surface, in a process (1) The electrode is surface-treated using the metal treatment agent A, and solder bumps are formed in the first region in the step (2), and the solder bumps are formed in the second region in the step (4). In the step (3), the flux residues in the first region generated in the step (2) are cleaned. At this time, the surface treatment of the electrode in the second region performed in the step (1) is damaged, and time passes, heat treatment and cleaning, etc. It may be discolored by Thereby, the soldering state in a process (4) deteriorates, and connection reliability may be impaired. In one or some embodiment which is not limited to this indication, when the cleaning composition for flux containing a specific imidazole compound is used for the washing|cleaning of a process (3), the electrode discoloration of the 2nd area|region in which the solder bump is not formed. based on the knowledge that it can suppress In addition, in one or a plurality of embodiments that are not limited by the present disclosure, when a cleaning composition for flux containing a specific imidazole compound is used for cleaning in step (3), in addition to suppressing discoloration of the electrode in the second region, It is based on the knowledge that the wettability of the solder in the electrode of a 2nd area|region can be improved.

That is, in one aspect, this indication relates to the manufacturing method (henceforth "the manufacturing method which concerns on this indication") including the following process (1)-(4) of the circuit board with solidified solder.

(1) Process of treating the electrode of at least 1st area|region of the circuit board which has an electrode which forms a circuit in the 1st area|region and 2nd area|region of a support base material with the metal treatment agent A containing an imidazole compound.

(2) After applying the flux B and arranging the solder to the electrodes in the first region of the circuit board obtained in the step (1), the circuit board is heated to a temperature equal to or higher than the liquidus temperature of the solder to melt the solder, A process of solidifying the solder on the electrode in region 1.

(3) The flux residue of the circuit board obtained in the step (2), the component a which is a glycol ether, the component b which is an alkanolamine, and 0.005 mass % or more and 4.0 mass % or less of an image represented by the following general formula (I) A step of washing using a detergent C containing component c, which is a dazole compound.

[Formula 2]

(In formula (I), R ₁ , R ₂ and R ₃ each represent at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 22 carbon atoms.)

(4) A step of solidifying the solder on the electrode in the second region of the circuit board following the step (3).

The electrode of the 1st area|region and the electrode of the 2nd area|region of a support base material in this indication means the electrode of the area|region where solder is solidified in each different process in the manufacturing process of a semiconductor package substrate. That is, in one or more embodiment, in this indication, "region of an electrode" means the range of an electrode in which solder is solidified in one solder solidification process.

Examples of the electrode in the first region and the electrode in the second region include a front electrode and a back electrode in a double-sided mounting substrate in one or more non-limited embodiments (see FIG. 1 ). In one or a plurality of other non-limiting embodiments, the electrode in the first region and the electrode in the second region include electrodes in two regions on the same main surface of the single-sided mounting substrate (Fig. see 2). In one or some embodiment, a circuit board may be equipped with three or more electrode areas on the same main surface, and may be equipped with each single or some area|region on two main surfaces. In the present disclosure, the ordinal number in the first region, the second region, the third region, etc. is for distinguishing each region, and there is no particular limitation. In one or more embodiments, the ordinal may mean the order in which the solder is solidified.

Although the detail of the mechanism which can suppress the discoloration in the electrode which solder has not solidified from the manufacturing method which concerns on this indication is not clear, it is guessed as follows. In the step (3), since the glycol ether (component a) and the alkanolamine (component b) in the cleaning agent C act to wash the flux B, when the cleaning agent C does not contain the imidazole compound (component c), It is thought that the metal processing agent A which protects an electrode washes off at the time of rinsing, and produces discoloration by oxidation after heat processing. And when the cleaning agent C contains a specific amount of the imidazole compound (component c), the imidazole compound is adsorbed to the electrode surface to form a protective film, and it is thought that the discoloration of the electrode by oxidation is suppressed. However, the present disclosure does not need to be interpreted as being limited to this mechanism.

[Cleaning agent C]

In the present disclosure, the cleaning agent C is a cleaning composition for cleaning flux residues, comprising glycol ether (component a), alkanolamine (component b), and 0.005 mass% or more and 4.0 mass% or less of the above general formula (I) It is a cleaning composition for flux containing the imidazole compound (component c) represented by As the flux to be cleaned, a rosin-based flux is preferable from the viewpoint of exhibiting cleaning properties.

[Component a of cleaning agent C]

The component a in the detergent C in this indication is a glycol ether. Component a, in one or more embodiments, preferably consists of one or more compounds represented by the following general formula (II) from the viewpoint of cleaning properties against flux residues.

[Formula 3]

RO-(CH ₂ CH ₂ O) _n -H (II)

(In formula (II), R represents a hydrocarbon group having 3 to 8 carbon atoms, and n represents 2 or 3.)

In the general formula (II), R is a hydrocarbon group having 3 to 8 carbon atoms, and in one or more embodiments, it is preferably a hydrocarbon group having 3 to 6 carbon atoms from the viewpoint of cleaning properties for flux residues. In one or a plurality of embodiments, the hydrocarbon group is preferably at least one selected from the group consisting of an alkyl group, an alkenyl group and an aryl group from the viewpoint of cleaning properties with respect to the flux residue, and more preferably an alkyl group. R is at least 1 sort(s) selected from the group which consists of a propyl group, a butyl group, a pentyl group, and a hexyl group in one or some embodiment. The added mole number n is 2 or 3 from the viewpoint of cleaning properties for the flux residue.

Component a is, in one or more embodiments, diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoisobutyl from the viewpoint of improving cleaning properties for flux residues. diethylene glycol monoalkyl ethers such as ether and diethylene glycol monohexyl ether; diethylene glycol monoalkenyl ethers such as diethylene glycol monoallyl ether; diethylene glycol monoaralkyl ethers such as diethylene glycol monobenzyl ether; triethylene glycol monoalkyl ethers such as triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, and triethylene glycol monoisobutyl ether; triethylene glycol monoalkenyl ethers such as triethylene glycol monoallyl ether; tetraethylene glycol monoalkyl ethers such as tetraethylene glycol monobutyl ether; At least one selected from the group consisting of pentaethylene glycol monoalkyl ethers such as pentaethylene glycol monobutyl ether is preferable. Among these, component a is selected from the group consisting of diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, diethylene glycol monohexyl ether and triethylene glycol monobutyl ether from the same viewpoint in one or more embodiments. At least one kind is more preferable, and at least one kind selected from the group consisting of diethylene glycol monobutyl ether and triethylene glycol monobutyl ether is still more preferable.

The content of component a in the cleaning agent C in the present disclosure is preferably 80.0 mass% or more, more preferably 85.0% by mass or more, from the viewpoint of improving the cleaning properties of the flux residue and suppressing discoloration of the electrode in one or more embodiments. It is mass % or more, More preferably, it is 85.5 mass % or more, More preferably, it is 86.4 mass % or more. Content of the component a in the washing|cleaning agent C is one or some embodiment. From the same viewpoint, Preferably it is 90.0 mass % or less, More preferably, it is 89.0 mass % or less, More preferably, it is 88.5 mass % or less. Content of the component a in the detergent C is 80.0 mass % or more and 90.0 mass % or less from the same viewpoint in one or some embodiment, Preferably it is 85.0 mass % or more and 89.0 mass % or less, More preferably, it is 85.5 mass %. It is 89.0 mass % or more, More preferably, it is 86.4 mass % or more and 88.5 mass % or less.

Component a preferably contains at least diethylene glycol monobutyl ether (in formula (II), R is a butyl group, and n=2) in one or more non-limiting embodiments. In the present disclosure, the butyl group refers to an n-butyl group unless otherwise specified.

In one or more embodiments, the content of diethylene glycol monobutyl ether in component a is preferably 50.0 mass % or more, more preferably 60.0 mass % or more, from the viewpoint of improving cleaning properties with respect to flux residues and suppressing discoloration of the electrode. % or more, more preferably 70.0 mass% or more, and still more preferably 80.0 mass% or more. Content in the component a of diethylene glycol monobutyl ether becomes like this in one or some embodiment. From the same viewpoint, Preferably it is 98.0 mass % or less, More preferably, it is 95.0 mass % or less.

