WO2022114110A1

WO2022114110A1 - Cleaning agent composition for detaching resin mask

Info

Publication number: WO2022114110A1
Application number: PCT/JP2021/043347
Authority: WO
Inventors: 山田晃平; 西勲; 久保元気
Original assignee: 花王株式会社
Priority date: 2020-11-30
Filing date: 2021-11-26
Publication date: 2022-06-02
Also published as: KR20230109148A; CN116648499A; JP2022087052A; TW202231863A

Abstract

One embodiment of the present invention provides a cleaning agent composition for detaching a resin mask, the composition exhibiting excellent resin mask removal properties while suppressing damage to a resin substrate.　One embodiment of the present disclosure relates to a cleaning agent composition for detaching a resin mask, wherein the composition contains a quaternary ammonium hydroxide (component A), an amino alcohol (component B), an aromatic alcohol (component C) and water (component D), the mass ratio of the component D and the component C (D/C) ) being 10 or more.

Description

Detergent composition for removing resin mask

The present disclosure relates to a cleaning agent composition for removing a resin mask and a method for manufacturing an electronic component using the same.

In recent years, in personal computers and various electronic devices, power consumption has been reduced, processing speed has been increased, and miniaturization has progressed, and wiring such as package boards mounted on these has been miniaturized year by year. The metal mask method has been mainly used for the formation of such fine wiring and connection terminals such as pillars and bumps, but its versatility is low and it has become difficult to deal with miniaturization of wiring and the like. Is changing to other new methods.

As one of the new methods, a method of using a dry film resist as a thick film resin mask instead of a metal mask is known. This resin mask is finally peeled off and removed, and at that time, an alkaline cleaning agent for peeling is used.

As the alkaline detergent for peeling, for example, Japanese Patent Application Laid-Open No. 2007-224165 (Patent Document 1) describes the total amount of the detergent as a dual-purpose cleaning agent capable of simultaneously cleaning the solder flux and the dry film resist. The amount of benzyl alcohol added was in the range of 5 to 94% by weight, the amine compound was in the range of 1 to 50% by weight, and water was in the range of 3 to 90% by weight. It is described as a dual-purpose cleaning agent characterized by the fact that it is used.
Further, in Japanese Patent Application Laid-Open No. 2015-7944 (Patent Document 2), it is possible to both promote the removal of the resin mask layer after the heat treatment of the solder bumps and suppress the solder corrosion, and the cleaning that can improve the solder connection reliability. As an agent, a specific quaternary ammonium hydroxide is contained in an amount of 0.5 parts by mass or more and 3.0 parts by mass or less, and a water-soluble amine is contained in an amount of 3.0 parts by mass or more and 10.0 parts by mass in 100 parts by mass of the cleaning agent composition. Cleaning agent for resin mask layer containing 0.3 parts by mass or less, acid or ammonium salt thereof in an amount of 0.3 parts by mass or more and 2.5 parts by mass or less, and water in an amount of 50.0 parts by mass or more and 95.0 parts by mass or less. The composition is described.

The present disclosure comprises, in one embodiment, a quaternary ammonium hydroxide (component A), an amino alcohol (component B), an aromatic alcohol (component C) and water (component D), with component D and component C. The present invention relates to a cleaning agent composition for removing a resin mask, which has a mass ratio D / C of 10 or more.

The present disclosure comprises, in one aspect, the step of peeling the resin mask from the object to be cleaned to which the resin mask is attached by using the cleaning agent composition of the present disclosure, wherein the resin mask is subjected to at least one treatment of exposure and development. It relates to a cleaning method which is a negative type dry film resist which has been applied.

The present disclosure relates to, in one aspect, a method for manufacturing an electronic component, which comprises a step of cleaning an electronic circuit board having a resin mask by using the cleaning agent composition of the present disclosure.

The present disclosure relates to, in one aspect, the use of the cleaning agent composition of the present disclosure for peeling a resin mask from an object to be cleaned to which a resin mask is attached.

1A is a photograph showing an example of the appearance of the substrate to be cleaned, and FIG. 1B is a photograph showing an example of the appearance of the surface of the substrate after cleaning using the detergent compositions of Examples 1 and 2. 1C is a photograph showing an example of the appearance of the surface of the substrate after cleaning using the detergent composition of Comparative Example 1.

