JP2001152192A - Cleaning agent composition, and cleaning method and maintenance method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cleaning agent composition permitting effective cleaning of contaminants represented by an insulating organic film deteriorated with the lapse of time, and a novel cleaning method using the same. SOLUTION: As a cleaning agent for effectively removing and organic contaminant such as a rosin-based flux, adhered to a fitting part, a connector part, or the like, of an electronic component or an electronic device, particularly a deteriorated organic contaminant, the cleaning agent composition is composed of a nonpolar solvent such as a hydrofluorocarbon, a polar solvent such as an aprotic solvent, and a soluble chelating agent such as an aminoalcohol, and its componental ratio is optimized to exhibit excellent electric insulating properties and excellent cleaning performances.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates mainly to semiconductor devices, electronic display devices typified by liquid crystal display devices and plasma display devices, and electronic components having a fine structure used in magnetic recording devices and the like. Related to a cleaning composition for efficiently cleaning and removing contaminants mainly composed of organic substances typified by solder flux in a process of manufacturing various components or an electronic device manufactured by combining the components. Further, the present invention relates to a cleaning method and a maintenance method using the cleaning composition, and more specifically, a method for manufacturing a semiconductor device or an electronic display device or a magnetic recording device and a semiconductor device manufactured using the method. It relates to an electronic device product such as an electronic display device or a magnetic recording device.

[0002]

2. Description of the Related Art In an electronic component having a solder connection portion or an electronic device using the same, a detailed example of a cleaning technique, such as a cleaning agent and a cleaning method for removing organic contaminants such as a solder flux at the connection portion, is disclosed by the Ministry of International Trade and Industry. It is disclosed on pages 10 to 200 (issued in February 1993) of the “Manual for Reduction and Elimination of 1,1,1-Trichloroethane” supervised by the Ozone Protection Countermeasures Office of the Industry Bureau. Non-aqueous detergent compositions are disclosed in JP-A-3-34942 and JP-A-3-173.
85, JP-A-5-283700, JP-A-6-4
9497, JP-A-6-228596 and the like disclose details thereof.

[0003]

However, even if the above-mentioned conventional cleaning technique is effective for flux cleaning immediately after soldering in any case, a considerable period of time has elapsed after soldering. In some cases, it is not always sufficient to remove contaminants such as those in which the initial deposits are altered. This is presumed to be caused by the polymerization of unsaturated carboxylic acids such as abietic acid and their derivatives contained in the solder flux, and by the increase of carboxyl groups due to oxygen in the air, thereby altering the deposits. In such a case, the cleaning ability of the conventional cleaning agent cannot be sufficiently exhibited.

[0004] In particular, when the flux component comes into contact with a metal, particularly a corrosive metal, the degree of deterioration tends to be deteriorated, and the cleaning ability of the cleaning agent has been significantly reduced. In such a case, it is presumed that the metal ions released by the corrosion combine with the flux component to form a carboxylate. Furthermore, if such a deteriorated substance adheres to a contact portion of a circuit board such as a connector, a strong insulating film may be formed on a metal contact such as gold. In some cases, this may be a factor such as poor conduction. Therefore, in order to improve the reliability of electronic equipment, there has been a demand for realizing a strong cleaning agent capable of exerting a sufficient cleaning power even with the above-mentioned deteriorated contaminants.

[0005] Further, in the case where the formation of the altered substance is caused by the flux remaining in the electronic component, the influence of the contaminant may occur after a long time from the start of using the electronic device. It is also necessary to clean and maintain circuit boards and connectors while the device is running. In such a case, the cleaning agent does not need only an excellent cleaning ability for dissolving and removing the deteriorated contaminants, and also performs a cleaning operation while improving the electrical insulation of the cleaning agent itself to prevent a short circuit of an electronic circuit. Need to be applied. That is, it is necessary to use a cleaning agent having excellent electrical insulation properties in addition to strong cleaning ability.

[0006] Conventional cleaning agents cannot effectively cope with such uses, and there has been a demand for a cleaning agent having high cleaning performance and excellent electrical insulation.

[0007] A first object of the present invention is to provide a cleaning composition which solves the above-mentioned problems and has excellent cleaning ability and electrical insulation. A second object of the present invention is to provide a method for cleaning electronic components using the cleaning composition of the present invention, and in particular, to provide a cleaning method capable of removing contaminants from required portions of the electronic device while the electronic device is energized and operated. Is to do.

[0008]

As means for solving the above-mentioned problems, the present invention uses the following detergent composition.