In one or more embodiments, the content of diethylene glycol monobutyl ether in the detergent C in the present disclosure is preferably 50.0 mass% or more from the viewpoint of improving the cleaning properties of the flux residue and suppressing discoloration of the electrode, More preferably, it is 60.0 mass % or more, More preferably, it is 70.0 mass % or more, More preferably, it is 75.0 mass % or more. Content in the detergent C of diethylene glycol monobutyl ether in one or some embodiment WHEREIN: From the same viewpoint, Preferably it is 90.0 mass % or less, More preferably, it is 88.0 mass % or less, More preferably, it is 85.0 mass % or less. am.

The content in component a of glycol ethers other than diethylene glycol monobutyl ether in the present disclosure (when there are multiple types of glycol ethers other than diethylene glycol monobutyl ether, the total content of the plural types of glycol ethers) is one Or in some embodiments, preferably 50.0 mass% or less, more preferably 40.0 mass% or less, still more preferably 30.0 mass% or less, even more preferably 20.0 mass% or less, from the viewpoint of improving the cleaning property of the flux residue. is below.

The content in the detergent C of glycol ethers other than diethylene glycol monobutyl ether in the present disclosure (when there are multiple types of glycol ethers other than diethylene glycol monobutyl ether, the total content of the plural types of glycol ethers) is one Or, in the plurality of embodiments, preferably 1.0 mass% or more, more preferably 3.0 mass% or more, still more preferably 4.0 mass% or more, and preferably 40 mass% or more, from the viewpoint of improving the cleaning property of the flux residue. Hereinafter, more preferably, it is 30.0 mass % or less, More preferably, it is 16.0 mass % or less.

[Component b of cleaning agent C]

The component b in the detergent C in this indication is an alkanolamine. Component b, in one or more embodiments, is preferably composed of one or more compounds represented by the following general formula (III) from the viewpoint of cleaning properties against flux residues.

[Formula 4]

(In formula (III), R ₄ represents at least one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group and an aminoethyl group, and R ₅ is a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group and an ethyl group. _{At least 1 type selected from the group which consists of is represented, and R<6>} represents at least 1 type chosen from the group which consists of a hydroxyethyl group and a hydroxypropyl group.)

As an alkanolamine of component b, in one or some embodiment, at least 1 sort(s) selected from the group which consists of monoethanolamine, a diethanolamine, these alkylates, and these aminoalkylates is mentioned . Component b is, in one or more embodiments, monoethanolamine, diethanolamine, monomethylmonoethanolamine, monomethyldiethanolamine, dimethylmonoethanolamine, monoethylmonoethanolamine, from the viewpoint of improving cleaning properties for flux residues. At least one selected from the group consisting of ethanolamine, monoethyldiethanolamine, monopropyldiethanolamine and monoaminoethylisopropanolamine is preferable, and diethanolamine, monoethylmonoethanolamine, monomethyldiethanolamine and monoamino At least one kind selected from the group consisting of ethylisopropanolamine is more preferable, and at least one kind selected from the group consisting of monoethylmonoethanolamine and monomethyldiethanolamine is more preferable.

The content of the component b in the cleaning agent C is, in one or more embodiments, preferably 0.3 mass% or more, more preferably 0.5 mass% or more, still more preferably from the viewpoint of improving the cleaning property with respect to the flux residue. It is 1.0 mass % or more. Content of the component b in the detergent C is one or some embodiment WHEREIN: From the same viewpoint, it is preferable, and is 5.0 mass % or less, More preferably, it is 4.5 mass % or less, More preferably, it is 4.0 mass % or less, More preferably, it is 4.0 mass % or less. Preferably, it is 3.5 mass % or less. Content of the component b in the detergent C is from the same viewpoint in one or more embodiment, Preferably it is 0.3 mass % or more and 5.0 mass % or less, More preferably, it is 0.5 mass % or more and 4.5 mass % or less, More preferably is 1.0 mass% or more and 4.0 mass% or less, and more preferably 1.0 mass% or more and 3.5 mass% or less. As described above, as the component b, one or a plurality of compounds represented by the general formula (III) can be used. Compounds corresponding to component b include those generated from other components (eg, salts of component d described later).

[Component c of cleaning agent C]

Component c in the cleaning agent C in the present disclosure is an imidazole compound represented by the general formula (I) from the viewpoint of suppressing discoloration of the electrode, and in one or a plurality of embodiments, one represented by the general formula (I) or It consists of a plurality of imidazole compounds.

_{R 1} , R ₂ and R ₃ in the general formula (I) represent at least one selected from a hydrogen atom and a hydrocarbon group having 1 to 22 carbon atoms, respectively. _{R 1} represented in the general formula (I) is, in one or more embodiments, a hydrogen atom, a substituted or unsubstituted aryl group having 5 to 22 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms, and substituted Or it is preferable that it is at least 1 sort(s) chosen from an unsubstituted C1-C22 alkenyl group. The alkyl group and the alkenyl group as used herein are linear or branched in one or more embodiments.

_{R 2} and R ₃ represented in the general formula (I), in one or more embodiments, are the same or different from each other independently of each other, and are a hydrogen atom, a substituted or unsubstituted C5-C22 aryl group, and a substituted Or it is preferable that it is at least 1 sort(s) chosen from an unsubstituted C1-C8 alkyl group.

In one or more embodiment of said substitution, substitution by one or a plurality of halogen atoms or substitution by a C1-C6 alkyl group is mentioned.

However, in one or more embodiment, the case where _R<1> , R<_2> and R<_3> shown in the said General formula (I) is an aryl group simultaneously is excluded.

Component c is selected from the group consisting of imidazole, methylimidazole, imidazole substituted with an alkyl group having 11 carbon atoms, methylethylimidazole and phenylimidazole from the viewpoint of suppressing discoloration of the electrode in one or more embodiments At least one species is preferred.

Specifically, as component c, in one or more embodiments, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole, 2- Butylimidazole, 2-t-butylimidazole, 2-pentylimidazole, 2-hexylimidazole, 2-heptylimidazole, 2-octylimidazole, 2-nonylimidazole, 2 -decylimidazole, 2-undecylimidazole, 2-dodecylimidazole, 2-tridecylimidazole, 2-tetradecylimidazole, 2-pentadecylimidazole, 2-hexadecyl Imidazole, 2-heptadecylimidazole, 2-(1-methylpentyl)imidazole, 2-(1-ethylpentyl)imidazole, 2-(1-heptyldecyl)imidazole, 2-(5- Hexenyl)imidazole, 2-(9-octenyl)imidazole, 2-(8-heptadecenyl)imidazole, 2-(4-chlorobutyl)imidazole, 2-(9-hydroxynonyl)imidazole Dazole, 2-ethyl-4-methylimidazole, 2-undecyl-4-methylimidazole, 2-heptadecyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4- Methylimidazole, 2-(1-naphthyl)imidazole, 2-(1-naphthyl)-4-methylimidazole, 2-(2-naphthyl)imidazole, 2-(2-naphthyl) )-4-methylimidazole, 2-methyl-4-phenylimidazole, 4-phenylimidazole, 4-methylimidazole, 4-isopropylimidazole, 4-octylimidazole, 2 ,4,5-trimethylimidazole, 4,5-dimethyl-2-octylimidazole, 2-undecyl-4-methyl-5-bromoimidazole and 4,5-dichloro-2-ethylimida It is at least 1 type selected from the group which consists of sol.

As component c, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 4-methylimidazole, 2-phenylimida from the viewpoint of inhibiting discoloration of the electrode At least one selected from the group consisting of sol and 4-phenylimidazole is preferable, and imidazole, 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 2- At least one selected from the group consisting of phenylimidazole and 4-phenylimidazole is more preferable, and from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole At least one selected from the group consisting of 2-methylimidazole and 2-ethyl-4-methylimidazole is more preferred than at least one selected from the group consisting of 2-methylimidazole and 2-ethyl-4-methylimidazole.

Content of the component c in the cleaning agent C is 0.005 mass % or more from a viewpoint of discoloration suppression of an electrode in one or some embodiment, Preferably it is 0.01 mass % or more, More preferably, it is 0.05 mass % or more. Content of the component c in the cleaning agent C is 4.0 mass % or less from a viewpoint of discoloration suppression of an electrode in one or some embodiment, Preferably it is 3.5 mass % or less, More preferably, it is 3.0 mass % or less, More preferably is 2.0 mass% or less. Content of the component c in the detergent C is 0.005 mass % or more and 4.0 mass % or less from a viewpoint of discoloration suppression of an electrode in one or some embodiment, Preferably it is 0.01 mass % or more and 3.5 mass % or less, More preferably 0.01 mass % or more and 3.0 mass % or less, More preferably, they are 0.05 mass % or more and 2.0 mass % or less. As described above, as the component c, one or a plurality of imidazole compounds represented by the general formula (I) can be used.

