KR20180092887A - Removing agent for rust-preventive film - Google Patents

Abstract

The present invention aims to provide a remover for a rust preventative film, which can remove a rust preventative film comprising a nitrogen-containing heterocyclic compound having at least two nitrogen atoms. The remover for the rust preventative film comprising the nitrogen-containing heterocyclic compound having at least two nitrogen atoms contains: alkanolamine (A) represented by general formula 1: R^1(NHCH_2CH_2)_n-OH, a glycol ether solvent (B) and an organic carboxylic acid and/or a salt thereof (C). In the 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

{REMOVING AGENT FOR RUST-PREVENTIVE FILM}

The present invention relates to a rust preventive film remover comprising a nitrogen-containing heterocyclic compound having at least two nitrogen atoms.

Conventionally, imidazoles or nitrogen-containing heterocyclic compounds having two or more nitrogen atoms such as triazole and benzotriazole have been used as rust inhibitors for the purpose of rusting metal surfaces. Particularly, these antirusting agents are commonly used on copper surfaces such as copper bumps, through holes, alignment marks, identification number parts, etc. of printed wiring boards and interposers, and the formed anti- Thereby protecting the hibernation and having high rust prevention effect.

However, the rust preventive film may be deteriorated after application to the hibernation, or may be colored due to exposure to heat in the solder jointing process. Particularly, when an alignment mark or an identification number portion is colored, the substrate may not be recognized by the sensor of the manufacturing apparatus, and alignment problems may arise.

As a technique for removing the rust preventive film to solve the above problems, for example, a method of removing a complex film on the surface of copper and copper alloy using a quaternary ammonium hydroxide solution is known, It is useful in the production of high-tech electronic components as needed, but since the anticorrosive film is completely removed, the hibernation is discolored again in a short period of time.

Japanese Patent Application Laid-Open No. 2002-097587

A problem to be solved by the present invention is to provide a rust preventive membrane remover capable of removing a rust preventive film composed of a nitrogen-containing heterocyclic compound having two or more nitrogen atoms in a short time.

The present inventors have intensively studied and found that a specific alkanolamine, a glycol ether solvent, and a rust preventive film-containing remover containing an organic carboxylic acid solve the problems in the rustproof film, thereby completing the present invention. That is, the present invention relates to the following anti-rust film removing agent.

1. A nitrogen-containing heterocyclic compound having two or more nitrogen atoms, which comprises an alkanolamine (A) represented by the general formula (1), a glycol ether solvent (B), and an organic carboxylic acid and / And

R ¹ - (NHCH ₂ CH ₂ ) _n -OH (1)

(In the 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 method according to item 1, wherein the component (A) comprises at least one member selected from the group consisting of N-methylethanolamine, N-ethylethanolamine, N-n-butylethanolamine and N- 1 < / RTI >

3. The remover for rust-preventive membrane according to item 1 or 2, wherein the component (B) is represented by the general formula (2).

R ² - (OCH ₂ CHX) _m -OH (2)

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

4. The remover for the rust inhibitor film according to any one of items 1 to 3, wherein the component (C) comprises at least one member selected from the group consisting of an organic monocarboxylic acid, an organic dicarboxylic acid, an organic tricarboxylic acid and salts thereof.

5. The remover for a rust inhibitor film according to any one of items 1 to 4, wherein the component (A) further comprises N-alkyldiethanolamine.

6. The remover for a rust inhibitor film according to any one of items 1 to 5, wherein the content in the remover is from 1 to 20% by weight of the component (A), from 75 to 98.5% by weight of the component (B) and from 0.1 to 5% by weight of the component (C).

7. A remover for a rust-preventive film according to any one of items 1 to 6, wherein the rust-inhibitive film formed on the alignment mark and / or identification number portion printed on the substrate is removed.

According to the removal agent for a rust preventive film of the present invention, a rust preventive film formed of a nitrogen-containing heterocyclic compound having two or more nitrogen atoms and formed on a substrate can be removed in a short period of time, but not completely removed but the film thickness of the rust- Therefore, the rust prevention effect is also maintained.