That is, the cleaning composition of the present invention is characterized by containing a nonpolar solvent, a polar solvent and a soluble complexing agent.
It should be emphasized that each of the components required for the above-mentioned composition has a unique role, and that the performance and ability are exhibited only after forming the mixture composition of the present invention.

The nonpolar solvent of the present invention occupies the most part of the detergent composition, and increases the electrical resistivity of the detergent as a whole and imparts the non-flammability property of the detergent as a whole. It acts to regulate the vapor pressure, viscosity, toxicity, etc. of the entire cleaning agent. These properties are achieved by the inherent properties of the non-polar solvent and its high proportion in the overall detergent. Therefore, the ratio of the above-mentioned non-polar solvent to the entire cleaning agent is about 80 to less than 100% by weight, more preferably 90 to less than 95% by weight. The lower limit of the composition is determined from the amount that simultaneously satisfies the two characteristics of non-flammability and insulating properties as a cleaning liquid, and the upper limit of the composition is determined from the amount that satisfies the cleaning ability. .

The polar solvent of the present invention occupies the next most part of the detergent composition, and has a function of solubilizing the complexing agent of the present invention in the detergent and a relatively polar contaminant in the detergent. It has a solubilizing effect. These properties are attained by the inherent properties of the polar solvent and the fact that it occupies the second largest percentage of the entire cleaning agent after the non-polar solvent. Therefore, the ratio of the polar solvent to the entire cleaning agent is about 0 to less than 20% by weight, and more preferably 5 to less than 10% by weight. The upper limit of the composition is determined from an amount that simultaneously satisfies the two characteristics of non-flammability and insulating properties as a cleaning liquid, and the lower limit of the composition is determined from an amount that satisfies the cleaning ability. is there.

The soluble complexing agent of the present invention occupies the second most part in the detergent composition after the polar solvent, and although its action has not been completely elucidated, it is generally complexed with metal ions. It has the property of an agent, and remarkably promotes the action of solubilizing relatively polar contaminants in the detergent, and has the property of being soluble in the detergent. These properties are attained by the intrinsic properties of the soluble complexing agent and by its proportion in the overall detergent following the polar solvent. Therefore,
The ratio of the soluble complexing agent to the total amount of the detergent is about 0.01 to 20% by weight, and more preferably 0.1 to 20% by weight.
It is 1 to 5% by weight. The upper limit of the composition is determined by an amount that simultaneously satisfies the two characteristics of non-flammability and insulating properties as a cleaning liquid, and the lower limit of the composition is determined by an amount that satisfies the cleaning ability.

The details of the components suitable for constituting the cleaning composition of the present invention are described below. In addition, the components shown below are representative of typical compounds, and the present invention is also applicable to the case where compounds having the same action with only a slight difference in structure are used, such as derivatives of those compounds. It should be emphasized that the effect is obtained.

The nonpolar solvents of the present invention include a group of solvents called hydrofluorocarbons, a group of solvents called perfluoroalkanes, and a group of solvents called chlorofluoroalkanes 1, 1, 1,-. A group of solvents called a chlorinated solvent represented by trichloroethane and a group of hydrocarbons can be used. Among these solvents, the use of hydrofluorocarbon is recommended from the viewpoints of excellent electrical insulation, non-combustibility, low toxicity, and environmental impact.
Preferably, the hydrofluorocarbon is a solvent selected from methoxyperfluoroalkane or ethoxyperfluoroalkane, which is a kind of hydrofluorocarbon.

[0015] Such solvents exhibit moderate vapor pressure and more complete non-combustibility under the proper conditions of use of the detergent, and also have better ozone layer protection when released to the atmosphere. And so on. However, the solvent used as the non-polar solvent is not limited to hydrofluorocarbon.

The polar solvent of the present invention is a solvent that is compatible with water at an arbitrary ratio, and is typified by an aprotic solvent such as dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, propylene carbonate, or ethyl cellosolve. Ethylene glycol ether-based or propylene glycol ether-based solvents or their methyl esters, ethyl esters, butyl esters,
Methyl ester, ethyl ester, butyl ester of hydroxycarboxylic acid represented by lactate ester and the like can be used. Among such polar solvents, aprotic such as dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, propylene carbonate, γ-butyrolactone, and the like, which have excellent solubilizing ability with respect to contaminants to be washed with the complexing agent of the present invention. The use of solvents is recommended. In the present invention, it does not prevent the use of a polar solvent generally used for a cleaning agent such as alcohols and limonene as a part of the polar solvent.

