JP3366955B2 - Detergent composition for hybrid integrated circuits - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning composition for a hybrid integrated circuit (hereinafter also referred to as "H-IC"), and more specifically, a cleaning composition for cleaning a flux residue attached to or remaining on the H-IC. It relates to a composition.

[0002]

2. Description of the Related Art Conventional H
As a cleaning agent for IC cleaning, a halogenated hydrocarbon solvent such as CFC-113 (including an alcohol compound) or 1,1,1-trichloroethane has been widely used.
Further, alcohols, ketones, hydrocarbon solvents or semi-aqueous detergents have also been used.

However, the above-mentioned halogenated hydrocarbon solvents such as CFC-113 and 1,1,1-trichloroethane have been severely reduced in use as substances causing destruction of the ozone layer, and are severely restricted in future use. There was a situation.

Alcohols, ketones or hydrocarbon solvents are not ozone-depleting substances, but are inferior in cleanability to the contaminants adhering to the material, and have low flammability in the case of alcohols and ketones. Because of this, we had to make a large capital investment in safety.

In addition, many of the semi-aqueous detergents widely used as the detergents for the above-mentioned purpose show a detergency of a practical level, but H due to the organic acid component contained in the flux residue and the constituent moisture. -There were problems such as a remarkable change in elution of the lead glass portion of the IC.

As a result, some of the semi-aqueous detergents suppress the remarkable elution change to the lead-glass part constituting the H-IC, but the ratio of the anionic surfactant as the elution inhibitor is compared. However, there is still concern about the electrical properties of the material when it remains, and it has been desired to suppress the addition ratio of this surfactant.

[0007]

SUMMARY OF THE INVENTION The present invention has been made by paying attention to such conventional problems. That is, the cleaning composition for a hybrid integrated circuit according to claim 1 is a perfluoroalkyl phosphate ester-based anionic surfactant.
01 to 1.0% by weight (hereinafter, simply referred to as “%”), a water-soluble glycol ether represented by the following general formula (1),
Water-soluble glycol ether represented by the following general formula (2): 75 to 90% in total, HLB: 13 to 18 polyoxyalkylene alkyl ether type nonionic surfactant 5-1
0% and the balance is water. ^{_{R 1 O- (CH 2 CH 2}} O) 2 -H ...... (1) ( wherein, ^{R 1} represents an alkyl group having 1 to 4 carbon ^{_{atoms) R 2 O- (CH 2 CH}} 2 O) 2 -R 3 (2) (In the formula, R ² and R ³ are each independently an alkyl group having 1 to 2 carbon atoms).

In the component (B), the proportion of the water-soluble glycol ether represented by the general formula (2) is preferably 15% or more.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Components (A) to (C) and other components will be described below.

Component (A) As the perfluoroalkyl phosphate ester-based anionic surfactant, monoperfluoroalkyl (having 6 to 6 carbon atoms) is used.
16) Ethyl phosphate ester can be exemplified, and specific examples thereof include Megafac F-191 (manufactured by Dainippon Ink and Chemicals, Inc.) and Surflon S-112 (manufactured by Asahi Glass Co., Ltd.).

The amount of the perfluoroalkyl phosphate ester-based surfactant added is 0.01 in the detergent composition.
The effect is recognized in the low concentration range of up to 1.0%.

If the above-mentioned addition amount is less than 0.01%, the lead elution suppressing effect is low, and if it exceeds 1.0%, there is a suppressing effect, but the residue when water rinse is insufficient deteriorates the electrical characteristics. This phenomenon is not desirable because it is seen.

Other examples of the phosphoric acid ester-based surfactant include polyoxyalkylene alkyl phosphoric acid ester-based anionic surfactants and the like, which exhibit the same effect as the perfluoroalkyl phosphoric acid ester-based surfactant. In order to do so, a large amount of absolute addition is required, so a great deal of labor is required for removal after the washing step, the effect on the next step when remaining and electrical characteristics, or foaming trouble caused by the addition of the relevant surfactant. Occurs, which is not preferable for practical use.

Component (B) The component (B) of the present invention is composed of at least one selected from the following (1) and at least one selected from the following (2).

[0015] (1) Diethylene glycol monomethyl ether Diethylene glycol monoethyl ether Diethylene glycol mononormal propyl ether Diethylene glycol monoisopropyl ether Diethylene glycol mono-n-butyl ether Diethylene glycol monoisobutyl ether (2) Diethylene glycol dimethyl ether Diethylene glycol ethyl methyl ether Diethylene glycol diethyl ether.

The blending ratio of the component (B) is 75 to 90% in total of the above (1) and (2). If it is less than 75%, the cleaning effect is poor.