The rust preventive film remover comprising a nitrogen-containing heterocyclic compound having two or more nitrogen atoms of the present invention (hereinafter briefly referred to as " rust-inhibiting film remover ") comprises an alkanolamine (A) represented by the general formula (1) (Hereinafter referred to as component (A)), a glycol ether solvent (B) (hereinafter referred to as component (B)), and an organic carboxylic acid and / or salt thereof (hereinafter referred to as component (C)).

As the component (A), the component represented by the formula (1) is a component necessary for removing the anticorrosive film in a short time.

R ¹ - (NHCH ₂ CH ₂ ) _n -OH (1)

(In the 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)

Examples of the compound represented by the formula (1) include monoethanolamine, N-methylethanolamine, N-ethylethanolamine, N-n-propylethanolamine, N-isopropylethanolamine, N- Amine, N-isobutylethanolamine, N-sec-butylethanolamine, N-tert-butylethanolamine, N- (2-aminoethyl) ethanolamine and the like. Maybe. Of these, N-methylethanolamine, N-ethylethanolamine, N-n-butylethanolamine or N- (2-aminoethyl) ethanolamine are preferable in view of the rinsability of the removing agent.

The weight ratio of the component (A) in the removing agent for a rust preventive film of the present invention is not particularly limited, but it is usually from 1 to 20% by weight in terms of solid content from the balance of the rinsing property and the removing effect of the removing agent Is about 1 to 15% by weight, and more preferably about 1 to 10% by weight.

The component (B) is not particularly limited and various known compounds can be used. Examples thereof include those represented by the following formula (2).

R ² - (OCH ₂ CHX) _m -OH (2)

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

As the value represented by the formula (2), the following values are respectively listed as m.

Examples of m = 1 include methyl glycol, ethyl glycol, n-propyl glycol, isopropyl glycol, n-butyl glycol, isobutyl glycol, sec-butyl glycol, tert-butyl glycol, methylpropylene glycol, Glycol, isopropyl propylene glycol, n-butyl propylene glycol, isobutyl propylene glycol, sec-butyl propylene glycol, tert-butyl propylene glycol and the like.

Examples of m = 2 include methyldiglycol, ethyldiglycol, n-propyldiglycol, isopropyldiglycol, n-butyldiglycol, isobutyldiglycol, sec-butyldiglycol, tert-butyldiglycol, Propyleneglycol, isopropylpropyleneglycol, n-butylpropyleneglycol, isobutylpropyleneglycol, sec-butylpropyleneglycol, tert-butylpropyleneglycol and the like can be mentioned .

Examples of m = 3 include methylene glycol, ethyltriglycol, n-propyltriglycol, isopropyltriglycol, n-butyltriglycol, isobutyltriglycol, sec-butyltriglycol, tert-butyltriglycol, , Ethyl propylene triglycol, n-propyl propylene triglycol, isopropyl propylene triglycol, n-butyl propylene triglycol, isobutyl propylene triglycol, sec-butyl propylene triglycol and tert- butyl propylene triglycol .

These components (B) may be used alone or in combination of two or more. Among them, R ¹ in the formula (2) preferably has an alkyl group having 3 or 4 carbon atoms in view of the removal effect of the removing agent and environmental characteristics, and is preferably an alkyl group having 3 or 4 carbon atoms such as n-butyl glycol, n-propyleneglycol, n-propyldiglycol, n-butyldiglycol and n-butyltriglycol.

The weight ratio of the component (B) in the removal agent for a rust preventive film of the present invention is not particularly limited, but is usually from 75 to 98.5% by weight, preferably from 80 to 97% by weight, in terms of solid content, Respectively.

The component (C) is not particularly limited and various known ones can be used, and examples thereof include organic monocarboxylic acids such as formic acid, acetic acid, propionic acid, lactic acid, benzoic acid and salicylic acid; Organic dicarboxylic acids such as tricarboxylic acid, citric acid, and trimellitic acid; organic dicarboxylic acids such as ethylene tetracarboxylic acid, butanetetracarboxylic acid, and the like Of organic tetracarboxylic acids. Examples of the salt include ammonium salts and the like. These may be used singly or in combination of two or more. Among them, at least one selected from the group consisting of an organic monocarboxylic acid, an organic dicarboxylic acid, an organic tricarboxylic acid and a salt thereof is preferable in view of the removal effect of the removing agent, and it is preferable to contain at least one member selected from the group consisting of formic acid, And more preferably at least one selected from the group consisting of succinic acid, malic acid, lactic acid, malonic acid and salicylic acid.