The soluble complexing agent of the present invention generally has the property of a complexing agent for metal ions, and includes moethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and the like.
Triisopropanolamine, amino alcohol represented by quadrol or a derivative thereof, or ethylenediamine, diethylenetriamine, polyamine represented by triethylenetetramine or a derivative thereof,
Or benzotriazoles or derivatives thereof, or imidazoles or derivatives thereof, or α-amino acids such as glycine, aminocarboxylic acids represented by iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid or derivatives thereof, or glycolic acid, tartaric acid, or citric acid Or a hydroxycarboxylic acid represented by a derivative thereof.

[0018] Among such complexing agents, a property of remarkably promoting the action of solubilizing relatively polar contaminants in a detergent,
Furthermore, the use of amino alcohols is recommended from the viewpoint of not deteriorating properties such as solubility in cleaning agents, low toxicity, and electrical resistivity of the cleaning agents, and more preferably amino alcohols having a plurality of alcohol residues in the molecule. Recommended. It is presumed that such a difference in molecular structure is related exclusively to the cohesive energy and complexing ability of the amino alcohol itself. The amino alcohol having a plurality of coordination sites in the molecule has a higher metal ion complexing ability, and at the same time, the cohesive energy density. Is assumed to be small and easily dissolved in the detergent.

The above-described cleaning composition of the present invention can maintain excellent insulating properties within the range of 0.01 to 100 MΩm, non-combustibility, and appropriate vapor pressure in an appropriate composition range. Not only can it be used as a cleaning agent for ordinary electronic parts, but it can also be used for cleaning required parts while the electronic device is kept energized or driven.

Such excellent properties are due to the high insulating properties of the cleaning composition of the present invention. Therefore, even if the cleaning composition wets the circuit in an energized state, it is unlikely that a short circuit will occur. This is possible because it is difficult to ignite and burn due to a typical spark, and it is difficult to fill a relatively narrow space in the electronic device with steam.

As described above, from another viewpoint, the present invention can be defined as a detergent composition in which a metal ion complexing agent is dissolved in hydrofluorocarbon. Although it is possible to define an electronic device as a cleaning agent that can be cleaned in an energized state using an object, the above definition does not unduly limit the scope of the present invention.

The present invention provides a cleaning composition having excellent insulating properties and cleaning ability. By using the cleaning composition of the present invention, it is difficult to clean such as caused by denatured residual flux components. A contaminant represented by an insulating organic film can be efficiently cleaned, and the cleaning operation can be performed without causing a malfunction of the electronic device while the electronic device is kept energized or driven.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described in detail with reference to the drawings.

Since the cleaning composition of this example is required to have a high insulation resistance and a high cleaning ability, a common criterion was set for each item.

(1) Electrical Insulation The insulation resistance characteristics of the detergent composition are measured using a well-known electric conductivity meter. As one example, the measured value exceeding about 0.1 MΩm is good. (○), 0.05MΩm
Those exceeding を were judged as good (△), and those less than 0.055 MΩm were judged as bad (不良).

The cleaning composition which has passed the above-mentioned criterion can be used for cleaning the plugs and connectors to which a voltage of about 10 V is applied, for example, when the electronic device is energized or driven. Has a resistance exceeding at least 100 kΩ, so that the cleaning operation can be performed without causing malfunction of the electronic device.

(2) Cleaning Ability A completed board obtained by soldering electronic components and the like to a printed circuit board on which an electronic circuit is formed by using a solder flux that is commonly used is allowed to stand, for example, in a normal atmosphere for about 6 months. . As a result, a 0.1 to 2 μm thick insulative organic film was formed on the gold-plated plug, in which the denatured residual flux component contained copper ions derived from the printed circuit board. A cleaning test was performed on the flux residue.

The criterion for determining the cleaning ability is, for example, that the film-like residue firmly adhered to the gold-plated plug is completely dissolved by immersion in a cleaning agent at room temperature for 10 minutes. Good (○), the one in which the residue was completely dissolved after immersion for 30 minutes was slightly good (△), and the one in which the residue was not completely dissolved even after immersion for 30 minutes was poor (×).

(First Embodiment) A first embodiment will be described in detail with reference to Table 1.

As the cleaning composition of this example, methoxyperfluorobutane (C ₄ F ₉ OCH ₃ ) was used as the nonpolar solvent, N-methylpyrrolidone was used as the polar solvent, and triethanolamine was used as the soluble complexing agent. Regarding the electrical insulation and cleaning ability of the cleaning agents, the results when their compositions were changed are shown in Table 1.
No. No. 1 to No. The results are shown in FIG. As a result, the cleaning composition contains 20 wt% or less, preferably 10 wt%, of the polar solvent.
% Or less, both electrical insulation and cleaning ability are good.
In such a composition range, the nonflammability as a detergent was also good.

