KR102335365B1 - Removing agent for rust-preventive film - Google Patents

Abstract

<task>
It is to provide the removal agent for rust preventive films which can remove the rust preventive film which consists of a nitrogen-containing heterocyclic compound which has two or more nitrogen atoms in a short time.
<Solutions>
Rust prevention comprising an alkanolamine (A) represented by the general formula (1), a glycol ether solvent (B), and a nitrogen-containing heterocyclic compound having two or more nitrogen atoms containing an organic carboxylic acid and/or a salt (C) thereof membrane remover.
R ¹ -(NHCH ₂ CH ₂ ) _n -OH ... (1)
(In formula (1), R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 2)

Description

Remover for rust prevention film {REMOVING AGENT FOR RUST-PREVENTIVE FILM}

This invention relates to the removal agent for rust prevention films, especially the removal agent for rust prevention films which consists of a nitrogen-containing heterocyclic compound which has 2 or more nitrogen atoms.

For the purpose of rust prevention of metal surfaces, imidazoles or nitrogen-containing heterocyclic compounds having two or more nitrogen atoms, such as triazole and benzotriazole, are conventionally used as rust inhibitors. In particular, these rust preventives are generally used in copper bumps, such as printed wiring boards or interposers, through holes, alignment marks, identification number parts, etc., and the formed rust preventive film is chelated with copper. By doing so, it protects the hibernation and has a high anti-rust effect.

However, the rust preventive film may deteriorate after application to the copper surface or be colored due to exposure to heat in the solder bonding process. In particular, when an alignment mark or an identification number portion is colored, there are cases in which the substrate is not recognized by the sensor of the manufacturing apparatus, and problems such as not being able to perform alignment may occur.

In order to solve the above problems, as a technique for removing the rust preventive film, for example, a method of removing the complex film on the surface of copper and copper alloy using a quaternary ammonium hydroxide solution is known, but the present invention is a fine wiring forming technique It is useful in the manufacturing of high-tech electronic components required, but since the rust-preventing film is completely removed, the hibernation is discolored again in a short period of time.

Japanese Patent Laid-Open No. 2002-097587

The subject of this invention is providing the removal agent for rust preventive films which can remove the rust preventive film which consists of a nitrogen-containing heterocyclic compound which has two or more nitrogen atoms in a short time.

As a result of earnest examination, this inventor discovered that the remover for rust preventive films containing a specific alkanolamine, a glycol ether solvent, and organic carboxylic acid solves the subject in the said rust preventive film, and came to complete this invention. That is, this invention relates to the following removal agents for rust preventive films.

1. A nitrogen-containing heterocyclic compound having two or more nitrogen atoms comprising an alkanolamine (A) represented by the general formula (1), a glycol ether solvent (B), and an organic carboxylic acid and/or a salt (C) thereof A remover for an anti-rust film.

R ¹ -(NHCH ₂ CH ₂ ) _n -OH ... (1)

(In formula (1), R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 2)

2. The preceding paragraph, wherein the component (A) contains at least one selected from the group consisting of N-methylethanolamine, N-ethylethanolamine, N-n-butylethanolamine and N-(2-aminoethyl)ethanolamine. 1. Rust-preventive film remover.

3. (B) The anti-rust film removal agent of the preceding paragraph 1 or 2 in which a component is represented by General formula (2).

R ² -(OCH ₂ CHX) _m -OH ... (2)

(In formula (2), R ² is an alkyl group having 1 to 4 carbon atoms, X is hydrogen or a methyl group, and m is an integer of 1 to 3)

4. (C) The remover for rust preventive films in any one of the preceding paragraphs 1-3 in which a component contains at least 1 sort(s) chosen from the group which consists of organic monocarboxylic acid, organic dicarboxylic acid, organic tricarboxylic acid, and these salts.

5. (A) The removal agent for rust prevention films in any one of the preceding paragraphs 1-4 in which component further contains N-alkyldiethanolamine.

6. The removal agent for rust preventive films in any one of the preceding paragraphs 1-5 whose content rate in a remover is 1 to 20 weight% of (A) component, 75 to 98.5 weight% of (B) component, and 0.1 to 5 weight% of (C) component.

7. The rust preventive film remover according to any one of the preceding items 1 to 6, which removes the rust preventive film formed on the alignment mark and/or the identification number printed on the substrate.

According to the remover for a rust preventive film of the present invention, the rust preventive film formed on the substrate formed of a nitrogen-containing heterocyclic compound having two or more nitrogen atoms can be removed in a short time, but it is not completely removed, but the film thickness of the rust preventive film is left about several tens of nm Therefore, the rust prevention effect is maintained.