The weight ratio of the component (C) to the component (C) in the rust preventive film of the present invention is not particularly limited, but is usually about 0.1 to 5% by weight, preferably 0.1 to 4% by weight in terms of solid content, , More preferably about 0.1 to 3 wt%.

The rust preventive membrane removing agent of the present invention may further contain an alkanolamine (D) (hereinafter referred to as (D) component) other than (A) in view of the rinsability of the removing agent. Examples of the component (D) include, but are not limited to, N-methyldiethanolamine, N-ethyldiethanolamine, N-n-propyldiethanolamine, N-isopropyldiethanolamine, N- Alkyldiethanolamines such as N, N-dimethylethanolamine, N, N-dimethylethanolamine, N, N-dimethylethanolamine, N, N-dimethyldiethanolamine, N-tert- butyldiethanolamine, Diethanolamine, N, N-di-n-butylethanolamine, N, N-diisobutylethanolamine, N, N-diisopropylethanolamine, N, N-dialkylethanolamines such as N, N-di-tert-butylethanolamine, N, N-di- And the like. These may be used singly or in combination of two or more.

The weight ratio of the component (D) in the removing agent for a rust preventive film of the present invention is not particularly limited, but is preferably about 0.1 to 10% by weight in terms of solid content.

The rust-preventive-film removing agent of the present invention may contain water as necessary in view of flammability. The weight ratio of water in the remover of the present invention is not particularly limited, but is preferably about 2 to 30% by weight.

The rust preventive film removing agent of the present invention may contain various known additives. The additive is not particularly limited, and examples thereof include a chelating agent, an antioxidant, a defoaming agent, a pH adjuster, an imidazole-based rheological agent, a triazole-based rheological agent, a stabilizer, a dispersant and a surfactant. The amount of the additive to be used is not particularly limited, but is usually less than 1 part by weight based on 100 parts by weight of the rust inhibitor removing agent.

The rust preventive film removing agent of the present invention is applied to a rust preventive film comprising a nitrogen-containing heterocyclic compound having two or more nitrogen atoms. Examples of the nitrogen-containing heterocyclic compound include, but are not limited to, imidazoles, triazoles, etc. These compounds may be used singly or in combination of two or more.

Examples of imidazoles include, but are not limited to, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-isopropylimidazole, (2-heptylimidazole, 2-heptylimidazole, 2- (1-ethylpentyl) imidazole, 2-octylimidazole, 2-undecylimidazole, 2-undecylimidazole, 2-tridecylimidazole, 2-tetradecylimidazole, 2-pentadecyl (1-methylpentyl) imidazole, 2- (1-ethylpentyl) imidazole, 2- (1-heptyldisilyl) imidazole, 2- Imidazole, 2- (8-heptadecenyl) imidazole, 2- (4-chlorobutyl) imidazole, 2- (9-hydroxynonyl) imidazole, 2-ethyl-4-methylimidazole, 2-undecyl- Phenylimidazole, 2-phenyl-4-methylimidazole, 2- (1-naphthyl) imidazole, 2- (1-naphthyl) Phenylimidazole, 4-phenylimidazole, 2- (2-naphthyl) imidazole, 2- 4-methylimidazole, 4-isopropylimidazole, 4-octylimidazole, 2,4,5-trimethylimidazole, and the like.

The triazoles are not particularly limited, and examples thereof include 1,2,3-triazole, 1,2,4-triazole, 1-methyl-1,2,4-triazole, Triazole, 1-propyl-1,2,4-triazole, 1-isopropyl-1,2,4-triazole, 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, and the like.

The rust-preventive film remover of the present invention is not particularly limited, and for example, a rust-preventive film or the like formed on a land (solder joint surface) such as a printed board or interposer, a through hole, an alignment mark, .

The treatment with the removing agent for a rust preventive film of the present invention is not particularly limited, but from the viewpoint of the removing effect of the removing agent, it is preferable to carry out the treatment at a temperature of about 50 to 75 캜 for about 1 to 5 minutes. As a result, the film thickness can be reduced to 50 nm or less in a short period of time, and the rust-preventive film is also left thin on the substrate after the removal. The method of using the remover is not particularly limited, and examples thereof include a shower, an immersion, a spray, and an ultrasonic wave.