Further, as the cleaning composition of this example, the non-polar solvent was methoxyperfluorobutane (C ₄ F ₉ OCH ₃ ), the polar solvent was N-methylpyrrolidone, and the soluble complexing agent was quadrol. The results are shown in Table 1. 5 to No. 8. As a result, in such a cleaning agent, 20
At less than 10 wt%, preferably less than 10 wt%, both electrical insulation and cleaning ability were good, and in such a composition range, nonflammability as a cleaning agent was also good.

[0032]

[Table 1]

When the composition of methoxyperfluorobutane and N-methylpyrrolidone was changed in a detergent containing 1 wt% of quadrol, the electrical resistivity of the detergent was N-, a polar solvent, as shown in FIG. The smaller the amount of methylpyrrolidone added, the larger the tendency. Then, the ratio of the polar solvent is 20 wt% or less, preferably 10 wt% or less.
It is possible to secure good electrical insulation at less than wt%.

(Second Embodiment) A second embodiment will be described in detail with reference to Table 2.

As the cleaning composition of this example, ethoxyperfluorobutane (C ₄ F ₉ OC ₂ H ₅ ) was used as the nonpolar solvent, N-methylpyrrolidone was used as the polar solvent, and triethanolamine was used as the soluble complexing agent. . The performance of the cleaning agent of this example was evaluated using the same method as that described in the first example,
The results are shown in Table 2. No. 1 to No. Example 6 In such a detergent, when the soluble complexing agent contained 20 wt% or less, and preferably 10 wt% or less, both the electrical insulating property and the cleaning ability were good, and in such a composition range, the nonflammability as the detergent was also good.

Further, as the cleaning composition of this example, the results obtained when ethoxyperfluorobutane was used as the non-polar solvent, dimethyl sulfoxide was used as the polar solvent, and quadrol was used as the soluble complexing agent are shown in Table 2. 7 is shown. As a result, the cleaning agent of the present composition has an electrical insulating property regardless of the type of the polar solvent,
It was found that the cleaning ability was good.

[0037]

[Table 2]

(Third Embodiment) A third embodiment will be described in detail with reference to Table 3.

As the cleaning composition of this example, the nonpolar solvent was a naphthenic hydrocarbon, the polar solvent was N-methylpyrrolidone, and the soluble complexing agent was monoethanolamine or quadrol. The results of evaluation of the performance of the cleaning agent at this time, that is, the electrical insulating property and the cleaning ability, using the same method as in the first embodiment, are shown in Table 3. No. 1 to No. 2 is shown. With such a cleaning agent, both the electrical insulation properties and the cleaning ability were good, and it was found that the desired effects of the present example could be obtained.

By the way, in the cleaning agent having the composition according to the present embodiment, the non-polar solvent is more flammable than the first or second embodiment. However, the effect of removing contaminants, which is the object of this embodiment, is not lost, and the present embodiment exhibits sufficient performance in a normal cleaning operation in a non-energized state.

Further, as the cleaning composition of this example, the non-polar solvent was perfluorooctane (C ₈ F ₁₈ ) and the polar solvent was N
-Methylpyrrolidone, the washing results when the soluble complexing agent was monoethanolamine or quadrol are shown in Table 3.
No. No. 3 to No. The results are shown in FIG. As a result, it was found that both the electrical insulation properties and the cleaning ability were good, and the desired effects of this example could be obtained.

From these results, it was found that the cleaning agent shown in this example had good electric insulation and good detergency regardless of the type of nonpolar solvent.

[0043]

[Table 3]

[0044]

According to the present invention, there is provided a detergent composition having excellent electrical insulation and cleaning ability, and is effective in removing contaminants typified by an insulating organic film resulting from denaturation of residual flux components. The cleaning and maintenance work can be performed as it is, without causing malfunction of electronic components or electronic devices in the energized or driven state.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a relationship between a composition of a cleaning composition and an electric resistivity in a first embodiment.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 7/34 C11D 7/34 17/00 17/00 H01L 21/304 647 H01L 21/304 647A H05K 3 / 26 H05K 3/26 E (72) Inventor Masaaki Okunaka 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa Prefecture Inside the Hitachi, Ltd.Production Technology Laboratory (72) Inventor Fumio Kataoka 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa Inside Hitachi, Ltd. Production Technology Research Laboratories (72) Inventor Kazufumi Higashi 2880 Kozu, Kodahara-shi, Kanagawa Prefecture Inside Hitachi Storage Systems Division (72) Inventor Kazunari Kano 2880 Kozu, Kodahara-shi, Kanagawa Prefecture F term in Hitachi Storage Systems Division (reference) 3B201 AA46 BB92 BB95 CC21 4H003 B A12 DA15 DB01 EB08 EB13 EB14 ED26 ED31 ED32 FA15 FA48 5E343 CC23 EE02 GG11