[Water of cleaning agent C]

Detergent C contains water in one or more embodiments. Distilled water, ion-exchanged water, or ultrapure water may be used as the water. Content of the water in the washing|cleaning agent C becomes like this from a viewpoint of reducing flammability in one or some embodiment. Preferably it is 5.0 mass % or more, More preferably, it is 5.5 mass % or more, More preferably, it is 6.5 mass % or more. The content of water in the detergent C is, in one or more embodiments, preferably 12.0 mass% or less, more preferably 11.0 mass% or less, still more preferably 10.0 mass% or less, from the viewpoint of improving the cleaning property with respect to the flux residue. is below. The content of water in the detergent C is preferably 5.0 mass% or more and 12.0 mass% or less, more preferably 5.5 mass% or more, from the viewpoint of improving the cleaning property to the flux residue and reducing the flammability in one or more embodiments. It is 11.0 mass % or more, More preferably, it is 6.5 mass % or more and 10.0 mass % or less.

[Component d of cleaning agent C]

In one or more embodiments, the detergent C is at least one component selected from the group consisting of benzenesulfonic acid (alkylbenzenesulfonic acid) having an alkyl group having 1 to 6 carbon atoms and salts thereof from the viewpoint of improving the cleaning properties of the flux residue. d may be included. You may have a some alkyl group in alkylbenzenesulfonic acid, and total carbon number of a some alkyl group is 1-6 in that case. The number of carbon atoms of the alkyl group in the component d is 1 to 6, preferably 1 to 4, more preferably 1 to 3, from the viewpoint of improving the cleaning power to the flux residue in one or more embodiments. or 2 is more preferable, and 1 is even more preferable. The salt of alkylbenzenesulfonic acid having an alkyl group having 1 to 6 carbon atoms is preferably at least one selected from the group consisting of alkali metal salts such as sodium and potassium, ammonium salts and organic amine salts from the viewpoint of being acceptable as a cleaning composition, and semiconductor quality At least one selected from the group consisting of ammonium salts and organic amine salts is more preferable from the viewpoint of stability. The organic amine salt may be the alkanolamine salt of component b.

Component d is, in one or more embodiments, toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, isopropylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, At least 1 sort(s) chosen from the group which consists of hexylbenzenesulfonic acid, 2, 4- dimethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, and these salts is mentioned. Any of the ortho position, the meta position, and the para position may be sufficient as the substitution position of these alkyl groups. Component d is more preferably at least one selected from the group consisting of p-toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, butylbenzenesulfonic acid, and salts thereof from the same viewpoint in one or more embodiments, p -Toluenesulfonic acid is more preferable.

Content of the component d in the detergent C (content of the component d in the detergent C in case component d is a salt converted into the acid form) In one or some embodiment, 0.3 mass % or more and 5.0 mass % or less, preferably 0.4 mass % or more, more preferably 0.5 mass % or more, from the viewpoint of improving the cleaning power against flux residues, and from the same viewpoint, preferably 4.5 mass % or less, more preferably 4.0 mass % or more % or less, more preferably 3.0 mass% or less. Component d may use one or more alkylbenzenesulfonic acids and/or salts thereof.

In the detergent C, the mass ratio of components a, b, and c (component a/component b/component c) is, in one or more embodiments, preferably from the viewpoint of improving handleability of the cleaning composition and cleaning power against flux residues. is 90 to 98/0.5 to 4/0.05 to 4. However, the sum of component a, component b, and component c is 100.0.

[Other components of cleaning agent C]

As other components in the detergent C, hydroxyethylaminoacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid, salts thereof, etc., which are normally used in detergents as needed, within the scope not impairing the effects of the present invention. A chelating agent typified by the aminocarboxylate of aminocarboxylate, a preservative, a rust inhibitor, a bactericide, an antibacterial agent, a silicone antifoaming agent, an antioxidant, an ester or alcohol such as methyl palm fatty acid or benzyl acetate can be appropriately used.

[Method for preparing cleaning agent C]

The cleaning composition according to the present disclosure is not particularly limited in its preparation method, and in one or more embodiments, it can be prepared by mixing component a, component b, component c, and water, more briefly, component d or other components. can The cleaning agent C can be prepared and stored as a concentrate from the viewpoint of addition operation, storage and transport, and diluted with water so that the components a, component b and component c become the contents in the cleaning liquid at the time of cleaning described above at the time of use. The concentration magnification is preferably 50 times or more, more preferably 67 times or more, still more preferably 90 times or more from the viewpoint of addition operation and storage stability, and preferably 200 times or less from the viewpoint of storage and transport. , more preferably 150 times or less, still more preferably 110 times or less. From the viewpoint of facilitating the measurement of the amount of water to be diluted, for example, a 100-fold concentrated solution is exemplified. In the present disclosure, the cleaning agent disclosed in the form of a 100-fold concentrate of the cleaning agent C, in one or more embodiments, preferably has a concentration of 1/50 to 1/200, more preferably 1/67 at the time of cleaning. It can be diluted to a concentration of - 1/150, more preferably of 1/90 - 1/110, even more preferably of 1/100 and used as the detergent C. Dilution water may be distilled water, ion-exchanged water, pure water or ultrapure water. In this indication, "at the time of washing|cleaning" means the time of washing|cleaning in one or some embodiment. In this indication, "at the time of washing|cleaning" of the cleaning composition of a concentrate means the state diluted in one or some embodiment.

[pH of cleaning agent C]

The pH of the cleaning composition according to the present disclosure is, in one or more embodiments, preferably pH 8 or more and pH 14 or less, from the viewpoint of improving the cleaning power against flux residues, and more preferably from the viewpoint of suppressing corrosion. Preferably, it is pH 8 or more and pH 12 or less, More preferably, it is pH 8 or more and pH 10 or less, Even more preferably, it is pH 8 or more and pH 9 or less. The pH is, if necessary, inorganic acids such as nitric acid and sulfuric acid, organic acids other than component d such as oxycarboxylic acid, polyhydric carboxylic acid, aminopolycarboxylic acid, and amino acid, metal salts and ammonium salts thereof, ammonia, sodium hydroxide, and hydroxide Basic substances other than component b, such as potassium and an amine, can be adjusted by mix|blending a desired amount suitably.

One or some embodiment which is not limited of the manufacturing method of the circuit board in which solder was solidified which is implemented using the cleaning agent C mentioned above is demonstrated with reference to FIG.

[Process (1)]

Step (1) is a metal containing an imidazole compound for at least a first region electrode of a circuit board comprising an electrode of a first region on one main surface and an electrode of a second region on the other main surface. It is a process processed with the processing agent A (refer FIG. 1).

The circuit board used in the process (1) includes the board|substrate used as an interposer in a semiconductor package in one or some embodiment which is not limited. The "circuit board having electrodes which form a circuit in the 1st area|region and 2nd area|region of a support base material" used in the process (1) is not limited, In one or some embodiment, the circuit board used for flip-chip mounting. am. The circuit board used in the process (1) is a circuit board provided with two or more regions of the electrode in which a solder bump should be formed in one or some embodiment which is not limited.

As a metal of the electrode of the circuit board used at a process (1), copper and a copper alloy are mentioned in one or some embodiment which is not limited. An electrode of a circuit board is a site|part where solder is solidified in one or some embodiment.

[Metal treatment agent A in step (1)]

The metal treatment agent A of the step (1) is a metal surface treatment agent containing an imidazole compound. As metal treatment agent A, a well-known surface treatment agent (For example, the thing disclosed by Unexamined-Japanese-Patent No. 2007-308776) and future developed can be used in one or some embodiment. The metal processing agent A is a processing agent which can form in the metal surface the chemical conversion film which can suppress oxidation of a metal in one or some embodiment. Step (1) is water-soluble preflux treatment of the metal surface in one or more embodiments.