The rust preventive film removal agent (hereinafter also simply referred to as "rust preventive film remover") comprising a nitrogen-containing heterocyclic compound having two or more nitrogen atoms of the present invention is an alkanolamine (A) represented by the general formula (1) (hereinafter ( A) component), glycol ether solvent (B) (hereinafter referred to as (B) component), and organic carboxylic acid and/or its salt (C) (hereinafter referred to as (C) component) are contained.

(A) As a component, what is represented by Formula (1) is a component required in order to remove a rust preventive film in a short time.

R ¹ -(NHCH ₂ CH ₂ ) _n -OH ... (1)

(In formula (1), R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 2)

As what is represented by Formula (1), monoethanolamine, N-methylethanolamine, N-ethylethanolamine, N-n-propylethanolamine, N-isopropylethanolamine, N-n-butylethanolamine, for example. amine, N-isobutylethanolamine, N-sec-butylethanolamine, N-tert-butylethanolamine, N-(2-aminoethyl)ethanolamine, etc. are mentioned, These are independent, and they combine 2 or more types. good to do Among these, the point of the rinse property of a removal agent to N-methylethanolamine, N-ethylethanolamine, N-n-butylethanolamine, or N-(2-aminoethyl) ethanolamine is preferable.

Although the weight ratio of (A) component in the remover for rust preventive films of this invention is not specifically limited, From the balance of the rinse property of a remover and a removal effect, in conversion of solid content, normally about 1-20 weight%, Preferably is about 1 to 15% by weight, more preferably about 1 to 10% by weight.

(B) It does not specifically limit as a component, Although various well-known things can be used, For example, the thing represented by following formula (2), etc. are mentioned.

R ² -(OCH ₂ CHX) _m -OH ... (2)

(In formula (2), R ² is an alkyl group having 1 to 4 carbon atoms, X is hydrogen or a methyl group, and m is an integer of 1 to 3)

As a thing represented by Formula (2), the following are mentioned as a value of m, respectively.

As m=1, methyl glycol, ethyl glycol, n-propyl glycol, isopropyl glycol, n-butyl glycol, isobutyl glycol, sec-butyl glycol, tert-butyl glycol, methyl propylene glycol, ethyl propylene glycol, n- propyl propylene Glycol, isopropyl propylene glycol, n-butyl propylene glycol, isobutyl propylene glycol, sec- butyl propylene glycol, tert- butyl propylene glycol, etc. are mentioned.

As m=2, methyldiglycol, ethyldiglycol, n-propyldiglycol, isopropyldiglycol, n-butyldiglycol, isobutyldiglycol, sec-butyldiglycol, tert-butyldiglycol, methylpropylenediglycol , ethylpropylene diglycol, n-propyl propylene diglycol, isopropyl propylene diglycol, n-butyl propylene diglycol, isobutyl propylene diglycol, sec-butyl propylene diglycol, tert-butyl propylene diglycol, etc. are mentioned. .

As m=3, methyltriglycol, ethyltriglycol, n-propyltriglycol, isopropyltriglycol, n-butyltriglycol, isobutyltriglycol, sec-butyltriglycol, tert-butyltriglycol, methylpropylenetriglycol , ethyl propylene triglycol, n-propyl propylene triglycol, isopropyl propylene tri glycol, n-butyl propylene tri glycol, isobutyl propylene tri glycol, sec-butyl propylene tri glycol, tert- butyl propylene tri glycol, etc. are mentioned. .

These (B) components may be individual or may combine 2 or more types. ^{Among these, it is preferable that R<2>} has a C3 or C4 alkyl group in Formula (2) from the point of the removal effect and environmental characteristic of a removal agent, n-butyl glycol, n-propyl propylene glycol, n-propyl diglycol; At least one selected from the group consisting of n-butyldiglycol and n-butyltriglycol is more preferable.

Although the weight ratio of (B) component in the remover for rust preventive films of this invention is not specifically limited, From the point of the removal effect of a remover, it is about 75 to 98.5 weight% normally in conversion of solid content, Preferably it is 80 to 97 weight%. it is about

(C) The component is not particularly limited, and various known ones can be used, for example, organic monocarboxylic acids such as formic acid, acetic acid, propionic acid, lactic acid, benzoic acid, and salicylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, Organic dicarboxylic acids such as dipic acid, sebacic acid, azelaic acid, dodecane diacid, malic acid, phthalic acid, isophthalic acid, and terephthalic acid; of organic tetracarboxylic acid. Moreover, an ammonium salt etc. are mentioned as the salt. These may be individual or may combine 2 or more types. Among these, from the viewpoint of the removal effect of the removing agent, it is preferable to contain at least one selected from the group consisting of organic monocarboxylic acids, organic dicarboxylic acids, organic tricarboxylic acids and salts thereof, formic acid, acetic acid, ammonium acetate, citric acid, It is more preferable to include at least one selected from the group consisting of succinic acid, malic acid, lactic acid, malonic acid and salicylic acid.