Claims (16)

[Claims] 1. A cleaning composition comprising a non-polar solvent, a polar solvent, and a soluble complexing agent. 2. The non-polar solvent is a hydrofluorocarbon, the polar solvent is a solvent compatible with water at an arbitrary ratio, and the soluble complexing agent is at least an amino alcohol or a polyamine, an aminocarboxylic acid or a hydroxycarboxylic acid. The cleaning composition according to claim 1, which is an acid. 3. The hydrofluorocarbon having a carbon number of 3
Or the polar solvent is an aprotic solvent, and each of the amino alcohol, polyamine, aminocarboxylic acid, or hydroxycarboxylic acid has at least a plurality of alcohol residues in its molecule, an amino group, The cleaning composition according to claim 2, wherein the cleaning composition contains either a carboxylic acid residue or a hydroxyl group. 4. The solvent according to claim 1, wherein the hydrofluorocarbon is a solvent selected from methoxyperfluoroalkane or ethoxyperfluoroalkane, and the aprotic solvent is a solvent selected from dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, or propylene carbonate. Wherein the amino alcohol is monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine,
4. The cleaning composition according to claim 3, wherein the composition is a polyhydric amino alcohol selected from triisopropanolamine, quadrol and derivatives thereof. 5. The method according to claim 1, wherein the hydrofluorocarbon is 80 to 1
The cleaning composition according to any one of claims 2 to 4, wherein the composition comprises less than 00% by weight, the polar solvent comprises 0 to less than 20% by weight, and the amino alcohol comprises 0.01 to 20% by weight. 6. The method according to claim 1, wherein the hydrofluorocarbon is 90 to 9%.
Less than 5% by weight, the polar solvent is less than 5 to 10% by weight,
The cleaning composition according to any one of claims 2 to 4, wherein the amino alcohol comprises 0.1 to 5% by weight. 7. A hydrofluorocarbon containing at least any of 4 to 10 carbon atoms in an amount of from 80 to less than 100% by weight, based on at least one of dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, propylene carbonate, and γ-butyrolactone. A cleaning composition comprising: 0 to less than 20% by weight of a selected solvent; and 0.01 to 20% by weight of at least one of triethanolamine, triisopropanolamine, and quadrol. 8. A hydrofluorocarbon containing at least any of 4 to 10 carbon atoms in an amount of from 90 to less than 95% by weight and at least one of dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, propylene carbonate, and γ-butyrolactone. A cleaning composition comprising: 5 to less than 10% by weight of a selected solvent; and 0.1 to 5% by weight of at least one of triethanolamine, triisopropanolamine, and quadrol. 9. The cleaning composition according to claim 1, wherein the electrical resistivity of the cleaning composition is at least in the range of 0.1 to 10 MΩm. 10. A method for cleaning an electronic component or an electronic device comprising an electronic circuit board, a terminal part of the electronic circuit board, and a fitting part for fitting the terminal part, wherein at least the terminal part is provided. A cleaning method, wherein the fitting portion is cleaned using the cleaning composition according to any one of claims 1 to 9. 11. The cleaning method according to claim 10, wherein at least the terminal portion or the fitting portion is cleaned while the electronic component or the electronic device is in an energized state. 12. A method for cleaning an electronic circuit board, an electronic component, or an electronic device provided with a solder joint, wherein the flux residue remaining in the solder joint is removed.
A cleaning method characterized by using the cleaning composition according to any one of the above. 13. A method for maintaining an electronic component or an electronic device comprising an electronic circuit board, a terminal portion of the electronic circuit board, and a fitting portion for fitting the terminal portion, wherein at least the terminal portion is provided. Alternatively, a maintenance method, wherein the fitting portion is cleaned using the cleaning composition according to any one of claims 1 to 9. 14. The maintenance method according to claim 13, wherein at least the terminal portion or the fitting portion is cleaned while the electronic component or the electronic device is in an energized state. 15. A detergent composition comprising a metal ion complexing agent dissolved in hydrofluorocarbon. 16. A method for cleaning an electronic component or an electronic device comprising an electronic circuit board, a terminal portion of the electronic circuit board, and a fitting portion for fitting the terminal portion, the method comprising: A cleaning method, wherein at least the terminal portion or the fitting portion is cleaned using the cleaning composition according to claim 15, while the electronic device is kept energized.