The metal processing agent A contains an imidazole compound. Content of the imidazole compound in metal processing agent A becomes like this. Preferably it is 0.01 mass % or more, More preferably, it is 0.1 mass % or more, Preferably it is 10 mass % or less, More preferably, it is 5 mass % or less.

Examples of the imidazole compound contained in the metal treatment agent A include imidazole, 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 4-methylimidazole, and 2- At least one selected from the group consisting of phenylimidazole and 4-phenylimidazole is preferable, and imidazole, 2-methylimidazole, 2-undecylimidazole, and 2-ethyl-4-methylimidazole , at least one selected from the group consisting of 2-phenylimidazole and 4-phenylimidazole is more preferable, and 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole At least one kind selected from the group consisting of is still more preferable, and at least one kind selected from the group consisting of 2-methylimidazole and 2-ethyl-4-methylimidazole is even more preferable.

It is preferable that the metal processing agent A contains an organic acid or an inorganic acid from a viewpoint of making an imidazole compound melt|dissolve (aqueous solution) in water. Organic acids include formic acid, acetic acid, propionic acid, butyric acid, glyoxylic acid, pyruvic acid, acetoacetic acid, levulinic acid, heptanoic acid, caprylic acid, capric acid, lauric acid, glycolic acid, glyceric acid, lactic acid, acrylic acid, and methyl acid. Toxyacetic acid, ethoxyacetic acid, propoxyacetic acid, butoxyacetic acid, 2-(2-methoxyethoxy)acetic acid, 2-[2-(2-ethoxyethoxy)ethoxy]acetic acid, 2-{2- [2-(2-ethoxyethoxy)ethoxy]ethoxy}acetic acid, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-propoxypropionic acid, 3-butoxypropionic acid, benzoic acid, paranitrobenzoic acid, para toluenesulfonic acid, salicylic acid, picric acid, oxalic acid, succinic acid, maleic acid, fumaric acid, tartaric acid, adipic acid, and the like. Examples of the inorganic acid include hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid. Content of an acid becomes like this. Preferably it is 0.1 mass % or more in metal processing agent A, More preferably, it is 1 mass % or more, Preferably it is 50 mass % or less, More preferably, it is 30 mass % or less. Organic or inorganic acids may be used in the form of salts. As a salt of an organic acid or an inorganic acid, an ammonium salt and a metal salt are mentioned, for example. Examples of the metal salt include sodium salt, zinc salt, iron salt, and aluminum salt.

Moreover, the metal treatment agent A can contain an organic solvent etc. as a solubilizer. As an organic solvent, Lower alcohols, such as methanol, ethanol, and isopropyl alcohol; Ketones, such as acetone; amides such as N,N-dimethylformamide; glycol ethers such as ethylene glycol; and those that are freely miscible with water such as these.

[Processing method with metal treatment agent A]

In one or some embodiment, the processing method of the circuit board by the metal processing agent A in a process (1) includes making the metal processing agent A contact the electrode of a circuit board. As contact conditions of the metal processing agent A with respect to an electrode, in one or some embodiment, the aspect made to contact the metal processing agent A with a liquid temperature of 10-70 degreeC with the contact time of 1 second - 10 minutes to the electrode of a circuit board is mentioned can As a contact method, methods, such as immersion, spraying, and application|coating, are mentioned in one or some embodiment.

[Process (2)]

In the step (2), in one or more embodiments, the flux B is applied to the electrodes in the first region of the circuit board obtained in the step (1), the solder is placed, and the circuit board is heated above the liquidus temperature of the solder. This is a step of melting the solder layer by heating to a temperature and solidifying the solder on the electrode in the first region (see Fig. 1).

The flux B and the solder used in the step (2) may be cream solder (solder paste), which is a mixture of solder and flux B, or solder formed by printing/applying flux B to an electrode to form a square or spherical shape. You may use it in the aspect which mounts on an electrode. As the solder in the present disclosure, a conventional general tin-lead eutectic solder alloy can also be used, but it is preferable to use a lead-free solder alloy such as a tin-silver type, a tin-copper type, or a tin-silver-copper type.

[Flux B in process (2)]

Regarding the flux B used in the step (2), in one or more embodiments, it is preferable that the flux residue can be washed from the viewpoint of connection reliability of the electrodes. A cleaning flux is good for cleaning the flux residue, and there is no particular limitation as long as it is a cleaning flux. As the cleaning flux, in one or more embodiments, a known or future developed flux may be used. As the cleaning flux, one disclosed in Japanese Patent Application Laid-Open No. 9-1388 can be used in one or more embodiments. The formation method of the solder bump using the flux B is not specifically limited, A well-known method is employable.

The flux B is preferably a cleaning flux, and more preferably a cleaning rosin-based flux. The flux B contains pine resin as a main component, and preferably has a content of pine resin of 50 mass% or more. Specific examples of the flux B include a flux containing pine resin and a pyrrolidone compound. The content of pine resin in the flux B is preferably 50 mass% or more, and preferably 97 mass% or less. The pyrrolidone compound is preferably at least one selected from the group consisting of pyrrolidone and disubstituted pyrrolidone having an alkyl group or phenyl group having 1 to 10 carbon atoms. The content of the pyrrolidone compound in the flux B is preferably 3 mass%, more preferably 5 mass% or more, and preferably 40 mass% or less, more preferably 20 mass% or less.

Flux B may contain an ester as a solvent. The content of the ester in the flux B is preferably 30 mass% or less, more preferably 10 mass% or less. As ester, at least 1 sort(s) selected from the group which consists of sebacate ester, phthalic acid ester, abietic acid ester, and stearic acid ester is mentioned.

[Process (3)]

The process (3) is a process of washing|cleaning the flux residue adhering to the circuit board obtained in the process (2) using the cleaning agent C. The cleaning agent C was mentioned above. The process (3) is a process of washing|cleaning with the cleaning agent C the flux residue which is generated when the solder of the process (2) is solidified in one or more embodiment (refer FIG. 1). As shown in Fig. 1, the solder is not solidified on the electrode in the second region during the cleaning in the step (3). When the conventional cleaning agent composition for flux is used, after cleaning in the step (3), there is a problem that the electrode in which the solder is not solidified is oxidized and/or discolored with the passage of time after cleaning or by heat treatment after cleaning. If the cleaning agent C is used, discoloration of the electrode in which the solder is not solidified can be suppressed in one or more embodiments.

Accordingly, the present disclosure relates to detergent C in another aspect. That is, the present disclosure provides a circuit board comprising an electrode treated with a metal treatment agent containing an imidazole compound and having no solidified solder, and an electrode having solidified solder using a cleaning flux, and also having a flux residue. As a cleaning composition for a flux for cleaning, glycol ether (component a), alkanolamine (component b), and an imidazole compound represented by the general formula (I) of 0.005 mass% or more and 4.0 mass% or less (component c) A detergent composition for flux containing

[Cleaning method with cleaning agent C]

The washing|cleaning method using the washing|cleaning agent C in a process (3) includes making the washing|cleaning agent C contact a to-be-cleaned object (circuit board obtained at the process (2)) in one or some embodiment. As a method of bringing the cleaning agent C into contact with the object to be cleaned, that is, the method of cleaning the object to be cleaned with the cleaning agent C, in one or more embodiments, the method of contacting the object to be cleaned in the bathtub of the ultrasonic cleaning device, or spraying the cleaning agent C The method of injecting into an upper part and making it contact (shower method) etc. are mentioned. In one or some embodiment, the cleaning agent C can be used for washing|cleaning as it is without dilution. It is preferable that the cleaning method of the present disclosure includes a step of rinsing with water and drying after contacting the cleaning agent C with the object to be cleaned.

Therefore, this indication relates to the washing|cleaning method using the washing|cleaning agent C in another aspect. That is, the present disclosure relates to an electrode treated with a metal treatment agent containing an imidazole compound, and having an electrode in which solder is not solidified, and an electrode in which solder is solidified using a cleaning flux, and further comprising a circuit board having a flux residue. As a cleaning method, the above circuit board, glycol ether (component a), alkanolamine (component b), and 0.005 mass% or more and 4.0 mass% or less of the imidazole compound (component c) represented by the general formula (I) It is a washing|cleaning method including making the containing cleaning composition for fluxes (cleaning agent C) contact.