Although the weight ratio of (C)component in the remover for rust preventive films of this invention is not specifically limited, From the point of the removal effect of a remover, it is about 0.1 to 5 weight% normally in conversion of solid content, Preferably it is 0.1 to 4 weight%. It is about 0.1 to 3 weight% more preferably.

The removal agent for rust preventive films of this invention may further contain alkanolamines (D) (henceforth (D) component) other than (A) from the point of the rinse property of a removal agent. (D) Although it does not specifically limit as a component, For example, N-methyldiethanolamine, N-ethyldiethanolamine, N-n-propyl diethanolamine, N-isopropyl diethanolamine, N-n-butyl N-alkyldiethanolamines such as diethanolamine, N-isobutyldiethanolamine, N-sec-butyldiethanolamine and N-tert-butyldiethanolamine; N,N-dimethylethanolamine, N,N- Diethylethanolamine, N,N-di-n-propylethanolamine, N,N-diisopropylethanolamine, N,N-di-n-butylethanolamine, N,N-diisobutylethanolamine, N N,N-dialkylethanolamines such as , N-di-sec-butylethanolamine, N,N-di-tert-butylethanolamine, and N,N-di(2-aminoethyl)ethanolamine; diethanolamine and the like. These may be individual or may combine 2 or more types.

Although the weight ratio of (D)component in the remover for rust preventive films of this invention is not specifically limited, About 0.1 to 10 weight% is preferable in conversion of solid content.

The removal agent for rust preventive films of this invention may contain water as needed from a flammable point. Although the weight ratio of the water in the removal agent of this invention is not specifically limited, either, About 2 to 30 weight% is preferable.

The removal agent for rust preventive films of this invention may contain various well-known additives. It does not specifically limit as an additive, For example, a chelating agent, antioxidant, an antifoamer, a pH adjuster, an imidazole-type rust preventive agent, a triazole-type rust preventive agent, a stabilizer, a dispersing agent, surfactant, etc. are mentioned. Moreover, the usage-amount of an additive is although it does not specifically limit, either, Usually, it is less than 1 weight part with respect to 100 weight part of removal agents for rust preventive films.

The removal agent for rust preventive films of this invention is applied to the rust preventive film which consists of a nitrogen-containing heterocyclic compound which has two or more nitrogen atoms. Although it does not specifically limit as said nitrogen-containing heterocyclic compound, For example, imidazole, triazole, etc. are mentioned, These may be used individually or in combination of 2 or more types.

Although it does not specifically limit as imidazole, For example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propyl imidazole, 2-isopropyl imidazole, 2-butylimidazole Sol, 2-t-butylimidazole, 2-pentylimidazole, 2-hexylimidazole, 2-heptylimidazole, 2-(1-ethylpentyl)imidazole, 2-octylimidazole; 2-nonylimidazole, 2-decylimidazole, 2-undecylimidazole, 2-dodecylimidazole, 2-tridecylimidazole, 2-tetradecylimidazole, 2-pentadecyl Imidazole, 2-hexadecylimidazole, 2-heptadecylimidazole, 2-(1-methylpentyl)imidazole, 2-(1-ethylpentyl)imidazole, 2-(1-heptyldisyl) Imidazole, 2-(5-hexenyl)imidazole, 2-(9-octenyl)imidazole, 2-(8-heptadecenyl)imidazole, 2-(4-chlorobutyl)imidazole, 2- (9-hydroxynonyl)imidazole, 2-ethyl-4-methylimidazole, 2-undecyl-4-methylimidazole, 2-heptadecyl-4-methylimidazole, 2-phenylimida Sol, 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, etc. are mentioned.

Although it does not specifically limit as triazole, For example, 1,2,3-triazole, 1,2,4-triazole, 1-methyl-1, 2, 4-triazole, 1-ethyl-1, 2 , 4-triazole, 1-propyl-1, 2, 4-triazole, 1-isopropyl-1, 2, 4-triazole, 1-butyl-1, 2, 4-triazole, 1-methyl- 1, 2, 3-triazole, 1-ethyl-1, 2, 3-triazole, 1-propyl-1, 2, 3-triazole, 1-isopropyl-1, 2, 3-triazole, 1 -Butyl-1, 2, 3-triazole, 1-methylbenzotriazole, etc. are mentioned.

The rust preventive film remover of the present invention is not particularly limited, and for example, it can remove the rust preventive film formed on copper lands (solder bonding surfaces) such as printed circuit boards and interposers, through holes, alignment marks, identification numbers, etc. .