In forming fine wiring on a printed circuit board, etc., not only the residual resin mask, but also the cleaning agent composition to reduce the residual auxiliary agents contained in the solder, plating solution, etc. used for fine wiring and bump formation. High detergency is required for objects.
Here, the resin mask is formed by using a resist whose physical properties such as solubility in a developing solution are changed by light, an electron beam, or the like. Resists are roughly classified into negative type and positive type according to the reaction method with light and electron beam.
The negative resist has the property that its solubility in a developing solution decreases when exposed, and the layer containing the negative resist (hereinafter, also referred to as “negative resist layer”) is formed by the exposed portion after exposure and development processing. Used as a resin mask.
The positive resist has the property of increasing its solubility in a developing solution when exposed, and the layer containing the positive resist (hereinafter, also referred to as “positive resist layer”) is exposed to the exposed portion after exposure and development processing. It is removed and the unexposed area is used as a resin mask. By using a resin mask having such characteristics, it is possible to form fine connection portions of a circuit board such as metal wiring, metal pillars and solder bumps.

However, as the wiring becomes finer, it becomes difficult to remove the resin mask in the fine gaps, and the detergent composition is required to have high resin mask removing property.
On the other hand, in order to reduce the size of electronic devices, increase the processing speed, and reduce power consumption, wiring miniaturization is progressing. If the wiring width is narrowed, the electric resistance becomes large, heat is generated, and the function of the electronic device may be deteriorated. In order to reduce the electrical resistance without increasing the area of the wiring board, measures are taken to increase the height of the wiring. Therefore, the resin mask used for wiring formation becomes thicker, the contact area with the wiring increases, and the wiring interval due to miniaturization becomes narrower, which makes it difficult to remove the resin mask. In particular, high-energy low-wavelength light is used to draw fine wiring, but the thick resin mask increases the distance from the resin mask surface to the substrate, and the reaction rate of photopolymerization due to exposure is higher than that of the surface. A difference occurs between the surface of the contact surface of the substrate, the reaction on the surface proceeds excessively, and the cleaning agent composition does not permeate from the surface of the resin mask unless the permeability is enhanced, and the resin mask becomes difficult to remove.
Further, in the technique of Patent Document 1, the resin such as solder resist used for the electronic circuit board may be damaged.

Therefore, the present disclosure provides a cleaning agent composition for removing a resin mask, which is excellent in resin mask removing property, and a method for manufacturing an electronic component using the same, while suppressing damage to the substrate resin.

According to the present disclosure, it is possible to provide a cleaning agent composition for removing a resin mask, which is excellent in resin mask removing property, and a method for manufacturing an electronic component using the same, while suppressing damage to the substrate resin.

In the present disclosure, by using a cleaning agent composition containing a specific alkaline compound and further containing water and an aromatic alcohol in a specific mass ratio, damage to the substrate resin can be suppressed and a resin mask can be efficiently applied from the substrate surface. Based on the finding that it can be removed well.

The present disclosure, in one embodiment, comprises a quaternary ammonium hydroxide (component A), an amino alcohol (component B), an aromatic alcohol (component C) and water (component D), with respect to component C of component D. The present invention relates to a detergent composition for removing a resin mask having a mass ratio (D / C) of 10 or more (hereinafter, also referred to as “detergent composition of the present disclosure”).

According to the present disclosure, it is possible to provide a detergent composition having excellent resin mask removing property and capable of suppressing damage to the substrate resin. Then, by using the cleaning agent composition of the present disclosure for cleaning electronic parts such as electronic circuit boards having a resin mask, high quality electronic parts can be obtained with high yield.

The details of the mechanism of action of the effect manifestation of the present disclosure are unclear, but it is presumed as follows.
The quaternary ammonium hydroxide (component A) and amino alcohol (component B) permeate into the resin mask to promote the dissociation of the alkali-soluble resin contained in the resin mask, and further repel the charge generated by the dissociation. It is considered that the peeling of the resin mask is promoted by causing the above. Since the quaternary ammonium hydroxide (component A) and the amino alcohol (component B) have different penetration rates into the resin mask, the alkali-soluble resin on the surface of the resin mask is suppressed from being rapidly dissociated and penetrated. It is considered that the charge repulsion only on the surface of the resin mask, which is an inhibitor, is suppressed.
On the other hand, the aromatic alcohol (component C) permeates the resin mask together with the quaternary ammonium hydroxide (component A) and the amino alcohol (component B) to promote the permeation and further improve the peelability of the alkali-soluble resin. It is thought to promote. Further, the aromatic alcohol (component C) causes damage to the resin when it permeates into the resin used for the substrate. However, by increasing the proportion of water (component D), the detergent for the aromatic alcohol (component C) is used. It is considered that the dissolution into the resin becomes dominant and the penetration of the substrate into the resin is suppressed.
However, the present disclosure may not be construed as being limited to this mechanism.

The odor resin mask in the present disclosure is a mask for protecting the surface of a substance from treatments such as etching, plating, and heating, that is, a mask that functions as a protective film. In one or more embodiments, the resin mask is subjected to at least one of the resist layer after the exposure and development steps, and the exposure and development (hereinafter, also referred to as “exposure and / or development treatment”). Examples thereof include a resist layer and a cured resist layer. Examples of the resin material forming the resin mask include a film-shaped photosensitive resin, a resist film, or a photoresist in one or more embodiments. A general-purpose resist film can be used.