[Process (4)]

The step (4) is a step of solidifying the solder on the electrodes of the second region of the circuit board following the step (3). The step (4) is a step of forming a solder bump on the electrode whose discoloration is suppressed by the washing of the step (3) in one or more embodiments. In one or more embodiments, by solidifying the solder in the step (4), it is possible to manufacture a circuit board in which the solder is solidified on the electrode to which the solder is to be solidified (see FIG. 1 ).

It is preferable to use a flux for solidification of the solder in step (4). The flux B may be used as the flux (flux D) to be used, but in one or more embodiments, it is preferable to use a flux capable of cleaning the flux residues from the viewpoint of connection reliability of the electrodes. As the flux for cleaning the flux residue, a cleaning flux is preferable, and in consideration of the environmental load, a water-soluble flux capable of cleaning the flux residue with a water-based cleaning agent is more preferable. Examples of the water-soluble flux include, in one or more embodiments, a water-soluble flux containing an ester of an organic acid and a polyhydric alcohol. The water-soluble flux may, in one or more embodiments, be known or developed in the future. As the water-soluble flux, the one disclosed in Example 6 of Japanese Patent Application Laid-Open No. 2000-42786 may be used in one or a plurality of embodiments. The method of solidifying the solder using the flux D is not specifically limited, A well-known method is employable.

Examples of the organic acid constituting the ester of flux D include, in one or more embodiments, at least one selected from the group consisting of capric acid, lauric acid, myristic acid, palmitic acid, linoleic acid and oleic acid. can Examples of the polyhydric alcohol constituting the ester of the flux D include at least one selected from the group consisting of butanediol, glycerol, and polyglycerol in one or more embodiments. Specifically, as the flux D, lauric acid polyglycerin ester, oleic acid glycerin ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, or the like may be used.

Flux D may contain water, organic solvents or other additives as solvents.

As for the flux D and the solder used in the step (4), cream solder (solder paste) that is a mixture of the solder and the flux D in one or more embodiments may be used, and the flux D is printed on the electrode to apply the solder to the part. It may be an aspect to be mounted on. The solder mentioned above can be used.

[Process (E)]

When the electrode which should form a solder bump does not remain in the circuit board which passed through the process (4), the manufacturing method which concerns on this indication further includes a washing|cleaning process (E) in one or some embodiment. That is, the process (E) is a process of washing|cleaning the flux residue of the circuit board obtained by the process (4) with the cleaning agent E.

As the washing|cleaning agent E in a process (E), water and a semi-aqueous solvent are mentioned in one or some embodiment. As a semi-aqueous solvent, in one or some embodiment which is not limited, a water-alcohol mixed solvent, a limonene-water mixed solvent, a glycol ether-water mixed solvent, etc. are mentioned. The washing|cleaning using the washing|cleaning agent E can be performed similarly to washing|cleaning using the washing|cleaning agent C mentioned above in one or some embodiment.

[Process (5)]

When a region (for example, a third region, a fourth region, etc.) including an electrode that solidifies the solder (the electrode on which the solder is not solidified) remains on the circuit board after the step (4), that is, the present When the circuit board to be manufactured by the manufacturing method according to the disclosure has a compartment (region) including three or more electrodes for solidifying solder, the manufacturing method according to the present disclosure includes, in one or a plurality of embodiments, 3) and step (5) of repeating step (4) may be included. In one or more embodiments, the step (5) is a step of cleaning the flux residue of the circuit board after the step (4) using a cleaning agent C, and soldering the electrodes in the third region on the circuit board after cleaning. a solidifying step. The operation in the step (5) can be performed similarly to the operation in the steps (3) and (4) described above. In one or more embodiments, the operation in step (5) may be repeated until there is no region on the circuit board including the electrode in which the solder is to be solidified. Then, it transfers to the washing|cleaning process (E) mentioned above.

[Method for manufacturing electronic components]

In one or more embodiments, the present disclosure includes a step of mounting at least one electronic component on a circuit board, wherein at least one of the circuit boards is a circuit board manufactured by a manufacturing method according to the present disclosure, It relates to a method of manufacturing a circuit board on which an electronic component is mounted. As an electronic component, a semiconductor chip, a chip resistor, a chip capacitor, a connector resistor, a chip coil, or various sensors etc. are mentioned, for example. A circuit board on which an electronic component is mounted includes a semiconductor package on which a semiconductor chip is not mounted, a semiconductor package on which a semiconductor chip is mounted, and a semiconductor device. The circuit board manufactured by the manufacturing method which concerns on this indication in one or some embodiment WHEREIN: Since discoloration of an electrode is suppressed and connection reliability is improved, the manufacturing method of the circuit board on which the electronic component of this indication was mounted. Silver enables, in one or more embodiments, to manufacture circuit boards on which highly reliable electronic components are mounted.

As it relates to embodiment mentioned above, this indication further discloses the following composition, manufacturing method, or use.

<1> The manufacturing method of the circuit board in which solder was solidified including the following processes (1)-(4).

(1) Process of treating the electrode of at least 1st area|region of the circuit board which has an electrode which forms a circuit in the 1st area|region and 2nd area|region of a support base material with the metal treatment agent A containing an imidazole compound.

(2) After applying the flux B and arranging the solder to the electrodes in the first region of the circuit board obtained in the step (1), the circuit board is heated to a temperature equal to or higher than the liquidus temperature of the solder to melt the solder, A process of solidifying the solder on the electrode in region 1.

(3) The flux residue of the circuit board obtained in the step (2), the component a which is a glycol ether, the component b which is an alkanolamine, and 0.005 mass % or more and 4.0 mass % or less of an image represented by the following general formula (I) A step of washing using a detergent C containing component c, which is a dazole compound.

[Formula 5]

(In formula (I), R ₁ , R ₂ and R ₃ each represent at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 22 carbon atoms.)

(4) A step of solidifying the solder on the electrode in the second region of the circuit board following the step (3).

<2> The method for manufacturing a circuit board according to <1>, wherein the flux B in the step (2) is a cleaning flux.

The manufacturing method of the circuit board as described in <1> or <2> whose component a in the cleaning agent C in <3> process (3) is a compound represented by the following general formula (II).

[Formula 6]

RO-(CH ₂ CH ₂ O) _n -H (II)

(In formula (II), R represents a hydrocarbon group having 3 to 8 carbon atoms, and n represents 2 or 3.)

<4> The content of the component a in the <4> detergent C is preferably 80.0 mass% or more, more preferably 85.0 mass% or more, still more preferably 85.5 mass% or more, still more preferably 86.4 mass% or more <1> to <3> The manufacturing method of the circuit board in any one of.

The content of the component a in the <5> cleaning agent C is preferably 90.0 mass% or less, more preferably 89.0 mass% or less, still more preferably 88.5 mass% or less of the circuit board according to any one of <1> to <4>. manufacturing method.

<6> The content of the component a in the cleaning agent C is preferably 85.0 mass% or more and 89.0 mass% or less, more preferably 85.5 mass% or more and 89.0 mass% or less, still more preferably 86.4 mass% or more and 88.5 mass% or less <1 The manufacturing method of the circuit board in any one of > to <5>.

Component a in <7> detergent C contains diethylene glycol monobutyl ether, and content in component a of diethylene glycol monobutyl ether is preferably 50.0 mass% or more, more preferably 60.0 mass% or more, further Preferably it is 70.0 mass % or more, More preferably, it is 80.0 mass % or more, The manufacturing method of the circuit board in any one of <1>-<6>.

<8> The component a in the detergent C contains diethylene glycol monobutyl ether, and the content in the component a of the diethylene glycol monobutyl ether is preferably 98.0 mass% or less, more preferably 95.0 mass% or less <1> The manufacturing method of the circuit board in any one of thru|or <7>.

<9> The component a in the detergent C contains diethylene glycol monobutyl ether, and the content of the diethylene glycol monobutyl ether in the detergent C is preferably 50.0 mass% or more, more preferably 60.0 mass% or more, further Preferably it is 70.0 mass % or more, More preferably, it is 75.0 mass % or more, The manufacturing method of the circuit board in any one of <1>-<8>.

<10> The component a in the detergent C contains diethylene glycol monobutyl ether, and the content of the diethylene glycol monobutyl ether in the detergent C is preferably 90.0 mass% or less, more preferably 88.0 mass% or less, still more preferably The manufacturing method of the circuit board in any one of <1>-<9> which is preferably 85.0 mass % or less.