The glycol diether (2) is preferably contained in the component (B) in an amount of 15% or more from the viewpoint of cleaning performance. A more preferable content ratio is 30 to 80%.
Is.

Monoethylene glycol monoalkyl ether has a very low flash point and is not preferable from the viewpoint of handling safety, and triethylene glycol monoalkyl ether does not exert a cleaning effect, and any of them uses the component (B) in the present invention. Is not preferable.

Further, monoethylene glycol dialkyl ether has a low flash point, and triethylene glycol dialkyl ether is not preferable because the cleaning effect is not exerted. Therefore, both are not preferable as the component (B) in the present invention. .

As the component (C) polyoxyalkylene alkyl ether type nonionic surfactant, one or more ethylene or propylene oxide adducts of a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, further, Include mixed adducts thereof. HLB is 13-18.
When the HLB is less than 13 or more than 18, the redeposition inhibiting function is inferior.

The mixing ratio is 5 to 1 in the detergent composition.
It is 0%. If it is less than 5%, the redeposition control is poor,
If it exceeds 10%, the cleaning effect is poor.

Others The quality of the water is preferably distilled water, ion-exchanged water, pure water or ultrapure water. The mixing ratio of water is not particularly limited, but is preferably 4 to 15%. If it is less than 4%, flammability may be exhibited, and if it exceeds 15%,
There is a possibility that the cleanability will be significantly reduced. The above components (A) to (C) and water are mixed in respective mixing ratios to bring the total amount to 100.

The composition of the present invention is a cleaning agent for a hybrid integrated circuit and is used in a stock solution by immersion or ultrasonic cleaning, optionally in a submerged jet or an air spray cleaning apparatus, and after reaching the purpose of cleaning. Is removed together with the flux residue, which is a substance to be polluted, in a water rinsing device or tank in the next step, and the operation is completed through a drying step.

The cleaning composition for a hybrid integrated circuit of the present invention having the above-mentioned constitution has the following functions (A) to (D). That is, (A) the solubility function of the flux residue of the water-soluble glycol ether, which is the main cleaning agent, (B) the function of suppressing the flux residue redeposition in the rinsing step by the polyoxyalkylene alkyl ether type nonionic surfactant (C) limited to a small amount The perfluoroalkyl phosphate ester anionic surfactant has a function of suppressing the elution of lead in the H-IC component lead glass part (D) a function of suppressing flammability by controlling water content.

[0025]

EXAMPLES Examples 1 to 5 and Comparative Examples 1 to 11 The components shown in the following [Table 1] and [Table 2] were mixed and adjusted in the ratios shown in the table to obtain a cleaning composition. It was

[0026]

[Table 1] .

[0027]

[Table 2] .

For each of the resulting detergent compositions,
The following tests were conducted. The results are shown in [Table 3].

(Cleaning effect test of model hybrid integrated circuit) A model hybrid integrated circuit material composed of lead glass was immersed in a stock solution of various detergent compositions heated to 60 ° C.
KHz / 600W ultrasonic cleaning was performed for 15 minutes. Then, after performing ultrasonic rinsing with pure water at 40 ° C. twice,
After the drying operation, the amount of residual flux was measured by an ultraviolet spectrophotometric method to evaluate the cleaning property. The evaluation was made according to the following criteria. ◎ Remaining flux amount less than 3 μg / cm ² ○ Remaining flux amount 3 or more and less than 5 μg / cm ² Δ Remaining flux amount 5 or more and less than 10 μg / cm ² × Remaining flux amount 10 μg or more / cm ² .

(Readhesion Inhibition Effect Test of Model Hybrid Integrated Circuit) 5% of flux to be cleaned is added to stock solutions of various cleaning compositions heated to 60 ° C. to prepare a deteriorated cleaning solution model. Then, the deteriorated cleaning liquid is added at a ratio of 5% to
A model rinsing solution was prepared by adding it to a 0 ° C. pure water rinsing tank, and the model hybrid integrated circuit material (not contaminated with flux) was washed in the same manner as in Experimental Example 1, and the amount of reattached flux was measured by infrared spectrophotometry. It was measured by the method and the redeposition inhibition property was evaluated. The evaluation was made according to the following criteria. ◎ Redeposition flux amount less than 0.1 μg / cm ² ○ Reattachment flux amount 0.1 or more and less than 0.3 μg / cm ² △ Reattachment flux amount 0.3 or more and less than 0.5 μg / cm ² × Reattachment flux amount 0 0.5 μg or more / cm ² .