[Quaternary ammonium hydroxide (component A)]
Examples of the quaternary ammonium hydroxide (hereinafter, also referred to as “component A”) contained in the detergent composition of the present disclosure include a quaternary ammonium hydroxide represented by the following formula (I). Be done. The component A may be one kind or a combination of two or more kinds.

In the above formula (I), R ¹ , R ² , R ³ and R ⁴ are each independently selected from at least one of a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group and a hydroxypropyl group. Is.

The quaternary ammonium hydroxide represented by the formula (I) is a salt composed of a quaternary ammonium cation and a hydroxide, for example, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, or tetrapropyl. Ammonium Hydroxide, 2-Hydroxyethyltrimethylammonium Hydroxide (Colin), 2-Hydroxyethyl Triethylammonium Hydroxide, 2-Hydroxyethyl Tripropylammonium Hydroxide, 2-Hydroxypropyltrimethylammonium Hydroxide, 2-Hydroxypropyltriethylammonium Hydroxide, 2-Hydroxypropyltripropylammonium Hydroxide, Dimethylbis (2-Hydroxyethyl) Ammonium Hydroxide, diethylbis (2-Hydroxyethyl) Ammonium Hydroxide, Dipropylbis (2-Hydroxyethyl) Ammonium Hydroxide, Tris (2) -Hydroxyethyl) Methylammonium Hydroxide, Tris (2-Hydroxyethyl) Ethylammonium Hydroxide, Tris (2-Hydroxyethyl) propylammonium Hydroxide, Tetrakiss (2-Hydroxyethyl) Ammonium Hydroxide, and Tetrakiss (2-Hydroxy) At least one selected from propyl) ammonium hydroxide is mentioned. Among these, tetramethylammonium hydroxide (TMAH) is more preferable from the viewpoint of improving the resin mask removability.

The content of component A at the time of use of the cleaning agent composition of the present disclosure is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1% by mass or more from the viewpoint of improving the resin mask removability. Is more preferable, and from the same viewpoint, 5% by mass or less is preferable, 4% by mass or less is more preferable, and 3% by mass or less is further preferable. From the same viewpoint, the content of the component A at the time of use of the detergent composition of the present disclosure is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 4% by mass or less. It is more preferably 1% by mass or more and 3% by mass or less. When the component A is a combination of two or more kinds, the content of the component A means the total content thereof.

In the present disclosure, the "content of each component at the time of using the detergent composition" means the content of each component at the time of cleaning, that is, at the time when the use of the detergent composition for cleaning is started.
The content of each component in the detergent composition of the present disclosure can be regarded as the blending amount of each component in the detergent composition of the present disclosure in one or more embodiments.

[Amino alcohol (component B)]
Examples of the amino alcohol (alkanolamine) (hereinafter, also referred to as “component B”) contained in the detergent composition of the present disclosure include compounds represented by the following formula (II). The component B may be one kind or a combination of two or more kinds.

In the above formula (II), R ⁵ represents a hydrogen atom, a methyl group, an ethyl group or an aminoethyl group, and R ⁶ represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group or an ethyl group, and R ⁷ indicates a hydroxyethyl group or a hydroxypropyl group.

Examples of the component B include monoethanolamine (MEA), monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine, and diisopropanolamine. N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-diethylmonoethanolamine, N-diethylmonoisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanol At least one selected from amines, N- (β-aminoethyl) ethanolamines, N- (β-aminoethyl) isopropanolamines, N- (β-aminoethyl) diethanolamines, N- (β-aminoethyl) diisopropanolamines. Seeds are mentioned. Among these, monoethanolamine (MEA) is preferable from the viewpoint of improving the resin mask removability.

The content of component B at the time of use of the cleaning agent composition of the present disclosure is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and 1% by mass or more from the viewpoint of improving the resin mask removability. More preferably, 4% by mass or more is further preferable, and from the same viewpoint, 30% by mass or less is more preferable, 15% by mass or less is more preferable, 10% by mass or less is further preferable, and 8% by mass or less is further preferable. From the same viewpoint, the content of component B at the time of use of the cleaning agent composition of the present disclosure is preferably 0.3% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less. It is more preferably 1% by mass or more and 10% by mass or less, and further preferably 4% by mass or more and 8% by mass or less. When the component B is a combination of two or more kinds, the content of the component B means the total content thereof.

[Aromatic alcohol (component C)]
The aromatic alcohol (hereinafter, also referred to as “component C”) contained in the detergent composition of the present disclosure may be a compound having an aromatic ring and a hydroxyl group. From the viewpoint of improving the resin mask removability, the carbon number of the aromatic alcohol is preferably 7 or more, preferably 10 or less, and more preferably 9 or less. The component C may be one kind or a combination of two or more kinds.