<11> The content of glycol ethers other than diethylene glycol monobutyl ether in component a is preferably 50.0 mass% or less, more preferably 40.0 mass% or less, still more preferably 30.0 mass% or less, still more preferably The manufacturing method of the circuit board in any one of <1>-<10> which is 20.0 mass % or less.

<12> Content in the detergent C of glycol ethers other than diethylene glycol monobutyl ether becomes like this. Preferably it is 1.0 mass % or more, More preferably, it is 3.0 mass % or more, More preferably, it is 4.0 mass % or more <1> to <11. > The manufacturing method of the circuit board in any one of.

<13> The content in the detergent C of glycol ethers other than diethylene glycol monobutyl ether is preferably 40 mass% or less, more preferably 30.0 mass% or less, still more preferably 16.0 mass% or less <1> to <12 > The manufacturing method of the circuit board in any one of.

<14> The method for manufacturing a circuit board according to any one of <1> to <13>, wherein the component b in the cleaning agent C is a compound represented by the following general formula (III).

[Formula 7]

(In formula (III), R ₄ represents at least one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group and an aminoethyl group, and R ₅ is a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group and an ethyl group. _{At least 1 type selected from the group which consists of is represented, and R<6>} represents at least 1 type chosen from the group which consists of a hydroxyethyl group and a hydroxypropyl group.)

Content of component b in <15> cleaning agent C becomes like this. Preferably it is 0.3 mass % or more, More preferably, it is 0.5 mass % or more, More preferably, it is 1.0 mass % or more, The circuit board in any one of <1>-<14>. manufacturing method.

<16> Content of the component b in the detergent C becomes like this. Preferably it is 5.0 mass % or less, More preferably, it is 4.5 mass % or less, More preferably, it is 4.0 mass % or less, More preferably, it is 3.5 mass % or less <1. The manufacturing method of the circuit board in any one of > to <15>.

<17> The content of the component b in the detergent C is preferably 0.3 mass% or more and 5.0 mass% or less, more preferably 0.5 mass% or more and 4.5 mass% or less, still more preferably 1.0 mass% or more and 4.0 mass% or less; Still more preferably, they are 1.0 mass % or more and 3.5 mass % or less, The manufacturing method of the circuit board in any one of <1>-<16>.

<18> In the step (3), component c in the detergent C is selected from the group consisting of imidazole, methylimidazole, imidazole substituted with an alkyl group having 11 carbon atoms, methylethylimidazole and phenylimidazole The manufacturing method of the circuit board in any one of <1>-<17> which is at least 1 type.

Content of component c in <19> cleaning agent C is 0.005 mass % or more, Preferably it is 0.01 mass % or more, More preferably, it is 0.05 mass % or more, The manufacturing method of the circuit board in any one of <1>-<18>.

<20> Among <1> to <19> whose content of component c in the detergent C is 4.0 mass % or less, Preferably it is 3.5 mass % or less, More preferably, it is 3.0 mass % or less, More preferably, it is 2.0 mass % or less. The manufacturing method of the circuit board as described in any one.

<21> Content of component c in detergent C is 0.005 mass % or more and 4.0 mass % or less, Preferably it is 0.01 mass % or more and 3.5 mass % or less, More preferably, 0.01 mass % or more and 3.0 mass % or less, More preferably, The manufacturing method of the circuit board in any one of <1>-<20> which are 0.05 mass % or more and 2.0 mass % or less.

<22> Content of the water in the cleaning agent C becomes like this. Preferably it is 5.0 mass % or more, More preferably, it is 5.5 mass % or more, More preferably, it is 6.5 mass % or more, The manufacturing method of the circuit board in any one of <1>-<21>. .

<23> Content of the water in the cleaning agent C becomes like this. Preferably it is 12.0 mass % or less, More preferably, it is 11.0 mass % or less, More preferably, it is 10.0 mass % or less, The manufacturing method of the circuit board in any one of <1>-<22>. .

<24> The content of water in the cleaning agent C is preferably 5.0 mass% or more and 12.0 mass% or less, more preferably 5.5 mass% or more and 11.0 mass% or less, and still more preferably <1> to 6.5 mass% or more and 10.0 mass% or less. The manufacturing method of the circuit board in any one of <23>.

<1> to which the detergent C in the <25> process (3) contains at least 1 sort(s) (component d) further selected from the group which consists of benzenesulfonic acid and its salt which has a C1-C6 alkyl group further The manufacturing method of the circuit board in any one of <24>.

Content of the component d in the <26> cleaning agent C becomes like this. The manufacturing method of the circuit board as described in <25> whose content is preferably 0.3 mass % or more and 5.0 mass % or less.

Content of the component d in <27> cleaning agent C becomes like this. Preferably it is 0.4 mass % or more, More preferably, it is 0.5 mass % or more, The manufacturing method of the circuit board as described in <25> or <26>.

<28> The content of the component d in the cleaning agent C is preferably 4.5 mass% or less, more preferably 4.0 mass% or less, still more preferably 3.0 mass% or less of the circuit board according to any one of <25> to <27>. manufacturing method.

In <29> any of <1> to <28> whose component a/component b/component c which shows the mass ratio of the components a, b and c in the <29> cleaning agent C is 90-98/0.5-4/0.05-4 preferably A method for manufacturing a circuit board as described.

<30> The method for manufacturing a circuit board according to any one of <1> to <29>, wherein a solder flux is used for solidification of the solder in the step (4), and the flux is a water-soluble flux.

<31> An electronic component comprising a step of mounting at least one electronic component on a circuit board, wherein at least one of the circuit board is a circuit board manufactured by the manufacturing method according to any one of <1> to <30> A method for manufacturing this mounted circuit board.

<32> A detergent composition for flux comprising a component a that is a glycol ether, a component b that is an alkanolamine, and a component c that is an imidazole compound represented by the following general formula (I) in an amount of 0.005 mass% or more and 4.0 mass% or less.

[Formula 8]

(In formula (I), R ₁ , R ₂ and R ₃ each represent at least one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 22 carbon atoms.)

<33> The cleaning composition for flux according to <32>, wherein the component a is a compound represented by the following general formula (II).

[Formula 9]

RO-(CH ₂ CH ₂ O) _n -H (II)

(In formula (II), R represents a hydrocarbon group having 3 to 8 carbon atoms, and n represents 2 or 3.)

<34> The content of component a in the cleaning composition for flux is preferably 80.0 mass% or more, more preferably 85.0 mass% or more, still more preferably 85.5 mass% or more, still more preferably 86.4 mass% or more <32 The cleaning composition for flux according to > or <33>.

<35> The flux according to any one of <32> to <34>, wherein the content of component a in the cleaning composition for flux is preferably 90.0 mass% or less, more preferably 89.0 mass% or less, and still more preferably 88.5 mass% or less. cleaning composition for use.

<36> The content of component a in the cleaning composition for flux is preferably 85.0 mass% or more and 89.0 mass% or less, more preferably 85.5 mass% or more and 89.0 mass% or less, still more preferably 86.4 mass% or more and 88.5 mass% or less. The cleaning composition for flux according to any one of <32> to <35>.

<37> Component a contains diethylene glycol monobutyl ether, and the content of diethylene glycol monobutyl ether in component a is preferably 50.0 mass % or more, more preferably 60.0 mass % or more, still more preferably The detergent composition for flux according to any one of <32> to <36>, wherein the cleaning composition is 70.0 mass% or more, and still more preferably 80.0 mass% or more.

<38> <32> to <37> wherein the component a contains diethylene glycol monobutyl ether, and the content of the diethylene glycol monobutyl ether in the component a is preferably 98.0 mass% or less, more preferably 95.0 mass% or less > The cleaning composition for flux according to any one of the above.

<39> Component a contains diethylene glycol monobutyl ether, and the content of diethylene glycol monobutyl ether in the detergent composition for flux is preferably 50.0 mass% or more, more preferably 60.0 mass% or more, still more preferably The detergent composition for flux according to any one of <32> to <38>, preferably 70.0 mass% or more, and still more preferably 75.0 mass% or more.

<40> Component a contains diethylene glycol monobutyl ether, and the content of diethylene glycol monobutyl ether in the detergent composition for flux is preferably 90.0 mass% or less, more preferably 88.0 mass% or less, still more preferably The detergent composition for flux according to any one of <32> to <39>, wherein is 85.0 mass% or less.