<Examples>

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but it goes without saying that the scope of the present invention is not limited by them. In the examples, &quot; part &quot; and &quot;% &quot; are by weight unless otherwise specified.

Example  One

1 part of N-methylethanolamine (hereinafter referred to as MEM), 93.7 parts of n-butyl diglycol (hereinafter referred to as BDG), 0.3 part of citric acid and 5 parts of water were mixed at room temperature until they became homogeneous, A remover was prepared. The composition is shown in Table 1 (hereinafter the same).

Example  2 to 23, Comparative Example  1 to 12

The composition shown in Table 1 was used in the same manner as in Example 1 to obtain a rust preventive film removing agent.

(Commercial name: Tough Ace F2 (LX), Shikoku Chemical Co., Ltd.) having a thickness of 300 nm on the copper surface of a copper plate (phosphorus acid copper plate C1220P (specified in JIS H3100) and dimensions: 50 mm x 50 mm x 0.5 mm) Manufactured by Kokusa Kogyo Co., Ltd.) for a predetermined period of time, followed by dehydration and drying to form a rust preventive film. The test copper board was immersed in the remover of Example 1 which had been heated to 60 DEG C and subjected to ultrasonic cleaning for 1 minute. Then, the surface of the test copper plate was dehydrated by nitrogen blowing, and then dried under reduced pressure at room temperature. Also, the removers of Examples 2 to 23 and Comparative Examples 1 to 12 were carried out in the same manner.

(Removal effect)

The copper surface of the test copper plate was measured by ESCA (apparatus name: PHI5000 VersaProbe II, manufactured by EINBAK PIE Co., Ltd.), etching was performed until no nitrogen atoms were detected, and the thickness of the rust preventive film remained on the copper surface of the test copper plate Respectively.

?: Film thickness after treatment less than 30 nm (etching time: within 2 minutes)

?: Film thickness after treatment of 30 nm or more and less than 60 nm (etching time: 2 to 4 minutes)

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

X: film thickness after processing: 90 nm or more (etching time: 6 minutes or more)

※ The amount of each component is expressed in% by weight.

The abbreviations in Table 1 represent the following compounds.

&Lt; Component (A) &gt;

MEM: N-ethylethanolamine

MMA: N-methylethanolamine

EA: N- (2-aminoethyl) ethanolamine

MBM: N-n-butylethanolamine

&Lt; Component (D) &gt;

MBD: N-n-butyl diethanolamine

MDA: N-methyl diethanolamine

&Lt; Component (B) &gt;

BDG: n-butyl diglycol

BG: n-butyl glycol

BTG: n-butyltriglycol

PDG: n-propyl diglycol

PFG: n-propyl propylene glycol

Claims (7)

(1), comprising an alkanolamine (A), a glycol ether solvent (B) and a nitrogen-containing heterocyclic compound having at least two nitrogen atoms including an organic carboxylic acid and / or a salt thereof Membrane remover.
R ¹ - (NHCH ₂ CH ₂ ) _n -OH (1)
(In the 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) The method according to claim 1,
(A) comprises at least one member selected from the group consisting of N-methylethanolamine, N-ethylethanolamine, N-n-butylethanolamine and N- (2-aminoethyl) ethanolamine A rust inhibitor. 3. The method according to claim 1 or 2,
And the component (B) is represented by the general formula (2).
R ² - (OCH ₂ CH _X ) _m -OH (2)
(In the formula (2), R ² represents an alkyl group having 1 to 4 carbon atoms, X represents a hydrogen or a methyl group, and m represents an integer of 1 to 3) 4. The method according to any one of claims 1 to 3,
(C) comprises at least one member selected from the group consisting of an organic monocarboxylic acid, an organic dicarboxylic acid, an organic tricarboxylic acid, and salts thereof. 5. The method according to any one of claims 1 to 4,
Alkyldiethanolamine. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 6. The method according to any one of claims 1 to 5,
Wherein the weight ratio of the components (A) to (C) is from 1 to 20% by weight of the component (A), from 75 to 98.9% by weight of the component (B) and from 0.1 to 5% by weight of the component (C). 7. The method according to any one of claims 1 to 6,
And removing the rust-preventive film formed on the alignment mark and / or identification number portion printed on the substrate.