Examples of the component C include at least one selected from benzyl alcohol, phenethyl alcohol, 4-methylbenzyl alcohol, 4-ethylbenzyl alcohol, 2-phenyl-1-propanol, and 2-phenyl-2-propanol, and a resin. Benzyl alcohol is more preferable from the viewpoint of improving mask removability.

The content of component C at the time of use of the cleaning agent composition of the present disclosure is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and 1% by mass or more from the viewpoint of improving the resin mask removability. Is more preferable, and from the viewpoint of suppressing damage to the substrate resin, 10% by mass or less is preferable, 9% by mass or less is more preferable, and 5% by mass or less is further preferable. From the viewpoint of improving the removability of the resin mask and suppressing damage to the substrate resin, the content of the component C in the cleaning agent composition of the present disclosure is preferably 0.1% by mass or more and 10% by mass or less, preferably 0.3% by mass or more and 10% by mass. More preferably, it is 0.3% by mass or more and 9% by mass or less, further preferably 1% by mass or more and 5% by mass or less. When the component C is a combination of two or more kinds, the content of the component C means the total content thereof.

[Water (component D)]
As the water contained in the cleaning agent composition of the present disclosure (hereinafter, also referred to as "component D"), ion-exchanged water, RO water, distilled water, pure water, ultrapure water and the like are used in one or more embodiments. Can be mentioned.

The content of component D in the detergent composition of the present disclosure can be the residue excluding component A, component B, component C and optional components described later. Specifically, the content of the component D when the cleaning agent composition of the present disclosure is used is preferably 60% by mass or more from the viewpoint of improving the resin mask removability, reducing the wastewater treatment load, and suppressing damage to the substrate resin. , 70% by mass or more is more preferable, 80% by mass or more is further preferable, and 99% by mass or less is preferable, 95% by mass or less is more preferable, and 90% by mass or less is further preferable from the viewpoint of improving the resin mask removability. .. From the same viewpoint, the content of the component D in use of the detergent composition of the present disclosure is preferably 60% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and more preferably 80% by mass or more. 90% by mass or less is more preferable.

The mass ratio D / C of the component D to the component C when the cleaning agent composition of the present disclosure is used is 10 or more, preferably 15 or more, from the viewpoint of improving the resin mask removability and suppressing damage to the substrate resin. , 20 or more is more preferable, and from the same viewpoint, 100 or less is preferable, 70 or less is more preferable, and 40 or less is further preferable. From the same viewpoint, the mass ratio D / C in the detergent composition of the present disclosure is preferably 10 or more and 100 or less, more preferably 15 or more and 70 or less, still more preferably 20 or more and 40 or less in one or more embodiments. .. The mass ratio D / C in the cleaning composition of the present disclosure is preferably 10 or more and 100 or less, more preferably 10 or more and 70 or less, and further preferably 10 or more and 40 or less in one or more embodiments.

[Organic solvent (component E)]
The detergent composition of the present disclosure may further contain an organic solvent (hereinafter, also referred to as "component E") in one or more embodiments. The component E may be one kind or a combination of two or more kinds.
The component E includes at least one organic solvent selected from glycol ethers and aromatic ketones in one or more embodiments.
Examples of the glycol ether include compounds having a structure in which ethylene glycol is added in an amount of 1 or more and 3 mol or less to an alcohol having 1 or more and 8 or less carbon atoms from the viewpoint of improving the resin mask removability. Specific examples of the glycol ether include at least one selected from diethylene glycol monobutyl ether (BDG), ethylene glycol monobenzyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and diethylene glycol diethyl ether.
Examples of the aromatic ketone include acetophenone and the like from the viewpoint of improving the resin mask removability.

When the cleaning agent composition of the present disclosure contains the component E, the content of the component E at the time of use of the cleaning agent composition of the present disclosure is preferably 0.1% by mass or more from the viewpoint of improving the resin mask removability. , 0.5% by mass or more is more preferable, 1% by mass or more is further preferable, 2% by mass or more is further preferable, and 10% by mass or less is preferable, and 7% by mass or less is preferable from the viewpoint of improving the resin mask removability. Is more preferable, 5% by mass or less is further preferable, and 4% by mass or less is further preferable. From the same viewpoint, the content of the component E at the time of use of the cleaning agent composition of the present disclosure is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 7% by mass or less. It is more preferably 1% by mass or more and 5% by mass or less, and even more preferably 2% by mass or more and 4% by mass or less. When the component E is a combination of two or more kinds, the content of the component E means the total content thereof.