(Discoloration Suppression Effect Test of Model Hybrid Integrated Circuit) A model hybrid integrated circuit made of lead glass by adding 5% of flux to be cleaned to undiluted solutions of various cleaning compositions heated to 60 ° C. The material was soaked for 12 hours. 40
After rinsing with pure water at ℃ for 5 minutes, it was dried at 80 ℃ for 10 minutes, and the discoloration inhibiting property was visually evaluated. The evaluation was judged according to the following criteria. ◎ No change in appearance color tone ○ Slight change in color tone is observed △ Change in color tone is observed × Significant change in color tone is observed

(Lead Elution Suppression Effect Test of Model Hybrid Integrated Circuit) 5% flux to be cleaned is added to undiluted solution of various cleaning compositions heated to 60 ° C. The integrated circuit material was soaked for 24 hours. After taking out the model hybrid integrated circuit material, the amount of eluted lead ions in the cleaning solution was measured by using the plasma spectrophotometric method, and the lead elution inhibitory property was evaluated. The evaluation was judged according to the following criteria. ◎ Less than 50 μg / elution amount of one H-IC material ○ 50 or more and less than 100 μg / elution amount of one H-IC material △ 100 or more and less than 1000 μg / elution amount of one H-IC material × 1000 μg or more / H-IC Elution amount of one material.

(Inhibitor Remaining Test on Model Hybrid Integrated Circuit) After performing the same washing operation as in Experimental Example 1, the model hybrid integrated circuit material was immersed in hot water at 80 ° C. for 2 hours. afterwards,
After pressure decomposing this solution with potassium peroxodisulfate,
The residual phosphate ion was analyzed by the ion chromatography method to evaluate the water rinsability. The evaluation was based on the following criteria. ◎ Residual phosphate ion amount less than 5 μg / one part ○ Residual phosphate ion amount 5 or more and less than 25 μg / one part △ Residual phosphate ion amount 25 or more and less than 50 μg / one part × Residual phosphate ion amount 50 μg or more / part 1 piece.

[0034]

[Table 3] As can be seen from [Table 3], only the cleaning composition of the present invention exhibits a well-balanced cleaning effect.

[0035]

EFFECT OF THE INVENTION The cleaning composition of the present invention is excellent in cleaning the flux residue adhering to the hybrid integrated circuit, and re-adhesion is suppressed even in an actual cleaning line, so that a stable cleaning effect is exhibited. .

Further, since it does not cause a change in appearance or physical change with respect to the material (object to be cleaned), safe cleaning and residual substances are suppressed, high cleaning reliability can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI H05K 3/26 H05K 3/26 E // (C11D 10/02 C11D 1:34 1:34 1:68 1:68 3:20 3:20) (72) Inventor Kazuo Nakano 7-5, Hishidayamanoshita, Seika-cho, Soraku-gun, Kyoto Prefecture (72) Inventor Shinkichi Obayashi 1-1-1, Showa-cho, Kariya city, Aichi Prefecture (72) Inventor Suzuki Yasuhiko, 1-1, Showa-cho, Kariya city, Aichi Prefecture, Nihon Denso Co., Ltd. (72) Inventor, Yasuhide Sonoda 1-1, Showa-cho, Kariya city, Aichi prefecture, Nihon Denso Co., Ltd. (56) 57899 (JP, A) JP 7-97596 (JP, A) JP 4-306297 (JP, A) JP 7-48599 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C23G 5/032 C23G 5/028 C11D 17/08 C11D 10/02 C11D 1:34 C11D 1:68 C11D 3:20

Claims (2)

(57) [Claims] 1. (A) 0.01 to 1.0% by weight of a perfluoroalkyl phosphate-based anionic surfactant; (B) a water-soluble glycol ether represented by the following general formula (1); A total of 75 to 90% by weight of the water-soluble glycol ether represented by the formula (2), (C) 5 to 10% by weight of a polyoxyalkylene alkyl ether type nonionic surfactant of HLB 13 to 18, and the balance being water. A cleaning composition for a hybrid integrated circuit, comprising: ^{_{R 1 O- (CH 2 CH 2}} O) 2 -H ...... (1) ( In the formula, ^{R 1} is an alkyl group having 1 to 4 carbon ^{_{atoms.) R 2 O- (CH 2}} CH 2 O) 2 -R ³ ...... (2) ^(wherein, the R 2, ^{R 3} is .R ² and ^{R 3} is an alkyl group having 1 to 2 carbon atoms, may be the same or may be different from one another.) 2. The cleaning for a hybrid integrated circuit according to claim 1, wherein the content of the water-soluble glycol ether represented by the general formula (2) in the component (B) is 15% by weight or more. Agent composition.