<41> The content in the component a of glycol ethers other than diethylene glycol monobutyl ether is preferably 50.0 mass% or less, more preferably 40.0 mass% or less, still more preferably 30.0 mass% or less, still more preferably The cleaning composition for flux according to any one of <32> to <40>, which is 20.0 mass% or less.

<42> The content of glycol ethers other than diethylene glycol monobutyl ether in the detergent composition for flux is preferably 1.0 mass % or more, more preferably 3.0 mass % or more, still more preferably 4.0 mass % or more <32> to The cleaning composition for flux according to any one of <41>.

<43> The content of glycol ethers other than diethylene glycol monobutyl ether in the detergent composition for flux is preferably 40 mass% or less, more preferably 30.0 mass% or less, still more preferably 16.0 mass% or less <32> to The cleaning composition for flux according to any one of <42>.

<44> The cleaning composition for flux according to any one of <32> to <43>, wherein the component b is a compound represented by the following general formula (III).

[Formula 10]

(In formula (III), R ₄ represents at least one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group and an aminoethyl group, and R ₅ is a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group and an ethyl group. _{At least 1 type selected from the group which consists of is represented, and R<6>} represents at least 1 type chosen from the group which consists of a hydroxyethyl group and a hydroxypropyl group.)

<45> The content of component b in the cleaning composition for flux is preferably 0.3 mass% or more, more preferably 0.5 mass% or more, still more preferably 1.0 mass% or more, according to any one of <32> to <44>. A cleaning composition for flux.

<46> The content of component b in the cleaning composition for flux is preferably 5.0 mass% or less, more preferably 4.5 mass% or less, still more preferably 4.0 mass% or less, even more preferably 3.5 mass% or less. The cleaning composition for flux according to any one of <32> to <45>.

<47> The content of component b in the cleaning composition for flux is preferably 0.3 mass% or more and 5.0 mass% or less, more preferably 0.5 mass% or more and 4.5 mass% or less, still more preferably 1.0 mass% or more and 4.0 mass% or less. Hereinafter, the cleaning composition for flux according to any one of <32> to <46>, further more preferably 1.0 mass% or more and 3.5 mass% or less.

<48> of <32> to <47>, wherein component c is at least one selected from the group consisting of imidazole, methylimidazole, imidazole substituted with an alkyl group having 11 carbon atoms, methylethylimidazole and phenylimidazole The cleaning composition for flux according to any one of them.

<49> The detergent composition for flux according to any one of <32> to <48>, wherein the content of component c in the detergent composition for flux is 0.005 mass% or more, preferably 0.01 mass% or more, and more preferably 0.05 mass% or more. .

<50> The content of component c in the cleaning composition for flux is 4.0 mass% or less, preferably 3.5 mass% or less, more preferably 3.0 mass% or less, still more preferably 2.0 mass% or less <32> to <49 > The cleaning composition for flux according to any one of the above.

<51> The content of component c in the cleaning composition for flux is 0.005 mass% or more and 4.0 mass% or less, preferably 0.01 mass% or more and 3.5 mass% or less, more preferably 0.01 mass% or more and 3.0 mass% or less, further preferably The detergent composition for flux according to any one of <32> to <50>, which is preferably 0.05 mass% or more and 2.0 mass% or less.

<52> <32> to <51> which further contains water, and the content of water in the cleaning composition for flux is preferably 5.0 mass% or more, more preferably 5.5 mass% or more, still more preferably 6.5 mass% or more The cleaning composition for flux according to any one of the preceding claims.

<53> <32> to <52> which further contains water, and the content of water in the cleaning composition for flux is preferably 12.0 mass% or less, more preferably 11.0 mass% or less, still more preferably 10.0 mass% or less The cleaning composition for flux according to any one of the preceding claims.

<54> The content of water in the cleaning composition for flux is preferably 5.0 mass% or more and 12.0 mass% or less, more preferably 5.5 mass% or more and 11.0 mass% or less, still more preferably 6.5 mass% or more and 10.0 mass% or less <32 The cleaning composition for flux according to any one of > to <53>.

<55> The detergent composition for flux according to any one of <32> to <54>, further comprising a component d which is at least one selected from the group consisting of benzenesulfonic acid having an alkyl group having 1 to 6 carbon atoms and a salt thereof.

<56> The cleaning composition for flux according to <55>, wherein the content of the component d in the cleaning composition for flux is preferably 0.3 mass% or more and 5.0 mass% or less.

<57> The cleaning composition for flux according to <55> or <56>, wherein the content of component d in the cleaning composition for flux is preferably 0.4 mass% or more, and more preferably 0.5 mass% or more.

<58> The flux according to any one of <55> to <57>, wherein the content of component d in the cleaning composition for flux is preferably 4.5 mass% or less, more preferably 4.0 mass% or less, and still more preferably 3.0 mass% or less. cleaning composition for use.

<59> For the flux according to any one of <32> to <58>, wherein the component a/component b/component c representing the mass ratio of the components a, b and c is preferably 90 to 98/0.5 to 4/0.05 to 4. detergent composition.

[Example]

1. Pre-flux treatment of the substrate

About the electrode of a test board|substrate, the preflux process was performed using the metal processing agent A in the following process and conditions.

[Test board]

The circuit board 1 shown in FIG. 2 was used as a test board|substrate. The circuit board 1 is a board|substrate provided with the copper electrode 2 of the 1st area|region A, the copper electrode 3 of the 2nd area|region B, and the wiring 4 on one main surface. The electrode 2 of the first region A has a Land of 0.36 mm and a pitch of 1.0 mm.

[Process (1): pre-flux treatment]

The preflux treatment was performed in the order including the following steps (a) to (d).

(a) degreasing process

After immersing a test board|substrate in the degreasing liquid (The Shikoku Chemical Industry Co., Ltd. make, brand name: Tough Cleaner W40G) at 20-30 degreeC for 30 second, the board|substrate was taken out and it washed with water for 1 minute.

(b) soft etching process

The substrate was immersed in a soft etching solution (manufactured by Shikoku Chemical Industry Co., Ltd., trade name: Tough Cleaner GB-1400, sulfuric acid-hydrogen peroxide type) at 30°C for 30 seconds, and then the substrate was taken out and washed with water for 1 minute.

(c) pickling process

After immersing the said board|substrate in the acid washing liquid (5% sulfuric acid aqueous solution) at 20-30 degreeC for 30 second, it took out and washed with water for 1 minute. Thereafter, the substrate was dehydrated with an air knife.

(d) pre-flux treatment process

After immersing the said board|substrate in the metal treatment agent A (water-soluble preflux, Shikoku Chemical Industry Co., Ltd. product name: Tough Ace F2(LX)PK) containing an imidazole compound at 40 degreeC for 30 to 90 second, take out a board|substrate and 1 minute was washed. Then, after dehydrating a board|substrate with an air knife, it dried at 100 degreeC for 1 minute. A chemical conversion film having a thickness of about 0.1 to 0.3 µm was formed on the copper surface.

The following tests were performed using the test board|substrate (henceforth "preflux-processed test board|substrate") which performed the process for forming the chemical conversion film by water-soluble preflux as mentioned above.

2. Formation and cleaning of solder bumps using cleaning flux

[Step (2): Formation of solder bumps in the first region A]

Using a stencil mask, cleaning flux B (manufactured by Senju Metal Industry Co., Ltd., trade name: Delta Lax MB-T100) was applied to the copper pad of the electrode 2 in the first region A of the prefluxed test substrate to a thickness of 100 μm. After printing, a 300 μm solder ball having a composition of Sn-3Ag-0.5Cu (each numerical value is mass%) was mounted at a flux printing point, using reflow to increase the temperature at a rate of 2.5°C/sec and a peak temperature of 250°C. was reflowed (oxygen concentration was 100 ppm).

[Preparation of cleaning agent C]

Glycol ether (component a) shown in Table 1 below, alkanolamine (component b), imidazole compound (component c), water and, if necessary, alkylbenzenesulfonic acid and/or its salt (component d) and other components was mixed so that it might become content shown in Table 1, and the washing|cleaning agent C (Examples 1-17 and Comparative Examples 1-8) was prepared.

[Step (3): Cleaning of Flux B Residue]

The solder bumps after reflow were washed under the following conditions, and flux cleaning properties were confirmed. The results are shown in Table 1.