[Other ingredients]
The detergent composition of the present disclosure may further contain other components, if necessary, in addition to the above-mentioned components A to E. Examples of other components include components that can be used in ordinary detergents, for example, alkaline agents other than component A and component B, amines other than component B, surfactants, chelating agents, thickeners, and the like. Dispersants, rust inhibitors, polymer compounds, solubilizers, antioxidants, preservatives, defoamers, antibacterial agents and the like can be mentioned.

The detergent composition of the present disclosure may be substantially free of acids or ammonium salts thereof in one or more embodiments. Examples of the content of the acid or its ammonium salt at the time of using the detergent composition of the present disclosure include less than 0.3% by mass.

The pH of the detergent composition of the present disclosure at the time of use is preferably 12 or more, more preferably 12.5 or more, and even more preferably 13 or more, from the viewpoint of improving the resin mask removability. In the present disclosure, the "pH at use" is the pH at 25 ° C. and can be measured using a pH meter. Specifically, it can be measured by the method described in Examples.

[Manufacturing method of detergent composition]
The detergent composition of the present disclosure can be produced by blending the above-mentioned components A to D and, if necessary, the above-mentioned optional components (component E and other components) in one or more embodiments by a known method. .. For example, the detergent composition of the present disclosure may be composed of at least the above-mentioned components A to D. Therefore, the present disclosure relates to a method for producing a detergent composition, which comprises at least a step of blending the components A to D. In the present disclosure, "blending" includes mixing components A to D and, if necessary, the above-mentioned optional components at the same time or in any order. In the method for producing the detergent composition of the present disclosure, the preferable blending amount of each component can be the same as the preferable content of each component of the detergent composition of the present disclosure described above.

The detergent composition of the present disclosure may be prepared as a concentrate in which the amount of water (component D) is reduced as long as it does not cause separation, precipitation, etc. and impair storage stability. The concentrate of the detergent composition is preferably a concentrate having a dilution ratio of 3 times or more from the viewpoint of transportation and storage, and preferably a concentrate having a dilution ratio of 30 times or less from the viewpoint of storage stability. .. The concentrate of the detergent composition can be diluted with water (component D) so that the components A to D and the optional components have the above-mentioned contents (that is, the contents at the time of washing) at the time of use. Further, the concentrate of the detergent composition can be used by adding each component separately at the time of use. In the present disclosure, "at the time of use" or "at the time of cleaning" of the detergent composition of the concentrate means a state in which the concentrate of the detergent composition is diluted.

[Item to be washed]
The cleaning agent composition of the present disclosure can be used in one or more embodiments for cleaning an object to be cleaned to which a resin mask is attached. The cleaning agent composition of the present disclosure can be used in one or more embodiments to peel off the resin mask from the object to be cleaned to which the resin mask is attached. That is, the present disclosure relates to, in one aspect, the use of the cleaning agent composition of the present disclosure for peeling a resin mask from an object to be cleaned to which a resin mask is attached.
Examples of the object to be cleaned include electronic parts and their manufacturing intermediates. Examples of the electronic component include at least one component selected from a metal plate such as a printed circuit board, a wafer, a copper plate, and an aluminum plate. The manufacturing intermediate product is an intermediate product in the manufacturing process of the electronic component, and includes an intermediate product after the resin mask treatment.
Examples of the object to be cleaned to which the resin mask is attached include an electronic circuit board having a cured resin mask in one or more embodiments. For example, examples of the object to be cleaned to which the resin mask is attached include a glass epoxy multilayer substrate having a metal foil (for example, copper foil) on the surface and a substrate having a cured resin mask on the surface.
The object to be cleaned to which the resin mask is attached is subjected to steps such as soldering and plating (copper plating, aluminum plating, nickel plating, etc.) using the resin mask in one or more embodiments. Examples thereof include electronic components in which wiring, connection terminals, and the like are formed on the surface of a substrate. Specifically, for example, an uncured resin mask on the surface of a glass epoxy multilayer substrate is subjected to at least one curing treatment of exposure and development, the uncured resin mask is removed, and then a circuit pattern is formed by a plating treatment. The substrate can be mentioned. A cured resin mask is present in the non-plated portion of the formed circuit pattern. The width of the fine wire portion by the plating treatment is preferably 1 μm or more, more preferably 5 μm or more, and preferably 50 μm or less, more preferably 30 μm or less, from the viewpoint of the cured resin mask removability. The width of the cured resin mask of the non-plated portion (between the circuit patterns) is preferably 1 μm or more, more preferably 5 μm or more, and preferably 50 μm or less, more preferably, from the viewpoint of the cured resin mask removability. Has a width of 30 μm or less. Further, as the electronic component, from the viewpoint of exhibiting the effect of suppressing damage to the substrate resin, a substrate having a resin on the surface can be mentioned, and for example, a substrate having a solder resist can be mentioned.
Accordingly, the present disclosure relates, in one aspect, to the use of the cleaning agent composition of the present disclosure as a cleaning agent in the manufacture of electronic components.