Although it does not specifically limit on the occasion of the process to the remover for rust preventive films of this invention, From the point of the removal effect of a remover, it is preferable to carry out for about 50-75 degreeC at temperature, and about 1 to 5 minutes for time. Thereby, it can remove to a film thickness of 50 nm or less in a short time, and also has a rust prevention effect because a rust prevention film remains thin on the board|substrate after removal. Moreover, the usage method of the said removal agent is not specifically limited, either, For example, shower, immersion, spray, ultrasonic wave etc. are mentioned.

<Example>

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples, but it goes without saying that the scope of the present invention is not limited thereto. In addition, "part" and "%" in an Example mean a weight basis unless there is particular notice.

Example One

In a 200 ml beaker, 1 part of N-methylethanolamine (hereinafter referred to as MEM), 93.7 parts of n-butyldiglycol (hereinafter referred to as BDG), 0.3 parts of citric acid, and 5 parts of water are mixed until uniform at room temperature to form a rust preventive film. A remover was prepared. A composition is shown in Table 1 (the same below).

Example 2-23, comparative example 1 to 12

With a composition as shown in Table 1, it carried out similarly to Example 1, and obtained the removers for rust preventive films, respectively.

Commercially available imidazole (trade name: Tough Ace F2 (LX), Shigoku Chemical Co., Ltd.) so that the film thickness is 300 nm on the copper plate (phosphoric acid copper plate C1220P (as stipulated in JIS H3100), dimensions: 50 mm x 50 mm x 0.5 mm). Industrial Co., Ltd. product), after immersion for a predetermined time, dehydration and drying, a copper plate for testing in which a rust-preventive film was formed was prepared. The copper plate for testing was immersed in the removal agent of Example 1 heated to 60° C., followed by ultrasonic cleaning for 1 minute. Then, it was rinsed with pure water, and the surface of the copper plate for test was dehydrated by blowing with nitrogen, and then dried under reduced pressure at room temperature. Moreover, it carried out similarly also about the removal agent of Examples 2-23 and Comparative Examples 1-12.

(removal effect)

Measure the hibernation of the copper plate for testing with ESCA (device name: PHI5000 VersaProbe II, manufactured by Ervac Pie Co., Ltd.), and etch until nitrogen atoms are no longer detected. From that time, the film thickness of the rust preventive film remaining on the hibernation of the copper plate for testing. was calculated.

(double-circle): The film thickness after treatment is less than 30 nm (etching time: within 2 minutes)

○: The film thickness after treatment is 30 nm or more and less than 60 nm (etching time: 2 to 4 minutes)

Δ: The film thickness after treatment is 60 nm or more and less than 90 nm (etching time: 4 to 6 minutes)

x: The film thickness after treatment is 90 nm or more (etching time: 6 minutes or more)

※ The amount used for each component is expressed in weight %.

The symbol in Table 1 shows the following compounds.

<(A) component>

·MEM: N-ethylethanolamine

MMA: N-methylethanolamine

EA: N-(2-aminoethyl)ethanolamine

·MBM: N-n-butylethanolamine

<(D) component>

MBD: N-n-butyldiethanolamine

MDA: N-methyldiethanolamine

<(B) component>

BDG: n-butyldiglycol

BG: n-butyl glycol

・BTG: n-butyltriglycol

PDG: n-propyldiglycol

·PFG: n-propylpropylene glycol

Claims (7)

containing an alkanolamine (A) represented by the general formula (1), a glycol ether solvent (B), and an organic carboxylic acid and/or a salt (C) thereof,
The component (A) consists of a nitrogen-containing heterocyclic compound having two or more nitrogen atoms containing at least one selected from the group consisting of N-methylethanolamine, N-ethylethanolamine and N-n-butylethanolamine. Anti-rust film remover.
R ¹ -(NHCH ₂ CH ₂ ) _n -OH ... (1)
(In formula (1), R ¹ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 2) According to claim 1,
(B) A component is represented by General formula (2), The removal agent for rust prevention films characterized by the above-mentioned.
R ² -(OCH ₂ CHX) _m -OH ... (2)
(In formula (2), R ² is an alkyl group having 1 to 4 carbon atoms, X is hydrogen or a methyl group, and m is an integer of 1 to 3) 3. The method of claim 1 or 2,
(C) A component contains at least 1 sort(s) chosen from the group which consists of organic monocarboxylic acid, organic dicarboxylic acid, organic tricarboxylic acid, and these salts, The removal agent for rust prevention films characterized by the above-mentioned. 3. The method of claim 1 or 2,
N-alkyldiethanolamine is further included, The removal agent for rust prevention films characterized by the above-mentioned. 3. The method of claim 1 or 2,
(A) to (C) The weight ratio of the component is (A) component 1 to 20% by weight, (B) component 75 to 98.5% by weight, and (C) component 0.1 to 5% by weight, the remover for a rust preventive film. 3. The method of claim 1 or 2,
A rust preventive film remover, characterized in that it removes the rust preventive film formed on the alignment mark and/or the identification number printed on the substrate. delete