Cleaning method: Immersion in detergent C → Pre-rinse → Rinse → Finish rinse → Air purge → Dry → Judgment

Liquid temperature = all 60℃

Physical force = all ultrasonic, 40 kHz, 400 W

Cleaning time = 1 min for each process

Air purge = 0.3 MPa, N2, 25 °C, 15 sec

Determination of cleaning properties was performed by observing the area around the flux residue before cleaning at 200 times using a DIGITAL MICROSCOPE VHX-2000 manufactured by Keyence Co., Ltd. The flux residue cleaning rate was calculated by using the area calculation mode by .

[Criteria]

A: Complete cleaning (cleaning rate 100%)

B: less than 98 to 100% cleaning rate

C: Less than 95 to 98% of cleaning rate

D: less than 95% cleaning rate

3. Discoloration property after washing|cleaning in the copper electrode 3 of 2nd area|region B

The discoloration of the copper electrode 3 of the second region B on the substrate after the cleaning of the above 2, in which the solder bump was not formed, was visually determined immediately after the cleaning and after the atmospheric baking (heat treatment) at 175° C. for 6 hours. The results are shown in Table 1.

[Criteria]

A: There is no color unevenness, and there is no discoloration.

B: There is no color unevenness, and discoloration is seen.

C: Discoloration is seen, and a part is browned.

D: The whole is browned.

4. Wettability of the solder in the copper electrode 3 in the second region B

[Step (4): Formation of solder bumps in the second region B]

Using a stencil mask, a water-soluble flux (flux D) was printed to a thickness of 100 μm on the copper electrode 3 in the second region B where the solder bump was not formed on the substrate after the cleaning in step 2, and Sn-3Ag-0.5Cu A solder ball having a composition having a diameter of 300 µm was mounted on a flux printing point, and the reflow was used to reflow at a temperature increase rate of 2.5°C/sec and a peak temperature of 250°C. The oxygen concentration in the reflow furnace at this time was 100 ppm.

As the water-soluble flux (flux D), the water-soluble flux (lauric acid polyglycerol ester: 99% by weight, sebacic acid: 1% by weight) used in Example 6 of JP-A-2000-42786 was used. As the water-soluble flux, a commercially available water-soluble flux (manufactured by Senju Metal Industries, Ltd., trade name: Sparkle Flux WF-6317) can also be used.

[judgment of wettability]

The length and width of the solder diffused after reflow was measured using a DIGITAL MICROSCOPE VHX-500 manufactured by Keyence Co., Ltd. (N = 12), and the rate of decrease in the diffusion area was calculated as compared with that of Comparative Example 3, and based on the following criteria: judged. The results are shown in Table 1.

[Criteria]

A: The magnified area is the same - less than 1% fall

B: A fall of less than 1% to 3% of an enlarged area

C: A fall of 3% to less than 5% of an enlarged area

D: The enlarged area decreases by 5% or more

As shown in Table 1, when the cleaning agent C of Examples 1 to 17 was used, as compared to Comparative Examples 1 to 8, discoloration after heat treatment of the electrode 3 of the second region B in which the solder bump was not formed can be significantly suppressed. there was. Moreover, when the cleaning agent C of Examples 1-5, 7, 8, and 10-17 was used, the wettability of the solder was improved compared with Examples 6 and 9. In the manufacture of a semiconductor package substrate, a cycle including printing/applying of a flux, heating for forming solder bumps, and cleaning for removing residual flux may be repeated multiple times. It can be said that the wettability of the solder further affects the connection reliability.

Claims (18)

A method for manufacturing a circuit board in which solder is solidified, comprising the following steps (1) to (4).
(1) The process of treating the electrode of at least 1st area|region of the circuit board which has an electrode which forms a circuit in the 1st area|region and 2nd area|region of a support base material with the metal treatment agent A containing an imidazole compound.
(2) After applying the flux B and arranging the solder to the electrodes in the first region of the circuit board obtained in the step (1), the circuit board is heated to a temperature equal to or higher than the liquidus temperature of the solder to melt the solder, A process of solidifying solder on the electrode in region 1.
(3) The flux residue of the circuit board obtained in the step (2), the component a which is glycol ether, the component b which is an alkanolamine represented by the following general formula (III), and 0.005 mass% or more and 4.0 mass% or less of the following The process of washing|cleaning using the washing|cleaning agent C containing the component c which is an imidazole compound represented by general formula (I).

In formula (I), R<_1> , R<_2>, and R<_3> respectively represent at least 1 sort(s) chosen from the group which consists of a hydrogen atom and a C1-C22 hydrocarbon group.

In formula (III), R ₄ represents at least one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group and an aminoethyl group, and R ₅ is a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group and an ethyl group. At least 1 type selected from the group is represented, and R ₆ represents at least 1 type selected from the group which consists of a hydroxyethyl group and a hydroxypropyl group.
(4) A step of solidifying the solder on the electrode in the second region of the circuit board following the step (3). The method of claim 1,
The method for manufacturing a circuit board, wherein the flux B in the step (2) is a flux for cleaning. The method of claim 1,
The manufacturing method of a circuit board whose component a in the cleaning agent C in a process (3) is a compound represented by the following general formula (II).
RO-(CH ₂ CH ₂ O) _n -H (II)
In formula (II), R represents a C3-C8 hydrocarbon group, and n represents 2 or 3. The method of claim 1,
Component c in the detergent C in the step (3) is at least one selected from the group consisting of imidazole, methylimidazole, imidazole substituted with an alkyl group having 11 carbon atoms, methylethylimidazole and phenylimidazole , a method of manufacturing a circuit board. The method of claim 1,
The method of manufacturing a circuit board, wherein the metal of the electrode is copper or a copper alloy. The method of claim 1,
The circuit in which component a/component b/component c which shows mass ratio of component a in detergent C, b and c is 90-98/0.5-4/0.05-4, and the sum total of component a, component b, and component c is 100.0 A method of manufacturing a substrate. The method of claim 1,
The manufacturing method of the circuit board whose content of the component a in the cleaning agent C is 85.0 mass % or more and 89.0 mass % or less. The method of claim 1,
The manufacturing method of the circuit board whose content of the component b in the cleaning agent C is 0.3 mass % or more and 5.0 mass % or less. The method of claim 1,
The manufacturing method of a circuit board in which the cleaning agent C in a process (3) contains the component d which is at least 1 sort(s) selected from the group which further consists of benzenesulfonic acid which has a C1-C6 alkyl group, and its salt. 10. The method of claim 9,
The manufacturing method of the circuit board whose content of the component d in the cleaning agent C is 0.3 mass % or more and 5.0 mass % or less. The method of claim 1,
The manufacturing method of the circuit board whose cleaning agent C contains water, and content of the water in the cleaning agent C is 5.0 mass % or more and 12.0 mass % or less. The method of claim 1,
The manufacturing method of the circuit board whose content of the imidazole compound in the metal processing agent A is 0.01 mass % or more and 10 mass % or less. The method of claim 1,
Process (1) WHEREIN: The manufacturing method of a circuit board in which the metal processing agent A with a liquid temperature of 10-70 degreeC is made to contact with the electrode of a circuit board in the contact time of 1 second - 10 minutes. The method of claim 1,
A method for manufacturing a circuit board, wherein a flux is used for solidification of the solder in the step (4), and the flux is a water-soluble flux. The method of claim 1,
The manufacturing method of a circuit board which further has the process of wash|cleaning the circuit board obtained by the process (4) with the cleaning agent E. An electronic component comprising a step of mounting at least one electronic component on a circuit board, wherein at least one of the circuit board is a circuit board manufactured by the manufacturing method according to any one of claims 1 to 15 A method for manufacturing this mounted circuit board. A flux containing component a which is a glycol ether, component b which is an alkanolamine represented by the following general formula (III), and an imidazole compound component c represented by the following general formula (I) in 0.005 mass% or more and 4.0 mass% or less cleaning composition for use.

In formula (I), R<_1> , R<_2>, and R<_3> respectively represent at least 1 sort(s) chosen from the group which consists of a hydrogen atom and a C1-C22 hydrocarbon group.

In formula (III), R ₄ represents at least one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group and an aminoethyl group, and R ₅ is a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group and an ethyl group. At least 1 type selected from the group is represented, and R ₆ represents at least 1 type selected from the group which consists of a hydroxyethyl group and a hydroxypropyl group. delete

Images