In one or more embodiments, the detergent composition of the present disclosure is suitable for cleaning a resin mask or an object to be cleaned to which a plating-treated and / or heat-treated resin mask is attached, from the viewpoint of cleaning effect. Can be used for. As the resin mask, for example, a negative type resin mask or a positive type resin mask may be used, and a negative type resin mask is preferable from the viewpoint that the effects of the present disclosure are easily exhibited. Examples of the negative resin mask include an exposed and / or developed negative dry film resist. In the present disclosure, the negative resin mask is formed by using a negative resist, and examples thereof include an exposed and / or developed negative resist layer. In the present disclosure, the positive resin mask is formed by using a positive resist, and examples thereof include an exposed and / or developed positive resist layer.

[Washing method]
The present disclosure comprises, in one aspect, the step of peeling the resin mask from the object to be cleaned to which the resin mask is attached by using the cleaning agent composition of the present disclosure, wherein the resin mask is subjected to at least one treatment of exposure and development. The present invention relates to a cleaning method (hereinafter, also referred to as “the cleaning method of the present disclosure”), which is a negative dry film resist applied. In the cleaning method of the present disclosure, the step of peeling the resin mask from the object to be cleaned includes, in one or more embodiments, bringing the object to be cleaned to which the resin mask is attached into contact with the cleaning agent composition of the present disclosure. According to the cleaning method of the present disclosure, the resin mask can be efficiently removed while suppressing damage to the substrate resin. Examples of the substrate resin include solder resist.

As a method of peeling the resin mask from the object to be cleaned using the cleaning agent composition of the present disclosure, or a method of contacting the cleaning agent composition of the present disclosure with the object to be cleaned, for example, a cleaning agent composition is added. Examples thereof include a method of contacting by immersing in a washing tub, a method of injecting a cleaning agent composition into contact by spraying it (shower method), and an ultrasonic cleaning method of irradiating ultrasonic waves during immersion. The detergent composition of the present disclosure can be used as it is for cleaning without being diluted. Examples of the object to be cleaned include the above-mentioned object to be cleaned. Examples of the soaking time include 1 minute or more and 10 minutes or less, and further, 3 minutes or more and 6 minutes or less. Examples of the spray time include 1 minute or more and 10 minutes or less, and further, 3 minutes or more and 6 minutes or less.

The cleaning method of the present disclosure may include, in one or more embodiments, a step of contacting the cleaning agent composition with the object to be cleaned, rinsing with water, and drying. Examples of the rinsing method include running water rinsing. Examples of the drying method include air blow drying.
The cleaning method of the present disclosure may include, in one or more embodiments, a step of contacting the cleaning agent composition with the object to be cleaned and then rinsing with water.

In the cleaning method of the present disclosure, it is preferable to irradiate ultrasonic waves at the time of contact between the cleaning agent composition of the present disclosure and the object to be cleaned, because the cleaning power of the cleaning agent composition of the present disclosure is easily exerted. It is more preferable that the sound wave has a relatively high frequency. From the same viewpoint, the ultrasonic irradiation conditions are preferably, for example, 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.

In the cleaning method of the present disclosure, the temperature of the detergent composition is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and the organic resin-containing substrate, from the viewpoint that the cleaning power of the detergent composition of the present disclosure is easily exhibited. From the viewpoint of reducing the influence on the temperature, 70 ° C. or lower is preferable, and 60 ° C. or lower is more preferable.

[Manufacturing method of electronic parts]
The present disclosure relates to, in one aspect, a method for manufacturing an electronic component, which comprises a step of peeling a resin mask from an object to be cleaned to which a resin mask is attached by using the cleaning agent composition of the present disclosure. Examples of the object to be cleaned include the above-mentioned object to be cleaned.
The present disclosure relates to a method for manufacturing an electronic component, comprising a step of cleaning an electronic circuit board having a resin mask (hereinafter, also referred to as a “cleaning step”) using the cleaning agent composition of the present disclosure in another aspect. .. Examples of the cleaning method in the cleaning step include the same method as the cleaning method of the present disclosure described above.
According to the method for manufacturing an electronic component of the present disclosure, by performing cleaning using the cleaning agent composition of the present disclosure, the resin mask adhering to the electronic component can be effectively removed, so that the electronic component can be highly reliable. Manufacture becomes possible.

[kit]
The present disclosure relates, in one aspect, to a kit for use in any of the cleaning methods of the present disclosure and the method of manufacturing electronic components of the present disclosure (hereinafter, also referred to as "kit of the present disclosure"). The kit of the present disclosure is a kit for producing the detergent composition of the present disclosure in one or more embodiments. According to the kit of the present disclosure, it is possible to obtain a detergent composition having excellent resin mask removability while suppressing damage to the substrate resin.

As one embodiment of the kit of the present disclosure, a solution containing component A (first solution), a solution containing component B (second solution), and a solution containing component C (third solution) are used. , In a state where they are not mixed with each other, and at least one selected from the first solution, the second solution and the third solution further contains a part or all of the component D (water), and the first solution and the second solution Examples of the third solution include a kit (three-component cleaning agent composition) that is mixed at the time of use. After the first liquid, the second liquid and the third liquid are mixed, they may be diluted with water (component D) if necessary. Each of the first liquid, the second liquid, and the third liquid may contain the above-mentioned optional components, if necessary.
As another embodiment of the kit of the present disclosure, a solution containing component A and component B (first solution) and a solution containing component C (second solution) are contained in a state in which they are not mixed with each other. At least one of the first solution and the second solution further contains a part or all of the component D (water), and the first solution and the second solution are mixed at the time of use. Things). After the first liquid and the second liquid are mixed, they may be diluted with component D (water) if necessary. Each of the first liquid and the second liquid may contain the above-mentioned optional components, if necessary.

Hereinafter, the present disclosure will be specifically described with reference to Examples, but the present disclosure is not limited to these Examples.

1. 1. Preparation of Detergent Compositions of Examples 1 to 6 and Comparative Examples 1 to 7 Each component shown in Tables 1 and 2 is blended in the blending amounts (mass%, effective content) shown in Tables 1 and 2, and the mixture is stirred. And mixed to prepare the detergent compositions of Examples 1 to 6 and Comparative Examples 1 to 7.
The pH of each detergent composition shown in Tables 1 and 2 at 25 ° C. is a value measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), and the electrode of the pH meter is used as the detergent composition. It is a numerical value 3 minutes after soaking.

The following were used to prepare the detergent compositions of Examples 1 to 6 and Comparative Examples 1 to 7.
(Component A)
TMAH: Tetramethylammonium hydroxide [manufactured by Showa Denko KK, concentration 25%]
(Non-ingredient A)
KOH: Potassium hydroxide [Fuji Film Wako Pure Chemical Industries, Ltd.]
(Component B)
MEA: Monoethanolamine [Fujifilm Wako Pure Chemical Industries, Ltd., special grade]
(Component C)
Benzyl alcohol [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade]
(Component D)
Water [Pure water of 1 μS / cm or less manufactured by G-10DSTSET, a pure water device manufactured by Organo Corporation]
(Component E)
BDG: Butyl diglycol [manufactured by Nippon Embroidery Co., Ltd., diethylene glycol monobutyl ether]

2. 2. Evaluation of Cleaning Agent Compositions of Examples 1 and 2 and Comparative Examples 1 to 3 and 5 to 7 The following evaluations were performed on the prepared cleaning agent compositions of Examples 1 and 2 and Comparative Examples 1 to 3 and 5 to 7. ..

[Washing test method]
To a 3L beaker, 2 kg of each of the cleaning agent compositions of Examples 1 and 2 and Comparative Examples 1 to 3 and 5 to 7 was added and heated to 55 ° C., and a 1-fluid nozzle (fan shape) VVP9060 (manufactured by Ikeuchi Co., Ltd.) The test piece is sprayed for 3 minutes (pressure: 0.15 MPa, spray distance: 10 cm) while circulating in a box-type spray washer equipped as a spray nozzle. Then, it is immersed in a rinsing tank in which 1 kg of water is added to a 1 L glass beaker, rinsed, and then dried with a nitrogen blow.
Using an optical microscope "Digital Microscope VHX-2000" (manufactured by KEYENCE CO., LTD.), The presence or absence of the resin mask remaining on the fine wire of the test piece after the cleaning test was visually observed at a magnification of 300 times. Check for residues. The results are shown in Table 1.
The test piece has a size of 120 mm × 120 mm, and is a resin mask which is a negative dry film resist cured between a fine wire circuit pattern formed by plating copper on the surface of a glass epoxy multilayer substrate and a thin copper wire circuit pattern formed. The thickness of the pattern is 50 μm, and the width of the thin wire portion is 20 μm. Further, it has an acrylic resin-based solder resist on the back surface of the substrate.

Here, FIG. 1A shows an example of an external photograph of the substrate to be cleaned before cleaning. The substrate to be cleaned shown in FIG. 1A is a glass epoxy substrate (pillar diameter: 200 μm, pitch: 400 μm) having a pillar pattern by copper plating, and a dry film resist is present in a portion other than the pillar pattern.
When the substrate to be cleaned shown in FIG. 1A was washed with the detergent composition of Comparative Example 1, when the appearance of the substrate surface after cleaning was observed, as shown in FIG. 1C, the resist residue as a whole was present. It was seen. On the other hand, when the cleaning agent composition of Examples 1 and 2 was used for cleaning, when the appearance of the substrate surface after cleaning was observed, as shown in FIG. 1B, no resist residue was observed, and the resin mask was efficiently used. It turned out that it could be removed.

[Evaluation of damage to substrate resin]
Before and after immersing the above test piece in 1 kg of each detergent composition at 55 ° C. for 10 minutes, visually confirm whether it occurs in the appearance of the solder resist portion of the test piece, and determine as follows. The results are shown in Table 1.
<Evaluation criteria>
No resin damage: No change is seen.
Resin damage: Changes can be seen.

As shown in Table 1, the detergent compositions of Examples 1 and 2 do not contain Component C, Comparative Examples 1 and 6, and Comparative Examples 2 to 3 which do not contain component A and have a mass ratio D / C of less than 10. It was found that the resin mask removability was excellent while suppressing damage to the substrate resin as compared with Comparative Example 5 containing no component A and Comparative Example 7 having a mass ratio D / C of less than 10.

3. 3. Evaluation of Cleaning Agent Compositions of Examples 3 to 6 and Comparative Example 4 The prepared cleaning agent compositions of Examples 3 to 6 and Comparative Example 4 were evaluated as follows.
[Washing test method]
To a 200 mL glass beaker, 200 g of each detergent composition of Examples 3 to 6 and Comparative Example 4 is added, heated to 60 ° C. in a warm bath, and the test piece is immersed without stirring. The time (peeling time) until the resin mask on the surface of the test piece is completely removed from the test piece after being immersed in each cleaning agent composition is measured. The results are shown in Table 2. In Table 2, when all of the resin mask was not removed even after soaking for 3 minutes, it was described as "not peeled off".
The test piece used was a solid pattern substrate having a size of 35 mm × 35 mm and having a resin mask, which is a negative dry film, attached to the surface of a glass epoxy multilayer substrate having a copper foil on the surface and then being exposed and cured.

As shown in Table 2, it was found that the detergent compositions of Examples 3 to 6 were superior in resin mask removability as compared with Comparative Example 4 containing no component B.

According to the present disclosure, it is possible to provide a detergent composition having excellent resin mask removability while suppressing damage to the substrate resin. Then, by using the cleaning agent composition of the present disclosure, it is possible to improve the performance and reliability of the manufactured electronic parts, and it is possible to improve the productivity of the semiconductor device.

Claims

Contains quaternary ammonium hydroxide (component A), amino alcohol (component B), aromatic alcohol (component C) and water (component D).
A detergent composition for removing a resin mask, wherein the mass ratio D / C of the component D to the component C is 10 or more.
The cleaning agent composition according to claim 1, wherein the content of component C is 0.1% by mass or more and 10% by mass or less.
The detergent composition according to claim 1 or 2, wherein the content of the component D is 60% by mass or more.
The detergent composition according to any one of claims 1 to 3, wherein the content of component B is 0.3% by mass or more and 30% by mass or less.
The detergent composition according to any one of claims 1 to 4, wherein the content of the component A is 0.1% by mass or more and 5% by mass or less.
The detergent composition according to any one of claims 1 to 5, wherein the component B is a compound represented by the following formula (II).

In the above formula (II), R 5 represents a hydrogen atom, a methyl group, an ethyl group or an aminoethyl group, and R 6 represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group or an ethyl group, and R 7 indicates a hydroxyethyl group or a hydroxypropyl group.
The detergent composition according to any one of claims 1 to 6, wherein the mass ratio D / C of the component D to the component C is 10 or more and 40 or less.
The detergent composition according to any one of claims 1 to 7, further containing at least one organic solvent (component E) selected from glycol ethers and aromatic ketones.
The cleaning agent composition according to claim 8, wherein the content of the component E is 0.1% by mass or more and 10% by mass or less.
The detergent composition according to any one of claims 1 to 9, wherein the pH is 12 or more.
The step of peeling the resin mask from the object to be cleaned to which the resin mask is attached by using the cleaning agent composition according to any one of claims 1 to 10 is included.
A cleaning method, wherein the resin mask is a negative photoresist that has been subjected to at least one of exposure and development treatments.
The cleaning method according to claim 11, wherein the line width of the thin line portion of the object to be cleaned to which the resin mask is attached is 1 μm or more and 50 μm or less.
The cleaning method according to claim 11 or 12, wherein the object to be cleaned is a substrate having a cured resin mask on the surface of a glass epoxy multilayer substrate having a metal foil on the surface.
A method for manufacturing an electronic component, which comprises a step of cleaning an electronic circuit board having a resin mask using the cleaning agent composition according to any one of claims 1 to 10.
Use of the cleaning agent composition according to any one of claims 1 to 10 for peeling the resin mask from the object to be cleaned to which the resin mask is attached.